Journal of Energy Storage 50 (2022) 104195

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Journal of Energy Storage

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Review Article

A review on high-density methane storage in confined nanospace by

adsorption-hydration hybrid technology
Zeyuan Wang a, b, 1, Jun Duan a, 1, Shujun Chen a, c, d, *, Yue Fu e, Xiangfu Li a, Di Wang a,
Ming Zhang a, Zhiqiang Zhang a, Dandan Liu e, Fenghao Wang b
a
College of Pipeline and Civil Engineering, China University of Petroleum (East China), Qingdao 266580, China
b
School of Human Settlements and Civil engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China
c
Qingdao engineering research center of efficient and clean utilization of fossil energy, Qingdao 266580, China
d
Shandong Key Laboratory of Oil & Gas Storage and Transport Safety, Qingdao 266580, China
e
College of New Energy, China University of Petroleum (East China), Qingdao 266580, China

A R T I C L E I N F O A B S T R A C T

Keywords: The technology of methane storage by the adsorption-hydration hybrid (AHH) combines the adsorbed natural gas
Adsorption-hydration hybrid (ANG) and natural gas hydrate (NGH) methods to store gas in porous materials. This technology can overcome
Methane hydrate the shortcomings of ANG and NGH methods and attract more and more attention, owning to high methane
Methane storage
storage performance, mild storage conditions, and promotion of hydrate formation kinetics. However, there is
Porous materials
Confined space
still a lack of a systematic review on the progress of this technology, and the understanding of the formation of
methane hydrate in confined nanospace is still insufficient. This review discusses the research on methane
storage by AHH technology in different porous materials, including carbon materials, silica, silica gel, zeolite,
and metal-organic frameworks materials. Subsequently, the main factors affecting the AHH technology are
detailed elucidated, including pore size, particle size, surface properties, water content, temperature, and
pressure conditions. In addition, this article discusses the mechanism of methane storage by AHH technology
from two aspects of experimental research and molecular simulations (including Monte Carlo and molecular
dynamics), which are helpful to understand the complex microscopic physical and chemical processes of this
technology. Finally, the main challenges faced by the AHH technology in industrial applications and future
development directions of this field are proposed.

1. Introduction
With the depletion of global oil resources and climate change caused
by massive emissions of carbon dioxide in the atmosphere, it is necessary
to find a new clean and abundant alternative energy source [1].
Compared with other fossil fuels, natural gas (NG) has been one of the
most important energy sources with advantages such as higher energy
per mass fuel, higher combustion efficiency, and lower CO2 emission.
The International Energy Outlook 2020 states that NG is the
fastest-growing primary energy source in the world, and its proportion
to other forms of primary energy will continue to increase at least 30
years until 2050 [2]. NG is expected to become the fuel of choice for
many countries in the future, unlike nuclear energy, which remains
controversial. Despite these advantages, the low volumetric energy
density (VED) of only 0.036 MJ/L under standard temperature and
pressure (STP) conditions is a key factor that limits the large-scale
application of NG. High-density storage remains a challenge, espe­
cially for light vehicles with limited space [3]. As the global economy
inevitably turns into a natural gas-based economy, new technologies
that can attain the efficient storage and transportation of NG are
increasingly required.
At present, available pathways for NG storage and transport are
provided in Fig. 1. Pipeline natural gas (PNG) as a most common mean
of transporting NG is utilized worldwide. However, PNG is not always
feasible due to the influences of distance and cost. The traditional so­
lutions of NG storage and transportation methods are compressed nat­
ural gas (CNG) and liquefied natural gas (LNG). CNG method achieves a
VED of 9.2 MJ/L at pressures above 20 MPa. However, the high costs

* Corresponding author: Mr. S. Chen

E-mail address: shujunchenfu@126.com (S. Chen).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.est.2022.104195
Received 12 October 2021; Received in revised form 7 February 2022; Accepted 8 February 2022
Available online 23 February 2022
2352-152X/© 2022 Elsevier Ltd. All rights reserved.
Z. Wang et al.
and energy-consuming multi-stage compression are required and the
large fuel tanks used reduce the space available for passengers and
cargo. Even when compressed to 20 MPa, the energy density of CNG is
only 27% that of gasoline, resulting in a significant reduction in the
distance over which CNG cars can travel [4]. LNG has a high gas storage
density (600 v/v under STP conditions) and is therefore considered to be
the most suitable for large-scale and long-distance transportation.
However, the extremely low temperature required (-162◦ C) to keep LNG
stable and the continuous boil-off issues hinder its application for stor­
age on large scales and over long periods. The two above methods are
therefore unfavorable in terms of safety and energy saving [4,5].
Adsorbed natural gas (ANG) and natural gas hydrate (NGH) are other
possible approaches of natural gas storage and transportation. ANG can
be used to store high-density methane in porous materials at room
temperature and medium pressure [3,6–8]. Compared with the methods
using CNG and LNG, the storage conditions of ANG are milder, safer and
less costly. To promote the development of ANG, the United States
Department of Energy (DOE) from 2012 requires methane storage and
transportation to achieve a volume storage capacity of 263 v/v or a
gravimetric storage capacity of 0.5 g/g (under STP conditions). How­
ever, because the currently porous materials have difficulty in meeting
the target of the DOE, large discrepancies between the storage that can
be obtained using the ANG method and the gas storage density required
still persist [4]. It is therefore necessary to synthesize more competitive
porous materials or find a more potential alternative methane stor­
age/transport method that can better meet the targets of the DOE.
Similar to porous materials, methane hydrate itself has excellent gas
storage capacity. If each cage is filled with methane, 1 m3 of methane
hydrate can be decomposed into 180 m3 of methane gas under standard
conditions [9]. The hydrate cages separate methane molecules by 0.5
nm, leading to the energy density of hydrate almost equal to that of
methane gas compressed at 0◦ C and 18 MPa [10]. NGH therefore has
great potential as a natural gas storage and transportation technology
[11–14]. Compared with the LNG and CNG, NGH storage is associated
with mild conditions, higher safety, lower transportation costs, the
storage of large amounts of gas, and an improved energy saving ability.
However, the nucleation of methane hydrate is random, the induction
time over which hydrates form is relatively long, and slow hydrate
growth kinetics render the application of NGH difficult [15–18]. If
methane hydrate can be formed under mild conditions (such as low
pressures and mild temperatures) and within a reasonable time, the
storage and transportation of NG by NGH is a particularly promising
alternative.
In the bulk water system, gas-water contact occurs at the gas-liquid
interface. Initially, the formation of hydrates will hinder further gas-
water contact, resulting in slow hydrate growth. Instead, the surface
of porous materials can provide nucleation sites that can change the
methane hydrate formation space and increase the gas-liquid contact
Fig. 1. Storage and transportation of natural gas in different ways.
2
Journal of Energy Storage 50 (2022) 104195
area available for methane and water, thus affecting the physical and
chemical properties under which methane hydrates form in the pores,
including the formation kinetics, pressure, temperature, and stability
[19–22]. Some scholars [19,23] have found that the methane adsorption
capacity in the porous materials with pre-adsorbed water is significantly
higher compared with dry materials under relatively low temperature
and high pressure conditions, because porous materials are used as the
storage medium for methane hydrate and water successfully converted
into hydrates within the pores. This method called adsorption-hydration
hybrid (AHH) technology has some significant advantages including the
following aspects [24,25]:
(i) The methane storage capacity can be greatly increased with the
formation of methane hydrate. Under the synergistic effect of
methane physisorption and hydrate formation, methane storage
capacity has an opportunity to exceed the DOE goals signifi­
cantly. Meanwhile, the temperature and pressure conditions
under the hydrate formation are very close to the DOE standard
[10,21,26–29].
(ii) When the appropriate amount of water is absorbed into the
porous material, the wall surface of porous materials under
appropriate temperature and pressure conditions and the inter­
action between water and methane will promote the formation of
methane hydrate. Compared with the free system, the formation
kinetics will be significantly improved [10,20,23,26,30–33].
(iii) Methane desorption takes place more rapidly in porous crystals
than it does in dry materials, and methane is almost completely
desorbed even under moderate pressure [10,34,35]. Moreover,
the formation of hydrate crystals will not damage the material
skeleton structure, meaning that it can be reused and the largest
methane reserves suffer almost no loss [28,36,37].
(iv) Compared with the ANG that methane is stored as adsorbed phase
in the dry materials, the pressure gradient driving the methane
storage and delivery process can be drastically reduced by
combining methane adsorbed phase and hydrate phase in the
AHH system. Compared with the conventional CNG, the methane
storage pressure for AHH technology can be reduced by more
than half [27,37].
In conclusion, the AHH technology combines the advantages of ANG
and NGH and overcomes the shortcomings of them by using the porous
materials with pre-adsorbed water to adsorb methane and form methane
hydrate. These advantages mean that this technology is expected to be
better applied in natural gas storage, transportation, and mobile sys­
tems, such as natural gas vehicles. Table 1 presents the comparison of
different technologies available for storage of natural gas. The Forma­
tion, storage conditions along with advantages and disadvantages of
each of these methods have been provided. Thus, the AHH technology is
Z. Wang et al. Journal of Energy Storage 50 (2022) 104195

Table 1
Comparison of different technologies available for natural gas storage and transport.
CNG LNG ANG NGH AHH

Gravimetric NA NA 0.22 NA 0.76**

capacity
(g/g)
Volumetric 222 600 267* 150~180 NA
capacity
(v/v)
Formation High pressure Phase-transition 6.5 MPa and 298.2 K 2 ~ 6MPa and 0 ~ 283.15 K 10 MPa and 275 K
conditions Multistage compression cooling at 0.1 MPa and 113.2
K
Storage High pressure Low temperature 6.5 MPa and 298.2 K Atmospheric pressure 10 MPa and 275 K
conditions 20 MPa and 293.2 K 0.20 MPa and 113.2 K and -15◦ C
Advantages Use widely without any High methane purity; with Mild storage conditions; Low transportation cost; mild storage Mild storage conditions;
complex step highest efficiency; volumetric light weight conditions; high security; high storage density
and energy density environmentally benign
Disadvantages High safety risk; Boil-off gas; cold energy loss Adsorbent efficiency and The technology is immature; low The technology is
Equipment is plentiful lifetime; thermal effects on hydrate formation rate and gas immature; low
and expensive adsorbent storage capacity volumetric storage
capacity
Application Vehicle; residential fuel Air separation vehicles, power Gas station; vehicles; Gas storage; seawater desalination High density methane
generation underground natural gas storage; vehicles
storage
*
Assuming HKUST-1 metal organic framework as the adsorbent material [42].
**
Assuming PW-AC carbon as the adsorbent material [43].

a noteworthy potential methane storage method [10,30,38].

Although methane storage by AHH technology has made a lot of
progress, to the best of our knowledge, there is no comprehensive review
paper summarizing the AHH technology for methane storage. Borchardt
et al. [39] reviewed the formation of methane hydrate in confined space.
Although the study of methane adsorption-hydration hybrid in
pre-humidified porous materials is also involved, they mainly focused
on the hydrate formation rather than the methane storage characteris­
tics, and ignored the link between methane adsorption and hydrate
formation. Moreover, the impacts of influencing factors on AHH were
not discussed systematically, and the microscopic mechanism of AHH
process was not analyzed. Zhou et al. [30] in their brief review only
analyzed the storage characteristics of methane in pre-humidified acti­
vated carbon, silica, and silica gel, and it has been 10 years until now. In
addition, Qin et al. [40] and Nguyen et al. [41] have reviewed the
particle size and solid surfaces of porous media on the formation of
methane hydrate, respectively. Despite these achievements, they have
been targeted toward hydrate formation failing to draw a holistic un­
derstanding of adsorption-hydration hybrid and methane storage char­
acteristics. Hence, this work aims to conduct a comprehensive and
detailed discussion of AHH technology along with providing insights
into the methane storage characteristic comprised of adsorption and
hydrate formation in the nanospace. The results of the discussion can
guide the synthesis of porous materials and storage conditions that are
suitable for AHH technology. The scope of the review is illustrated in
Fig. 2. Firstly, an overview of various porous materials used in AHH
technology, including carbon materials, silica, silica gel, zeolites, and Fig. 2. The scope of this review.
metal-organic frameworks materials (MOFs), is presented. Then, we
analyze the various factors affecting methane storage and hydrate for­ 2. Methane hydrate
mation when AHH technology is used, including pore size, particle size,
water content (Rw) i.e. water-to-materials mass ratio, surface properties, Gas hydrates, also known as cage hydrates, are non-stoichiometric
temperature, and pressure. Furthermore, the results of the experimental crystalline solids with a structure that is similar to ice [44]. The water
research and molecular simulation are reviewed to understand the molecules that are connected by hydrogen bonds to form cavities are
mechanism of methane storage in the confined nanospace during the defined as cage structures and can incorporate large numbers of specific
process of AHH. In addition, the challenges of the large-scale application guest molecules, such as SO2, CH4, CO2, C2H6, and H2, to form gas hy­
for methane storage by AHH technology have been discussed. At last, drates under favorable thermodynamic conditions [45,46]. No chemical
some future perspectives for developing AHH technology are also bond is present between the host water molecule and the guest molecule
provided. in these structures, meaning that the guest molecules can retain their
inherent characteristics in the host cage structure and maintain a stable
structure via the van der Waals force.
Methane hydrate is formed by accommodating methane molecules in

