Letter

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Developing Ideal Metalorganic Hydrides for

Hydrogen Storage: From Theoretical
Prediction to Rational Fabrication
Zijun Jing, Qinqin Yuan, Yang Yu, Xiangtao Kong, Khai Chen Tan, Jintao Wang, Qijun Pei,
Xue-Bin Wang,* Wei Zhou, Hui Wu,* Anan Wu,* Teng He,* and Ping Chen
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sı Supporting Information

ABSTRACT: Materials for hydrogen storage have been

extensively explored for a few decades. Thousands of materials
have been synthesized and tested; however, few systems could
meet the practical requirements. Metalorganic hydrides
discovered recently offer new opportunities. It is, however,
extremely time-consuming and inefficient to experimentally
screen potential materials from a large variety of metal cations
and organic anions. In the present study, we performed wide-
ranging theoretical predictions and screened more than 90
metalorganic hydrides; 20 of them were identified with both
high hydrogen capacities (≥5 wt %) and suitable thermody-
namics (heat of H2 desorption: 25−35 kJ/mol-H2) that allow
hydrogen uptake and release near ambient condition. We
picked up four of them, i.e., Li/Na indolides and 7-azaindolides, for experimental validation. All the four candidates can be
easily synthesized via the reactions between the metal hydrides and the corresponding organic precursors. Among them the
structures of lithium indolide (P21/c (no. 14)) and sodium 7-azaindolide (P4̅21c (no. 114) were successfully resolved.
Photoelectron spectroscopy and quantum chemical calculations confirmed that the charge density of the organic ring
increased with the introduction of an alkali metal, thus optimizing their ΔHd for hydrogen storage. Importantly, we
demonstrated experimentally that lithium indolide with a theoretical hydrogen capacity of 6.1 wt % has a heat of hydrogen
absorption of ca. 33.7 kJ/mol-H2 which is in excellent agreement with the value (33.6 kJ/mol-H2) predicted theoretically. The
partially reversible hydrogen release and uptake can be can be achieved at the temperature as low as 100 °C. These results
illustrate the great potential of metalorganic hydrides for tackling the grand challenge of hydrogen storage and manifest the
effectiveness of theoretical prediction in guiding materials fabrication.

With the rapid growth of population and economy, the world capacity (≥5.0 wt %) and suitable thermodynamic properties
is facing an energy shortage and environmental pollution. The (the heat of hydrogen desorption (ΔHd) is around 30 kJ/mol-
utilization of renewable and clean energy is an urgent task of H2). However, it is extremely difficult to meet both criteria
recent research.1 Hydrogen has long been considered as a simultaneously with one material. For instance, sorbents with
clean and efficient energy carrier due to its abundance, high surface area can store more than 5.0 wt % hydrogen
environmental friendliness, high energy density, and recycla- through physisorption; however, they have low ΔHd (0−10 kJ/
bility.2−6 However, one of the bottlenecks and challenges in
mol-H2) which results in low operating temperature.7 Complex
the implementation of hydrogen energy is the lack of efficient
hydrides and LOHCs with high hydrogen densities dehydro-
hydrogen storage method.7,8 Tremendous research efforts have
been made in the past half-century on hydrogen storage,
including physical (such as compression,9 liquefaction,10 and Received: August 11, 2021
physisorption11−14) and chemical methods (such as metal Accepted: August 18, 2021
hydrides,15,16 complex hydrides,17−20 chemical hydrides,21−24
and liquid organic hydrogen carriers (LOHCs)25−28). To
uptake and release a large amount of hydrogen reversibly under
mild conditions, two criteria are to be met, i.e., high hydrogen

© XXXX American Chemical Society https://doi.org/10.1021/acsmaterialslett.1c00488

1417 ACS Materials Lett. 2021, 3, 1417−1425
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Figure 1. Selected organic compounds having “reactive protic H” for metal substitution.
genate via breaking strong N−H, B−H, and C−H bonds,
leading to strong endothermicities with high ΔHd (>40 kJ/
mol-H2).17,18,25,29−32 Several transition metal hydrides includ-
ing LaNi5H6, TiV2H4, and FeTiH2, etc., on the other hand,
possess suitable thermodynamics and high volumetric hydro-
gen density, unfortunately, their gravimetric hydrogen densities
are usually lower than 3.0 wt %.15,33 Therefore, the
development of new materials with both ideal thermodynamics
and high hydrogen capacities is a great challenge.
