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Density Functional Theory Study of Superalkali NLi4‑Decorated

Graphdiyne Nanosheets as Hydrogen Storage Materials
Qi Jiang,∥ Xue Bai,∥ Zepeng Jia, Sen Lu, Pei Song, Yunjian Chen, Pengyue Shan, Hong Cui,* Rong Feng,
Qin Kang, Zhiyong Liang, and Hongkuan Yuan
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ABSTRACT: The properties and mechanism of adsorption of hydrogen molecules on

NLi4-decorated graphdiyne nanosheets (NLi4-GDY) were investigated based on the
density functional theory. Accordingly, the 76 hydrogen storage configurations of NLi4-
SGDY, NLi4-GDY-A, and NLi4-SGDY-A were constructed by nonmetallic B/N
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substitution and A (A = B, N, Si, P) adsorption. The electronic structure of each

configuration and the structure with the desired high hydrogen storage capacity were
explored. The results showed that the charge on the lithium atom in the NLi4-GDY
structure was transferred to the pristine GDY, thus forming a partial electron field around
each lithium atom, which subsequently led to the polarized adsorption of the hydrogen
molecule. Through B/N substitution and A adsorption, we have modulated the degree of
charge transfer in Li atoms across different configurations, thereby manipulating the
strength of partial electric fields and resulting in varying hydrogen storage capacities for
NLi4-SGDY, NLi4-GDY-A, and NLi4-SGDY-A configurations. According to DFT
calculations, the optimal hydrogen storage structures for NLi4-GDY, NLi4-SGDY, NLi4-GDY-A, and NLi4-SGDY-A were 6H2-
2NLi4-GDY, 14H2-2NLi4-N11′, 14H2-2NLi4-GDY-Si, and 18H2-2NLi4-N1-P, respectively, with gravimetric densities of 3.85, 8.09,
7.29, and 8.91 wt %, respectively. Considering the exceptional hydrogen storage properties of the aforementioned configurations, we
propose that NLi4-decorated GDY with B/N substitution and A adsorption offers a promising avenue for discovering novel
hydrogen storage materials.
KEYWORDS: design of hydrogen storage materials, NLi4-decorated graphdiyne nanosheets, nonmetallic modulation,
density functional theory

1. INTRODUCTION material with good hydrogen storage potential due to its high
As the most abundant element on earth, hydrogen is stability, uniform pore size distribution, wide surface spacing,
considered to be an ideal source of energy owing to its rapid and low density.24−27 However, pristine GDY is considered to
be unsuitable for direct hydrogen storage because of its weak
combustion rate, high energy density, and nontoxicity.1,2
van der Waals interactions with hydrogen molecules, resulting
Hydrogen not only plays a pivotal role in the chemical
in an insufficient hydrogen adsorption capacity and resultant
industry, power generation, heating, and cooling but is also a
low hydrogen storage gravimetric density.28 The ideal
green energy source with the potential to replace petro-
hydrogen adsorption energy should be between −0.15 and
leum.3−6 In the past decades, researchers have conducted
−0.60 eV to ensure efficient adsorption and release under
extensive studies on hydrogen storage methods.7−11 Examples
appropriate operating conditions.29,30 Metal atom decorating is
include high-pressure gaseous hydrogen storage and low-
an effective strategy for functionalizing materials to enhance
temperature liquid hydrogen storage; however, these two
their hydrogen adsorption energy and storage capacity.31−33
storage methods have many limitations in their applications:
Mohajeri et al. theoretically investigated the hydrogen storage
high storage cost, low hydrogen storage capacity, and potential
performance of Li- or Na-decorated NS dual-doped graphyne
hazards of hydrogen leakage and vessel burst.12 The use of
(GYNS). They showed that Li- and Na-decorated GYNS
solid-state materials for hydrogen storage to achieve safe,
efficient, and high-density hydrogen storage has attracted
considerable interest of researchers.13−15 Carbon-based Received: May 3, 2023
materials, such as fullerenes, graphene, nanotubes, and Accepted: July 13, 2023
graphdiyne (GDY), are promising solid-state hydrogen storage Published: July 27, 2023
carriers owing to their high specific surface area, electrical
conductivity, and corrosion resistance, and these have been
widely investigated as a result.16−23 GDY is considered to be a