3
Z. Wang et al.
the hydrogen-bonded water network under favorable thermodynamic
conditions of high pressure (usually more than 6 MPa) and relatively low
temperature (slightly lower than room temperature) [44]. Under natural
conditions, methane hydrate is usually found in the permanent or sea­
sonal permafrost in polar regions or in marine sediments at critical
temperature/pressures. Under these conditions, natural hydrates usu­
ally form crystals with a cubic structure, which are referred to as sI. This
structure consists of two different types of cage: (i) six large cages
consisting of 12 pentagonal faces and two hexagonal faces (51262) that
are composed of 24 water molecules, and (ii) two small cages consisting
of 12 pentagonal faces (512) that are composed of 20 water molecules
[47]. The average radii of these water cage cavities are 0.433 and 0.391
nm, respectively. The nominal stoichiometry of methane hydrate with
an sI structure can be expressed as 8methane•46water (or meth­
ane•5.75water) and it can occupy both types of cavities within the sI
structure simultaneously.
2.1. Crystal structure of hydrate
Gas hydrate can take three main forms: structure I (sI), structure II
(sII), and a hexagonal from (sH). Each structure has a specific cage size,
lattice parameters and the number of water molecules that form the unit
structure [44,46]. The type of hydrate structure depends on the size of
the guest molecules and the conditions under which the hydrate forms.
With a diameter of 4-6 Å, gas molecules (such as CH4 and C2H6)
generally form sI hydrates with a unit cell size of 1.21 nm. Gas molecules
with a diameter of 6-7 Å (such as C3H8) generally form sII hydrates, but
there are some exceptions, hydrogen, argon, and nitrogen molecules
smaller than 4 Å, which form sII hydrates because they are more inclined
to occupy smaller cages, and there is a large proportion of small cages in
sII hydrate. sII hydrate is composed of two different types of cages: (i) 16
small cages (512) that are composed of 12 pentagonal faces and (ii) eight
large cages (51264) that are composed of 12 pentagonal faces and 4
hexagonal faces. The cubic unit cell size is 1.72 nm. Generally, gas
molecules with a diameter of more than 7 Å will form sH-type hydrates,
which are composed of three different types of cages: (i) three small
cages (512) that are composed of 12 pentagonal faces (512), (ii) one large
cage (51268) that is composed of 12 pentagonal faces and 8 hexagonal
faces, and (iii) two middle cages that are composed of three quadrilat­
erals, six pentagons, and eight hexagonal faces (435663). The size range
of the hexagonal unit cell is between 1.01 nm and 1.22 nm [44].
2.2. Formation mechanism of methane hydrate
The formation of methane hydrate is the result of two main pro­
cesses. Firstly, crystal nuclei are formed at the gas-liquid interface. This
occurs because the Gibbs free energy of nucleation at the interface is
relatively small and the host and guest molecules are at higher con­
centrations at the interface due to adsorption, promoting the growth of
molecular clusters. Hydrate crystals also grow continually around the
nucleus. Specifically, Vysniauskas et al. [48] suggested that the first
process in such agglomeration is the formation of partial hydrates. After
the formation of initial clusters, clusters continue to grow until they
reach a critical size and become thermodynamically stable owing to
interaction between the water molecules and the gas molecules. The
clusters are considered to be hydrate nuclei. Once a stable crystal nu­
cleus is formed, the system spontaneously enters a rapid growth phase,
during which the hydrate crystals grow in an irreversible manner. The
author proposes that the hydrate crystal formation mechanism is
composed of the following three parts:
M + H2 O + (H2 O)y− 1 ⇋M⋯(H2 O)y (1)
M + H2 O + M(H2 O)z ⇌M.(H2 O)c (2)
M + H2 O + M(H2 O)m ⇌M.(H2 O)n (3)
4
Journal of Energy Storage 50 (2022) 104195
where y, z, m, n represent the size of cluster, and the Eq. (1) is used in
depicting gas hydrates formation of an initial clustering process, M is a
gas molecule. The Eq. (2) is used in depicting the critical size cluster
formed, c represents the critical size clusters. The Eq. (3) is used in
depicting the hydrate crystal growth around a stable nucleus.
The key step in the formation of methane hydrate is the formation of
a crystal nucleus, which is essential because water molecules must
cooperate with gas molecules to form clusters of critical size [49]. This
step is the “starting point” for hydrate research. Ke et al. [50] proposed
that the hydrate nucleation process is driven randomly by free energy.
Only nuclei that reach the critical size have a chance to break through
the free energy barrier and enter the next stage in which the spontaneous
and sustainable growth of hydrate crystals occurs. Khurana et al. [51]
presented a detailed review of the hydrate nucleation theories.
Regarding the growth of gas hydrates, it is generally believed that the
Gibbs free energy of the system reaches a maximum when the gas hy­
drate crystal nucleus is formed. Once this occurs, the hydration reaction
proceeds spontaneously in the direction of decreasing Gibbs free energy.
It is difficult to use tracking and characterization techniques in routine
experiments to describe in detail the hydrate formation process owing to
the limitations of time and space. With the advancement of computer
simulation technology, molecular simulation technology, especially
molecular dynamics (MD) simulation, can clearly show the microscopic
formation mechanism of hydrates and therefore plays an increasingly
important role in studying the hydrate formation. BÁEZ et al. [52] used
non-equilibrium MD simulations for the first time to study the kinetics of
hydrate crystals in the early stage of growth or dissolution. They
implanted spherical crystal nuclei in a methane solution system to
simulate growth and found that gas molecules diffuse easily from the
liquid to the hydrate lattice position on the surface of the crystal nucleus
even if the cages in which the gas molecules are located are incomplete.
The growth of the hydrate slows down over time, however, there was no
indication that the growth stopped altogether. The author proposed that
the combination of angular order parameters and the number of
five-membered rings per water molecule forms a criterion that can well
distinguish between the hydrate phase, liquid phase, and ice. Tung et al.
[53] used MD simulation to study the key factors affecting the growth of
methane hydrate and suggested that the growth rate was mainly affected
by the solubility of methane in the liquid phase, the diffusion of methane
in water, and the adsorption capacity of methane molecules at the hy­
drate interface, indicating that the adsorption of methane at the inter­
face plays a key role in the growth of hydrates. Ke et al. [50] reviewed
both the hydrate nucleation theory and the growth model.
The use of hydrate to store methane is a new method that simulates
the formation of methane hydrate under natural conditions, such as the
deep-sea environment. Utilizing the confinement effect of porous ma­
terials allows water to form a clathrate structure in the porous materials,
forming a water cage into which methane is adsorbed to form hydrate.
The resulting hydrates are reversible and have a nominal stoichiometry
ratio that is consistent with that of natural methane hydrates. The
confinement effect of porous materials not only acts as a medium for the
physical adsorption of methane, but also accelerates the nucleation and
growth of artificial methane hydrates. It is therefore necessary to study
the use of the AHH technology to store methane in the confined
nanospace.
3. Methane storage in confined nanospace by AHH technology
3.1. Formation and decomposition of methane hydrate in confined
nanospaces
Methane can be stored in both adsorption and hydrate states in
nanoporous materials because of the large adsorption potential and
confinement effect of the confined space [39]. Compared with a pure
water system, the formation of methane hydrate in such materials is
Z. Wang et al.
more complex. The nano-confinement effect is a key factor of the AHH
technology, affecting both the adsorption and storage of methane. The
pore diameter and interfacial tension of the nanospace are key param­
eters of the confinement effect. Wang et al. [54] investigated the for­
mation of methane hydrate in quartz sand with particles of differing
sizes and shapes. The effect of interfacial tension on hydrate formation
was discussed and the fact that the capillary pressure in the confined
space decreases with the increase in interfacial tension was pointed out.
The permeability in porous media is reduced by excessive interfacial
tension between methane and water, and there is an optimal size that is
suitable for methane hydrate formation in confined space. Kim et al.
[55] reviewed the phase transition behavior of hydrate formation in
confined nanospace, and pointed out that the interfacial tension and
capillarity in confined space will affect the activity of water, signifi­
cantly influencing the formation of hydrates. In nature, the activity of
water in sediments changes owing to the presence of dissolved salts and
capillary pressure, rendering the phase equilibrium and thermodynamic
properties required for the formation of hydrate problematic as
compared to hydrate formation in free systems [56]. The influence that
confinement effect has on hydrate formation includes the following
aspects:
First, a large number of studies have shown that more harsher con­
ditions are required for hydrate formation in confined spaces. This can
be explained by the fact that higher pressures are needed to promote the
formation of hydrates at a certain temperature [23,57,58]. Some
scholars have suggested that this is due to a combination of the hin­
drance of methane diffusion in pores and the capillary effect [23,34,59].
In a cylindrical hole with diameter w, the capillary pressureΔP is [34]:
4σ lh cosθ
ΔP = (4)
w Td
where σ lh is the surface tension between the liquid water and the hydrate
phase and water is assumed to diffuse into the hydrate phase at the zero-
contact angle θ. Compared with the Pfw (the formation pressure in bulk
water) of the free system, the formation pressure of hydrate Pf is:
Pf = Pfw + ΔP (5)
According to the above formula, hydrate will first appear in the
widest pores at the lowest pressure and will further form in narrower
pores as the pressure increases. Second, compared with the free system,
the confinement effect can promote the formation kinetics of hydrate
[10]. In the bulk water, owing to the low solubility of methane in water
and the confined gas-liquid contact area, the mass transfer resistance of
methane at the gas-liquid interface has a significant inhibitory effect on
the growth of the hydrate film at the gas-liquid interface [60]. In the
porous media, hydrate forms at gas-liquid interface and grows towards
the gas phase [61]. At the same time, the formation of a hydrate film at
the gas-liquid interface further hinders the contact between methane
and water and reduces the rate at which hydrates form [16]. Some
scholars reported a unique phenomenon that differs from the free system
called the quasi-high-pressure effect, and it has been used to induce
high-pressure gas phase reactions [62–65]. A large number of experi­
mental and theoretical data show that when water is confined in
nanopores, its properties are different from those in the free system [66,
67]. Specifically, confinement may lead to a change in the freezing point
of the fluid, meaning that the freezing point of pure water will signifi­
cantly decrease in small pores [56,63]. When the temperature is lower
than the freezing point of water, water may form an ice-like structure in
the confined space. However, at a specific temperature, the limitation
effect induces the pre-adsorbed water to form an ordered structure, and
the water within the nano-space may undergo phase transformation and
spontaneously form an ice-like ordered structure that is different from
the volume phase [64–66]. Because the activation energy of quasi-solid
water is lower than that of liquid water, the accumulation of methane on
the ice surface and the formation of the defective structure greatly
5
Journal of Energy Storage 50 (2022) 104195
promotes hydrate nucleation, which has a shorter induction period
compared with the formation of hydrates in free systems [68]. The
transition from ordered solid water to the crystal phase requires a small
change in enthalpy, and even milder conditions are favorable for hy­
drate formation. Additionally, the higher specific surface area of porous
media can significantly increase the contact area between methane and
water, providing more potential nucleation sites. These factors together
improve the kinetics of hydrate formation. However, this promoting
effect is limited by the water content. Celzard et al. [34] found that
water saturation in the pore space will slow down the formation kinetics.
Unlike the free systems that occur in aqueous porous carbon materials,
the kinetic constant decreases with an increase in pressure owing to the
increasing difficulty for methane to diffuse into pore networks that
contain hydrate crystals and are filled with water. Increasing the
methane pressure can therefore accelerate the formation of hydrates in
free systems [69].
The confinement effect has a certain influence on the stability of
methane hydrates. Compared with free systems, the stability of hydrates
is weaker in porous media and the decomposition of hydrates is slightly
promoted, which facilitates higher gas production and energy utilization
efficiency [70]. The decomposition pressure increases slightly when the
temperature is constant, whereas the decomposition temperature de­
creases when the pressure is constant [23,27,71]. The influence that
confinement has on the phase balance is mainly related to changes in the
water activity [56,71]. Under a certain pressure, the decomposition
temperature of methane hydrate decreases alongside the pore size. The
relationship between temperature change and pore size satisfies the
Gibbs-Thomson equation [71]:
/
ΔT
bulk
= − 4γHW ρH LH (6)
where ΔT = Tdpore − Tdbulk . Tdpore and Tdbulk represent the decomposition
temperature in porous media and free systems, respectively; γHW is the
interfacial tension between methane hydrate and confined water; ρH
and LH represent the density and heat of decomposition of the hydrate,
respectively; and d is the pore size of the porous medium.
3.2. Application of AHH technology for methane storage in different
materials
Table 2 summarize the methane storage capacity by AHH technology
in various porous materials, including activated carbon, silica, silica gel,
zeolites, and MOFs materials. Fig. 3 illustrates a timeline for different
materials employed to explore the methane storage by AHH technology.
In this review, a comprehensive and detailed discussion will be given
that describes the different types of porous materials utilized in the field
of methane storage using the AHH technology.
3.2.1. Porous carbon materials
Nanoporous carbon material, mainly including activated carbon and
carbon nanotube, is a potentially interesting alternative material that
can be used to store methane at high pressures. The performance of
carbon materials in storing methane was first studied more than 20 years
ago and these materials were found to have good performance for this
purpose [78,79]. Carbon materials exhibit high mechanical strength and
avoid packaging-related efficiency loss [80]. Many scholars have
investigated the storage of methane in porous carbon materials by AHH
technology because of the advantages inherent in using this technique.
In 1998, Miyawaki et al. [72] used pre-humidified microporous carbon
materials to adsorb methane at 303 K and found that methane storage
capacity was increased significantly. Especially, when water content is
0.4, the methane adsorption capacity exceeded 180 mg/g at 10 kPa,
which was much higher than that of dry carbon materials at 10 MPa.
They attributed the increase of methane adsorption to the formation of
nano-hydrate with methane-to-water molar ratio of 1:2 in the
Z. Wang et al. Journal of Energy Storage 50 (2022) 104195

Table 2
Methane storage capacity by AHH technology in different materials.
Compounds Pore size Methane storage condition Methane storage capacity Ref.

nm T/K P/MPa Dry material Wet material Percentage increase *

ACFs(P20) 0.75/0.86/0.94/1.1 303 0.01 2.6 wt% 18 wt% 5.92 [72]

Activated carbon 275 9.26 19 wt% 32 wt% 0.68 [59]
Silica gel 60 8 275 10 2.9 wt%/ 5.2 wt% 0.79 [73]
MCM-41 4.4 243 6 8.6 wt% 16.5 wt% 0.93 [29]
B-PMO 3.8 243 6 5.7 wt% 12.1 wt% 1.125 [29]
Activated carbon (PP-AC) meso/micropore 275.15 10 24 wt% 63 wt% 1.625 [10]
Activated carbon (PAC) 1.6-2.8 275 7 23.6 wt% 63 wt% 1.67 [38]
Activated carbon (PP-AC) 275.15 10 26 wt% 76 wt% 1.92 [43]
Activated carbon (PP-AC_Ox) meso/micropore 275.15 10 24 wt% 36 wt% 0.50 [33]
porous organic cage (CC3) 0.5 273 15.4 2.6 wt% 13 wt% 4.06 [74]
3A-type zeolite 0.3 273.5 8.3 62 v/v [75]
5A-type zeolite 0.5 273.5 8.3 54 v/v [75]
Phillipsite 0.38 275.15 5.1 0.38 wt% 1.62 wt% 3.26 [76]
8.7 4.1 wt%
HKUST-1 0.35/0.9 274.15 12 10.4 wt% 2.02 wt% -0.81 [37]
MIL-53(Al) 0.85 274.15 6 13.3 wt% 1.2 wt% -0.91 [37]
ZIF-8 1.16 269.15 2.85 9.5 wt% 14.9 wt% 0.56 [36]
275.15 8 10 wt% 18 wt% 0.8 [28]
258.15 8 12.6 wt% [77]
ZIF-67 1.2 258.15 8 13 wt% [77]
MIL-100(Fe) 2.4-2.9 275.15 9 8.3 wt% 8.4 wt% 0.01 [28]
Y-shp-MOF-5 1.2 275 10 12 wt% 10 wt% -0.17 [27]
Cr-Soc-MOF-1 1.5/1.7 275 10 22 wt%/ 33 wt% 0.50 [27]
*
The percentage increase in methane storage capacity using AHH technology in wet materials compared with dry materials.