Very recently, metalorganic hydrides, a new family of
hydrogen storage materials spanning across the domain of
inorganic and organic hydrides, were developed.34,35 Thanks to
the electron-donating ability of alkali or alkaline earth metal,
the thermodynamics of metalorganic hydrides could be
rationally modulated. The versatile chemistry of organics and
metal provides a vast opportunity for discovering new and
promising materials for hydrogen storage. However, every coin
has two sides. The variable properties of organics and metals
inevitably complicate the material development. Screening
promising materials from a larger number of candidates via
routine experimental syntheses and property evaluations is
extremely inefficient. Until now, only a couple of candidates
which satisfy the two aforementioned key criteria were
developed, such as lithium and sodium carbazolides.36
Therefore, it is highly demanding to screen materials by
wide-ranging theoretical prediction, aiming to guide exper-
imental synthesis and improve efficiency. In the present study,
more than 90 metalorganic hydrides are screened theoretically
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for the first time, among which 20 pairs show both high
hydrogen capacities (≥5 wt %) and suitable thermodynamics
(25−35 kJ/mol-H2) for hydrogen storage, showing the
efficiency of theoretical prediction and great potential of
metalorganic hydrides. Based on the calculations, four of them
are selected as examples to be synthesized, characterized, and
investigated in detail. Specifically, lithium indolide/lithium
octahydroindolide pair with a theoretical hydrogen capacity of
6.1 wt % and an ideal ΔHd of 33.7 kJ/mol-H2 achieves partially
reversible hydrogen uptake and release at the temperature as
low as 100 °C. The successfulness of theoretical prediction to
rational fabrication shown in this paper provides an efficient
and inspiring method to develop promising materials for
hydrogen storage.
Theoretical Screen. The strategy employed here is the
metal substitution of reactive H in organic compounds forming
metalorganic hydrides to modulate the dehydrogenation
thermodynamics. As shown in Figure 1, selected organic
compounds employed as potential candidates for the metal
substitution include carbocyclic or heterocyclic molecules
having “reactive protic H” that bonds to N, O, or S within or
out of the organic ring. All the organic compounds selected are
commercially available.
Light alkali metals, Li and Na, are employed to replace the
reactive H in the selected 47 organic compounds (Figure 1) to
form 94 metalorganic compounds to be screened in the
present study. The X1s method37 was used to calculate the
hydrogenation enthalpy change (ΔHh) of the H-lean to H-rich
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Figure 2. (a) Hydrogen storage properties (ΔHd and gravimetric hydrogen density) of metalorganic hydrides (gray for the pristine organics,
blue and red for lithium- and sodium-substituted compounds, respectively) compared with representative materials (green). (b) ΔHd of 8H-
M-ID and 8H-M-AD versus electronegativities of H and metals. (c) The lengths of C−H bonds at the α site of 8H-M-ID and 8H-M-AD
versus electronegativities of H and metals.

