Applied Surface Science 570 (2021) 151211

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Applied Surface Science

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Full Length Article

Hydrogen evolution reaction on transition metal nanoparticles from

first-principles
Jiake Cui, Xiaojing Liu, Yifeng Wang, Dandan Song, Yugang Ren, Xiangjian Shen *
Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education, Zhengzhou University, Zhengzhou 450001, China

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

Keywords: An atomic-level understanding of hydrogen evolution reaction (HER) on transition metal nanoparticles is of great
Hydrogen coverage importance in exploring highly efficient and potential electro-catalysts for water splitting. We herein present a
Metal nanoparticles study of HER on some Ni- and Cu-group metal nanoparticles constructed from (1 0 0), (1 1 0) and (1 1 1) surfaces
DFT
based on the principle of Wulff structure. The Gibbs free energies of hydrogen adsorption on three typical sur­
faces are calculated by using density functional theory (DFT) calculations. The coverage effect on the surface
energy at different hydrogen coverage is considered due to the important influence of the hydrogen–hydrogen
interaction. The Ni-group metal nanoparticles prefer the (1 1 1) surface exposed and the Cu-group metal nano­
particles prefer the (1 1 0) surface exposed. The Wulff structures of nanoparticles at different hydrogen coverage
clearly show the different reaction rates. These theoretical results are helpful for understanding the HER
mechanism on metal nanoparticles.

1. Introduction
Developing sustainable and pollution-free non-fossil energy is an
inevitable trend. Hydrogen (H) is believed to be one of the most prom­
ising clean energy sources in the future [1]. Hydrogen evolution reaction
(HER) from water splitting is one potential and efficient approach to
produce hydrogen as a high purity [2,3]. Usually, the HER mechanism
involves two reaction pathways with the Volmer-Tafel pathway and the
Volmer-Heyrovsky pathway [4,5]. Importantly, the efficiency of the
HER strongly depends on the types of catalysts. Transition metal cata­
lysts are the most potential candidates due to the excellent electronic
structures [6–8]. Hence, a thorough understanding of the HER on some
model metal catalysts would advance the fields of water splitting.
To explore the HER on model metal catalysts at an atomic level, a
large number of experiments and theoretical studies have been devoted
to clarify the processes of adsorption[9–11], diffusion[12–15] and
desorption[16–18] of hydrogen on the single crystal metal surfaces. For
example, Pt as a model catalyst, effectively promotes the HER with a
large cathode current density under low overpotential[19–22]. The
early experimental results clearly show that the order of hydrogen
evolution activity on Pt surfaces follows as Pt(1 1 0) > Pt(1 0 0) > Pt
(1 1 1) and the current density on the (1 1 0) surface is about three times
as large as that on the (1 1 1) surface[20]. Some additional studies on Ni
[23,24], Pd[25], Au[26] and other model transition metals [27] have
been explored to support a clear understanding of the HER on the single-
crystal metal surfaces. However, the synthesized transition metal cata­
lysts are usually consisted of multiple crystal surfaces including the
common exposed (1 1 1), (1 0 0) and (1 1 0) surfaces. The different HER
performances strongly depend on the activities of the exposed surfaces.
Therefore, it is necessary and urgent to study the HER on model metal
nanoparticles at an atomic level.
Density functional theory (DFT) calculations have provided great
convenience for exploring the atomic interaction between hydrogen and
model metal nanoparticles at a quantum–mechanical level[28,29].
Based on the principle of Wulff structure, the surface energy and work
function are crucial to construct the models of metal nanoparticles
[30,31]. These two physical parameters determine the reactivity and
number of active sites of a model metal nanoparticle. That is to say, the
morphology of model metal nanoparticles plays an important role in
affecting the number of active sites. Ab initio thermodynamics calcula­
tions can provide an efficient approach to accurately describe the
morphology of the nanoparticles under different reaction conditions.
These ab initio thermodynamics results can reproduce well the evolution
processes of metal nanoparticles and have good agreement with those
in-situ experiments [32–34]. Moreover, besides of important tempera­
ture and pressure effects[35,36], surface-adsorbed species still largely

* Corresponding author.
E-mail address: xjshen85@zzu.edu.cn (X. Shen).

