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Catalytic hydrogenation of phenanthrene over

NiMo/Al2O3 catalysts as hydrogen storage
intermediate

Dexiang Zhang*, Jing Zhao, Yuanyuan Zhang, Xilan Lu

Department of Chemical Engineering for Energy Resources, Key Laboratory of Coal Gasification and Energy Chemical
Engineering of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

article info abstract

Article history: Hydrogen storage as an expanding research topic was investigated to discover and study
Received 18 August 2015 new materials. However, phenanthrene (PHE) for the deeply hydrogenation reaction and
Received in revised form hydrogen storage capacity can be used as a promising liquid organic hydrogen carrier. The
27 November 2015 hydrogenation of phenanthrene over the NiMo/Al2O3 catalysts was carried out in the 30 mL
Accepted 30 November 2015 tubing-bomb micro-reactor. The catalysts were prepared by coprecipitation and charac-
Available online xxx terized by X-ray diffraction(XRD), Scanning electronic microscopy coupled with Energy
dispersive spectrometer (SEM-EDS), N2 physical adsorption, X-ray photoelectron spec-
Keywords: troscopy(XPS), temperature programmed reduction (TPR) and temperature-programmed
Hydrogen storage desorption (TPD) of H2. The results show that the interaction between the NiMo and the
Organic intermediate support increase with the calcination temperature and that Ni and Mo were present as Ni2þ
Phenanthrene and Mo4þ on the support. The hydrogenated products were analyzed by Gas
Catalytic hydrogenation Chromatography-Mass Spectrometer (GC-MS). The results show that the catalyst calci-
NiMo/Al2O3 catalyst nated at 600  C, exhibits excellent high activity performance and the hydrogenation con-
version of phenanthrene over the catalyst can reach above 70% at 400  C. The selectivity of
octahydrophenanthrene (OHP), octahydroanthracene (OHA), tetrahydrophenanthrene
(THP) and dihydrophenanthrene (DHP) are 9.07%, 34.84%, 18.36% and 32.85%. The reaction
pathway of phenanthrene hydrogenation is proposed.
Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

can be used as an alternative energy carrier. An efficient

Introduction
In order to meet the ever increasing clean energy demand,
zero carbon emission fuel such as hydrogen is required [1,2].
Hydrogen is a light element that has low volumetric density
(84 g/m3), and high gravimetric energy density of 28.68 kcal/g
and is three times more than that of gasoline [3]. Hydrogen
method for hydrogen storage, transportation and delivery to
point of usage is a prerequisite for any hydrogen fuel energy
system [2]. Among wide variety of hydrogen storage technol-
ogies liquid organic hydrides provide several advantages such
as relatively higher hydrogen capacity on both the weight and
volume basis [1,2]. Moreover, liquid organic hydride carriers
are simple, safe and feasible handling for hydrogen storage.

* Corresponding author. Tel.: þ86 21 64252367; fax: þ86 21 64252737.