Fig. 3. Timeline showing reports of different materials employed to explore methane storage by AHH technology.

micropores. This study creates a precedent for the investigation of
methane storage by AHH technology in porous carbon materials. More
and more studies have shown that the use of porous carbon materials
can significantly improve methane storage capacity under pre-adsorbed
water conditions [10,20,23,35,38,43,59,81,82]. Zhou et al. [59] con­
ducted methane adsorption experiments at a higher pressure (10 MPa)
to observed the effects of water content on methane adsorption (Fig. 4).
Pre-adsorbed water occupies the surface or pore volume of activated
carbon, resulting in significantly lower methane adsorption capacity
than dry activated carbon before pressure inflection point, while
methane adsorption capacity can increase by 63.3% after inflection
point. In addition, the water content significantly affects methane stor­
age. A significant decrease in the adsorption capacity before the pressure
inflection point was also reported in follow-up studies [23,38,81].
Perrin et al. [81] further investigated the adsorption kinetics of
coupled adsorption-hydration methane storage and found that when the
pressure is higher than the critical pressure required for hydrate for­
mation, the change in methane storage over time follows the first-order

6
Z. Wang et al.
Fig. 4. Methane adsorption/desorption isotherms at 2℃ for dry and wet carbon material. (a) activated carbon [30]. (b) petroleum pitch activated carbon
PP-AC [10].
kinetic law, with the kinetic constant increasing alongside the increase
in pressure. Zhou et al. [82] observed that the methane adsorption ca­
pacity of wet activated carbon was always lower than that of dry ma­
terial, indicating that the pore structure of the material has a significant
impact on the hydrate formation. Zhou et al. [35] studied the relation­
ship between the adsorption capacity of materials and the packing
density of water and found that the methane storage increased slowly as
the packing density of the materials increased. The methane storage
capacity was observed to decrease sharply when the packing density
exceeded a certain upper limit. Liu et al. [38] suggested that pore vol­
ume and pore size were the decisive factors in determining the storage
capacity of carbon materials. Casco et al. [10] further observed two steps
in the wet activated carbon adsorption process that were revealed as two
inflection points under conditions of supersaturation with a methane
adsorption isotherm at 3.8 MPa and the pressure above 6 MPa. For the
first time, the synthesis of methane hydrate in the spaces of nanocarbon
materials was verified by in situ INS measurement and in situ X-ray
diffraction technology, which proved that sI-type methane hydrate
formed in wet activated carbon. However, the presence of activated
carbon was found to complicate the non-stoichiometric measurement of
methane hydrate, and the hydrate formed is called “surpass the natural
hydrate.” Under unsaturated conditions, the stoichiometry of methane
hydrates range from 3.6 to 4.1, which is attributed to the following
reasons: 1) non-stoichiometric hydrates form in small pores due to steric
hindrance, and 2) additional free adsorbed methane is present within
the narrow cavity (less than 1 nm). Zhang et al. [32] further suggested
that the high-density methane hydrate generated in the above experi­
ments resulted from the use of activated carbon. Because the accumu­
lation of activated carbon can hinder the diffusion of methane, the
methane storage capacity increases with a decrease in the loading
height. Casco et al. [33] oxidized hydrophobic carbon materials to
obtain hydrophilic materials and found that the modified treatment
significantly reduced the maximum adsorption performance for
methane. However, the water-hydrate conversion rate increased
significantly at the pressure required for hydrate formation. Therefore, a
higher water-hydrate conversion rate does not necessarily improve the
methane storage performance in carbon materials and the relationship
between them remains unclear.
In conclusion, the adsorption of methane in porous carbon materials
that are treated with pre-adsorbed water usually needs to be carried out
at lower temperatures (approximately 0◦ C). Although the methane
adsorption capacity is significantly lower than that of dry materials
under low pressure, methane adsorption can be significantly increased
at high pressure, reaching up to twice as that of dry materials [10]. Most
of the methane adsorption-desorption curves demonstrated obvious
7
Journal of Energy Storage 50 (2022) 104195
hysteresis, which is related to the metastable hydrate formation process
that occurs in a confined space [83]. Scholars have mainly investigated
the effects of water content, pore size, temperature, surface chemical
properties, and particle size on the methane storage by AHH technology.
Under the suitable external environment and materials properties, this
technique can not only significantly increase the adsorption capacity of
methane, but it can also lead hydrates to be formed under more favor­
able conditions, even consistent with free system. In section 3.3, the
effects of different factors on the methane storage by AHH technology in
porous materials are discussed.
3.2.2. Silica and silica Gel
The formation of methane hydrate in nature mostly occurs in rocks
with silicates as a base component. To better emulate natural conditions,
several scholars have used silicas and silica gel as the basic materials to
study the methane adsorption-hydration process. Wang et al. [84]
studied the adsorption of methane in dry and wet silica H-380, and
found that storage capacity reaches a maximum value of 2.49 mmol/g at
308.15 K and 8 MPa when the water content is 50.35 wt%. Ab initio
calculations show that the presence of water changes the geometry of
the material surface, and further experiments have also indicated that
hydrating silica promotes the adsorption of methane. Casco et al. [29]
studied the effects of two hydrophilic and hydrophobic mesoporous
silica materials B-PMO and MCM-41 with pre-adsorbed water on the
methane storage, as shown in Fig. 5. The methane storage capacity of
MCM-41and B-PMO with water content of 150% at 243 K and 6 MPa
increased significantly compared with dry materials. Their methane
sorption isotherms appeared two discrete methane gas consumption
steps, and they attributed this phenomenon to the rapid consumption of
"core water" in the first step to form massive hydrates, while the
“adsorbed water” was consumed more slowly to form unstable restricted
hydrates in the second step. Moreover, methane adsorption kinetics
were found to be promoted with an increase in the water content of the
material, and the adsorption rate was greatly improved [85]. Gun’ko
et al. [86] reported the methane storage by adsorption-hydration in
silica A-300, A-380, and silica gel Gasil 200DF. They found that when
the Rw = 0.1, the maximum methane storage capacity of silica A-300
was 1~2 wt%. For Gasil 200DF, as the increase of water content, the
amount of methane adsorbed decreased and the ability for hydrate
formation weakened. This may be related to the fact that hydrates
cannot exist stably in the confined space of Gasil 200DF [56]. The main
reason for this is that the formation of water clusters and ice nano­
crystals hinders the movement of methane molecules in microporous
material. Zhou et al. [73] used the volumetric method to measure the
effect of using pre-adsorbed water on methane adsorption by silica gel. It
Z. Wang et al.
Fig. 5. Methane adsorption and desorption isotherms at 243, 258, and 275 K for dry and wet MCM-41 and B-PMO with two different water content of 80%Vp and
150 %Vp [29].
was found that the content of the pre-adsorbed water had a significant
influence on the methane adsorption capacity in silica gel. It was sug­
gested that the formation of methane hydrate is closely related to
physical adsorption and that the adsorption capacity of methane in­
creases alongside the water content, which differs from the conclusions
obtained by Gun’ko et al [86]. This may be attributed to the continuous
change in the pore structure of silica gel and the hydrolysis of the hy­
droxyl groups present on the silicon surface when the pore structure is in
contact with water.
Nowadays, few studies have investigated the use of silica and silica
gel materials for the storage of methane by AHH technology, and some
research have mainly focused on the influence of silica materials on the
formation of methane hydrate and methane storage capacity by
changing the ratio of silica materials to water [87–89]. To separate and
purify methane, Zanjani et al. [90] studied the hydrate formation from a
ternary CH4/C2H6/C3H8 gas mixture in nanostructure silica-based
porous material (SIPM) and its chemically modified version (CHMPM1
and CHMPM2). It was found that the methane uptake in the presence of
CHMPM1 was higher than pure water and SIPM by hydrate formation.
The highest hydrate growth rate was observed in the CHMPM2. How­
ever, it showed less increase in the amount of methane uptake compared
CHMPM1. Zhang et al. [91] established the kinetic model for hydrate
formation in silica gels. They found that the formation rate of the
methane hydrate was controlled by the gas diffusion process in 129.5 Å
and 179.6 Å silica gels, while was controlled by the reaction process in
332 Å silica gels.
In summary, although few studies have been conducted using silica
and silica gel, the results of those that have been carried out clearly
predict the key role that water content and hydrophobic surface prop­
erties have on methane adsorption-hydration and indirectly predict the
formation of methane hydrate as associated with the influence of water
in silica [84,86]. It can be seen that both water content and hydro­
philic/hydrophobic surface properties significantly affect the final
methane storage capacity in silica and silica gel. Under high water
content, the final adsorption capacity of methane can reach twice as that
of dry materials. In addition, the hydrophilic silica MCM-41 is more
conducive to the adsorption-hydration of methane than the hydrophobic
silica B-PMO, and methane storage capacity is increased by nearly 36%
[29], which is contrast to the results in the hydrophilic and hydrophobic
activated carbon [92]. The reason may be related to the materials
properties of the silica and activated carbon.
3.2.3. Zeolite
Several scholars have conducted research on the use of activated
carbon for the formation of methane hydrate; however, very few studies
8
Journal of Energy Storage 50 (2022) 104195
have investigated methane adsorption-hydration in zeolites. Liu et al.
[37] reported the phase equilibrium of methane hydrate in
pre-humidified microporous zeolite 13X. Although water molecules can
fill its pores, the dissociation conditions of methane hydrate formed
were found to also be nearly identical to that formed in bulk water,
indicating that 13X was difficult to form stable hydrates due to the
limitation of pore diameter. Zhao et al. [93] studied the reaction kinetics
of methane hydrate in pre-humidified zeolite 5A with different pro­
moters. They found that 5A can enhance the reaction rate to form hy­
drate compared with bulk water, which was contributed to micropores
cage reduces the surface energy and chemistry potential barrier of hy­
drate formation. In addition, 5A provides the nucleation sites on the
surface and micropores, thereby reducing the randomness of nucleation.
Andres-Garcia et al. [94] used In situ powder X-ray diffraction to
observe the formation of methane hydrate in pre-humidified RHO
zeolite. The similarity between the molecular size of methane and the
pore size of RHO limits the process of methane adsorption and diffusion.
The small pore size of RHO leads to the hydrates formed on the surface of
the zeolite rather than in the pores. Moreover, because the flexibility of
the RHO framework means that the pore size can be changed by hy­
dration, methane hydrate was observed to begin crystallization in the
confined space at 3 MPa and 253 K. The process of methane hydrate
formation involves the outward migration of water molecules in the
pores, the formation of amorphous ice on the surface of the zeolite
particles, and the consumption of a significant number of methane
molecules. This study reveals the mechanism of methane
adsorption-hydration hybrid in the confined nanospace of zeolite.
Al-Asheh et al. [76] proved that using AHH technology on the natural
zeolite phillipsite can enhance the methane storage capacity, which was
attributed to the hydrate formation in the material interspace. The
methane storage capacity for zeolite reached 138 v/v at 3.5 MPa when
the optimum water content of 350 g was used, which was 2.2 times the
methane adsorption capacity of the dry material. Smirnov [95] used MD
simulation to investigate the behavior of methane hydrate between the
surfaces of silicalite-1 zeolite, and found that the contact between its
hydrophilic surface and methane hydrate causes the methane hydrate to
be decomposed, which was followed by re-adsorption into the zeolite. In
this process, the water became tighter and a meniscus formed on the
surface of the zeolite particles, causing methane to diffuse onto the
surface and into the pores of the zeolite. The increase in meniscus wall
thickness led to a decrease in the rate at which methane is absorbed.
In summary, most of the current literature is focused on experimental
research and includes both the formation and kinetics of methane hy­
drates in zeolite. Stable methane hydrates are considered unlikely to
form in the micropores of zeolites. The sites at which hydrate nucleation
Z. Wang et al.
and formation occurs are concentrated in the particles of the materials,
which also explains why the addition of zeolite can increase the methane
storage capacity. Therefore, the use of zeolite to store methane via AHH
technology requires the combined effects of pore size, nucleation sites,
and water content to be considered.
3.2.4. Metal-organic frameworks
Although the adsorption-hydration hybrid has a preferable promot­
ing effect on methane storage, the materials are constrained by factors,
such as structural porosity, surface chemical properties, and so on [28].
Among the many porous materials, MOFs materials are the best candi­
dates for meeting DOE target due to their highly developed porous
structure, high specific surface area, adjustable pore size and ease of
chemical modification. MOFs materials are considered able to achieve
this goal at a medium pressure of approximately 6 ~ 7 MPa, whereas
activated carbon requires a higher pressure about 10 MPa [42,80],
indicating that MOFs materials have significant potential in methane
storage [96]. The use of the MOFs to store methane by AHH technology
has only been studied in recently years, and only a few types of MOFs
have been involved. Methane adsorption-hydration hybrid experiments
using ZIF-8 were first carried out by Mu et al. [36], who investigated the
effects of water content and temperature on the storage capacity in
ZIF-8. Compared with dry ZIF-8, the methane adsorption performance
was found to increase by 56% with pre-adsorbed water, and hydrate
formation accounted for 45% of the total amount of methane stored.
Results that were obtained with Scanning electron microscopy and X-ray
diffraction showed that ZIF-8 can be used repeatedly because of its
stable framework. These results suggest that MOFs exhibit excellent
Fig. 6. Effect of methane adsorption capacity of different MOFs by AHH technology under different water contents. (a) MIL-100 (Fe). (b) ZIF-8 [28]. (c)Y-shp-MOF-5.
(d) Cr-soc-MOF-1 [27].
9
Journal of Energy Storage 50 (2022) 104195
methane storage performance and better reusability in AHH technology.
Based on these studies, Liu et al. [37] extended the study of MOFs to
other hydrophilic materials HKUST-1 and MIL-53. The effect that the
hydrophilic and hydrophobic properties of MOFs has on the methane
storage by AHH technology was also discussed by Casco et al. [28], who
compared ZIF-8 with the hydrophilic mesoporous MIL-100 (Fe). Fig. 6a
shows that methane storage capacity is significantly reduced in MIL-100
(Fe), which promotes strong water network interactions that are
accompanied by associated structural blockages. Fig. 6b shows that the
amount of methane storage in ZIF-8 increases with the increase of water
content. In addition, the authors observed that the hydrate formation
pressure decreased and the adsorption-desorption curve hysteresis dis­
appeared following the second cycle of water addition to ZIF-8, indi­
cating that the surface memory effect was present as a result of the
formation of methane hydrate in ZIF-8. They suggested that pre­
organization resulting from an increase in the volume of water after the
first cycle is beneficial to hydrate formation. Alternatively, some
remaining methane may have become dissolved in the water. In addi­
tion, the jump in magnitude associated with the two cyclic adsorption
isotherms in ZIF-8 were completely matched, indicating the high recy­
clability of the nucleation and growth of methane hydrate in ZIF-8. Kim
et al. [97] used pre-humidified MIL-53 to carry out methane and carbon
dioxide adsorption experiments, which mainly focused on the hydrate
formation mechanism of methane and carbon dioxide in MIL-53 and the
relationship between phase equilibrium and pore size. It was found that
limiting the pore size (to approximately 0.6 nm < 1.2 nm) means that
hydrate can only form in the mesoporous/macropores of the crystal
particles. The confined and volumetric phases were observed in the P-T
Z. Wang et al. Journal of Energy Storage 50 (2022) 104195