metalorganic hydrides compared with their parent compounds
as shown in Table S1. Note that the absolute value of ΔHh
equals to the ΔHd of H-rich counterpart. It is shown that the
ΔHd of organic compounds can be efficiently reduced through
metalation, which is consistent with the previous reports.34,36,38
The reason can be ascribed to the fact that both H-lean and H-
rich compounds are stabilized upon metalation. However, the
H-lean counterparts are more stabilized than the H-rich ones
due to the fact that the magnitude of the conjugation effect is
significantly greater than that of the hyper-conjugation effect;
i.e., the electrons transferred from the metal to the aromatic
ring in H-lean compounds are more easily delocalized than
those of H-rich compounds, resulting in more stabilized H-lean
counterparts as well as a substantial decrease in ΔHd upon
metalation. Moreover, the metal substitution effect in the
organic compounds that have reactive H on the organic ring is
more significant than those with the reactive H out of the
organic ring. For instance, the ΔHh of 22, 23, 27, 28, and 29
having reactive H on the ring are changed more significantly
upon metal substitution than those of 25, 26, and 30 that have
reactive H out of the organic ring. It is worth mentioning that
hydrogenation of H-lean metalorganic hydride could result in
the decrease of ΔHh in some cases especially the ones with S in
the ring (data in blue in Table S1), which is ascribed to the
ring-opening reaction during hydrogenation.
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As mentioned in the introduction part, promising hydrogen
storage materials should meet two criteria, i.e., suitable
thermodynamics and high hydrogen capacity. To identify
potential candidates, the calculated ΔHd of metalorganic
hydrides and their hydrogen capacities are summarized in
Figure 2a. It is obvious that these parent compounds (gray)
move to low ΔHd region upon metalation (blue and red) with
slightly scarifying hydrogen capacities. Theoretically, to achieve
reversible hydrogen uptake and release at moderate conditions,
ΔGr for one reaction should be around zero. Assuming ΔSd is
around 100−120 J/(K mol-H2), an ideal area for hydrogen
storage (25 kJ/mol-H2 ≤ ΔHd ≤ 35 kJ/mol-H2 and hydrogen
capacity ≥5.0 wt %) is marked in orange in the figure. Barely
any reversible hydrogen storage materials developed to date
could meet both criteria at the same time (green). Importantly,
based on our calculations about 20 metalorganic hydrides, i.e.,
lithiated and/or sodiated 14, 22, 23, 26, 27, 31, 32, 34, 39, 44,
45, 46, and 47, exhibit both high gravimetric hydrogen
capacities and suitable ΔHd and sit within this area (red data in
Table S1), holding great promise for hydrogen storage
application as compared with representative LOHCs (such as
12H-NEC and MCH). Comparatively, metalorganic hydrides
with fused-ring structures exhibit superior properties to their
single-ring counterparts (such as 3, 4, 7, 9, etc.), which may be
due to the facts that 1) the fused-ring structure could average
the electron donation effect of metal and avoid over
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Figure 3. Simulated photoelectron spectra (black lines) of the lowest energy isomer for [(indole)2·H]− (a) and [(indole)2·M]− (M = Li, Na,
K) (b−d) in comparison with the corresponding experimental spectra (red lines). The calculated stick spectrum for each complex was
generated using the measured VDE and TDDFT excitation energies. The simulated spectrum was obtained by convoluting each stick with
Gaussian functions of 0.03 eV fwhm in accord with the experimental conditions. In simulations the binding energies are explicitly
considered, but with the assumption of uniform peak intensity. (e) Electron localization function of [(indole)2·H]− and [(indole)2·M]− (M =
Li, Na, K).

Table 1. Comparison of Experimental VDE and ADE Values to the Calculated Ones of Lowest-Energy Isomers for [(indole)2·
H]− and [(indole)2·M]− (M = Li, Na, K)a
complex [(indole)2·H]− [(indole)2·Li]− [(indole)2·Na]− [(indole)2·K]−
expt VDE (eV) 3.26 3.83 3.80 3.83
expt ADE (eV) 3.13 3.81 3.77 3.72
calc VDE (eV) 3.27 3.66/3.66 3.61/3.62 3.52/3.52
calc ADE (eV) 3.03 3.58/3.58 3.53/3.54 3.44/3.44
natural charge of H/Li/Na/K (e) 0.476 0.834/0.831 0.884/0.886 0.923/0.922
natural charge of indole ring (e) −1.476 −1.834/-1.831 −1.884/-1.886 −1.923/-1.922
a
The natural charge of the metal and indole ring are also listed.