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Figure 1. Geometry-optimized (a) monolayer GDY (1 × 1) and (b) NLi4-GDY. (c) PDOS of NLi4-GDY. The Fermi energy is set at zero.

storage capacities were 8.98 and 9.34 wt % at an NS superalkali cluster NLi4 has been identified by researchers as a
concentration of 33.3%, respectively, and the adsorption highly promising material due to its low atomic mass, high
energy was in the reversible hydrogen storage range.34 Kaur stability, and inability to react with the substrate readily.40−42
et al. investigated the hydrogen storage capacity of alkali metal Daniel J et al. confirmed the experimental synthesis of NLi4
(Li/Na/K)-decorated two-dimensional carbon nitride (C9N4) functional groups using time-of-flight powder neutron
monolayers based on first-principles density functional theory diffraction.43 The stability and electronic properties of
(DFT) calculations. They found that each Li-doped C9N4 superalkali NM4 (M = Li, Na, K) were investigated via density
(Li@C9N4) can stably bind six H2 molecules with an average functional theory calculations by Zhang and Chen Results
adsorption energy of 0.20 eV, resulting in a high hydrogen indicate that NLi4 is the most stable superalkali NM4, with a
storage capacity of 11.9 wt %.35 Kaewmaraya et al. found that binding energy of 9.25 eV in G3 energy level calculations. The
efficient hydrogen storage can be achieved by Li-, Ca-, K-, and strong N−Li interaction results in positive charge accumu-
Na-functionalized divacancy BPL, where Li- and Na-decorated lation on the Li atom, which favors H2 adsorption.44 Wang et
divacancy BPL have H2 storage capacities of 6.76 and 6.66 wt al. reported that NLi4-modified graphene exhibited a hydrogen
%, respectively, exceeding the DOE target value for 2025.36 To storage density of 10.75 wt % by adsorbing 10H2 molecules,40
improve the hydrogen storage capacity of GDY, researchers while Chen et al. found that NLi4-decorated B2O could store
have used metal atoms to decorate GDY. Ebadi et al. studied up to 9.1 wt % of H2 with the adsorption capacity of 11H2
the stability and hydrogen storage properties of Ca@GDY molecules.41 Jason J et al. study showed that NLi4-decorated
using the density functional theory (DFT) method; the results graphene-like haeckelite (r57) sheets had an excellent storage
showed that the energy of binding to GDY is higher than the capacity of 17.01 wt %, which could adsorb as many as 28H2
cohesion energy of Ca when Ca is located in the 18-ring molecules.42
center, and the Ca-modified GDY has the ideal hydrogen In this study, we constructed NLi4-decorated GDY (NLi4-
adsorption strength (−0.17 eV/H2) and hydrogen storage GDY) as the initial configuration and investigated its electronic
gravimetric density (17.95 wt %).37 Panigrahi et al. investigated structure, hydrogen storage capacity, and hydrogen storage
the hydrogen storage capacity of light metal-modified GDY- mechanism using DFT. Next, we constructed various hydrogen
based materials using DFT and showed that structures storage configurations, including NLi4-SGDY, NLi4-GDY-A,
modified with alkali metals such as Li, Na, and K have a and NLi4-SGDY-A by substituting nonmetallic B/N atoms and
higher hydrogen storage gravimetric density than those adsorbing A (A = B, N, Si, P). Furthermore, we analyzed the
modified with Sc and Ti. Among them, the Li-modified effects of nonmetallic B/N doping and A adsorption on the
structure has the highest hydrogen storage capacity with a electronic structure and hydrogen storage properties of NLi4-
hydrogen storage gravimetric density of 6.50 wt %.38 GDY. Our simulations reveal the effect of nonmetallic atom
substitution or adsorption on the H2 storage capacity of the
Nonmetallic atoms are also commonly used to assist in
NLi4-GDY structure and the operation mechanism.
enhancing the binding ability between metals and GDY,
thereby improving the hydrogen storage properties. Wang et al.
effectively changed the preferred adsorption sites of Li and Na 2. COMPUTATIONAL METHODS
by doping the GDY aromatic ring with B atoms, and the All DFT calculations in this study were performed using the Vienna
binding energy between Li or Na and GDY was much higher Ab initio Simulation Package.45 The Perdew−Burke−Ernzerhof
than their own cohesion energy. In the B-doped structure, a generalized gradient approximation was used to calculate exchange-
correlation energies. Further, dispersion correction was performed by
single Li or Na atom can adsorb five H2 molecules, and the Grimme’s DFT-D3 method.46,47 In the calculation, the cutoff energy
hydrogen storage gravimetric densities are 8.81 and 7.73 wt %, of the configurations was set to 500 eV, and the energy and force
respectively.39 convergence criteria were 1 × 10−5 eV and 0.02 eV/Å, respectively.
In addition to utilizing alkali metal, alkaline earth metal, and The Brillouin zone was sampled using the Monkhorst−Pack scheme,
transition-metal atoms as dopants for hydrogen storage, the and the K-point grid was set to 5 × 5 × 1 and 7 × 7 × 1 for the