curve for MIL-53. The confined phase formed in the mesopor­

es/macropores of the crystal particles, whereas the volumetric phase
existed in the large pores over hundreds of nanometers and on the outer
MOF surface. The phenomenon of two hydrate phases was also observed
by Casco et al.[10]. The phase behavior of the hydrate in MIL-53 was
inhibited by thermodynamics owing to the influence of the surface
properties and pore size. Combining the results of Liu et al. [36] and Kim
et al. [97], it suggests that due to the hydrophilicity and microporous of
MIL-53, pre-adsorbed water will block the pores and reduces the
adsorption capacity under H2O-undersaturated condition, whereas
methane hydrate can form between the particles of MIL-53 under
H2O-oversaturated condition. This also shows that both the water con­
tent and the pore size of MOFs materials significantly affect the methane
storage capacity by AHH technology.
Recently, Denning et al. [26] used differential scanning calorimeter
(DSC) experiments to study the methane storage of HKUST-1 by AHH
technology. The authors observed a methane storage capacity of 0.89
mmol/g under high pressure, which was accompanied by the formation
of methane hydrate and reached a maximum methane storage of 9.8
times that of dry materials. Compared with the pure water system,
HKUST-1 increased the conversion rate of water-hydrate from 5.9% to
87.2%, and the induction period of hydrate was reduced by 4.4 h,
confirming that the use of pre-adsorbed water with HKUST-1 promotes
the hydrate formation. The author analyzed the main reasons for the
promotion of hydrate formation include: 1) the larger surface area of the
material increases the gas-water interface; 2) the hydrophilicity of the
structure leads to the dispersion of water molecules on the surface,
which increases the gas-water contact area; 3) the high thermal con­
ductivity and copper nodes of HKUST-1 promotes heat transfer.
Cuadrado-Collados et al. [27] reported on the use of two types of hy­
drophilic MOFs, Cr-soc-MOF-1 and Y-shp-MOF-5, for methane storage
by AHH technology. The results indicated that Cr-soc-MOF-1 (with an
average pore size of 1.6 nm) can promote the formation of methane
hydrate with an optimal pore size. The methane adsorption isotherms
are shown Fig. 6c and 6d. This is also the first report of hydrate for­
mation in the micropore of MOFs with optimal cavity dimensions.
Importantly, the total gas storage capacity of Cr-soc-MOF-1 with
pre-adsorbed water at 10 MPa was 50% higher than that of dry materials
(up to 0.33 g/g), which is one of the highest values reported so far in
studies of carbon materials and MOFs. Denning et al. [77] suggested that
ZIF-8 and ZIF-67 have long lifecycles as methane hydrate formation
promoters. Compared with pure water system, the methane hydrate
nucleation induction time was reduced by 51.6% and 92.2%, respec­
tively. Moreover, the impact of AHH method on the methane storage
capacity was also investigated from molecular level, and the MOF ma­
terials involved include ZIF-8 [98] and MIL-101 [99].
In summary, storing methane by AHH technology that use MOFs
materials is also affected by physical properties, surface properties,
water content, and other factors, which is similar to the results obtained
using carbon materials. Although few studies have been conducted
investigating the use of MOFs in AHH technology, these studies provide
guidance for the selection of MOFs materials for use as AHH technology.
Thus, it is necessary to fully consider the effects of different factors when
designing and synthesizing MOFs materials for storing methane by AHH
technology.
3.3. Main factors effecting methane storage by AHH technology
Clarifying the important role of different parameters is key to both
designing suitable porous media and studying the high-density storage
associated with AHH technology. As shown in Fig. 7. The key influ­
encing factors and variables can be classified, and the contribution and
connection of each parameter that restricts methane adsorption-
hydration can be obtained systematically to maximize the methane
storage capacity to that required for industrial applications from a sci­
entific point of view.
Fig. 7. Main factors affecting the methane storage by AHH technology.
3.3.1. Pore size
Of the factors affecting the storage of methane adsorption-hydration
hybrid, pore size is considered to be one of the most significant factors.
Pore size not only plays an important role in promoting the formation of
methane hydrate in pores [27], but also may improve the gas storage
capacity of porous media fundamentally [30]. Much research has indi­
cated that pore size can significantly affect both the methane gas storage
capacity of porous media and the threshold pressure for hydrate for­
mation. In terms of the gas storage capacity, as shown in Fig. 8a,
Borchardt et al. [23] carried out AHH experiments in microporous,
mesoporous, and macroporous carbon models with average pore sizes of
0.2 nm, 10 nm, and 25 nm, respectively. Mesoporous material with an
average pore size of 25 nm and pre-absorbed water demonstrated an
increase of 173% of the methane storage capacity compared with the dry
same material. They found that gas storage capacity of mesoporous was
the highest, while gas storage capacity of macropore was the lowest, and
suggested that the optimal pore size of carbon material for the storage of
methane by AHH technology lies within the mesoporous range
(approximately 30 nm), under which the highest number of hydrate
nanocrystals could be generated with stoichiometry similar to that of
natural hydrate. As shown in Fig. 8b, Liu et al. [38] pointed out that an
optimal pore size distribution of 1.6 ~ 2.8 nm can significantly increase
methane storage capacity. Because methane adsorption is often
accompanied by the formation of hydrate, this should be considered
when selecting the pore size of materials. Some scholars have suggested
that a pore size of at least 1.6 nm is required for methane hydrate for­
mation [30,34] In theory, a pore size of at least 3 nm is required to
maintain the stability of methane hydrate [71], which indicates that
methane hydrate is more likely to form in larger pores. It is almost
impossible for hydrates to form when water is present within micropores
because of the associated size limitation and strong adsorption potential.
At the same time, the repulsive force of water hinders the entry of
non-polar methane molecules, and methane adsorption is significantly
reduced [100–102]. When water molecules are adsorbed in macropores
or mesopores because of an increase in the water content, the inhibition
of methane storage can change as a result of the formation of methane
hydrate [34,37]. The significant reduction in methane adsorption as a
result of using pre-adsorbed water with microporous materials was also

10
Z. Wang et al. Journal of Energy Storage 50 (2022) 104195

Fig. 8. Influence of pore size of material on the methane adsorption-hydration hybrid. (a) Methane hydrate formation in porous model carbons covering the range
from micro- to meso- and macropores [23]. (b) Adaptation of pore size to methane hydrates [38].

confirmed by Liu [37]. It is thus important to prevent water from micropores is almost useless and that because hydrates are preferentially
entering the pore cavities of microporous materials. Similarly, Perrin formed in larger pores, and the presence of macropores or mesopores is
et al. [19] and Celzard et al. [34] suggested that adding water to necessary to improve methane storage capacity.

Fig. 9. (a) Methane hydrate forms on the outer surface of the material pore (modified from Denning et al.[26]). (b) Methane hydrate forms on the inside the
pore [27].