optimization of ΔHd, and 2) the fused-ring has more C−H
bonds and larger molecular weight that could lessen the
scarifying effect of the weight of metal elements (Li or Na) on
the hydrogen capacity. In the following sections, a few
examples selected from the marked area will be investigated
in detail.
Thermodynamics vs Electron Properties. Among these
materials in the ideal area, metal indolide/octahydroindolide
(22, M-ID/8H-M-ID for short) and metal 7-azaindolide/
octahydro-7-azaindolide (23, M-AD/8H-M-AD for short)
pairs were selected for further investigation due to their low-
cost, high hydrogen capacities, suitable thermodynamics, and
ease of syntheses. To figure out the relationship between
hydrogen storage thermodynamic properties and electron
properties of these metalorganic hydrides, the ΔHd of M-ID/
8H-M-ID pairs and M-AD/8H-M-AD pairs (M = Li, Na, K,
Mg, Ca) are calculated using the X1s method (Figure 2b). It is
shown that the ΔHd of 8H-M-ID and 8H-M-AD decreases
with the Pauling electronegativity (χ) of metals, exhibiting a
nearly linear relationship and manifesting that the ΔHd could
1420
be tailored via changing metal. For instance, the ΔHd of 8H-Li-
ID and 8H-Na-ID decrease significantly from that of 8H-ID
(53.0 kJ/mol-H2) to suitable values of 33.7 and 30.8 kJ/mol-
H2, respectively. This is because both H-lean and H-rich
compounds are stabilized upon metalation, while the
conjugation effect in H-lean compounds is significantly greater
than the hyper-conjugation effect in H-rich compounds; thus
the metalation causes a stronger stabilization for the H-lean
compounds resulting in a decrease in ΔHd.34,36,38 It is also
found that the lengths of C−H bond at the α-site of 8H-M-ID
and 8H-M-AD increase upon metalation; more importantly,
they increase as the decrease of electronegativity of metal as
shown in Figure 2c, manifesting that the C−H bond at α-site
can be activated to a certain extent such that it is likely to be
dissociated first upon dehydrogenation.
To further provide direct experimental evidence that metal
substitution can stabilize the electron of indole and azaindole
rings, the negatively charged complexes consisting of two
indole/azaindole rings and one cation (H+, Li+, Na+, K+) were
studied in the gas phase using anion photoelectron spectros-
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Figure 4. (a and b) 1H and 13C NMR spectra of synthesized M-ID and M-AD compared to their parent organic compounds in DMSO-d6. (c)
XRD patterns of synthesized M-ID and M-AD compared to pristine reagents. Crystal structures (left) and local coordination of cations
(right) of (d) Li-ID and (e) Na-AD. Color: blue sphere, nitrogen; yellow sphere, lithium; green sphere, sodium; black sphere, carbon; pink
sphere, hydrogen.