https://doi.org/10.1016/j.apsusc.2021.151211
Received 9 June 2021; Received in revised form 6 August 2021; Accepted 4 September 2021
Available online 11 September 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
J. Cui et al.
affect the morphology of metal nanoparticles. Wang et al combined the
spin-polarization DFT and ab initio thermodynamics to exhibit the
hydrogen adsorption induced structural evolutions of Fe nanoparticles
based on the principle of Wulff structure [37]. Vlachos et al found that
the hydrogen coverage has a strong influence on the conformation of the
hydrogenation reaction on the covered Pd(1 1 1) surface[38]. Similarly,
other molecular gas adsorption, e.g., CO[34,39] and H2O[40] also
strongly affect the morphologies of metal nanoparticles and metal sur­
faces at different reaction conditions. Therefore, in the process of the
HER, different hydrogen adsorption behavior and the hydrogen
coverage may greatly affect the catalytic performance of the metal
nanoparticles.
In this work, we present a theoretical study of HER on some model
transition metal nanoparticles constructed based on three common
exposed (1 0 0), (1 1 0) and (1 1 1) surfaces. Six transition metal nano­
particles of Ni-group and Cu-group are considered for the HER by
calculating thermodynamic and kinetic results. We calculated the
adsorption energy of atomic hydrogen on different surfaces and ob­
tained the scaling relationship of adsorption energy and the hydrogen
coverage. As a descriptor of the HER performance, the Gibbs free energy
of hydrogen adsorption are calculated. Some Wulff structures based on
surface energy, are discussed for temperature, pressure and hydrogen
coverage effects. A kinetic model was proposed to study the hydrogen
evolution rates on the model metal nanoparticles. The paper is orga­
nized as follows. In section 2, some computational methods are given,
and in section 3, the thermodynamic and kinetic results are given, and in
section 4, a summary is given.
2. Computational methods
2.1. Density functional theory (DFT)
All the periodic spin-polarization density functional theory (DFT)
calculations in this work are performed in the Vienna ab initio simula­
tion package (VASP)[41] to implement the generalized gradient
approximation (GGA) of the Perdew-Burke-Ernzerhof (PBE) functional
[42,43]. A plane wave function is used to describe the electron orbits in
the DFT calculation. The interaction between valence electrons and ion
cores is studied by the projected enhanced wave method. A slab model of
four metallic layers is used to represent the metal substrate. Ni- and Cu-
group, i.e., Ni, Pd, Pt, Cu, Ag, and Au are taken into account. For surface
relaxation of the adsorbed systems, two bottom metallic layers remain to
be fixed, and two top metallic layers and the adsorbate are allowed to
relax until each atomic force is less than 0.01 eV/Å. A large super cell of
(3 × 3) is used to simulate hydrogen adsorption. The Brillouin zone
sampling with a cutoff energy of 450 eV and a Monkhorst-Pack grid[44]
of 5 × 5 × 1 k-points was used. The zero-point energy(ZPE) correction is
also considered. In the previous work[45], we have explored the stable