11
Z. Wang et al.
However, some scholars have found the opposite. Cuadrado-Collados
et al. [27] proposed that in order to form hydrate in the confined cavity,
the cavity size should be slightly larger than the single crystal size of
methane hydrate (1.2 nm). This investigation also confirmed that hy­
drophilic microporous materials have the potential to form methane
hydrate in the cavity when the pore size is slightly larger than 1.2 nm,
which is beneficial for the methane storage by AHH technology. How­
ever, Denning et al. [26] reported that hydrate formation occurred only
on the surface of the HKUST-1, although it has the pores with 1.4 nm.
Fig. 9 shows the schematic diagram of hydrate formation in porous
media with different pore sizes. Comprehensive analysis showed that
appropriate pore structures (pore shape and size) and surface properties
are essential for the formation of confined hydrates in hydrophilic
microporous materials. Therefore, one possible direction for future
research would be to find materials that have a suitable pore structure
and surface chemical properties for hydrate formation. Several scholars
have found that the adsorption capacity of methane in wet microporous
materials with smaller pore sizes than that of the hydrate lattice is
significantly higher than that of dry materials [23,72]. They attributed it
to water and methane form amorphous structure with a low
non-stoichiometry in micropores, which are different from the tradi­
tional sI hydrate and are denoted "hydrate species,” or "nano hydrates".
There are few studies on nano-hydrates and further exploration of the
micro-mechanisms is therefore required.
Some experimental studies have found that the pore size of macro­
pores is not conducive to the formation of methane hydrate, which may
be due to the lower adsorption capacity of water at saturation, and that
the methane adsorption potential of macropores is weaker than that of
micropores, resulting in lower water-hydrate conversion [23]. In addi­
tion to considering the formation of hydrates in pores, some scholars
have analyzed the effect of pore size on methane storage capacity from
the perspective of gas diffusion. Casco et al. [10] used activated carbon
with highly developed pores (including micropores, mesopores, and
macropores) and found that hydrate formed preferentially in the larger
pores (macropores and large mesopores) whereas methane entered the
internal pores (small mesopores and micropores). This process is in
contrast to that observed in porous materials that contain only small
pores because in such materials hydrates occupy the pore network and
methane diffusion into the inner pore becomes particularly difficult,
reducing the final methane storage capacity. These results indicate that
porous media with larger pores are more conducive to methane diffu­
sion. This conclusion has been confirmed in several studies, with the
introduction of mesopores found beneficial for improving the methane
storage capacity and the conversion rate of water-hydrate, including
those investigating activated carbon [103] and MOFs materials [97].
Pore size can also affect the pressure at which methane hydrates form
in the process of adsorption-hydration hybrid. Hydrate appears to form
preferentially in the larger pores of wet porous media and gradually
forms in smaller pores as the increasing of pressure. Kim et al. [97]
found two types of hydrates, confined and bulk phases, in
pre-humidified MIL-53 after methane adsorption, indicating that hy­
drate forms in differently sized pores. The main reason is that the
capillary force of pores and the interaction between restricted water and
the inner surface of porous media means that the activity of the
restricted water in the pores is reduced to a certain extent [71], and the
inhibition becomes stronger under smaller pore sizes. Moreover, the
diffusion speed of methane in porous media also affects the formation of
hydrate [10,23]. Due to the occupation of hydrates, the slow diffusion of
methane into smaller pores inhibits adsorption and hydrate formation,
ultimately affecting methane storage capacity. The presence of larger
pores is therefore beneficial to the diffusion of methane and the for­
mation of hydrates, further increasing the conversion rate of
water-hydrate. In summary, combined with the current research on
AHH technology, micropores (slightly larger than the size of methane
hydrate) and mesoporous materials are may be most suitable for the
storage of methane by AHH technology.
12
Journal of Energy Storage 50 (2022) 104195
3.3.2. Particle size
Particle size of porous materials not only influence methane
adsorption but have influence if hydrate formation. Some scholars found
hydrate can be formed in intergranular space. Kim et al. [97] proposed
that the synergistic effect of hydrate formation in the intergranular
mesopores/macropores and the methane adsorption in micropores can
effectively promote methane storage. Some studies have reported that
the existence of intergranular mesopores and macropores can signifi­
cantly affect the kinetics and thermodynamics of hydrate formation,
further affecting the methane storage capacity [10]. Due to the rela­
tionship exists between intergranular space and particle size [103], the
particle size can affect the methane storage by AHH technology. Wang
et al. [104] used different particle size (20, 40, and 80 nm) hydrophobic
nano-SiO2 in investigating the effect of hydrate formation and proposed
the mechanism of nano silica promotes hydrate formation, as shown in
Fig. 10a. Zhang et al. [32] carried out adsorption-hydration experiments
with activated carbon of two different sizes: AC1 (1.5 nm) and AC2 (0.1
nm). They found that smaller activated carbons are related to higher
hydrate formation kinetics. The larger interstitial pore spaces in acti­
vated carbons are comparably beneficial to the mass transfer of
methane, with particle size appearing to be an important factor that
affects the methane storage capacity by AHH technology. Siangsai et al.
[103] studied the effects of activated carbon comprising different par­
ticle sizes (250-420 μm, 420-841 μm, and 841-1680 μm) on the forma­
tion of methane hydrate under pre-adsorbed water conditions. Fig. 10b
shows the methane consumption and temperature change at 6 MPa. It
can be seen that the methane storage capacity increases again before
reaching the plateau, the authors suggested that it is due to the methane
hydrate can be formed in the interstitial space between porous particles,
enhancing the rate at which hydrate forms. However, the hydrate con­
version rate is contrary to this suggestion and is positively correlated
with particle size. This may be attributed to the larger interstitial spaces
that occur between large particles in which hydrate can further form
[105]. Bagherzadeh et al. [106] also used nuclear magnetic resonance
imaging technology to observe that smaller particles increase the rate of
hydrate formation and that the rate of hydrate formation was faster
under lower water content. This is because low water contents provide
more free channels, which are beneficial to both the transport of gas and
its contact with water. Other studies have shown that the formation rate
of hydrates in beds with smaller particle sizes is faster than that in beds
with larger particle size [107,108]. Chong et al. [109] studied the effects
of four silica sand particle sizes (1.5–3 mm, 0.56–1.3 mm, 0.1–0.5 mm,
and 0.1–0.63 mm) on the formation of hydrate. It was found that the fine
sand at 0.1–0.5 mm showed the highest gas absorptivity, which in­
dicates that there is a critical particle size in methane storage. Zhang
et al. [110] observed that there is a critical particle size in the hydrate
nucleation induction time, as shown in Fig. 10c, they established pore
model and deduced from the theoretical model formula. The induction
time of hydrate nucleation decreases with increasing particle size when
it is larger than a certain particle size range, while the induction time
increases with increased particle size when it is smaller than this range.
Lu et al. [111] further proposed that the conversion of water-hydrate
decreased monotonously when the particle size was lower than 0.2
mm. Therefore, the effects that particle size have on hydrate formation
and methane storage capacity are complicated.
In addition, several scholars have also investigated the effect of
particle size on the adsorption performance of porous materials. By
controlling the synthesis of specific size and uniform nanoparticle MOFs
that exhibited rapid adsorption and desorption kinetics [112–115],
Wang et al. [116] reviewed how to stably synthesize specific size and
uniform nanoparticle MOFs materials. Babaei et al. [117] found that the
size of MOFs particles affects the heat and mass transfer characteristics
during methane adsorption. The use of small-sized MOF particles is
conducive to methane storage, but smaller particle sizes are detrimental
to the rapid release of adsorbed heat.
In summary, the large interstitial pore space comprising small
Z. Wang et al.
Fig. 10. (a) Mechanism of hydrate promotion for hydrophobic nano-SiO2 [104]. (b) Typical methane consumption and temperature profiles during the methane
hydrate formation experiments conducted with the activated carbon size of 841–1680 mm at 4◦ C and 6MPa [103]. (c) Pore model [110].
particles increases the contact area between methane and water [103,
107], thereby increasing the hydrate formation rate. However, at a
certain particle size, slow growth kinetics are caused by greater trans­
port resistance and the lower permeability of gas [109]. At the same
time, the stronger water-material surface interaction reduces the avail­
ability of volumetric water with which hydrate can be formed [111],
inhibiting the formation of hydrate. The conclusions on this relationship
are not consistent, including particle size, hydrate conversion rate, and
gas consumption [103,109]. The results indicate that the hydrate con­
version rate is not only affected by the particle size, but also by the
surface properties and the experimental conditions under which a ma­
terial is utilized. The effects that the particle size has on the storage
capacity and methane storage rate of porous materials that are used to
store methane via the AHH technology should therefore be given more
attention.
3.3.3. Water content
The effects of Rw on the methane adsorption-hydration hybrid have
also been widely studied. Casco et al. [33] carried out methane AHH
experiments using activated carbon. As shown in Fig. 11a, when the Rw
is 2.0, the methane adsorption capacity decreases sharply, indicating
that the pores are blocked by pre-absorbed water so that the methane
cannot be adsorbed. The conversion rate of the water-hydrate remains
low, even under high pressure. When the Rw is 4.1 which is supersatu­
rated, the methane adsorption isotherm shows a sharp vertical jump in
adsorption capacity at the threshold pressure of 3.3 MPa, exceeding the
saturated adsorption capacity of dry materials and no hysteresis occurs,
indicating that the adsorption is in thermodynamic equilibrium. How­
ever, when the Rw is 6.0, the saturated adsorption capacity of methane
decreases to close to that of dry materials. Therefore, there is a limit to
the water content for the methane storage when using the AHH
13
Journal of Energy Storage 50 (2022) 104195
technology.
Many scholars also observed this phenomenon in experiments,
indicating the presence of a critical or optimum water content in the
AHH technology [20,27,32–34,36,59]. When the water content is low,
even under very high pressures, the methane adsorption capacity is
lower than that of dry materials. When the water content increases to a
certain extent, the methane adsorption capacity is higher than that of
dry materials. Most studies have indicated that the saturated adsorption
capacity of methane is lower or even significantly lower than that of dry
materials when the water content is low and unsaturated, which is likely
due to the pre-absorbed water occupying the pore volumes and
rendering some micropores unavailable. This can occur even under high
pressure, and leads to a particularly low water-hydrate conversion rate
that often shows a sharp decrease [28,33,34,37,59]. Under these con­
ditions, no methane hydrate formation has been observed in certain
types of materials, such as Y-shp-MOF-5 [27]. As the amount of water
increases to reach saturation, the pores may be completely blocked by
water over the entire pressure range. Even with the formation of hy­
drates, the methane adsorption capacity is further reduced as the
physical adsorption of methane is inhibited [27].
However, there are some exceptions. For wet petroleum pitch acti­
vated carbon, the methane storage increases as the increase of water
content and rises to levels that are significantly larger than that of dry
materials. The common point is that the physical adsorption of methane
decreases with an increase in the water content at low pressure [10],
which also indicates that the effect of water content on methane
adsorption capacity is related to the properties of the material used.
Further, when the water content reaches oversaturation, the methane
storage performance shows a more favorable trend than that associated
with saturated water content, and the adsorption isotherm shows “jump
phenomenon” that is due to the formation of methane hydrate. Under
Z. Wang et al.
Fig. 11. (a) Methane storage capacity in activated carbon under different water contents [33]. (b) Amount of methane adsorbed into the cavity of MIL-101 under
different water contents [99]. (c) Microscopic simulation of the adsorption-hydration in MIL-101 under different water contents [99]. (d) Visualized growth of
methane hydrate under different water contents in activated carbon [118].
high pressure, methane storage increases greatly [10,27,28,33,37] and
can significantly exceed the methane storage capacity of some dry ma­
terials [27,33,37]. Some scholars have suggested that this is related to
the distribution of water in different pore sizes under different water
contents [37]. For microporous materials, such as activated carbon, due
to the existence of excess water on the outer surface of the nanoporous,
the methane hydrate could form outside the pores, causing the storage
capacity increased significantly and reached a value similar to that of
dry materials [37]. For mesoporous materials, He et al. [99] through MD
simulation suggested that methane hydrate formed in the outer space of
MIL-101 cavities when MIL-101 was oversaturated and the hydrate
growth is no longer limited by the cavities under these conditions. Thus,
when excess pre-absorbed water is present, the water existing on the
outer surface of the pores or intergranular space is beneficial for the
hydrate formation and increase methane storage capacity. Some
scholars have suggested that the purpose of adding excess water to the
material is to promote the formation of methane hydrate. The high
productivity of the hydrate requires supersaturated conditions and
promotes nucleation at the orifice. However, there is a limit for water
content and methane storage capacity could decrease with a further
increase under supersaturated conditions [27,33,34,36,59]. By contrast,
a higher water content may be more beneficial for methane storage
capacity in PP-AC, which may be related to the hydrophobicity of the
material [10]. Because water molecules are adsorbed with difficulty into
the pores of the hydrophobic materials, and the amount adsorbed is not
particularly reduced by blocking the pores, methane hydrate is mainly
formed on the outer surface or in the intergranular space of materials.
Thus a further increase in the oversaturated water content could lead to
an increase in the methane storage capacity [28]. These results indicate
that the effect of water content on the methane storage properties is
related to the surface properties of the material used.
In addition to the effect that water content has on methane storage,
some scholars have investigated the effect of water content on the
14
Journal of Energy Storage 50 (2022) 104195
pressure at which hydrate forms. Celzard et al. [34] pointed out that
higher water content also reduces the hydrate formation pressure owing
to the hydrate formation occurring in larger pores, indicating that higher
water content can exist in larger pores. A phenomenon in which the
hydrate formation pressure decreased when the water content was
increased to supersaturation was also observed by Casco et al. [10,92],
with a second pressure inflection point appearing under high pressure.
The low-pressure and high-pressure inflection points correspond to the
hydrate growing outside the larger pores and smaller pores, respec­
tively. This may be because the water content affects the spatial distri­
bution of the water molecules in porous materials and further affects the
priority position at which hydrate nucleation occurs. Micropores have a
stronger adsorption potential in hydrophilic materials, and water mol­
ecules preferentially exist in smaller pores. An increase in the water
content leads to the preferential formation of hydrates in the larger
pores or outside the pores because the water molecules are generally
found in the larger pores, reducing the pressure required for hydrate
formation. When the optimum water content is exceeded, the diffusion
path lessens over the whole pore network, gas diffusion becomes more
difficult, and hydrate cannot form in the pores, resulting in a small
amount of hydrate growing in the particle voids and on the surfaces of
the pores [34,39,59]. However, the hydrate formation pressure does not
monotonously decrease with the increase in water content; although
when the water content increased to a certain amount, the hydrate
formation threshold pressure increases when the water content in­
creases by a certain amount and the water-hydrate conversion rate de­
creases [33]. It is likely that a higher water content hinders the diffusion
of methane into the pores, which is not conducive to the formation of
methane hydrate [119]. In addition, the larger diffusion resistance will
also reduce the amount of methane that can be adsorbed into the pores,
and the two factors jointly inhibit the storage of methane.
Water content also has a significant effect on the kinetics of methane
hydrate formation in porous materials. Fig. 11b and c1-c3 show that the
Z. Wang et al.
large and small cavities of MIL-101 were observed to form methane
hydrate under different water contents by MD simulations and the
methane adsorption capacity of large and small pore phases varied
under different water contents. This reveals the influence of water
content on the formation of methane hydrate in confined space at the
micro level. Casco et al. [28] pointed out that higher amounts of
pre-adsorbed water correspond to smaller water nanodroplets, whereas
the smaller water nanodroplets in hydrophobic materials have a larger
solid-liquid interface, resulting in a shorter induction period [28]. On
the other hand, based on the adsorption-induced nano-convection
mechanism proposed by Zhang et al. [32], under higher water content,
the internal voids of the activated carbon can become clogged, weak­
ening the connection between the methane and the water molecules and
slowing down the kinetics of hydrate nucleation. Meanwhile, it also
reduced the hydrate growth kinetics, which was attributed to the sharp
decrease in nano-convection and the number of nucleation sites that are
a result of the higher pre-absorbed water content.
In addition, the existence of porous media leads to the distribution of
water becoming discontinuous and water migrating under capillary
action, leading to the formation of structurally complex hydrate. Some
scholars have found that the water content has a significant effect on the
morphology of methane hydrate in porous media. Few hydrate chunks
were observed by Zhang et al. [32] when the Rw is less than or equal to
0.5 because the water was mainly in the internal pores. The increase in
water content led to the appearance of hydrate fibers with increasing
diameters. However, only block hydrate can form when the Rw is greater
than 1 because at this point the internal pores are almost completely
occupied by water. Subsequently, Zhang et al. [118] further observed
rime-like hydrate on the bulge of wet activated carbon, as shown in
Fig. 11d, which formed at low water content. A small number of hydrate
chunks and fibers were observed when the Water content increased to
0.5, and the internal pores could be properly filled at Water content was
0.7, resulting in the maximum hydrate fiber formation. However, a
further increase in the Water content causes that the internal pores
gradually became completely filled, blocking the diffusion of methane
into the internal pores and no hydrate fibers are observed. Combined
with these hydrate forms, the authors suggest that the significant in­
crease in the micro-gas-liquid contact that results from the large number
of surface micro-bulges and adsorption-induced two-way convection
may be the reason for hydrate formation. Therefore, the observation of
special hydrate morphology provides a new perspective for under­
standing the mechanism of the adsorption-hydration hybrid. At present,
research into the hydrate morphology in porous materials is limited to
activated carbon, and more attention should be paid to other kinds of
porous materials in the future.
Although the water content has a significant effect on the adsorption-
hydration hybrid, there is no clear conclusion on the optimal water
content for methane storage via the AHH technology. Some scholars
have considered the hydrate formation rate, methane storage, hydrate
non-stoichiometric ratio, and other factors, and suggested that the op­
timum water content is close to 1.0 [32,34]. For example, Calzard et al.
[34] found that the optimum water content of activated carbon with
different pore structures was close to 1.0, with almost all contents
observed were less than the saturated water content. The optimum
water content and maximum methane storage capacity have no obvious
correlation with pore volume. They suggested that the optimum water
content depends more on how difficult it is for methane molecules to
enter the pores. Some scholars have found that the optimum water
content is at supersaturation [10,27,33,92], whereas others have pro­
posed that the optimum water content is less than saturation condition
[34]. Thus, no unanimous conclusion has yet been made on whether
there is an inevitable relationship between the optimal water content
and saturation condition. Some scholars have proposed that when the
adsorbent is freely accumulated, the optimum pre-absorbent content is a
function of the adsorbent packing density [32]. In summary, the opti­
mum water content may be affected by physical properties (such as the
15
Journal of Energy Storage 50 (2022) 104195
size of pores or particles), surface chemical properties (such as hydro­
philicity and hydrophobicity), and the packing density of the porous
materials.
3.3.4. Surface properties
In terms of the surface properties of porous materials, scholars have
mainly focused on the effect that hydrophilic and hydrophobic proper­
ties have on storage when using the methane AHH technology, because
this property determines the wettability of the water in the pores. The
study of hydrophilic and hydrophobic properties is mainly related to the
surface groups on the porous materials and the interaction between
water and adsorbents. Casco et al. [33] modified the oxygen functional
groups of carbon materials to obtain hydrophilic activated carbon.
Compared with hydrophobic activated carbon and under the threshold