copy (PES) and quantum chemical calculations. [(indole)2·
X]− and [(azaindole)2·X]− (X = H, Li, Na, K) anions are
produced by electrospray ionization method and characterized
by PES (see Supporting Information for more details). As
shown in Figure 3, two relatively broad spectral bands in the
binding energy range of 3.0−4.3 eV can be seen in [(indole)2·
H]−. In contrast, the [(indole)2·M]− anions exhibit narrower
peaks with their electron binding energies ∼0.7 eV higher
compared to [(indole)2·H]−, showing metal substitution
stabilizes the organic structure, consistent with the discussion
above. Theoretical calculations indicated the optimized
structure of [(indole)2·H]− with two indole rings perpendic-
ular to each other along the N−H−N axis, while each metal
substitution cluster has two close-lying structures with the two
indole rings in the same planar but with different directions
(Figure 3, Table S3). The calculated vertical and adiabatic
detachment energies (VDEs and ADEs) (Table 1) and
simulated spectra (Figure 3) compare reasonably well with
experimental data in term of the spectral pattern and peak
position (see Supporting Information for the details of
simulations). The congested spectral band in [(indole)2·H]−
(Figure 3a) and an extra peak in [(indole)2·Li]− (Figure 3b),
compared to the their corresponding simulated ones, is most
likely due to vibrational excitations that are not considered in
the simulations. Since both isomers of [(indole)2·M]− show
close spectral bands and VDEs compared to the experiments, it
is likely that they are both formed and coexist in the
experiments. Figure 3e shows the calculated renderings of
the electron localization function surface using the optimized
structures indicating dominant electrostatic interactions
between M and indole rings. The natural charge analyses
(Table 1) provide an apparent indication that the charge
density of indole ring increased with the introduction of alkali
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Letter
metal, more importantly, as the increase of the electron-
donating ability of alkali metal, the electron density in indole
ring increases, agreeing well with the discussion above. The
PES and quantum chemical calculations results of [(azain-
dole)2·H]− and [(azaindole)2·M]− (M = Li, Na, K) are shown
in Figure S2, Table S2, and Table S3, which show a similar
tendency to that of M-ID.
Material Syntheses, Characterizations, and Crystal
Structures. Two methods, i.e., wet chemical method and
heat-treatment method, were used to synthesize M-ID and M-
AD by reacting metal hydrides (lithium hydride and sodium
hydride) and pristine indole and 7-azaindole via reactions 1
and 2, respectively. Around 1 equiv of hydrogen can be
released from all the reactions as shown in Figures S3−S5,
indicating the formation of corresponding metalorganic
hydrides.
X-ray diffraction (XRD) and nuclear magnetic resonance
(NMR) were used to characterize the synthesized compounds
(Li/Na-ID and Li/Na-AD). As shown in 1H NMR spectra
(Figure 4a), the 1H signals of N−H at 11.09 and 11.62 ppm in
indole and 7-azaindole disappear in all of the synthesized
metalorganic hydrides, showing that the reactive H on N−H
was replaced by metal. In addition, 1H signals of C−H move to
the high field after the metal substitution, indicating the
enhancement of the shielding effect due to the increase of
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Figure 5. (a) TEM images of in situ synthesized Ru nanoparticles. The inset figure is the magnified image of Ru nanoparticles. (b)
Conversion of hydrogenation of Li-ID to 8H-Li-ID catalyzed by Ru nanoparticles. (c) 1H NMR spectra of hydrogenated Li-ID catalyzed by
Ru nanoparticles and dehydrogenated Li-8H-ID catalyzed by Pt nanoparticles in DMSO-d6. (d) Microcalorimetry measurements of
hydrogenation of Li-ID catalyzed by in situ formed Ru nanoparticles.

electron density on the organic ring. Moreover, the chemical
shifts of sodium-substituted organic compounds are larger than
that of lithium reflecting the stronger electron-donating effect
of sodium, which is consistent with our theoretical calculation
results. Nevertheless, the 13C NMR signals move to different
directions upon metalation (Figure 4b). For instance, the
signals of C atoms at 1, 3, 7, and 8 sites move to the low field,
and the ones at 2, 4, 5, and 6 sites move to the high field in Li-
ID (Figure S6). This is attributed to the charge redistribution
due to the conjugation effect on the organic ring, which is also
demonstrated by the merging of several 1H signals in Na/Li-ID
(Figure S6). Furthermore, the appearance of strong 7Li and
23
Na NMR signals of M-ID and M-AD in DMSO-d6 suggests
the formation of soluble metal salts (Figure S8). The
diffraction patterns of the synthesized metalorganic hydrides
are different from those of the pristine metal hydrides and
organic compounds (Figure 4c), indicating the formation of
new compounds.