hydrogen adsorption sites on the three common surfaces. On (1 0 0)
surface, hollow sites are stable for Ni, Pd, Cu, Ag and short-bridge sites
Fig. 1. Adsorption sites of (1 0 0), (1 1 0) and (1 1 1) surfaces. Brown and light balls are the topmost and second topmost metallic layers, and dark red is the third layer.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
2
Applied Surface Science 570 (2021) 151211
are stable for Pt and Au. On (1 1 0) surface, pseudo three-fold hollow
(P3H) sites are stable for Ni and Pd [36], and short-bridge sites are stable
for other metals. On the (1 1 1) surface, the fcc sites are stable. The
schematic diagram of different adsorption sites on (1 0 0), (1 1 0) and
(1 1 1) surfaces is shown in Fig. 1.
To understand the HER performance of metal nanoparticles, we have
investigated some important physical parameters including the
hydrogen adsorption energy(ΔEads ), the free energy of hydrogen
adsorption(ΔGH* ), the change in the free energy of hydrogen adsorption
as a function of the number of the adsorbed hydrogen ΔGads M (T, P, nH),
the surface energy(γads M (T, P, nH)) and the reaction rate (r). More details
can be found in the Supporting Materials. To obtain the hydrogen
adsorption energy, some DFT calculations are performed. The expres­
sion of hydrogen adsorption energy is defined as
1( n )
ΔEads = E(nH/surface) − E(surface) − EH2 (1)
n 2
where n is the number of the adsorbed hydrogen atoms, E(nH/surface) is
the total energy of the covered surface with n hydrogen atoms, E(surface) is
the total energy of the clean slab, and EH2 is the total energy of hydrogen
molecule in the gas phase.
As an important descriptor for appraising the HER, the Gibbs free
energy of hydrogen adsorption on the active site ΔGH* is defined. It is
given as
ΔGH* = ΔEads + ΔZPE − TΔS (2)
where ΔEads is the adsorption energy of hydrogen, and △ZPE is the
zero-point energy correction of reaction 12H2 (g)→H* calculated by DFT.
ΔS is the change in entropy, which can be obtained from the standard
molecular table. T is the temperature. And for different pH values of the
solution, the correction item G(pH) needs to be added by
G(pH) = − kB Tln(H + ) = kB T⋅pH⋅ln10 (3)
2.2. Wulff structures of metal nanoparticles
In this work, we consider three common exposed surfaces ((1 0 0),
(1 1 0) and (1 1 1)) to simulate the actual metal electrodes. The surface
energies of metal nanoparticles are calculated by DFT and used to
construct the corresponding morphology by VESTA software[37](See
supporting information for details). Based on the proportion of the
active sites of each surface in the nanoparticles, we discussed the
hydrogen adsorption energy, Gibbs free energy of hydrogen adsorption
and rate of the hydrogen evolution reaction on the model metal nano­
particles. Based on the scaling relationship of the active sites and the
corresponding surface area, we analogize the proportion of the area of
the exposed surface in the nanoparticles to the total area of the nano­
particles for representing the proportion of the active sites. Therefore,
we defined the adsorption energy ΔENPs and Gibbs free energy of
hydrogen adsorption ΔGNPs on model metal nanoparticles as
J. Cui et al. Applied Surface Science 570 (2021) 151211