E-mail address: zdx@ecust.edu.cn (D. Zhang).
http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
0360-3199/Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Zhang D, et al., Catalytic hydrogenation of phenanthrene over NiMo/Al2O3 catalysts as hydrogen
storage intermediate, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e7
Hydrogen addition via liquid organic hydride carriers is based
on the reversible catalytic hydrogenationedehydrogenation
reactions and covalently bound to a liquid carrier substance
via hydrogenation [4e6]. Hydrogen is released via dehydro-
genation in place of energy demand. The hydrogen carrying
liquid itself is not consumed but can be reloaded and used in
further cycles [7]. Dehydrogenation process substances have
been discussed as potential liquid organic hydrides candi-
dates, e.g. methylcyclohexane-toluene [4], cycloalkanes [8],
ammonia-borane-based systems [6,9] and heterocyclic aro-
matic hydrocarbons like N-ethylcarbazole [10], 9-
ethylcarbazole [11], while hydrogenation of unsaturated
organic compounds as liquid organic hydrogen carriers for
hydrogen storage is investigated little. Generally, alkenes, al-
kynes and unsaturated aromatic can be used as hydrogen
storage materials. It is reported that benzene, toluene, and
naphthalene [12] as the useful model compounds are hydro-
genated to upgrade of coal liquids and diesel fuels.
Considering the sources and toxicity, phenanthrene is the
more aromatic compounds in the coal tar and the lower
toxicity than others. However, one of the main difficulties in
the hydrogenation is the acquisition of a hydrogenation
catalyst that is capable of optimizing the hydrogenation ac-
tivity, the selectivity toward hydrogenated aromatic hydro-
carbons under extreme operating conditions (high pressure,
high temperature). Previous research has indicated that Pt
based catalysts are reported as the most efficient catalysts for
selective hydrogenation of phenanthrene [13]. However, Pt is
high cost and less abundance so that researchers use various
non-noble monometallic and bimetallic catalysts to reduce
the Pt contents [1,14e17]. Many experimentals [18e20] provide
many insights into the nature of the active phase on hydro-
treating catalysts. These catalysts consist of well-dispersed
MoS2 nanocrystallites supported on g-alumina and pro-
moted by cobalt or nickel atoms.
In the present work, the catalysts of the alumina (Al2O3) as
a support for nickel (Ni) and molybdenum (Mo) have been
investigated for the hydrogenation of phenanthrene as
hydrogen storage materials. In order to determine various
physico-chemical and morphological, the NieMo catalyst was
characterized by the Scanning Electronic Microscopy coupled
to Energy Dispersive Spectrometer (SEM-EDS), N2-physical
adsorption, temperature programmed reduction(TPR), tem-
perature programmed desorption(TPD) and X-ray photoelec-
tron spectroscopy(XPS) analysis. Moreover, we carried out
hydrogenation experimentals using model compounds: PHE
to elucidate the properties of catalyst and proposed the reac-
tion pathways.
Experimental
Catalysts preparation
The NiMo/Al2O3 catalysts were synthesized by co-
precipitation. Briefly, the sample was obtained from well-
mixed aluminum nitrate, nickel nitrate and ammonium
molybdate solutions by dropping the solution of ammo-
nium carbonate and keeping the pH about 9. The precipi-
tate was filtered, thoroughly washed with deionized water,
Please cite this article in press as: Zhang D, et al., Catalytic hydrogenation of phenanthrene over NiMo/Al2O3 catalysts as hydrogen
storage intermediate, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
aged for 12 h and then dried overnight at 110  C, and
calcined at 500  C for 5 h to prepare a mixed oxide sample.
Additionally, the calcination temperature of other catalysts
was 600  C, 700  C and 800  C, respectively. The catalysts
are denoted as Catx, where x is the calcination temperature
of catalysts.
Catalyst characterization
The specific surface areas of the support and oxide catalysts
were evaluated from the nitrogen adsorptionedesorption
isotherms at 196  C in a Micromeritics ASAP 2020 apparatus,
after being degassed at 200  C and 1.3  102 Pa for 24 h.
The XRD analysis was obtained with a Siemens D5000
diffractometer. The XRD analysis was carried out in the
scanning angle (2q) range of 10e80  C.
The SEM tests were used the Field Emission Scanning
Electron Microscope (S-4800, Hitachi Ltd.) to observe the
morphology and surface distribution of Nickel and Molybde-
num at 15.0 kV. All samples have been placed on the
conductive Tapes and sputtered with gold under vacuum
using K550 unit and then observed with back-scattered elec-
trons detectors, equipped with an energy dispersive spec-
trometer (EDS analysis).
H2-TPR experiments were carried out using a AMI300 auto-
absorber with a TCD detector. The TPR analysis of the oxidic
NiMo/g-Al2O3 catalyst (150 mg) was performed in a quartz
reactor. The catalyst sample and reactor were placed in a
furnace and heated up. Firstly for the samples pretreatment,
the temperature was increased from room temperature to
350  C, at a rate of 10  C/min and held for 1 h. Then, the
temperature was again decreased up to 50  C at a rate of 20  C/
min and then held for 30 min.The temperature was increased
from 50  C to 900  C, at a rate of 10  C/min and held for 1 h.
H2-TPD experiments were carried out using a AMI300 auto-
absorber with a TCD detector. About 150 mg of catalyst sample
was placed in the center of a quartz tube reactor with quartz
wool plugs. Prior to reduction, the operation condition of
reduction was similar to those used in the TPR analysis and
then the samples were cooled in 30 mL/min Ar flow to a final
temperature of 50  C at 10  C/min. The Ar was replaced by
H2(10%)/Ar gas mixture with a flow-rate of 30 mL/min and
held for 60 min. Then the H2(10%)/Ar was replaced Ar gas with
a flow rate of 30 mL/min and the temperature of the reactor
was increased linearly to 600  C at 10  C/min and then