The crystal structures of Li-ID and Na-AD were determined
using powder XRD, optimized by DFT calculations, and
refined with the GSAS package (see Supporting Information
for more details). Li-ID and Na-AD crystallize in monoclinic
P21/c (no. 14) and tetragonal P4̅21c (no. 114) space groups
with lattice parameters of a = 9.2902(5) Å, b = 5.1956(4) Å, c
= 13.7739(16) Å, β = 94.759(4)°, V = 662.55(16) Å3, and a =
13.5659(6) Å, c = 7.1869(4) Å, V = 1322.64(15) Å3,
respectively (Figures S9 and S10). The crystal structures of
Li-ID and Na-AD and the local coordination of the Li+/Na+
cations are shown in Figures 4d and 4e, respectively. For Li-ID,
each Li+ cation is interacting with three surrounding indolides
by facing the aromatic ring of one indolide via cation−π
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interaction and directly contacting with Ns of the other two
indolides via cation−N σ bonding. The indolide fragments are
thus linked together by Li+ cations through alternating cation−
N σ bonding and cation−π interaction, forming a 1-D chain in
a herringbone fashion along the b-axis of the unit cell. The
adjacent chains are interacting each other through hydrogen
bonding, which helps construct a 3-D structure. For Na-AD,
each Na+ cation connects with four surrounding azaindolides
through cation−π interaction with one azaindolide, and σ−N
bonding with the Ns from the pyrrole rings of two anions, and
with the N from the pyridine ring of the fourth azaindolide.
The azaindolide anions are knitted together by sodium cations
and woven into a hollow cage-like cluster extending infinitely
along the c-axis of the unit cell. Such extended cage-like
clusters interact with the adjacent ones through hydrogen
bonding, forming a stable 3-D structure. It is worth noting that
the planar structures of the gaseous [(indole)2·M]− and
[(azaindole)2·M]− (M = Li, Na, K) anions, mentioned in
Figures 3 and S2, are not found in the local structures of the
crystals, which may be ascribed to the facts that 1) cation−N σ
bonding is usually stronger than that of cation−π interaction,
preferably leading to formation of cation−N bonding in the
planar anions that are calculated from gas phase simulation,
and 2) the 3-D structures in the crystals allow steric interaction
between cation and anion, resulting in both cation−N σ
bonding and cation−π interaction. The existence of cation−π
interaction in these two structures inevitably stabilizes the H-
lean counterparts, which will further optimize the energy gap
between H-lean and H-rich metalorganic hydrides. These
crystal structures provide insightful details about cation−anion
and cation−π arrangement, which will conversely help
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modulate their thermodynamic parameters from DFT
calculations.
Hydrogen Storage Properties. Guided by the thermody-
namic prediction, experiments on reversible hydrogen release
and uptake are conducted. Among these four synthesized
metalorganic hydrides (Li/Na-ID and Li/Na-AD), Li-ID with
a hydrogen storage capacity of 6.1 wt % and theoretical ΔHh of
−33.7 kJ/mol-H2 as shown in reaction 3 is selected and
investigated for hydrogen storage. The as-prepared Li-ID is
hard to be hydrogenated under 50 bar hydrogen at 100 °C
without catalyst likely due to the presence of high kinetic
barrier since catalysts are always needed in the hydrogenation
and dehydrogenation of LOCHs.25,39,40 Therefore, Ru and Pt
nanoparticles were in situ synthesized as the hydrogenation
and dehydrogenation catalysts, respectively (see Supporting
Information for more detail). Ru nanoparticles with an
averaging particle size of 2.1 nm are well dispersed in Li-ID
sample (Figures 5 and S11−S13). It is shown that the
hydrogenation of Li-ID can be achieved under 50 bar
hydrogen at 100 °C in the presence of Ru nanoparticles
(Figure 5b). Conversion of Li-ID higher than 99% was
obtained in 15 min with selectivity to 8H-Li-ID higher than
99% as evidenced by the quantitative 1H NMR analysis (Figure
5c). Since Li-ID can be almost totally converted to 8H-Li-ID
(Figure 5b), the hydrogenation enthalpy change (ΔHh) was
measured using a C80 calorimeter. The ΔHh of Li-AD
determined experimentally is −33.6 kJ/mol-H2 (Figure 5d),
which is in excellent agreement with the calculated value (33.7
kJ/mol-H2 for ΔHd), validating the accuracy of our simulation
(see Figure S14 for more details).