∑ SM(hkl) adsorption energy is negative), while it is difficult on Ag and Au (the

ΔENPs = ΔEM(hkl) ⋅
SWulff
∑ SM(hkl)
ΔGNPs = ΔGM(hkl) ⋅
SWulff
where ΔEM(hkl) and ΔGM(hkl) are the adsorption energy and Gibbs free
energy of hydrogen adsorption on the exposed surface of the metal
nanoparticles. SM(hkl) is the total area of the exposed surface on the metal
nanoparticles and SWulff is the total surface area of the metal nano­
SM(hkl)
particles. And SWulff
is used to represent the proportion of the number of
active sites on the exposed surface to that on metal nanoparticles.
The reaction rate of HER on model metal nanoparticles is defined by
∑ hydrogen coverage on the exposed (1 0 0) surface is shown in Fig. 2a. It is
SM(hkl)
RNPs = rM(hkl) ⋅
SWulff
where rM(hkl) is reaction rate on the exposed surface of the metal
nanoparticles.
3. Results and discussions
3.1. H adsorption on (1 0 0), (1 1 0) and (1 1 1) surfaces
The hydrogen coverage effect is mainly discussed in this work. We
have calculated the adsorption energy of hydrogen on three common
exposed (1 0 0), (1 1 0), and (1 1 1) surfaces as the hydrogen coverage
varied from 1/9 monolayer (ML) to 1.0 ML. At different hydrogen
coverage, all possible adsorption configurations of the adsorbed
hydrogen were considered to weaken the configuration effect on the
adsorption energy (seen in the support materials). Our DFT results show
that, hydrogen is easy to be adsorbed on Ni, Pd, Pt, and Cu (the
(4)
adsorption energy is positive). Although the adsorption energy is
affected by the presence of the water layer and the electric field, it is very
little at low coverage so that we ignore these two factors in this work.
(5)
At different hydrogen coverage, the hydrogen adsorption energies
are totally different. As shown in Fig. 2, on different metal surfaces, the
hydrogen adsorption energy has different relationships as the increasing
hydrogen coverage (1 / 9 ML < θ less than 1.0 ML). The solid line in the
figure represents the adsorption energy is greater than zero, and the
dashed line represents the adsorption energy is less than zero. As the
coverage increases, the strong interaction between the adsorbed H
atoms makes the adsorption energy increase especially on the exposed
(1 1 1) surface. Different variations of adsorption energy and the
(6) found that the hydrogen energy is decreased from − 0.487 eV to − 0.56
eV for H/Ni(1 0 0); decreased from − 0.461 eV to − 0.503 eV for H/Pd
(1 0 0); increased from − 0.615 eV to − 0.606 eV for H/Pt(1 0 0);
increased from − 0.148 eV to − 0.068 eV for H/Cu(1 0 0); increased from
0.283 eV to 0.32 eV for H/Ag(1 0 0) and increased from 0.066 eV to
0.143 eV for H/Au(1 0 0). Clearly, the adsorption energy is increased as
the increase of hydrogen coverage except for Ni and Pd. For hydrogen
adsorption on the (1 1 0) surface (seen in Fig. 2b), the adsorption energy
is decreased from − 0.411 eV to − 0.426 eV for H/Ni(1 1 0); from − 0.491
eV to − 0.503 eV for H/Pd(1 1 0); from − 0.593 eV to − 0.607 eV for H/Pt
(1 1 0); − 0.031 eV to − 0.051 eV for H/Au(1 1 0). It is increased from
− 0.202 eV to − 0.168 eV for H/Cu(1 1 0) and from 0.175 eV to 0.191 eV
for H/Ag(1 1 0). As the hydrogen coverage increases on the (1 1 0) sur­
face, the adsorption energy of hydrogen on Ni, Pd, Pt and Au decrease,
while it increases on Cu and Ag. The weak repulsive interaction between
the adsorbed H atoms affects the hydrogen adsorption energy. For
hydrogen adsorption on the exposed (1 1 1) surface (seen in Fig. 2c), the