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Figure 2. (a, b) 2D contour plots of electron localization function (ELF) for GDY and NLi4-GDY, respectively. (c, d) Electrostatic potential maps
(EPM) for GDY and NLi4-GDY, respectively. (e, f) Top and side views of charge density difference (CDD) for NLi4-GDY; yellow and blue regions
represent charge aggregation and loss, respectively, and the numbers show the charge carried by atoms.

structural optimization and electronic structure calculation, respec- Figure 1c shows the partial density of state (PDOS) of NLi4-
tively. A vacuum layer of 20 Å in the z-axis direction was set up to GDY. The results show that the main contribution to the
eliminate possible interlayer interactions. During the geometric valence and conduction band regions is from the 2p orbital of
optimization, only the ions are relaxed.
the C atom. Around the Fermi energy level, the orbital
coupling of C 2p, N 2p, and Li 2s indicates a strong interaction
3. RESULTS AND DISCUSSION
between NLi4 and GDY. Interestingly, only tiny peaks
3.1. Stability and Electronic Properties of the NLi4- correspond to the Li 2s orbital in the NLi4-GDY structure,
GDY Structure. Graphdiyne (GDY) has previously been indicating charge transfer from the Li 2s orbital to other atoms.
synthesized and demonstrated to be the most stable carbon Electron localization function (ELF), electrostatic potential
allotrope containing diacetylenic linkages, with the heat of map (EPM), charge density difference (CDD), and Bader
formation of 18.3 kcal per g-atom C.48−52 In this study, γ-GDY charge analyses were used to identify the interactions between
(1 × 1) was chosen as the substrate. Its optimized structure NLi4 and GDY.
and band structure are presented in Figures 1a and S1, Figure 2a,c shows the ELF and EPM of GDY, respectively.
respectively. The calculated lattice parameter of GDY is 9.432 Six pairs of protruding red charge regions exist in pristine
Å, while the band structures indicate that the direct band gap GDY, which correspond to the local π-electron regions
of GDY is estimated to be 0.43 eV at PBE levels, which agrees
corresponding to the six carbon−carbon triple bonds in
well with previous theoretical calculations and experimental
GDY, its role as an anchor in the adsorption of NLi4.54 Figure
studies.24,25,52,53
Then, GDY was decorated with the superalkali NLi4 to form 2b,d shows the ELF and EPM of NLi4-GDY, respectively. The
the NLi4-GDY structure, and to verify the stability of the hybridization occurs between the Li atom at the bottom of
structure, the binding energy Eb was defined as follows NLi4 and the six carbon−carbon triple bonds in GDY. To
study the charge transfer between NLi4 and GDY, the CDD
E b = E NLi4 GDY EGDY E NLi4 (1) and Bader charge are calculated and shown in Figure 2e,f,
respectively; the results show that when NLi4 is loaded on
where ENLi4‑GDY represents the total energy of NLi4-
d
GDY, Li in the structure transfers charge to the C and N
decorated GDY, and EGDY and ENLi4 represent the energies of
d
atoms. At this time, the Li atoms at the top and bottom have
GDY and NLi4, respectively. +0.861 and +0.852 charges, respectively. In contrast, the
As shown in Figure 1b, the optimized NLi4 in NLi4-GDY is surrounding C atoms have a certain amount of negative charge,
in the 18MR-hole center of GDY.54 At this point, the three Li thus forming an electrostatic field between NLi4 and GDY. The
atoms (Li1, Li2, Li3) at the bottom of NLi4 are mainly bonded electrostatic field contributes to the polarization and
to the 12 C atoms nearby, and the average bond length adsorption of hydrogen molecules.
between the 12 C atoms is 1.230 Å, which is close to the 3.2. Hydrogen Storage by NLi4-GDY. To analyze the
acetylene bond length (1.200 Å), i.e., a typical carbon−carbon hydrogen storage properties of NLi4-GDY, the most stable H2
triple bond. Further, the binding energy between NLi4 and adsorption sites on NLi4-GDY were explored. The Li4 atoms
GDY is −2.804 eV, indicating the structure has excellent were selected as Up sites, and Li1, Li2, and Li3 atoms were
stability. selected as Down sites for H2 adsorption, as shown in Figure
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Figure 3. (a, b) Optimized 3H2-NLi4-GDY(Up) geometry and CDD; yellow and blue regions represent charge aggregation and loss, respectively.
(c, d) Optimized 3H2-NLi4-GDY(Down) geometry and CDD. (e, f) PDOS of 3H2-NLi4-GDY(Up) and 3H2-NLi4-GDY(Down), respectively.