pressure of hydrate formation in oxidized activated carbon with the
same water content, the yield of water hydrate increased from 13% to
51%. This is because the oxygen functional group changed the distri­
bution of water, and the water in the hydrophobic material was
randomly distributed throughout the pores. The oxygen functional
group acted as a nucleation center for the water cluster, which promoted
the preferential distribution of water into the larger cavities and pores.
Although the introduction of oxygen functional groups has the above
advantages, the methane storage capacity under high pressure was
much lower than that in the original hydrophobic materials. In a further
study of mesoporous carbon materials, Casco et al. [92] found that hy­
drophilic and hydrophobic properties had a significant effect on
methane storage capacity and explored the formation mechanism of
methane hydrate in hydrophobic carbon materials. The methane
adsorption capacity of the hydrophobic materials showed little differ­
ence when the water content reached supersaturation. When the water
content was unsaturated, the methane adsorption capacity of the hy­
drophobic materials was significantly higher than that of the hydro­
philic materials. The authors suggested that the main reasons are: 1) the
hydrogen bonds that form between the nitrogen atoms and the oxygen
atoms in the water molecules on the pore surface of hydrophilic mate­
rials is much stronger than that of the water-methane interaction that
stabilizes cages, inhibiting the formation of hydrates; 2) The surface
chemical properties have an important influence on the distribution of
water. The water on the pore surface of the hydrophilic material is
uniformly distributed, whereas the water on the pore surface of the
hydrophobic material is mainly distributed around the oxygen atoms in
the form of clusters, which leads to an increase in the physical adsorp­
tion of methane onto the surface of the hydrophobic material at low
pressure, further increasing the methane storage capacity; 3) The sur­
face properties affect the mobility of the water molecules on the pore
wall. In hydrophobic materials, methane hydrate is formed by confined
liquid water but it decomposes into ice, resulting in high displacement at
the entrance or outside the pore. However, the displacement of liquid
water in hydrophilic materials is limited, which hinders the formation of
methane hydrate and further affects the conversion of water-hydrate,
leading to the differences in methane adsorption capacity. It can be
seen that although the increase in hydrophilic groups of porous mate­
rials can increase the conversion of water-hydrate under the threshold
pressure of hydrate formation, hydrophobic materials tend to show
higher storage of methane capacity by the AHH technology under high
pressures.
Several studies have discussed the effects of hydrophilic and hy­
drophobic MOFs materials on the methane adsorption-hydration hybrid.
Casco et al. [28] compared the methane storage capacity for hydrophilic
MIL-100 (Fe) with that of hydrophobic ZIF-8, as shown in Fig. 6a and b,
respectively. Due to the strong hydrophobicity of ZIF-8, it was difficult
for water to enter the inner cavity, resulting in the formation of a
considerable amount of methane hydrate between the particles. In
addition, the cavities almost retained the original physical adsorption
capacity of methane. Thus, methane storage capacity was significantly
increased compared to dry ZIF-8. However, for MIL-101(Fe), both the
Z. Wang et al.
conversion rate of water-hydrate and the methane storage capacity were
lower than that of dry materials due to the intrusion and blockage of
water. Thus, authors suggested that the weak water-adsorbent interac­
tion is necessary for methane storage by AHH. A consistent conclusion
was also reported by Liu et al. [37], and they proposed that to make use
of the synergistic effect of methane adsorption and hydrate formation
and increase methane storage capacity in microporous materials, it was
very important to prevent water molecules from permeating into the
pores of the adsorbents.
Some scholars have focused on the influence that hydrophilic and
hydrophobic properties of porous media surfaces have on the charac­
teristics of gas hydrate formation. Some experimental studies have
found that hydrophobic materials promote hydrate formation. Wang
et al. [120] reported that water molecules tend to form hydrates near the
hydrophobic surface if the contact angle of the water molecules on the
hydrophobic surface is increased, which significantly reduces the
nucleation induction time. Liyama et al. [64] used XRD to observe that
the water adsorbed by hydrophobic nanospaces presented an orderly
assembly structure, and Li et al. [121] used Raman spectroscopy to
observe that the water molecules on the hydrophobic surface presented
an orderly ice-like shape, which proved that hydrate forms more easily
on hydrophobic surfaces. Guo et al. [122] compared the surface
methane hydrate nucleation process under the use of hydrophobic
graphite, silicon dioxide particles, and hydrophilic silica particles and
found that a hydrophobic surface can promote hydrate nucleation. The
author also used atomic force microscopy to observe that a large number
of methane bubbles can form on the hydrophobic surface of graphite,
whereas few formed on the hydrophilic silica surface. The nucleation
mechanism was confirmed on the nanoscale because methane bubbles
that form on a hydrophobic surface can provide sites for methane hy­
drate nucleation. Similarly, preferential hydrate formation was also
observed on the surface of hydrophobic materials by Nguyen et al.
[123].
However, some scholars have suggested that a hydrophilic surface is
conducive to hydrate formation. Yan et al. [20] believed that the acti­
vated carbon on the hydrophilic surface provided more nucleation sites
for methane hydrate. Smirnov et al. [124] proposed that the coal surface
is an active region for methane hydrate nucleation. Several researchers
have found that water molecules can be adsorbed onto the copper atoms
on the surface of the hydrophilic HKUST-1. As more water molecules
were adsorbed, the exchange of water molecules would be faster over
the entire structure [125], and the rapid exchange of water molecules on
the surface of HKUST-1 resulted in relatively effective water dispersion
[26], as shown in Fig. 9a, which provided a large gas-water interface to
facilitate the formation of methane hydrate. However, the authors
suggested that despite the increased gas-liquid interface, the interaction
between the surface of the MOFs and the water molecules also played an
important role in hydrate nucleation. The hydrophilic surface of
HKUST-1 arranges water molecules in such a way that hydrate forma­
tion may be restricted, limiting the growth of hydrate. Therefore, the
water-adsorbent surface interaction is also a factor to be considered
In addition, some scholars using molecular simulations reveal that
the effect of hydrophobic and hydrophilic properties of materials on the
methane hydrate formation. He et al. [126] used MD simulation to
explore the mechanism of methane hydrate formation on hydrophobic
graphite and hydrophilic silica nanopores. The results showed that
different surfaces affect the curvature of methane bubbles, the structure
of the interfacial water, and the formation of hydrogen bonds on the
surface with different effects on the formation of methane hydrate. The
hydrophobic graphite surface had a strong ability to adsorb methane
molecules, induce methane to dissolve in water, and improve the solu­
bility of methane in water and was found to induce water molecules to
form a hydrate-like ordered water layer on the graphite surface, pro­
moting contact between the hydrate solids and graphite surfaces. These
two factors promote hydrate formation, which confirms the above
experimental conclusion that hydrophobic surfaces will induce water to
16
Journal of Energy Storage 50 (2022) 104195
form ordered structures [64,121], whereas hydrophilic silica surfaces
tend to be hydrated. The solubility of methane that was near the surface
was lower than that obtained with average solubility and dissolution
rate, which is consistent with the conclusion proposed by Nguyen et al.
[123]. The above research indicated that the hydrophobic surface pro­
motes the adsorption of gas molecules onto the material surface and
promotes hydrate formation. However, this conclusion is not consistent
with the formation of liquid water or an ice-like ordered structure of
water molecules on the hydrophobic surface, and the effects of hydro­
philic and hydrophobic surfaces on the water molecule structure and
hydrate formation requires further study. By contrast, some literatures
have drawn the opposite conclusion. They suggested that hydrophilic
materials affect the interfacial curvature of methane nanobubbles and
hydrophilic materials are beneficial for the dissolution of methane in
solution. On a hydrophilic surface, the gas-liquid interface will form a
positive interfacial curvature, which is beneficial for promoting the
dissolution of methane in water and hydrate formation [126,127]. The
reason for this is that the Young-Laplace pressure caused by the
gas-liquid interface curvature will promote the dissolution of gas in
water [128,129], whereas the gas-liquid interface on the hydrophobic
material surface will generate a negative or flat gas-liquid interface
curvature, resulting in low methane solubility and affecting hydrate
formation [126]. Similarly, Cox et al. [130] used MD simulation to
observe that the temperature of hydrate nucleation increased with an
increase in surface hydrophilicity. The authors suggested that the cur­
vature of the methane-water interface increased with an increase in the
hydrophilicity of the surface, and the concentration of methane dis­
solved in the solution increased owing to the Laplace pressure effect,
which showed that hydrophilic surfaces are beneficial for the formation
of hydrates. A similar conclusion was also proposed by Hu et al. [127].
Comparing hydrate formation on hydrophilic and hydrophobic metal
surfaces, the authors found that hydrophilic metal surfaces increased the
curvature of the gas-liquid interface, promoted the dissolution of
methane, and increased the kinetics of hydrate formation and the con­
version rate of water-hydrate, whereas hydrophobic metal surfaces
showed the contrary. A common feature of these studies was that a
gas-liquid two-phase interface existed in the system, which is the main
reason for the inconsistency in the above conclusions.
In conclusion, according to previous studies, hydrophobic surface is
more conducive to the storage of methane by AHH technology, which
not only promote the formation of hydrates, but also increase methane
storage capacity. The main reasons were as follows. 1) The mass transfer
at the interface is enhanced owing to the increase in the contact area at
the gas-liquid interface; 2) Owing to the increase in the water contact
angle on the hydrophobic surface, some clathrate hydrates form on the
hydrophobic surface [120]; 3) The thermodynamic study shows that the
hydrophobicity originates from a change in the water structure of the
medium and generates a type force of hydrophobicity. Water molecules
have difficulty forming hydrogen bonds with hydrophobic surfaces and
prefer to form clusters, minimizing the free energy [120,131]. More­
over, the hydrophobic surface reduces the enthalpy and entropy of the
system, which indicates the formation of clathrate hydrates or
low-density liquids; 4) Due to the enhanced hydrophobicity, the number
of water molecules bonding to the hydrophobic surface decreases and
the mobility of the water molecules increases, which promotes hydrate
nucleation and changes the position at which hydrate nucleation occurs,
increasing the rate at which the water-hydrate conversion occurs [92,
132]; 5) The water that forms on the hydrophobic surface is in an or­
dered or ice-like structure, and the nucleation induction time is reduced
[126].
3.3.5. Temperature and pressure
The influence of the adsorption temperature and pressure on
methane storage with the adsorption-hydration hybrid has been
explored in some experiments. Some scholars have proposed 2◦ C as the
upper temperature limit for the AHH technology and suggest that
Z. Wang et al.
temperature has a significant effect on the adsorption-hydration hybrid
[10]. The influence of temperature is mainly manifested in the forma­
tion of methane hydrate and the methane storage performance. Hydrate
formation is highly sensitive to temperature, especially near the freezing
point of water. Casco et al. [33] found that the pressure required for
hydrate formation changed little over a temperature increase of 0◦ C to
2◦ C, whereas the formation pressure increased significantly at 5◦ C, as
shown in Fig. 12a, and almost no hydrate formed at 10◦ C (Fig. 12b). The
phenomenon of requiring high pressures for hydrate to form at higher
temperatures has also been reported in other studies [10,23]. The main
reasons for this are: 1) Under constant pressure, the activity of water
increases as the temperature decreases, and because the equilibrium
condition of hydrate depends on the water activity, the increase in ac­
tivity leads to methane hydrate formation and the equilibrium pressure
of the hydrate phase decreases [56,133]; 2) The temperature can affect
the form that water takes in the pores. When the adsorption temperature
is lower than the freezing point of water, the pre-absorbed water pref­
erentially forms a solid-like structure in the larger micropores or mes­
opores. The limited range of molecular activity in the ice phase as
compared with liquid water means that an orderly structure is main­
tained [83], which requires less activation energy for reorganization
into hydrates, reducing the pressure required for hydrate to form. In
addition, the accumulation of methane on the ice surface and the for­
mation of defect structures have also been observed to greatly promote
the nucleation of hydrates [68].
Some scholars have found that the methane storage capacity de­
creases as the temperature increases in porous materials [10,29,33,59].
Casco et al. [33] found that at 0◦ C, the methane adsorption isotherm
showed a second “jump” in the high-pressure region (at pressures
exceeding 8 MPa). Compared with the plateaus at 2◦ C and 5◦ C, a tem­
perature of 0◦ C significantly increased the methane storage capacity, as
shown in Fig. 12a. However, according to the experimental results re­
ported by Borchardt et al. [23], the influence of temperature on the
methane storage capacity is also related to the pore size. The methane
storage capacity of microporous carbon materials is almost the same at
different temperatures and pressures; however, a significant inhibitory
influence of temperature on methane storage capacity was observed in
mesoporous carbon materials. Some scholars have reported that the
influence of temperature on methane storage capacity is related to
pressure. Yan et al. [20] found that the methane storage capacity in­
creases with temperature over a higher-pressure range in wet activated
carbon, whereas the methane storage capacity decreases with increasing
temperature at lower pressures. The reason for the inconsistency be­
tween temperature and methane storage capacity in the
above-mentioned studies may be that the methane storage capacity is
affected by multiple factors, such as water content, pressure, and the
properties of the material used. However, some scholars have explored
the influence of temperature on the rate of hydrate formation, which
Fig. 12. Effect of temperature on methane storage by AHH technology. (a) oxidized petroleum pitch-derived activated carbon PP-AC _Ox, Rw = 4.1 [33]. (b) pe­
troleum pitch-derived activated carbon PP-AC, Rw = 1.8 [10].
17
Journal of Energy Storage 50 (2022) 104195
increases as the temperature decreases and decreases rapidly at lower
temperatures.
The porous media system differs from the pure water system in terms
of pressure. The change in external pressure significantly affects the
pressure environment in the pores, especially the high-pressure phase
and reaction inside the micropores and small mesopores; therefore, the
degree of sensitivity to pressure is very significant in the pore environ­
ment [134]. The influence of pressure on the adsorption-hydration
hybrid mainly has the following aspects: (1) Pressure affects the distri­
bution of methane hydrate in the pores of porous materials. At low
pressures, methane hydrate forms initially on the surface of the mac­
ropores and materials, further form in the smaller pores as the pressure
increases [10,34]; (2) Pressure can affect the methane storage kinetics.
In wet porous materials that are at pressures below that required for
hydrate formation (physical adsorption stage), increasing the pressure is
conducive to the diffusion and dissolution of methane, further
improving the kinetics of methane adsorption. When hydrates form, the
methane storage kinetics become much slower. As the pressure in­
creases, the formation of more hydrates makes it more difficult for
methane to diffuse into the pores, reducing the methane storage kinetics
[34]; (3) Increasing the pressure can induce the formation of hydrates in
small mesopores and wide micropores, further increasing the methane
storage capacity, and a second pressure inflexion point may appear in
the adsorption isotherm, leading to the initiation of a two-step adsorp­
tion process [10,33] (Fig. 12a). In summary, the influence that pressure
has on methane storage when using AHH technology is not independent,
but is affected by a combination of multiple factors.
4. Mechanism of methane storage in confined nanospace by
AHH technology
At present, the mechanism of methane storage by AHH technology in
confined nanospace is still not clear, and understanding the formation
mechanism of hydrate in porous media has been challenging in both
experimental and molecular simulation research. The relationship be­
tween adsorption and hydrate formation under the confinement effect
therefore requires further exploration.
4.1. Experimental research
For methane storage by AHH in pre-humidified porous materials,
researchers have confirmed that a two-step adsorption-hydration pro­
cess occurred [10,92]. Nowadays, some studies have investigated the
migration behavior of methane and water in porous media during
adsorption-hydration process. Zhang et al. [32] proposed a two-way
nano-convection mechanism of methane and water that was induced
by methane adsorption, and the schematic diagram is shown in Fig. 13.
Methane molecules penetrated the obstruction of water molecule in
Z. Wang et al.
Fig. 13. Schematic of the adsorption-induced two-way nanoconvection mechanism and methane hydrate morphologies in AC during the process of AHH [32].
inner pores and entered micro pores induced by strong physical
adsorption, while water molecules were displaced and migrate out­
wards. The two-way convection/displacement phenomenon also pro­
posed in other studies [27,92]. This study also reported that the AHH in
activated carbon was discrete two-stage adsorption process: the former
being physical adsorption and the latter hydrate formation. Specifically,
due to the two-way convection phenomenon, methane physical
adsorption promoted the nucleation of hydrate fibers inside the nano­
pores, which reveals the relationship between the physical adsorption
and hydrate formation. Casco et al. [29] reported that there may be two
mechanisms of methane consumption in confined spaces, that is,
methane molecules can be diffused through the hydrate layer into the
inner pores, or water can be diffused into the outer pores to maintain the
growth of methane hydrate. In situ X-ray synchrotron imaging was used
to observe the water movements caused by cryogenic water suction
during the formation of methane hydrate, and this water migration is
sporadic-fast water movements followed by periods of stability [135].
Compared with previous experimental studies, experimental imaging
can achieve results at high spatial and temporal resolutions, and can
therefore more intuitively observe dynamic changes in the growth of
methane hydrate in a confined space, as well as the distribution and
migration behavior of water over the entire process [136]. The results
show that the competitive adsorption of methane and water causes the
extrusion for water from the pores to the outer space, which is consistent
with the two-way nanoconvection mechanism of methane and water in
nanospaces [32]. The capillary force caused by the pores of porous
media could enhance the liquid phase migration in the pores which
change the distribution of hydrate formation [137]. Besides, the direc­
tion of the methane flow may also cause aqueous water redistribution
[138]. In conclusion, revealing the migration behavior of methane and
water in porous media is helpful to understand the AHH mechanism.
However, at present, scholars only put forward the two-way nano-­
convection phenomenon according to the experimental results, the
cause and regulation mechanism of this phenomenon has not been
thoroughly studied, which is crucial for the application of AHH
18
Journal of Energy Storage 50 (2022) 104195
technology.
In addition, scholars have investigated the phase transition process
of water and the state of pore water in the confined spaces. In the process
of methane hydrate formation, frozen water and ice are observed in the
pores. Casco et al. [29] reported that there were three types of water
(external water (solid), core water (solid), and adsorbed water) before
and after methane adsorption in the pores of MCM-41 and B-PMO. It was
found that after the absorption of methane in B-PMO, two discontinuous
steps occurred that consumed the methane. Step 1 consumed a large
amount of external and “core water” to form bulk-like hydrates, and step
2 involved the formation of confined hydrates in a confined space. Jin
et al. [105] prove that the formation process of methane hydrate in the
porous media was divided into two steps. The first step was the forma­
tion of a film-like hydrate at the gas-liquid interface, from which water
molecules enter the pores from cracks in the broken hydrate film. Sec­
ondly, the hydrate changes from film-like shape to a cement-like shape
in porous media, which further promotes the growth of hydrate. Casco
et al. [92] explored the conditions under which methane hydrate forms
inside the micropores (Fig. 14b). It was difficult to convert liquid water
into hydrates in the hydrophilic ordered mesoporous carbon (HOMC),
and the stacking disordered ice (Isd) structure created suitable condi­
tions for hydrate nucleation (Fig. 14c and d). However, the methane
hydrate inside the ordered mesoporous carbon (OMC) was generated
from the confined liquid water and was finally converted into ice. The
results showed that methane hydrate was formed from ice both inside
and outside the mesopores, which indicates that the ice phase may be
another key factor in the hydrate formation. Interestingly, a water film
between the hydrate and the pore wall exists in a liquid rather than a
frozen form. Smirnov et al. [139] further confirmed through experiment
that this is related to the ability of the pore wall to change the energetic
state of the water, and the chemical potential of water molecules de­
creases as the distance between the water molecules and the pore wall
decreases, which also proves that not all the water in the pores can be
converted to hydrates. In hydrophobic pores, water molecules are fixed
onto the pore wall in the form of clusters, indicating that the phase
Z. Wang et al. Journal of Energy Storage 50 (2022) 104195