Fig. 2. Adsorption energy (△Eads) for hydrogen on Ni, Pd, Pt, Cu, Ag and Au of (1 0 0), (1 1 0) and (1 1 1) surfaces with different coverages. (a) on (1 0 0) surface (b)
on (1 1 0) surface (c) on (1 1 1) surface and (d) on metal Nanoparticles (NPs).

3
J. Cui et al.
hydrogen adsorption energy is increased from − 0.56 eV to − 0.543 eV
for H/Ni(1 1 1), from − 0.575 eV to − 0.484 eV for H/Pd(1 1 1), from
− 0.431 eV to − 0.332 eV for H/Pt(1 1 1), from − 0.247 eV to − 0.164 eV
for H/Cu(1 1 1), from 0.159 eV to 0.225 eV for H/Ag(1 1 1) and from
0.079 eV to 0.278 eV for H/Au(1 1 1). The adsorption energy is gradually
increased due to the obvious repulsive interaction between the adsorbed
H atoms.
To appraise the HER on different metal nanoparticles, the Gibbs free
energy of hydrogen adsorption on three common exposed surfaces of Ni-
and Cu-group metals are shown in Fig. 3. On the (1 0 0) surface in Fig. 3a,
the values of ΔGH* are − 0.312 eV for H/Ni(1 0 0), − 0.32 eV for H/Pd
(1 0 0), − 0.375 eV for H/Pt(1 0 0), 0.026 eV for H/Cu(1 0 0), 0.419 eV for
H/Ag(1 0 0) and 0.294 eV for H/Au(1 0 0), respectively. On the (1 1 0)
surface in Fig. 3b, the values of ΔGH* are − 0.169 eV for H/Ni(1 1 0),
− 0.254 eV for H/Pd(1 1 0), − 0.351 eV for H/Pt(1 1 0), 0.035 eV for H/Cu
(1 1 0), 0.39 eV for H/Ag(1 1 0) and 0.197 eV for H/Au(1 1 0), respec­
tively. And on the (1 1 1) surface in Fig. 3c, the values of ΔGH* are − 0.32
eV for H/Ni(1 1 1), − 0.342 eV for H/Pd(1 1 1), − 0.222 eV for H/Pt
(1 1 1), − 0.01 eV for H/Cu(1 1 1), 0.372 eV for H/Ag(1 1 1) and 0.288 eV
for H/Au(1 1 1), respectively. From our DFT results, it is found that Cu
has a good HER performance on three exposed surfaces because the
values of ΔGH* are close to zero. Using the ΔGH* for appraising the HER,
all the reaction steps of the hydrogen evolution reaction on the Cu
surfaces have the thermal neutralities. Interestingly, the absolute values
of ΔGH* of hydrogen on the Pt surfaces are larger than those on the Cu
surfaces at 1/9ML (seen in Fig. 3), especially on the exposed (1 0 0) and
(1 1 0) surfaces. In this work, we used the (3x3) supercell with one
hydrogen adsorption (1/9ML), and the adsorption energies of hydrogen
on different Pt surfaces are − 0.615 eV for H/Pt(1 0 0), − 0.593 eV for H/
Pt(1 1 0), − 0.431 eV for H/Pt(1 1 1) respectively. Our DFT results about
hydrogen adsorption energy on Pt surfaces are very close to that of Shi
Fig. 3. Free energy diagrams of hydrogen adsorption on different metals in equilibrium. (a) on (1 0 0) surface (b) on (1 1 0) surface (c) on (1 1 1) surface (d) on metal
Nanoparticles (NPs). The adsorption energy data is from Fig. 1, which has been corrected by zero-point energy and entropy. The environmental condition is normal
pressure, pH = 0 at 300 K, and the coverage of hydrogen is 1/9 here.
4
Applied Surface Science 570 (2021) 151211
et al.[11] due to the same computational model and method (the cor­
responding hydrogen adsorption energy are − 0.64 eV for H/Pt(1 0 0),
− 0.59 eV for H/Pt(1 1 0), − 0.50 eV for H/Pt(1 0 0), respectively) [11].
Similarly, using the computational settings, the adsorption energies of
hydrogen different Cu surfaces are calculated as − 0.148 eV for H/Cu
(1 0 0), − 0.202 eV for H/Cu(1 1 0), − 0.247 eV for H/Cu(1 1 1), respec­
tively. With the correction of the zero-point energy and entropy, the
final ΔGH* of hydrogen on different Cu surfaces are lower than those on
Pt surfaces. Cu and Pt metal nanoparticles have the good HER perfor­
mances due to the low values of ΔGH* under different reaction condi­
tions. In addition, we analyzed the results of hydrogen adsorption on Cu
(1 0 0), Cu(1 1 0) and Cu(1 1 1) surfaces and presented the averaged
distance of the adsorbed hydrogen on these surfaces. It is found that, the
tendency of the distance of the adsorbed hydrogen on these surfaces is
inverse relative to that of the free energy of hydrogen adsorption (seen in
the supporting materials). Importantly, as the hydrogen coverage in­
creases, the values of the averaged distance are shortened by 0.185 Å for
H/Cu(1 0 0), 0.065 Å for H/Cu(1 1 0) and 0.122 Å for H/Cu(1 1 1),
respectively. It indicates that, the shorter the distance of the adsorbed
hydrogen on the exposed surface is, the stronger the free energy of
hydrogen adsorption(ΔG(H*)) on the exposed surface is. The enhanced
free energy of hydrogen adsorption is mainly contributed to the shorten
distance of the adsorbed hydrogen on the exposed surface.
3.2. Hydrogen coverage effect
The reactivity of the metal nanoparticles is affected by the exposed
surface and composition of the nanoparticles. Simultaneously, the
morphology of the nanoparticles is often determined by the gas envi­
ronment, such as the presence of hydrogen species [37]. We therefore
investigated the influence of hydrogen coverage on the surface stability
J. Cui et al. Applied Surface Science 570 (2021) 151211