In the attempt of dehydrogenation of 8H-Li-ID, we used Pt
nanoparticles as catalysts because Ru nanoparticles are inactive
to catalyze the dehydrogenation. It is shown that around 51.4%
8H-Li-ID converts to Li-ID under vacuum at 100 °C in the
presence of Pt nanoparticles (Figure 5c), indicating 3.1 wt %
hydrogen is reversibly stored. Because the conversion to Li-ID
remained constant even after long dehydrogenation time, we
suppose that Pt nanoparticles were covered or separated by Li-
ID from contacting 8H-Li-ID, leading to mass transfer
constrain which is a common issue in solid-state catalysis.
The development of efficient catalysts or optimization of
dehydrogenation process are thus very important. Catalysis in
solution may overcome this mass transfer issue; however, it
may sacrifice the hydrogen capacity. There are several good
examples of solid-state catalysis in hydrogen storage area, such
as Ti-based catalysts for NaAlH417 and K-based catalyst for
amide-hydride system,41 which highlight unique function of
nonconventional catalysts. Nevertheless, we managed to
demonstrate a reversible hydrogenation and dehydrogenation
of Li-ID/8H-Li-ID pair at a temperature as low as 100 °C in
the presence of Ru and Pt nanoparticles, albeit the conversion
and kinetics still need to be optimized. It should be noted that
no conversion of pristine octahydroindole to indole can be
obtained under the same conditions in the presence of the
same catalyst. It is also worth mentioning that the dehydrogen-
ation of conventional LOHCs usually needs much higher
temperatures. For instance, the dehydrogenation of cyclo-
alkanes (such as methylcyclohexane and dodecahydro-
benzyltoluene) is a strong endothermic process (ΔHd is
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Letter
usually high than 65.0 kJ/mol-H2); the thermal dehydrogen-
ation temperature is higher than 300 °C.42,43 For the well-
developed N-heterocycles (such as 12H-NEC), the thermal
dehydrogenation temperatures are also higher than 170
°C.44,45
With an ideal thermodynamic property and high hydrogen
content, the Li-ID/8H-Li-ID pair would facilitate the ease of
hydrogen uptake and release in the present study. Considering
that indole and 7-azaindole, the precursors of metalorganic
hydrides, are low-cost chemicals with high annual production,
together with their facile syntheses, high hydrogen capacities,
and suitable thermodynamic properties, M-ID and M-AD hold
great promise for both on-board application and large-scale
long-distance hydrogen transportation. In addition to them,
other potential candidates predicted with high hydrogen
capacity and suitable thermodynamic properties in the ideal
area (Figure 2) are worthy of investigation in the future.
Theoretical calculations were used to screen promising
metalorganic hydrides for hydrogen storage. More than 90
metalorganic hydrides were calculated, among which 20
candidates with high hydrogen storage capacity (≥5.0 wt %)
and suitable thermodynamic (ΔHd of 25−35 kJ/mol-H2) were
identified. It is found that the ΔHd of metalorganic hydrides
can be tailored by the electronegativity of the metal. Four of
them, i.e., Li/Na-ID and Li/Na-AD, are selected for
experimental validation. All the four candidates can be easily
synthesized via the reactions between metal hydrides and
corresponding organic precursors. Among them, the structures
of lithium indolide (P21/c (no. 14)) and sodium 7-azaindolide
(P4̅21c (no. 114) were successfully resolved. PES and quantum
chemical calculations confirmed that the charge density of the
organic ring increased with the introduction of the alkali metal,
thus optimizing their ΔHd for hydrogen storage. Importantly,
the partially reversible hydrogenation and dehydrogenation of
Li-ID/8H-Li-ID pair with an ideal ΔHd of 33.7 kJ/mol-H2
were successfully achieved at the temperature as low as 100 °C
in the presence of Ru and Pt nanoparticles. The theoretical
hydrogen storage capacity of this material is as high as 6.1 wt
%. The development of efficient catalysts for hydrogenation
and dehydrogenation is highly needed to further optimize the
kinetics. In addition, other potential candidates predicted with
high hydrogen capacity and suitable thermodynamic properties
in the ideal area are worthy of investigation in the future.