1b. Figure 3a,c shows the geometric structure of H2 at Up and H2. The adsorption energy and geometric parameters for H2
Down sites. The average adsorption energy Eavg is as follows adsorbed on NLi4-GDY are listed in Table S1.
The results show that the distance between H2 and Li atoms
Eavg = (EmH2 conf Econf mE H2)/m (2) and the H−H bond length when H2 is adsorbed at the Up site
where EmH2‑conf represents the energy of m hydrogen molecules is shorter and longer, respectively, compared to those in the
case of adsorption at the Down site; this indicates stronger
d

adsorbed on the hydrogen adsorption configuration; Econf and

adsorption of H2 at the Up sites. According to the adsorption
EH 2 represent the energy of the hydrogen adsorption
d

energy data, the average adsorption energy Eavg = −0.189 eV

configuration and the energy of H2, respectively; and m for 3H2 adsorbed at the Up site of the NLi4-GDY structure is
represents the number of adsorbed hydrogen molecules. The stronger than that for 3H2 adsorbed at the Down site.
continuous adsorption energy of hydrogen Ecot is as follows Therefore, the most stable adsorption site of H2 on the NLi4-
Ecot = EmH 2 conf E(m 1)H 2 conf E H2 (3) GDY structure is the Up site.
To clarify the origin of H2 adsorption at NLi4-GDY, the
where EmH2‑conf and E(m−1)H2‑conf represent the energy of m
d d
partial density of state (PDOS) with charge density difference
adsorbed hydrogen molecules and (m − 1) adsorbed hydrogen (CDD) was considered. Figure 3e,f shows the PDOS of 3H2 at
molecules, respectively, and EH2 represents the total energy of
d
Up and Down sites, respectively: the σ orbitals of H2 located
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Figure 4. (a−l) Top view of 12 SGDY structures.