Fig. 14. State of water and the effect of disordered ice on methane adsorption and hydration/the mechanism of water-ice-methane hydrate micro-change. (a)
Mechanistic model of methane hydrate formation in MCM-41 and B-PMO loaded with water up to reach 150% of the total pore volume at 243 K [29]. (b) Mechanistic
model of methane hydrate formation in model carbons. (c) Kinetics of ice-to methane hydrate conversion by in situ wide-angle neutron scattering. (d) Peak areas of
fitted main signals (Gaussian function) of ice (red) at 1.60 Å− 1 and methane hydrate (blue) at 1.96 Å− 1 [92].

change of water may occur from the pore wall to the pore center, at the
entrance of the pore, or on the outer surface of the crystal growth space.
This conclusion is similar to that of Pirzadeh et al. [68], who observed
that water molecules form ice-like structures in the form of clusters and
further combine with methane molecules to form hydrates and that
methane can diffuse through the Isd. At the same time, the Isd structure
can be completely converted into methane hydrate in the HOMC, which
is a repeatable process [92]. In addition, based on the activated carbon
material (PP-AC), the hydrate ice samples were compared after forma­
tion and decomposition, and the crystal growth was found to be aniso­
tropic, which verifies the existence of the disordered structure of the ice
on the side. The reorientation of water molecules is hindered at low
temperatures, which is an important reason for the partial Isd structure.
However, the interior of the water molecules can be redirected to
completely restore the methane hydrate structure within a few minutes
at high pressure [31]. Other scholars have also confirmed that the Isd
structure can promote the formation of methane hydrate in the pores
[23,92]. These studies provide a new perspective for studying the
methane AHH technology in a nano-confined space.
Interestingly, at a low degree of supercooling, Smirnov et al. [139]
observed that the water absorbed on coal sample was bound and
no-freezing by DSC. Studies have shown that the methane hydrates may
be formed by both bound water and free water. By checking the dynamic
characteristics of the adsorbed water, it was concluded that at water
content higher than 10%, the combination of the water and the coal
matrix was weak. When it was subcooled, the bound water occurred a
glass-like transition rather than formed ice. Some of the water is strongly
bound to the main adsorption site, whereas some of the weakly bound
water will also be in the secondary coal. Hydrates are formed on the
adsorption sites, and heterogeneous nucleation active sites form pref­
erentially in the hydrophilic regions of the secondary adsorption sites
[124].
In summary, through experimental observation, the study of the
methane adsorption-hydration hybrid in a nano-confined space can be
divided into two parts: the physical adsorption of methane and the
combination of the hydrate process and methane adsorption. The above
research found that water molecules can be replaced by methane mol­
ecules in the confined nanospace, forming a two-way nanoconvection
phenomenon [32]. This is a step forward in explaining the mechanism of
the methane adsorption-hydration hybrid in the nano-confined space. At
the same time, there is a phase transition in which ice forms from water
during the formation of methane hydrate in the nanopores, which de­
pends on the surface properties of the materials, the temperature, and
the water content. The formation of this ice phase affects the formation
of methane, the ability to diffuse within the pores, and the formation of
methane hydrate. The above studies may provide a new idea for an
in-depth study of the formation mechanism of methane hydrate in the
nano-confined porespace.
4.2. Molecular simulation research
Molecular simulation technology is currently a popular and widely
used research method. It can overcome the limitations of traditional
experimental methods and explain the essential reason for phenomena
from a microscopic mechanism perspective. MD and Monte Carlo (MC)
simulation are effective tools to reveal the microscopic process of porous
media system. For MD simulation, the state of motion of each particle
depends on the potential function and is determined by solving New­
ton’s equation of motion. It is used to study the dynamic evolution
process and obtain the kinetics properties of systems. However, for MC
simulation, the motion of each particle is determined by random sam­
pling based on a probability distribution. This method is more suitable
for phase equilibrium simulation. In the previous studies, MC and MD
simulation have been widely applied to study methane storage by ANG
and NGH. However, the investigation of the microscopic mechanism of
AHH in confined nanospace by molecular simulation is still need to be