retained isothermally for 30 min.
X-ray photoelectron spectra (XPS) were analyzed by a
Thermo Scientific ESCALAB 250Xi spectrometer with a
monochromatic Al K Alpha radiation (300 W, 15 kV, 1486.6 eV)
and with a multi-channel detector. Samples were transferred
to the analysis chamber under inert atmosphere. Spectra of
powder samples were recorded in the constant pass energy
mode at 29.35 eV, using a 720 mm diameter analysis area.
Charge referencing was measured against adventitious car-
bon (C1s 284.8 eV).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e7
Catalytic reaction: effect on hydrogenation depth and the
amount of hydrogen storage by using different catalysts
The NiMo/Al2O3 catalysts were presulfided in the autoclave.
Initially, 10 g catalyst and 100 mL CS2 (5% in the n-heptane)
solution was joined in the autoclave and then ventilated with
nitrogen leak detection. Then the temperature was increased
to 230  C and held isothermally for 4 h at this temperature
with a hydrogen initial pressure of 7 MPa and the stirring rate
of 200 r/min.
The hydroprocessing experiments of phenanthrene (95%,
CP) used in the present study without further purification
were performed in the 30 mL tubing-bomb micro-reactor.
Initially, 0.3 g phenanthrene, 0.025 g catalysts and 2 g n-
dodecane solution were added into micro oscillation reactor.
Experiments were performed under 9 MPa (H2 initial pressure)
and contact time 30 min and carried out at 400  C.
Identification of the hydrogeneration products of phenan-
threne was analyzed by GC/MS using an Agilent 7890A gas
chromatograph coupled with Agilent 5975C mass detector
equipped with a HP-5 capillary column, a flame ionization
detector (FID) and helium as carrier gas with a flow rate of
0.7 mL/min. The detector and injector temperatures were
310  C and the column temperature was started at 60  C for
8 min, then heated to 300  C at a heating rate of 5  C/min and
holding 5 min at 300  C. And the mass spectrum condition is
as follows: solvent delay, 6 min; electron impact ion source
temperature, 230  C; quadruple spectrometer temperature,
150  C; and scan from 50 to 300.
Results and discussion
Catalysts phase analysis and surface structure
The X-ray powder diffraction patterns of all the samples are
shown in Fig. 1 and the SEM-EDS photographs of the catalysts
are given in Fig. 2. The XRD patterns in Fig. 1 show three broad
peaks at 37 , 46 and 67 , respectively, which are corre-
sponding to the characteristic value of 2 theta for the g-Al2O3
phase as it closely matched with JCPDS card No. 48-367.
Moreover, crystallinity increases with the calcination
Fig. 1 e XRD patterns of catalysts.
Please cite this article in press as: Zhang D, et al., Catalytic hydrogenation of phenanthrene over NiMo/Al2O3 catalysts as hydrogen
storage intermediate, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
3
temperature rising, which is shown by the high intensity and
narrower diffraction peak. After the loading of Ni and Mo, no
high intensity peak which can be attributed to NiO and MoO3
was observed. From Fig. 2, the surface structure of catalysts
presents only a morphological habit and the surface distri-
bution of Nickel and Molybdenum is uniform. Therefore, this
indicates active component well disperse on the surface of
support. But some small peaks at 2q ¼ 19 , 31 , 57 charac-
teristic of NiAl2O4 (PDF 10-339), are found in the XRD patterns
of Cat3 and Cat4. It is suggested that the interaction between
the nickel and Al2O3 gradually increases when the calcination
temperature is above 600  C.
Specific surface areas and pore size of catalysts
The BET surface areas and pore volumes determined by ni-
trogen physical adsorption and surface active component
ratio of Ni/Mo amount of all the catalysts are presented in
Table 1 and the N2 adsorption isotherms were shown in Fig. 3.
The nitrogen adsorptionedesorption isotherms are of type IV
in the IUPAC classification and with a similar shape to that
observed in the case of the support. All the pore of catalysts
are mesopores, the specific surface areas decrease and mean
pore size increases with increasing the calcination tempera-
ture, in spite of that pore volume has no obvious change.
Meanwhile, the ratio of Ni/Mo amount on the surface of cat-
alysts firstly increases and then decreases through EDS test.
The variation can be attributed not only to the presence of
large particles that the higher calcination temperature, the
more crystallinity, but also to the increase interaction be-
tween active component and support.
Reducibility of catalysts
TPR is complimentary technique that helps identify the
oxidation states of a reducible metal oxide and estimate the
interaction of the metal oxide with the support. The H2-TPR
profiles of all the samples are presented in Fig. 4. All the
samples exhibit one main reduction peak at relatively high
temperature and shifts to high temperature region with
increasing the calcination temperature. It may be attributed to
the reduction of Ni(II) species being in a strong interaction
with the alumina support, that is, amorphous Ni aluminate
species, which are visible in the XRD patterns (Fig. 1). While,
the lower reduction peak at around 370  C, can be assigned to
the reduction of Mo species particles with no interaction with
the support and correspond to the reduction of Mo (VI) to Mo
(IV) of NiMoO4 or MoO3. It demonstrates the difference in the
interactions between Ni2þ and the support with varying
calcination temperature and the reducibility of the Mo4þ
species increased with increasing the calcination tempera-
ture. This leads to a shift in the peaks corresponding to the
reduction of Ni2þ species interacting with the support from
around 700  C to around 780  C.
Dispersion of the active metal component
The dispersion of the active metal component of the sample is
estimated by temperature programmed desorption of H2. The
strength of H2 desorption can be determined by the
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e7