below the Fermi energy level show energy level splitting, as shown in Figures S2 and S3. Figures S2 and S3 show that
indicative of the electrostatic repulsion between the adsorbed the B−C and N−C bond lengths in the BGDY and NGDY
H2. In addition, the hybridization of the 1s orbital of the H2 structures are quite different due to the unique hybridization of
molecule and the 2s orbital of the Li atoms are quite weak, the B/N atoms with the adjacent C atoms at different
implying that the main factor resulting in the H2 adsorption substitution sites. Moreover, all optimized SGDY structures
behavior is not the hybridization between Li and H2. CDD was maintain a geometry similar to that of pristine GDY because of
used to clarify the interactions between 3H2 and NLi4-GDY. the similar atomic radii of C, B, and N.
Figure 3b,d shows the CDD of the 3H2 at Up and Down sites To evaluate the stability of the SGDY structure, the cohesion
in NLi4-GDY, respectively. When H2 is adsorbed on NLi4, the energy Ecoh is defined as follows
H2 ends carry negative charges, while the Li atoms in NLi4
carry positive charges. The polarities of H2 and Li atoms are Ecoh = [ESGDY xES yEC] /(x + y) (4)
opposite, and electrostatic attraction exits between 3H2 and where ESDGY is the total energy of the SGDY structure; ES and
NLi4. In addition to electrostatic attraction, H2 molecules with EC represent the isolated atomic energies of the adsorbed
the same polarity also experience electrostatic repulsion. When atoms B/N and C atoms, respectively; and x and y are the
electrostatic attraction and repulsion reach equilibrium, H2 is numbers of adsorbed B/N and C atoms, respectively. More
adsorbed on the structure. negative cohesion energy means that the formation of the
Upon stable adsorption of 3H2 at the Up site, adding H2 SGDY structure is thermodynamically more favorable.55 The
molecules was continued until saturation was reached (Ecot cohesive energy of BGDY with the NGDY structure is shown
below −0.1 eV). The maximum hydrogen storage quantity, in Figure S6. Figure S6a,b shows that the cohesion energy of
adsorption energy, and bond length of the structure are shown BGDY and NGDY structures are similar to the cohesion
in Table S1. H2 molecules are mainly adsorbed at the Up site, energy of pristine GDY (−7.210 eV), indicating the stable
and adsorption at the Down site is difficult. Moreover, only up thermodynamic performance of SGDY.56
to 3H2 molecules can be adsorbed at the Up site, so the To understand the charge distribution of SGDY structures
hydrogen storage in the NLi4-GDY structure is limited. after B/N substitution, the Bader charges in 24 BGDY and
3.3. Structure and Hydrogen Storage Capacity of NGDY structures were calculated. For comparison, we also
NLi4-SGDY. The substitution GDY (SGDY) structure is computed the Bader charge of pristine GDY. The results
formed by the replacement of the C atoms in pristine GDY by indicate that the diacetylene carbon atoms possess negligible
B or N atoms; SGDY is used to modulate the Li atom negative charges (0.05e−), consistent with previous calcu-
coordination environment of the NLi4 to improve the lations.56 The charges of B atoms with adjacent C atoms in the
hydrogen storage properties of the NLi4-decorated structure. BGDY structure and N atoms with adjacent C atoms in the
The main atoms replaced by B/N are three nonequivalent C NGDY structure are listed in Tables S2 and S3, respectively.
atoms in GDY, such as C1, C2, and C3, and the corresponding The results presented in Table S2 demonstrate that all boron-
C1′, C2′, and C3′, as shown in Figure 1a. Based on the substituted structures exhibit positively charged B atoms at the
substitution sites and the number of substitutions, 12 different substitution sites and negatively charged adjacent C atoms.
nonmetallic atomic substitution structures were proposed, as This observation suggests a significant charge transfer from the
shown in Figure 4. The SGDY structures formed by B and N boron to the graphdiyne monolayer upon substitution.
atoms substitution are named BGDY and NGDY, respectively, However, in the NGDY structure, all substitution sites’ N
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Figure 5. (a, b) Optimized structures of 3H2-NLi4-B12(Up) and 3H2-NLi4-N11′(Up). (c) Comparison of energy of adsorption of H2 on 24 NLi4-
SGDY at Up and Down sites.