These results illustrated that the strategy from theoretical
prediction to rational fabrication is successful and represents
an efficient methodology to develop promising materials for
hydrogen storage.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsmaterialslett.1c00488.
Experimental procedures, Table S1−S3 (enthalpies and
hydrogen capacities, comparison of VDE and ADE
values, relative energies), and Figure S1−S14 (TPD-MS,
photoelectron spectra, hydrogen evolution, NMR
spectra, XRD profiles, TEM images and particle size
distribution, EDS, microcalorimetry) (PDF)
https://doi.org/10.1021/acsmaterialslett.1c00488
ACS Materials Lett. 2021, 3, 1417−1425
ACS Materials Letters
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www.acsmaterialsletters.org
AUTHOR INFORMATION
Corresponding Authors
Xue-Bin Wang − Physical Sciences Division, Pacific Northwest
National Laboratory, Richland, Washington 99352, United
States; orcid.org/0000-0001-8326-1780;
Email: xuebin.wang@pnnl.gov
Hui Wu − NIST Center for Neutron Research, National
Institute of Standards and Technology, Gaithersburg,
Maryland 20899-6102, United States; orcid.org/0000-
0003-0296-5204; Email: huiwu@nist.gov
Anan Wu − Fujian Provincial Key Laboratory of Theoretical
and Computational Chemistry, College of Chemistry and
Chemical Engineering, Xiamen University, Xiamen 361005,
China; orcid.org/0000-0001-5243-9291;
Email: ananwu@xmu.edu.cn
Teng He − Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China; orcid.org/
0000-0003-2900-7612; Email: heteng@dicp.ac.cn
Authors
Zijun Jing − Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China; University of
Chinese Academy of Sciences, Beijing 100049, China
Qinqin Yuan − Physical Sciences Division, Pacific Northwest
National Laboratory, Richland, Washington 99352, United
States; orcid.org/0000-0001-5771-6147
Yang Yu − Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China
Xiangtao Kong − College of Chemistry and Chemical
Engineering, Anyang Normal University, Anyang 455000, P.
R. China
Khai Chen Tan − Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian 116023, China;
University of Chinese Academy of Sciences, Beijing 100049,
China
Jintao Wang − Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China; University of
Chinese Academy of Sciences, Beijing 100049, China
Qijun Pei − Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China
Wei Zhou − NIST Center for Neutron Research, National
Institute of Standards and Technology, Gaithersburg,
Maryland 20899-6102, United States; orcid.org/0000-
0002-5461-3617
Ping Chen − Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China; orcid.org/
0000-0002-0625-0639
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsmaterialslett.1c00488
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is partially supported by the National Key R&D
Program of China (2019YFE0103600), the National Natural
Science Foundation of China (21875246, 21988101,
21773193), the LiaoNing Revitalization Talents Program
1424
Letter
(XLYC1807157), the K. C. Wong Education Foundation
(GJTD-2018-06), and the Dalian high-level talents program
(2019RD09). We also are thankful for beam time from
BL14B1 at SSRF for the XRD experiment. The PES work was
supported by the U.S. Department of Energy (DOE), Office of
Science, Office of Basic Energy Sciences, Division of Chemical
Sciences, Geosciences, and Biosciences, and performed using
EMSL, a national scientific user facility sponsored by DOE’s
Office of Biological and Environmental Research and located at
Pacific Northwest National Laboratory, which is operated by
Battelle Memorial Institute for the DOE.
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