Fig. 2 e The SEM-EDS photographs of Catalysts.

temperature at which the adsorbed H2 desorbs. Based on the

desorption temperature, there are mainly two kinds of at-
tractions leading to absorption of hydrogen molecules onto
solid surface, physical adsorption and chemical adsorption.
All of the samples exhibit that a very small peak at approxi-
mately 120  C is attributed to physisorption on the catalyst
surface and that the peak at the high temperature region
represents chemisorption in the catalyst. However, dispersion
values calculated the peak area in all samples are very small.
These low dispersion values are largely due to the presence of
a low surface concentration of Ni2þ and Mo4þ in the samples,
which form the amorphous or poorly crystalline Ni silicate
species, and which are visible in the XRD patterns (Fig. 1),
Fig. 3 e The N2 adsorption isotherms of different catalysts.
SEM-EDS photographs (Fig. 2) and TPR profiles (Fig. 4). From
the Fig. 5, Cat1 and Cat4 are similar to the monocomponent
NiO and Al2O3 sample, It indicates that active component Mo X-ray photoelectron spectroscopy
species are finely dispersed on the support surface. Compar-
ison with Cat3, the active components of Cat2 are well The chemical species present on the surface of the sulfided
dispersed on the surfaces of the carriers. samples were evaluated by XPS. Fig. 6 shows the Ni2p, Mo3d,
S2p and C1s XPS spectra of the sulfide catalysts as being
representative of this series of samples. In the catalysts, the Ni
2p photoemission line was deconvoluted into two compo-
Table 1 e The characteristic parameters and surface nents at ca.853.6 eV and 856.5 eV, which can be ascribed to
active component ratio of Ni/Mo amount of NiMo sulfide nickel and nickel remaining as NiMoO4, respectively.
catalysts. Considering that the B.E. for Ni2þ ions in NiS is close to
Sample ABET y Mean pore d Ratio of Ni/Mo 852.9 eV [21], it indicates that Ni2þ ions are embedded in the
(m2/g) (mL/g) (nm) amount structure of MoS2, probably forming the NieMoeS phase, i.e.
(wt%) after sulfidation at 400  C [22]. In the XPS spectrum, The Mo 3d
Cat1 306.85 0.55 6.92 1.80 photoemission line region of XPS spectra centered at 226.9 eV
Cat2 215.82 0.46 8.06 1.71 exhibit the typical Mo 3d5/2 photoemission, which is charac-
Cat3 245.23 0.57 9.48 2.21 teristic of MoS2 species. The Mo 3d5/2 value is typical of Mo(VI)
Cat4 117.78 0.40 14.22 2.15
[23] and is very close to those observed for MoO3 (232.6 eV) and

Please cite this article in press as: Zhang D, et al., Catalytic hydrogenation of phenanthrene over NiMo/Al2O3 catalysts as hydrogen
storage intermediate, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e7 5

NiMoO4 (232.5 eV) due to partially sulfided OeMoeS [24]. The

sulfided catalyst presents a lower binding energy peak at
161.9 eV in the S 2p energy region, which is characteristic of
sulfide (S2) species.

Catalytic hydrogenation of phenanthrene for hydrogen

storage intermediate

Recently, hydrogenation of aromatic molecules in general has

Fig. 4 e H2-TPR profiles of catalysts.
Fig. 5 e H2-TPD profiles of catalysts.
received a lot of attention for the production of high perfor-
mance diesel fuels [25]. In this study, phenanthrene as the
liquid organic hydride is chosen to hydrogenate carrier
because it is one of the main components of polycyclic aro-
matic compounds in low temperature coal tar that the output
has reached thousands of tons every day and their nature is
very aromatic that results in low-quality fuel products. How-
ever, there is no in-depth study concerning the mechanism of
catalytic hydrogenation of phenanthrene for hydrogen stor-
age purpose.
The catalytic hydrogenation (HYD) of PHE over the NiMo/
Al2O3 sulfide catalysts at 400  C and 9 MPa (hydrogen initial
pressure) was investigated and the results are presented in
Fig. 7. During the HYD reaction, several products (see Table 2)
were detected and confirmed by the combination of GCeMS.
DHP, THP and OHP are hydrogenated and main hydrogenation
products. DP and 6-BTN are the products of the hydrocracking
pathway, while the contents are less. Besides products from
the HYD and hydrocracking pathways, three other products,
PHA, OHA and THA, were detected as well. These three
products might be due to subsequent isomerization (ISO) re-
actions of the HDA products. Fig. 7 shows that at 400  C, the

Fig. 6 e XPS of Ni 2p, Mo 3d, S 2p and C1s for the Cat2.