Figure 6. (a−d) Optimized structure of NLi4-B12 with adsorption of 3, 4, and 7H2 molecules, and (e−h) optimized structure of NLi4-N11′ with
adsorption of 3, 4, and 7H2 molecules.

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Figure 7. (a−d) Geometry and bond length of optimized NLi4-GDY-A structures: (a) NLi4-GDY-B, (b) NLi4-GDY-N, (c) NLi4-GDY-Si, and (d)
NLi4-GDY-P. (e) Comparison of energy of A adsorption at different adsorption sites of NLi4-GDY.

atoms carry negative charges while their adjacent C atoms are +0.851 to +0.873. For the NLi4-NGDY configuration, the top
positively charged. This indicates that the charge is transferred charge of the NLi4 cluster is in the range of +0.853 to +0.861,
from the C atom to the N atom in the NGDY structure. while the bottom charge is in the range of +0.853 to +0.872,
In summary, for the BGDY and NGDY structures, the B/N which indicates that the B/N substituted greatly changes the
substitution changes the charge distribution of the adjacent C charge of the NLi4 cluster resulting in different charge states of
atoms at the substitution site, and the B/N atoms also lose or the cluster in different SGDYs. It is known that the adsorption
gain charge from the nearby C atoms. The uneven charge of H2 molecules on NLi4 clusters is mainly electrostatic,41,57 so
distribution of the 24 SGDY structures will affect the charge the degree of charge of NLi4 will significantly affect the
transfer between NLi4 and the substrate, resulting in varying adsorption properties of H2, and therefore it is known that H2
stability and hydrogen storage capacity of NLi4 on different will exhibit different adsorption properties in different SGDY.
substrates. To systematically investigate the H2 adsorption ability of 24
The optimized 24 NLi4-SGDY structures are shown in NLi4-SGDY structures, the initial H2 adsorption sites on NLi4-
Figures S4 and S5: Figure S4 shows 12 NLi4-BGDY structures, SGDY need to be explored first. The bottom and top Li atoms
and Figure S5 shows 12 NLi4-NGDY structures. The stability of NLi4 were selected as the Down and Up sites for H2
of NLi4-SGDY structures was verified based on the binding adsorption, respectively.
energy Eb Figure 5a,b shows the structures of 3H2 adsorption on NLi4-
B12(Up) and NLi4-N11′(Up), respectively. In the above
E b = E NLi4 SGDY E NLi4 ESGDY (5) structures, the adsorption morphology of H2 is very similar to
that in the NLi4-GDY(Up) structure. 3H2 adsorbed at the
where ENLi4‑SGDY represents the total energy of NLi4-decorated
d