19
Z. Wang et al.
explored. The applications of molecular simulation methods in the
related studies of methane adsorption and hydrate hydration in porous
media are described as follows.
4.2.1. Molecular dynamics simulation
Compared with MC simulation, the advantages of MD simulation
include the following aspects. i) Studying the dynamic evolution process
of hydrate formation in porous media and obtaining the kinetics prop­
erties of systems, including hydrate formation kinetics, hydrate nucle­
ation location, the evolution of cage structure, and degree of hydrate
crystallinity. ii) Observing the transport properties of methane and
water in the process of AHH and revealing the mechanism of AHH, such
as the effect of solid surface on hydrate formation; the relationship be­
tween methane adsorption and hydrate formation in porous media.
At present, literature describing the use of the MD method to
investigate methane storage by AHH technology in porous materials is
relatively scarce, and the relationship between adsorption and hydrate
formation is often studied separately. Recently, Wang et al. [98] per­
formed MD and MC simulations to investigate the hybrid methane
physisorption-hydrate growth in hydrophobic ZIF-8, which is the first
time to establish the relationship between adsorption and hydrate for­
mation at molecular level. The two-way migration between water
molecules inside the cavities and methane molecules outside the cavities
was found and occurred before hydrate formation (Fig. 15a). It was
demonstrated that this mechanism increased the methane adsorption
capacity in wet ZIF-8 to a level close to that of dry ZIF-8. The competitive
adsorption for methane between ZIF-8 and intergranular hydrate was
not conducive to the formation and stability of intergranular hydrate.
When the adsorption of methane by ZIF-8 was in equilibrium, inter­
granular hydrate could exist stably and grow (Fig. 15b). In the end,
methane storage capacity was increased by 72.5% in H2O-oversaturated
ZIF-8 compared with dry ZIF-8 (Fig. 15c). Moreover, He et al. [99]
studied the formation of methane hydrate in mesoporous hydrophilic
MIL-101 by MD simulation. They found that methane hydrate was
preferentially formed in the outer space of the MIL-101 cavity. As the
hydrate continued to grow, a methane concentration gradient formed
between the cavity and the outer space, promoting the outward diffu­
sion of the methane molecules. Hydrates can only form stably in the
MIL-101 cavity when hydrate formation was complete in outer space
(Fig. 15d and e). In addition, methane storage was significantly reduced
Fig. 15. Microscopic mechanism of AHH in ZIF-8 and MIL-101. (a) Two-way migration between water and methane molecules (b) Growth process of methane
hydrate in ZIF-8. (c) Variation in methane storage capacity of ZIF-8 during AHH process in ZIF-8 [98]. (d) Four stages of hydration formation in MIL-101 cavities. (e)
Formation process of methane hydrate in MIL-101 system [99].
20
Journal of Energy Storage 50 (2022) 104195
in H2O-saturated MIL-101 compared to dry MIL-101 because cavities
were occupied by water. However, in H2O-supersaturated MIL-101, the
excess water in outer space significantly increased methane storage,
indicating that water content has a significant impact on methane
storage capacity. Although the effects of physical adsorption on the
hydrate formation were not considered, the simulation results provide
theoretical guidance for AHH technology in porous materials. To fully
understand the mechanism of AHH in the confined nanospace, the
mechanism of two-way migration between water and methane mole­
cules requires further studies.
In addition to the microscopic mechanism of AHH, the formation
mechanism of methane hydrate in porous media by MD simulation has
been widely focused on in recently years. The porous materials involved
mainly include silica [126,140–142], clay sediments [119,130,
143–147], metal nanoparticles [127,148], carbon materials nanopore
(including graphite and graphene) [126,130], and MOFs materials [98,
99], and the influence of hydrate formation in porous media on the
influencing factors has been extensively discussed. Yan et al. [119]
established a three-phase system that included a montmorillonite layer
and a volumetric solution of methane and water. Through MD simula­
tion, it was found that the formation of hydrate in the volumetric so­
lution led to methane molecules mainly diffusing in the volumetric
solution, followed by the diffusion of some methane molecules from the
volumetric solution into the montmorillonite layer to form "interlayer
hydrates" and "surface hydrates”. The author suggested that the diffu­
sion of methane molecules is an important factor in determining the
formation of hydrates and that the growth and diffusion of hydrates are
synergistic. At the same time, the authors found that hydrates tend to
form preferentially at the throats of pores, slowing down the diffusion
rate of methane from the volumetric solution into the pores and hin­
dering the formation of hydrates in the pores. In addition, the presence
of cations in the pores and hydroxyl groups on the surface of montmo­
rillonite affects the formation of hydrates in the pores. Therefore, the
author suggested that the pore size of montmorillonite and the diffusion
of methane are the two main factors affecting the formation of hydrates
in the pores of montmorillonite. On this basis, Yan et al. [143] further
analyzed the influence of the gas-water ratio on the formation of volu­
metric solution and hydrate in the pores of montmorillonite and found
that a higher gas-water ratio would promote the formation of volumetric
solution and hydrate in the pores. For surface groups, scholars found
Z. Wang et al.
that the silicon-oxygen ring on the surface of montmorillonite can form
hydrogen bonds with water, which is conducive to the stability of the
hydrate structure [143,149]. He et al. [126] observed that the silanol
groups on the surface of silica formed strong hydrogen bonds with
water. When the hydrate cage is in contact with the surface, the
arrangement of the silanol is required to match that of the cage in order
to form more hydrogen bonds, which promote contact between the
hydrate cage and the solid surface. It can be seen that the surface groups
maintain the stability of the hydrate cage and promote the growth of
hydrates on the solid surface by interacting with the water at the
interface, which provides theoretical guidance for the design and syn­
thesis of new materials with surface groups.
The stability of the hydrate is not only affected by the interaction
between solid surface and water molecules, but also has a close rela­
tionship with the affinity between solid surface and methane molecules.
Ma et al. [150] observed that the adsorption of guest molecules by the
solid surface with strong affinity to the guest molecule and the surface of
the hydrate core is competitive and leads to the decomposition of the
hydrate core and that the stability of the hydrate is only maintained
when the solid surface has a low affinity for the guest molecule. They
therefore suggested that hydrates cannot directly nucleate and grow
onto a solid surface unless it shows an appropriate affinity for the guest
molecule. Similarly, Cox et al. [130] suggested that due to the different
chemical properties of methane and water, it is unlikely that a solid
surface will exhibit a strong affinity for these two substances at the same
time, promoting the mixing of the two. It has therefore been observed
that, regardless of whether the solid surface is hydrophobic or hydro­
philic, methane hydrates often nucleate and grow preferentially in the
volumetric region away from the solid surface [126,130,142,147]. In
addition, He et al. [126] found that despite the formation of strong
hydrogen bonds between the hydrate cage and the surface groups of
silica, the low methane concentration of the aqueous solution on the
silica surface eventually causes the liquid water to separate the hydrate
cage from the solid surface. The methane concentration near the solid
surface was also found to affect the stability of the hydrate on the solid
surface. It can be seen that the formation of hydrates on the surface of
porous media is affected by complex host-methane/water molecular
interactions. The formation and growth of hydrates on the surface can be
promoted only when the surface of the porous media exhibits an
appropriate affinity for methane and water simultaneously. In addition,
some scholars have studied the influence that the hydrophilic and hy­
drophobic surface properties of porous media have on the formation
mechanism of methane hydrate. The hydrophilic and hydrophobic
properties can change the spatial distribution of the methane molecules
and water in porous media, further affecting the concentration of
methane in the liquid phase. The kinetics and mechanisms affecting the
formation of hydrates are described in detail in Section 3.3.4. The above
research revealed that the microscopic mechanism of the surface of
porous media affects the formation of methane hydrate; thus, inspiring
us to focus on the interaction between the surface of the porous media
and methane/water in promoting the formation of solid surface hy­
drates. The above research results show that the main factors involved in
growth and structural stability affect the nucleation of methane hydrate,
both on the surface and in the pores of the porous medium, including the
surface group, pore size, the hydrophilic and hydrophobic characteris­
tics of the porous medium, the diffusion of methane into the pores, and
the affinity of a solid material for methane.
In summary, MD simulation method is an effective tool to study the
mechanism of AHH. Despite these achievements, scholars have mainly
focused on the nucleation and growth mechanisms of methane hydrate
in porous media. Because the adsorption-hydration hybrid is an alter­
nate process of methane adsorption and hydrate formation, the rela­
tionship between the adsorption and hydrate formation cannot be
ignored, especially in terms of excellent natural gas adsorbents such as
MOFs and porous carbon materials. In addition, experiments have found
that hydrophobic MOFs are more conducive to the methane storage by
21
Journal of Energy Storage 50 (2022) 104195
AHH technology than hydrophilic MOFs [28,37]. It is recommended
that the follow-up studies focus on the application of hydrophobic MOFs
in AHH technology by MD simulation. It is necessary to clarify the
mechanism of AHH to provide theoretical guidance for further design
and synthesis of porous media with better gas storage performance.
4.2.2. Monte Carlo simulation
MC simulation is also an important method for studying structure
and thermodynamic properties of system, which is helpful to understand
the mechanism of AHH in porous media. MC simulation has some ad­
vantages compared with MD simulation. Firstly, MC simulation plays an
important role in examining three-phase hydrate equilibria and stability
of methane hydrates. In the area of AHH, three-phase hydrate equilibria
and stability of methane hydrate in porous materials can be studied by
MC simulation [151]. In addition, MC simulation has advantages in
revealing the adsorption behavior of methane in the process of AHH. For
example, calculating the gas storage capacities (or occupancy) of hy­
drate cages and gas adsorption capacity in porous materials through
grand canonical MC simulation; observing the adsorption sites of gas
molecules in hydrate cages and porous materials were observed;
calculating the interaction energy between gas, hydrate, and porous
materials. Previous studies have revealed the adsorption behavior of gas
in the hydrate cages and porous media by MC simulation [152–157].
For three-phase hydrate equilibria and stability of methane hydrates,
researchers have widely focused on the methane hydrate in bulk water.
Tsimpanogiannis et al. [151] have discussed the studies that report
three-phase hydrate equilibrium calculations in the bulk water by MC
simulation in their review. However, three-phase equilibria of methane
hydrate in porous media remains not clear to the best of our knowledge.
In terms of porous media system, Chakraborty et al. [158] used three
different water models to examine the structure, stability, and dissoci­
ation mechanism of methane hydrate in carbon-like slit pores. They had
shown that different water models exhibited different behavior, and
water models must be quite carefully chosen on confined hydrate
systems.
In terms of adsorption behavior of methane in the hydrate cages,
studies have been mainly related to cage occupancies of methane hy­
drate in bulk water. Henley [76] calculated cage occupancies of sI
methane hydrate along with considering both a flexible and a rigid
lattice by Gibbs ensemble MC simulation. Tsimpanogiannis et al. [151]
also reviewed the studies on the gas storage capacity of methane hy­
drate. However, when methane is stored by AHH, it is necessary to apply
the gas storage capacity of methane hydrate to porous media and
explore the impact of confinement effect on the gas storage capacity of
methane hydrate. In addition, there are a wide of researches investi­
gated the methane adsorption behavior in pre-humidified porous ma­
terials by MC simulation. Jin et al. [159] studied the adsorption of
methane and carbon dioxide in wet clay minerals on using MC simula­
tion. It was observed that water and methane were adsorbed in the same
layer in the 1 nm pores, whereas water was adsorbed in the first layer
and methane in the second layer of larger pores. The water molecules in
the clay surface formed a hydrophilic water adsorption layer that
significantly reduced the adsorption of methane and carbon dioxide.
Wang et al. [153] investigated the adsorption and diffusion properties of
methane and water in ZIF-8. Because pre-adsorbed water occupies the
methane preferential adsorption sites and reduces effective adsorption
volume, methane adsorption capacity of ZIF-8 decreases with increasing
water content. The negative effect of pre-humidified porous materials on
the adsorption performance of methane has also been described in some
literature by MC simulation, including carbon material [160], zeolite
[161], coal [162]. In inclusion, the studies of methane adsorption in
pre-humidified porous media mainly focus on physical adsorption, while
they are not involved in hydrate formation.
However, MC and MD simulations have been combined to explore
hydrate formation in porous media. Stable interlayer methane clathrate
structures were found in the interlayers of hydrated Na-montmorillonite
Z. Wang et al.
in equilibrium with seawater under ambient conditions by Park et al.
[163]. The mechanism of adsorption and hydrate growth in ZIF-8 was
also investigated by performing MD and MC simulations. Billemont et al.
[164] have reported that the hydrate formation in wet nanoporous
carbon was not observed by Monte Carlo simulation. They contributed it
to the insufficient number and inadequate nature of polar sites in the
numerical model. Therefore, it is difficult to explore the formation of
methane hydrate in porous media through MC simulation alone.
Furthermore, the combination of MD and MC can be used to for further
understand the mechanism of methane storage by AHH technology in
the future.
5. Challenges of large-scale application for methane storage by
AHH technology
5.1. Effective thermal management method
The use of an AHH technology that comprises porous material to
store methane is a two-stage adsorption process that includes both the
physical adsorption of methane and the formation of methane hydrate.
Therefore, the heat released during the adsorption and storage of
methane is composed of the heat from adsorption and hydrate forma­
tion. Because the porous materials in ANG storage systems usually have
low thermal conductivity, especially MOFs with great application po­
tential, the thermal conductivity is approximately (< 2 W m− 1K− 1)
[165], which hinders the rapid removal of heat during gas adsorption.
The rapid adsorption therefore leads to an increase in temperature,
which severely reduces the methane storage capacity [166]. During the
degassing process, the temperature is reduced owing to the heat of
desorption, and the useless adsorbates remain in the pores under the
exhaustion pressure. Therefore, under actual conditions, the storage
capacity of methane is always lower than that under completely
isothermal conditions. When considering the use of ANG to replace
traditional petroleum-based fuels for transportation vehicles, this
bottleneck is often mentioned [4,167,168]. This problem is common in
materials such as MOFs, activated carbon, and zeolites [169,170].
Similarly, some scholars found that during the formation of methane
hydrate, the heat released by hydration must be quickly removed;
otherwise, it will affect the rate of hydrate formation [171,172]. Den­
ning et al. [26] considered using HKUST-1 to eliminate the local heat of
hydrate formation and promote the growth of hydrates because of its
higher thermal conductivity. Fan et al. [173] found that porous
aluminum foam has excellent thermal conductivity and can accelerate
the formation of methane hydrate by enhancing the heat transferred by
hydration. Li et al. [174] found that the addition of aluminum honey­
comb is beneficial for dissipating the heat of hydration. Owing to its
excellent thermal conductivity, the maximum gas consumption rate of
methane can be increased by 9.62~14.30% and the rate at which gas
can be stored can be increased. It can be seen that the thermal effect is
also crucial for the formation of hydrates. Therefore, to increase the
methane storage capacity and the gas charging and discharging rates of
the AHH system, the problem of thermal effects must be solved. This
challenge can be solved using effective thermal-management methods.
Because the AHH system uses an adsorbent as a carrier for methane
storage, it is necessary to find an effective heat management method that
is suitable for the ANG system. Many scholars have explored the appli­
cation of thermal management methods in the ANG system and have
mainly considered the addition of heat exchangers and non-adsorbent
heat-conducting materials to adsorption storage tanks. Rahma et al.
[175] added fin and tube heat exchangers to the adsorbent bed, with
results showing that the heat exchange efficiency of the gas storage
container significantly increased, and the inflation and deflation pro­
cesses were significantly improved. Ybyraiymkul et al. [168] optimized
the design of the finned tube heat exchanger to reduce the volume
occupied by fins and tube fins, and proposed a new optimized structure
for the heat exchanger. The results demonstrated that the gas storage
22
Journal of Energy Storage 50 (2022) 104195
capacity of the ANG tank was increased by 10%, and the volume of the
storage container occupied by the heat exchanger was reduced from
13.5% to 4.3%. Amigo et al. [176] distributed non-adsorbent steel onto
the adsorbent bed to design optimized ANG storage tanks that could
achieve a high storage density faster than full carbon tanks. Patil et al.
[177] added graphite powder to activated carbon to enhance heat
transfer and found that the storage efficiency can be significantly
improved and that the gas storage capacity could reach 150 v/v.
Although the above methods can improve the thermal conductivity and
reduce the influence of adsorbed heat, the introduction of heat ex­
changers and non-adsorbent materials reduces the effective volume of
the adsorbent in the adsorption tank while increasing the energy con­
sumption and cost of the system, thermal management methods that are
economical and easily industrialized are yet to be developed. Therefore,
the current AHH system still presents practical challenges in designing
high-capacity systems and managing thermal fluctuations associated
with adsorbent adsorption and desorption of gases [168].
Although the effective heat transfer in the material is ultimately
limited by its intrinsic chemical diversity and porosity, in order to
reduce the cost of thermal management, it is necessary to understand
and improve the intrinsic thermal properties of porous materials [178].
At the same time, understanding the mechanism of heat transport in
porous media can help to improve the thermal effect of the
adsorption-hydration hybrid. Wieme et al. [178] found that compared
with other standard materials (metals, polymers, and ceramics), the
thermal conductivity and heat capacity of MOFs are generally lower,
and it is difficult to fundamentally improve the performance of the
materials. Beckner et al. [170] found that activated carbon exhibits a
higher heat transfer rate than MOFs during the adsorption and desorp­
tion processes, indicating that activated carbon has superior thermal
conductivity. Recently, Zhu et al. [179] prepared a new phase change
heat storage material: coal-based three-dimensional graphite porous
carbon. The ultrathin graphite wall of the material was found to enhance
the thermal conductivity. These studies provide guidance for the design
and synthesis of materials with higher thermal conductivities. Babaei
et al. have studied the factors that affect the thermal conductivity of
MOFs, including the influence of permeation [180], the size and shape of
the pores [181], missing linker defects [165], and the presence of ad­
sorbates [117,182,183]. The authors found that the thermal conduc­
tivity of the system decreased as the methane concentration in the pores
increased in the porous crystal-methane system [182]. In addition, the
significant thermal resistance of the MOFs-methane interface constitutes
a bottleneck in the adsorption process and hinders the rapid release of
the adsorption heat [117]. These findings provide theoretical insight for
the thermal management of MOFs in the AHH technology. However, the
mechanism by which heat is transferred during the storage of methane
by AHH technology has not yet been reported, and the mechanism of
heat generation and dissipation during the formation of hydrate in
porous media is not clear. In addition, porous carbon materials have
excellent methane storage performance in AHH technology, whereas the
heat transfer mechanism of the material is still unclear.
Moreover, it is worth noting that Mason et al. [184] reported MOFs
with gate-opening behavior and stepped (s-shaped) methane adsorption
isotherms. When flexible MOFs are applied in an ANG storage system,
the phase transition of framework occurs under a specific pressure,
which can provide greater methane storage performance than tradi­
tional MOFs. Such MOFs can also reduce the amount of heat released
during adsorption and the impact of cooling during desorption. In
particular, the endothermic expansion of the Co(bdp) framework re­
duces the heat released by the methane adsorption under the open gate
pressure by 28%. Fig. 16 shows the schematic diagram of heat transfer
process when AHH technology and flexible MOFs are combined. The
application of flexible MOFs provides new insights for the thermal
management of AHH systems. Hiraide et al. [185] further found that
flexible MOFs: ELM-11 exhibited a two-step gate-adsorption isotherm,
and that the thermal management of carbon dioxide two-step gate
Z. Wang et al.
Fig. 16. Schematic diagram of phase transition thermal management of flexible MOFs with large and small pores.
control at lower and higher pressures are almost the same, which in­
dicates that flexible MOFs with multiple “gate openings/closings” are
expected to become promising materials with intrinsic thermal man­
agement mechanisms. This study provides a new idea for applying
flexible MOFs to methane storage.
Therefore, the inherent thermal management capabilities of flexible
MOFs contribute to the development of efficient AHH systems that not
only use reversible phase transitions to maximize methane transport
capacity, but also reduce thermal management costs. However, the
intrinsic thermal management of AHH using flexible MOFs has not been
reported. Compared with the ANG system alone, the AHH system is
more complicated. Nowadays, the matching mechanism between heat of
AHH and phase transition heat of flexible MOFs is not clear. According
to the above studies, it can be inferred that in the process of AHH, the
desorption isotherm and the adsorption isotherm show obvious hyster­
esis. Similarly, the desorption isotherm of flexible MOFs exhibits hys­
teresis (the gate closing pressure is lower than the gate opening
pressure) [185]. Establishing a potential connection between them is
expected to match the intrinsic thermal management of flexible MOFs
with the thermal effects of the AHH technology. In addition, to accu­
rately predict the intrinsic thermal management performance of flexible
MOFs, it is necessary to establish a thermodynamic model that could
describe the “gate opening/closing” behavior during the process of
AHH.
5.2. Synthesize specific porous materials
Many studies on methane storage by AHH technology have reported
that activated carbon materials and MOFs materials are extremely po­
tential methane storage materials [10,27,28,31,32]. When the water
content reaches saturation or oversaturation, the storage capacity of
methane by using AHH technology in these materials is higher than that
of other porous materials such as zeolite [186]. In addition, activated
carbon materials have always been considered one of the most suitable
materials for high-density storage of methane owing to their porous
23
Journal of Energy Storage 50 (2022) 104195
characteristics, stability, and low price. However, materials with un­
certain pore size and distribution and the characteristics of the materials
on the surface render the factors involved in the adsorption-hydration
hybrid process uncertain. The formation of hydrates in narrow pores
may block the pores, further hindering the adsorption of methane and
reducing the kinetics of methane hydrate formation. Therefore, the
synthesis and preparation of carbon materials with specific pore di­
ameters and uniform distributions is very important for the storage of
methane via AHH technology.
Over the last 10 years, metal-organic framework materials have been
extensively investigated and applied in various processes, and many
specific MOFs materials have been synthesized. Some of these materials
have been applied to the study of methane storage by AHH technology,
including MIL-100 (Fe) [28], MIL-53 [37,97], ZIF-8 [28,36,77], ZIF-67
[77], HKUST-1 [26,37], Y-shpMOF-5 [27], and Cr-soc-MOF-1 [27].
However, the materials currently explored still have some distance to
achieve the goal of DOE. On the one hand, the surface characteristics of
the materials and the size of the internal confined nanospace signifi­
cantly affects the formation of methane hydrate. On the other hand, the
internal confined space of a wet material is complicated, which causes
the effect of different water content on the nucleation and growth of
hydrate is significant, including the nucleation position, kinetics of
formation, hydrate morphology, methane storage capacity, and so on.
Therefore, the synthesis of specific materials should aim at achieving
high density capacity and rapid hydrate formation kinetics under
appropriate temperature and pressure conditions. Meanwhile, the
design of the material framework should consider the uniformity and
connectivity of the pore size and distribution, hydrophilicity and hy­
drophobicity of the surface, particle size, and material ingredients. Some
studies have shown that the pore size and distribution of the MOFs can
be adjusted by changing the organic ligands, metal sources, reaction
solvents, and other methods [187–190]. However, the preparation of
uniform nanoparticles is still a major challenge [191]. At present, the
preparation of uniform nanoparticles remains a major challenge. For
MOFs materials, they are mostly adjusted by three methods, including
Z. Wang et al.
rapid nucleation, nanoreactor limitation, and coordination adjustment.
The synthesize nanoparticle materials of specific size and uniformity is
helpful for the further investigation of high-density methane storage
materials by using AHH technology.
Recent studies have begun to obtain composite materials of hydro­
phobic carbon and MOFs materials using certain methods based on the
original theory [192]. Graphite oxide was added to HKUST-1, and the
introduction of graphite oxide creates a more hydrophobic environment
around the metal sites and prevents the coordination bonds from being
corroded by water molecules. The water stability of the materials was
significantly improved. Therefore, combining the respective advantages
of carbon materials and MOFs materials, the two materials can be
combined to design and synthesize new composite materials suitable for
the storage of high-density methane by AHH technology.
6. Future perspectives
This article systematically reviews the advances in methane storage
by using porous materials as AHH technology. Researchers worldwide
have made some progress in the past 20 years, and have shown that the
application of adsorption-hydration hybrid technology has great po­
tential. However, because the development of this technology is still in
its infancy and urgent problems still need to be solved, it cannot be used
for large-scale industrial applications at present. In the following sec­
tions, this review provides our perspectives on how future research
should be directed to address the challenges and achieve the wide
application of this technology.
6.1. Synthesize suitable materials
The key to realizing the industrial application of methane storage by
AHH technology lies in the design and synthesis of new materials. On the
one hand, under the synergistic effect of adsorption and hydrate for­
mation, the methane storage capacity could be increased sharply. On the
other hand, methane hydrate formation is effectively promoted in the
complex pore network, which improves the water-hydrate conversion
rate and formation rate. Materials should have a suitable pore structure
and surface chemical properties, which needs to be considered
comprehensively in terms of pore size, particle size, hydrophilicity/hy­
drophobicity, and the surface groups of porous materials. However,
current research has focused on the influence of a single factor on the
methane storage by adsorption-hydration hybrid process and the inter­
action between different factors in methane storage remains unclear.
Therefore, to guide the synthesis of porous materials that are suitable for
use as adsorption-hydration hybrid technology, future research should
focus on coupling the relationship between material properties and
explore the best properties of materials suitable for methane storage.
Carbon materials have been extensively studied in AHH technology.
However, owing to their high modularity in terms of porous structure
and surface chemistry, MOF materials have great potential for methane
storage and help to reveal the coupling relationship between different
factors. Therefore, MOF materials with different pore structures and
chemical properties should be designed and synthesized in subsequent
studies, and their application in AHH technology should also be
expanded.
6.2. Microscopic mechanism of AHH
The technology of methane storage by AHH technology in confined
space is essentially a multi-factor mixing process involving thermal-
flow-phase transition. However, the research on the mechanism of this
process is still in the preliminary stage. The main aspects that need to be
explored include the relationship between methane adsorption and hy­
drate formation, the mechanism by which methane hydrate forms in
confined nanospaces, the influence of the pore structure and surface
chemistry of porous media on the formation of methane hydrate, and the
24
Journal of Energy Storage 50 (2022) 104195
heat and mass transport mechanism in the process of adsorption-
hydration hybrid. The above research provides a means of solving the
problems associated with the AHH technology. Owing to the size limi­
tation of the porous media system, it is difficult to explore the mecha­
nism of adsorption-hydration hybrid. Molecular simulation techniques
(including MD and MC simulations) can provide insights into the
mechanism of methane adsorption-hydration hybrid at the molecular
level. Therefore, further investigation should adopt molecular simula­
tion technology in order to conduct in-depth research on the micro­
scopic mechanism, which is the storage of methane by AHH technology
in porous materials. At present, most simulation studies on hydrate
formation focus on simple nanopores and study the mechanism of hy­
drate formation in isolation. Further research should focus on the
mechanism of methane adsorption-hydration hybrid in porous media
systems with complex pore structures (such as MOFs), and provide
theoretical guidance for the design and synthesis of new porous
materials.
6.3. Heat and mass transfer in porous media
Methane storage by AHH technology is a complex problem including
multi-phase, multi-component flow, and heat transfer when using
porous medium. The current research mainly focuses on the heat and
mass transfer model of hydrate formation. The heat and mass transfer
mathematical model of the adsorption-hydration hybrid, which is of
great significance for revealing the heat and mass transfer mechanism of
adsorption-hydration hybrid and solving thermal management prob­
lems, has not been developed. A representative heat and mass transfer
mathematical model for the storage of methane by the AHH technology
should be investigated by combining the micro-scale heat transfer the­
ory, adsorption kinetics, and hydrate formation kinetics. By combining
the physical parameters and properties of the multiphase system and the
microstructure parameters of porous materials the effects of tempera­
ture, pressure, and concentration can be further considered. The heat
and mass transfer law and resistance to heat and mass transfer are
explored through mathematical models, and the total heat produced by
storing methane via the AHH technology is accurately obtained,
providing a theoretical basis for solving the problem of thermal
management.
6.4. Application of flexible MOFs
So far, some scholars have studied MOFs materials to store methane
by AHH technology, but the application of flexible MOFs in AHH tech­
nology has not been explored. Research has found that the pore phase
can be transferred under certain conditions when flexible MOFs adsorb
methane or water [193], which provides an opportunity for flexible
MOFs to be applied in AHH technology. The pore phase of flexible MOFs
can undergo reversible structural transformations between the large and
small pore phases, and the energy absorption caused by the "breathing
effect" can be related to the heat of adsorption, which is conducive to the
realization of heat transfer and management in the confined space. In
future research, attention should be paid to the combination of
adsorption heat and hydrate formation heat, and the flexible MOF
framework size pore phase transition should be used to reduce the
adverse effects of thermal effects, so as to effectively solve the thermal
effect of methane adsorption and hydrate formation. The use of flexible
MOFs for the storage of methane by AHH technology provides a new
direction for exploring efficient methane storage materials, which is
expected to provide technological innovation in the field of natural gas
storage.
6.5. Large-scale application
At present, research on the storage of methane by AHH technology
generally compares the performance of adsorbents on a small number of
Z. Wang et al.
materials on a laboratory scale. If the technology of AHH is used in light
vehicles, the weight of the storage container will reach the kilogram
level after being filled with materials. Therefore, it is necessary to
evaluate the methane storage behavior of adsorbents on a larger scale.
Although some laboratory studies have focused on the large-scale per­
formance of adsorbents for gas storage, such as the performance of ad­
sorbents in the circulation process and the use of adsorption models to
predict gas storage capacity. However, large-scale performance experi­
mental tests have not been carried out on the storage of methane by AHH
technology. In the future, the adsorption-hydration hybrid model should
be used to predict methane storage capacity and realize the storage of
methane by AHH technology for commercialization.
7. Conclusion
Due to the demand for natural gas increase sharply, to achieve the
purpose of more mild, safe, and efficient natural gas storage/trans­
portation, the technology of methane storage by the adsorption-
hydration hybrid technology has attracted wide attention. This review
comprehensively summarizes the research advances of the technology of
methane storage by the adsorption-hydration hybrid technology. First,
the application of different porous materials in this technology was
discussed, including carbon materials, silica, silica gel, zeolite and MOFs
materials. The adsorption-hydration hybrid technology is mainly
investigated by researchers from methane storage performance, water-
hydrate conversion rate, and methane hydrate formation pressure. It is
concluded that the technology is affected by multiple factors, and the
factors affecting the technology, including pore size, particle size, sur­
face properties, water content, temperature and pressure conditions,
were further discussed. The results of the discussion provide theoretical
guidance for the synthesis of porous materials suitable for this tech­
nology in the future. Next, this review elucidated the mechanisms from
two aspects: experimental research and molecular simulation. Although
some remarkable achievements have been made, researchers often pay
more attention to the formation mechanism of methane hydrates in
porous media, ignoring the relationship between adsorption and hydrate
formation. Furthermore, to promote the application of adsorption-
hydration hybrid technology in the storage and transportation of natu­
ral gas, the main challenges were provided in this review, which are
currently encountered in terms of effective thermal management and
synthesis of specific materials. Finally, the future direction of the tech­
nology was prospected. This review also provides a perspective for un­
derstanding the methane hydrate formation in confined nanospace.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper
Acknowledgements
We acknowledge funding support from the project 52176028 sup­
ported by National Natural Science Foundation of China, the project
ZR2019MEE005 supported by Shandong Provincial Natural Science
Foundation, and the project 18CX02080A supported by the Funda­
mental Research Funds for the Central Universities.
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