Please cite this article in press as: Zhang D, et al., Catalytic hydrogenation of phenanthrene over NiMo/Al2O3 catalysts as hydrogen
storage intermediate, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e7

hydrogenation reaction pathways of phenanthrene under the

experimental condition were proposed in the Fig. 8. In the
process, the main products consist of OHP, OHA, THP and
DHP, and their selectivity rate are 9.07%, 34.84%, 18.36% and
32.85%, respectively. Moreover, the effect on the reaction
temperature is remarkable that OHA and OHP are easier to
dehydrogenation than THP at high reaction temperature. It
indicates that the double ring compounds are prior mono-ring
compounds to dehydrogenation reaction. Hydrogenation re-
actions are divided into three types: hydrogenation, isom-
erism and hydrocracking. During in the process, one hydrogen
molecule is added to the unsaturated double CeC bond and
finally makes it saturated. Hydrogenation of phenanthrene
Fig. 7 e Catalytic results for HDA of phenanthrene over potentially results into 7 mol of H2 per each mole of phenan-
NiMo catalysts. threne. This results in higher hydrogen production contents of
hydrogenated phenanthrene for hydrogen storage, and
bimetallic NiMo/Al2O3 is non-noble metal based potential
candidate catalyst for hydrogenation of liquid organic inter-
mediate and worth in the industrial application.
Table 2 e Compound and its abbreviation.
Compound Abbreviation
Phenanthrene PHE Conclusions
9,10-dihydrophenanthrene DHP
1,2,3,4-tetrahydrophenanthrene THP The main goal of this study was to prepare the NiMo catalysts
1,2,3,4,4a,5,6,10b-octahydrophenanthrene(cis) Cis-OHP
and evaluate their hydrogenation activity of phenanthrene for
1,2,3,4,4a,5,6,10b-octahydrophenanthrene(trans) Trans-OHP
1,2,3,4-tetrahydroanthracene THA
hydrogen storage. The NiMo catalysts are prepared by copre-
1,2,3,4,5,6,7,8-octahydroanthracene OHA cipitation. The characteristics of the catalysts show that the
Perhydroanthracene(cis) Cis-PHA interaction between active component and support increases
Perhydroanthracene(trans) Trans-PHA with the calcination temperature, especially the formation of
NiAl2O4 by NiO and Al2O3 can affect the surface active
component ratio of Ni/Mo amount and decrease the catalytic
PHE conversion rate decreased in the order: activity when the calcination temperature exceeds 700  C.
Cat2 > Cat3 > Cat4 > Cat1, and that the Cat2 (calcination Moreover, Ni and Mo are presented as Ni2þ and Mo4þ on the
temperature 600  C) exhibited higher HDA activity than the support. The Cat2 at calcination temperature of 600  C ex-
other catalysts. hibits excellent catalytic activity for the hydrogenation of
It is important to identify the structures of the reaction phenanthrene. The conversion yield of phenanthrene exceeds
products which would lead to a better understanding of the 70% based on Cat2 and is higher than that of other catalysts.
mechanism of this reversible reaction. Based on the genera- Moreover, the selectivity of OHP, OHA, THP and DHP are 9.07%,
tion and concentration variation of the intermediate products, 34.84%, 18.36% and 32.85% in the hydrotreating process with

Fig. 8 e Reaction pathways for PHE hydrogenation.

Please cite this article in press as: Zhang D, et al., Catalytic hydrogenation of phenanthrene over NiMo/Al2O3 catalysts as hydrogen
storage intermediate, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2015.11.173
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e7
Cat2. Further, the reaction pathway of phenanthrene hydro-
genation was speculated and the double ring hydrogenated
phenanthrene is easier to dehydrogenation than the mono
ring compounds. These results provide a new perspective on
the preparation of highly active metal oxide catalysts sup-
ported on alumina and phenanthrene might be a potential
hydrogen storage material.
Acknowledgments
This work was supported by the China 973 Program
(2011CB201304).
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