and morphology of the model metal nanoparticles. Ab initio thermody­
namics was applied to address the influence of different hydrogen
adsorption on the surface energy. According to the construction prin­
ciple, the Wulff structure was used to reveal the morphology of several
model metal nanoparticles under the given condition of 1.0 atm at 300
K.
Using ab initio thermodynamics calculations, the surface energies of
hydrogen interaction with the exposed (1 0 0), (1 1 0) and (1 1 1) surfaces
are presented in Table 1. On the Ni, Pd and Pt surfaces, the surface
energies decrease as increasing the hydrogen coverage. On the Ag sur­
faces, the surface energies increase as increasing the hydrogen coverage.
The surface energy of the exposed Cu (1 1 0) and (1 1 1) surfaces decrease
with the increase of hydrogen coverage. The surface energy of the
exposed Cu(1 0 0) surface increases from 1/9 ML to 6/9 ML, and slightly
decreases from 7/9 ML to 1.0 ML. The varied value is only 0.065 J/m2
for the surface energy on Cu(1 0 0) from 1/9 ML to 1.0 ML. Similarly, on
the exposed Au surfaces, the surface energy increases on the exposed
(1 0 0) and (1 1 1) surfaces and decreases on (1 1 0) surface (it is about
0.017 J/m2). Based on the obtained surface energies at different
hydrogen coverage, we constructed the stable morphology of model
metal nanoparticles through ab initio thermodynamic results (Seen in
Support Materials). We also calculated the proportions of three exposed
surfaces of model metal nanoparticles at different hydrogen coverage in
Table 2.
It is found that for most metal nanoparticles, the exposed (1 1 1)
surface has the lowest surface energy and it is the easiest to be exposed.
On the contrary, the surface energy of the exposed (1 1 0) surface is the
highest and it is the most difficult to be exposed. At the given condition,
on the Ni, Pd and Pt nanoparticles, there are only (1 0 0) and (1 1 1)
exposed surfaces, and no (1 1 0) exposed surface. On the Ag and Au
nanoparticles, the proportion of the exposed (1 1 0) surface increases
significantly with the increase of hydrogen coverage, while the pro­
portions of the exposed (1 0 0) and (1 1 1) surfaces gradually decrease.
Interestingly, the proportion of the exposed (1 1 1) surface of Cu in­
creases with the increase of hydrogen coverage, and the proportions of
the exposed (1 0 0) and (1 1 0) surfaces gradually decrease. For example,
when the coverage is less than 5/9ML, there is only a small amount of
the exposed Cu (1 1 0) surface. When the coverage is increased from 5/
9ML and 1.0ML, proportion of the exposed Cu(1 1 0) surface is zero.
Therefore, our ab initio thermodynamics results show that the pro­
portions of the exposed surfaces have the strong dependence on the
hydrogen coverage.
3.3. Temperature and pressure effects
According to ab initio thermodynamics calculations, the effects of
temperature and pressure are still important on affecting the Wulff
morphology and HER performance of model metal nanoparticles. In
general, the HER usually occurs under relatively mild conditions, such as
room temperature and standard pressure. We discussed the temperature
and pressure effects on the morphology evolution. At the hydrogen
coverage is 1/9ML, the given temperatures are 300 K, 400 K and 500 K,
respectively. In addition, the given pressures are 1.0 atm, 5.0 atm and
10.0 atm, respectively. Our thermodynamics results clearly show that,
the proportions of three exposed surfaces of model metal nanoparticles
have not been changed significantly. Therefore, the temperature effect
(from 300 K to 500 K) is very weak on affecting Wulff morphology (Seen
in Support Materials). Similarly, when the hydrogen pressure increases
from 1.0 atm to 10.0 atm, the proportions of the exposed surfaces are
slightly changed (Seen in Support Materials). Therefore, the hydrogen
pressure effect is also very weak.
In comparison with the hydrogen coverage effect, it is found that
increasing hydrogen coverage can significantly affect the Wulff
morphology of all model metal nanoparticles. The weak temperature
and hydrogen pressure effects would not affect the morphology evolu­
tion. According to the definition of Gibbs free energy of hydrogen
adsorption ΔGNPs of model nanoparticles, the proportions of the exposed
surfaces in model metal nanoparticles have the strong dependence on
the free energy of hydrogen adsorption on the exposed surfaces.
Hydrogen coverage is an important factor on affecting the HER perfor­
mance of metal nanoparticles. Accurately controlling the hydrogen
coverage on the exposed (1 1 0) surface can greatly improve the HER
performance of model metal nanoparticles.
3.4. Thermodynamic and kinetic properties of model metal nanoparticles
According to Wulff structures and definitions of nanoparticles, we
discussed the hydrogen adsorption energies on model metal nano­
particles in Fig. 2d. Clearly, Ni nanoparticles have the smallest differ­
ence in the adsorption energy (~0.007 eV) as the variation of hydrogen
coverage. The Au nanoparticles have the largest difference in adsorption
energy ~ 0.094 eV due to the strong interaction between the adsorbed
hydrogen atoms. Using ab initio thermodynamics, the free energies of
hydrogen adsorption on model metal nanoparticles seen in Fig. 3d are
obtained as − 0.319 eV for Ni, − 0.338 eV for Pd, − 0.246 eV for Pt, 0.003
eV for Cu, 0.39 eV for Ag and 0.271 eV for Au, respectively. It is found
that the free energies of Ni, Pd and Pt nanoparticles are close to that of

Table 1
The surface energy γads
M under different hydrogen coverages on (1 0 0), (1 1 0) and (1 1 1) surfaces.

Metal Surface γads 2

M (J/m )

1/9ML 2/9ML 3/9ML 4/9ML 5/9ML 6/9ML 7/9ML 8/9ML 1ML

100 1.624 1.554 1.481 1.405 1.326 1.246 1.165 1.083 1.000
Ni 110 1.889 1.850 1.810 1.769 1.729 1.688 1.646 1.604 1.562
111 1.317 1.230 1.143 1.056 0.971 0.887 0.802 0.718 0.634
100 1.451 1.397 1.343 1.287 1.230 1.171 1.113 1.053 0.995
Pd 110 1.549 1.510 1.471 1.431 1.391 1.351 1.311 1.270 1.230
111 1.207 1.135 1.068 1.003 0.942 0.883 0.827 0.773 0.721
100 1.763 1.695 1.626 1.558 1.490 1.423 1.357 1.290 1.226
Pt 110 1.868 1.821 1.774 1.726 1.678 1.631 1.583 1.534 1.485
111 1.433 1.383 1.337 1.293 1.252 1.215 1.180 1.148 1.117
100 1.543 1.525 1.508 1.494 1.484 1.478 1.479 1.487 1.506
Cu 110 1.553 1.534 1.517 1.502 1.488 1.476 1.464 1.455 1.445
111 1.335 1.302 1.269 1.241 1.218 1.201 1.184 1.173 1.172
100 0.896 0.927 0.957 0.991 1.023 1.057 1.093 1.135 1.192
Ag 110 0.886 0.897 0.910 0.924 0.939 0.958 0.976 0.997 1.017
111 0.842 0.865 0.889 0.912 0.942 0.976 1.010 1.047 1.095
100 0.932 0.944 0.957 0.970 0.988 1.009 1.032 1.054 1.083
Au 110 0.907 0.904 0.902 0.900 0.899 0.897 0.896 0.893 0.890
111 0.805 0.822 0.841 0.869 0.909 0.959 1.012 1.070 1.128

5
J. Cui et al. Applied Surface Science 570 (2021) 151211

Table 2
The proportion of each exposed surface on the metal nanoparticles at different coverages.
Metal Surface P(%)

1/9ML 2/9ML 3/9ML 4/9ML 5/9ML 6/9ML 7/9ML 8/9ML 1ML

100 16 14 12 10 8 6 5 3 1
Ni 110 0 0 0 0 0 0 0 0 0
111 84 86 88 90 92 94 95 97 99
100 18 16 14 13 11 10 9 8 8
Pd 110 0 0 0 0 0 0 0 0 0
111 82 84 86 87 89 90 91 92 92
100 16 17 17 18 19 21 23 25 28
Pt 110 0 0 0 0 0 0 0 0 0
111 84 83 83 82 81 79 77 75 72
100 22 21 20 18 17 16 15 14 13
Cu 110 11 8 5 3 1 0 0 0 0
111 67 71 75 79 82 84 85 86 87
100 25 23 21 19 17 15 14 12 9
Ag 110 34 40 45 50 56 62 67 72 80
111 41 37 34 31 27 23 19 16 11
100 20 20 19 18 16 13 10 8 6
Au 110 20 27 34 45 59 74 85 91 94
111 60 53 47 37 25 13 5 1 0

the exposed (1 1 1) surface. According to the Wulff structures of Ni, Pd
and Pt nanoparticles, the proportion of the exposed (1 1 1) surface is the
largest and the proportion of the exposed (1 1 0) surface is zero. Similar
conclusions are drawn on the Cu, Ag and Au nanoparticles. According to
the Gibbs free energy of model metal nanoparticles given in Fig. 3d, it is
found that Cu nanoparticle is preferable for HER due to the small Gibbs
free energy value.
We further studied the reaction rate of HER following the Volmer-
Tafel step. It is generally believed that the Volmer reaction quickly
reaches equilibrium, while the Tafel reaction is the rate determining
step. According to the definition of the reaction rate on metal nano­
particles, the reaction rates of HER on model metal nanoparticles as a
function of hydrogen coverage are shown in Fig. 4. As shown in Fig. 4, it
is clear to note that, different metal nanoparticles have different reaction
rates as a function of hydrogen coverage. On the Ni and Pd nano­
particles, the reaction rates gradually decrease as the increase of
hydrogen coverage (seen in Fig. 4a and 4b). Furthermore, the reaction
rate on the Pd nanoparticle is larger than that on the Ni nanoparticle
(about one order of magnitude). Interestingly, on the Cu nanoparticle,
the reaction rate has the non-monotonic character as a function of

Fig. 4. The change trend of the reaction rate of HER on several metal Nanoparticles (NPs) under different coverages, Where the pH is equal to 0 and the temperature
is 300 K.

6
J. Cui et al.
hydrogen coverage, i.e., the reaction rate decreases as the hydrogen
coverage increases, and then increases as the hydrogen coverage in­
creases. The reaction rate on the Cu nanoparticle is the largest due to the
weak hydrogen adsorption ability. Importantly, on the Pt, Ag and Au
nanoparticles, the reaction rates increase as the increase of hydrogen
coverage (seen in Fig. 4c, 4e and 4f). The reaction rate on the Pt nano­
particle is larger than that on Ag and Au nanoparticles. The reaction
rates on the Ag and Au nanoparticles are very small. It has about several
orders of magnitude smaller than that on the Pt nanoparticle. From our
theoretical results, the reaction rate on the Cu nanoparticle is the largest,
and then that on the Pd nanoparticle is the second largest. The order of
the reaction rate on the metal nanoparticles is followed as Cu, Pd, Ni Pt,
Au, and Ag. In addition, the pH effect on the reaction rate is also
investigated with three different values of pH = 4, 7 and 14 (Seen in
Support Materials). It is found that at different pH values, the reaction
rates of model metal nanoparticles decrease with the increase of pH.
Importantly, the hydrogen coverage still affects the reaction rate of the
nanoparticles. Based on the kinetic model, increasing the pH value can
hinder the adsorption of hydrogen ions in the solution, and the equi­
librium reaction of the Volmer step will be affected. Further the
desorption rate of hydrogen will also decrease.
4. Conclusions
In summary, the adsorption energies of atomic hydrogen on some Ni-
and Cu-group metal nanoparticles (Ni, Pd, Pt, Cu, Ag and Au) have been
presented by using density functional theory calculations, which reveals
the interaction between the adsorbed H atoms under different hydrogen
coverage. The Gibbs free energy of hydrogen adsorption (including the
correction of zero-point energy and entropy) shows that Cu nanoparticle
is a strong candidate for HER due to the small Gibbs free energy value.
The influence of hydrogen adsorption on the metal nanoparticles was
mainly discussed by using the principle of Wulff structure. Some sig­
nificant changes of morphology were found at different hydrogen
coverage, while the weak temperature and hydrogen pressures effects
are found. We have used the scaling relationship of the area of single
crystal surface to the total area in the Wulff structure to represent the
proportion of the corresponding active center. By using the kinetic
model, the high coverage increases the reaction rate, and increasing the
pH generally decreases the reaction rate. These works will provide some
ideas for the study of HER on more complex metal nanoparticles.
Contributions
X.J.S. directed the project and wrote the manuscript, J.K.Cui carried
out the DFT calculations, X.J. Liu and Y.F. Wang give some useful dis­
cussions on the hydrogen coverage, D.D. Song and Y.G. Ren discussed
the works and revised the manuscript, and all authors contributed to
scientific and technical discussions and manuscript revising.
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.
Acknowledgment
This work was supported by the National Natural Science Foundation
of China (Grant Nos. 21873086). We also acknowledge the computa­
tional time supported by National Supercomputer Center in Zhengzhou
and Henan Supercomputer Center.
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