Down site of NLi4-B12 with NLi4-N11′ is shown in Figure S7,

SGDY, and ESGDY and ENLi4 represent the energies of SGDY
d
and a comparison of the adsorption energies is shown in Figure
and NLi4, respectively. The more negative the binding energy 5c. The results showed that for the 24 NLi4-SGDY structures,
is, the stronger the interaction force between NLi4 and SGDY. the H2 adsorption energy at the Up site was higher than that at
The binding energy of NLi4-SGDY is shown in Figure S6. The the Down site, so the Up site was the most stable adsorption
binding energy of NLi4-BGDY is between −3.78 and −5.73 site for H2 on the NLi4-SGDY structure.
eV, while that of NLi4-GDY is between −2.03 and −3.09 eV. To further investigate the hydrogen absorption threshold of
Thus, B substitution is more beneficial than N substitution for the NLi4-SGDY structure, H2 molecules were added until
improving the interaction between GDY and NLi4. saturation was reached (Ecot below −0.1 eV). The NLi4-B12
The Bader charges of 24 NLi4-SGDY are calculated and and NLi4-N11′ structures showed the highest hydrogen
shown in Figures S4 and S5. It is clear that the charge of NLi4 storage capacities among the NLi4-BGDY and NLi4-NGDY
when adsorbed on BGDY or NGDY is significantly different configurations, respectively, and a single NLi4 molecule in
from that when adsorbed on GDY, and for the NLi4-BGDY NLi4-B12 and NLi4-N11′ can store up to 7H2 molecules.
configuration, the top charge of the NLi4 cluster is in the range Figure 6a,b shows the NLi4-B12 structure and the adsorption
of +0.862 to +0.888, while the bottom charge is in the range of of 3, 4, and 7 hydrogen molecules, and Figure 6e−h shows the
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NLi4-N11′ structure and the adsorption of 3, 4, and 7 increase to 1.950, 1.853, 1.959, and 1.872 Å, and the top N−Li
hydrogen molecules. Table S4 shows the parameters related to bond lengths increase to 1.838, 1.754, 1.840, and 1.720 Å for
hydrogen adsorption on NLi4-B12 and NLi4-N11′. the adsorbed structures with B, N, Si, and P, respectively. The
The results showed that the H−H bond length of H2 changes in bond lengths indicate that there are different
adsorbed on NLi4-B12 and NLi4-N11′ structures increased interactions between A and NLi4-GDY.
more substantially than that of pristine H2, and the H2 To reveal the interaction between A and NLi4-GDY, the
adsorption energy decreased with the increase in the amount partial density of state (PDOS) of NLi4-GDY-A structures was
of hydrogen stored. calculated. Figure S10a−d shows the PDOS of NLi4-GDY-A:
Partial density of state (PDOS) with electrostatic potential When the A atom is adsorbed on NLi4-GDY, the 2p orbital of
maps (EPM) of 7H2-NLi4-B12 and 7H2-NLi4-N11′ structures the N atom shows a new peak in the energy range between
were plotted to reveal their hydrogen storage mechanisms. −7.5 and −2.5 eV. In addition, the 2s orbital of the Li atoms
Figure S8a,b shows the PDOS of 7H2-NLi4-B12 and 7H2-NLi4- has a reduced peak at the Fermi energy level, which indicates
N11′, respectively: when NLi4-B12 and NLi4-N11′ adsorb that the adsorption of A mainly affects the charge distribution
seven H2 molecules, the density of states of the 1s orbital of H of NLi4 in NLi4-GDY.The charge density difference (CDD)
undergoes splitting at −10 to −5 eV, which indicates the with Bader charge was calculated to analyze charge transfer in
electrostatic repulsion existing between the adsorbed H2 the NLi4-GDY-A structure after A adsorption. Figure S11a−d
molecules. The 1s orbital of the H2 molecules and the 2p shows the CDD plots of NLi4-GDY-B, NLi4-GDY-N, NLi4-
orbital of the Li atoms are extremely weakly hybridized, and GDY-Si, and NLi4-GDY-P structures, respectively, and Table
according to the analysis results described previously in this S5 shows the corresponding Bader charge. The results show
paper, this indicates that the H2 adsorption on 7H2-NLi4-B12 that in the four NLi4-GDY-A structures, the charge is gathered
and 7H2-NLi4-N11′ is due to electrostatic attraction. Figure between the NLi4 and GDY but lost between the Li and N
S8c,d shows the EPM of 7H2 in the case of adsorption on atoms in NLi4, which leads to a longer N−Li bond. As shown
NLi4-B12 and NLi4-N11′, respectively, where the red region is in Table S5, the Li and N atoms of NLi4 in various NLi4-GDY-
dominated by electrons and the blue region is dominated by A structures carry different positive and negative charges. The
nuclei. In both structures, the N atom at the center of the NLi4 results show that the positive charge of Li(Up) follows the
cluster is negatively charged, while the Li atom is positively order NLi4-GDY-Si < NLi4-GDY-B < NLi4-GDY-P < NLi4-
charged. When H2 is adsorbed on NLi4, the H atoms at the GDY-N; the positive charge of Li(Down) follows the order
two ends carry a negative charge in contrast to the positive NLi4-GDY-N < NLi4-GDY-P < NLi4-GDY-B < NLi4-GDY-Si.
charge carried by the Li atoms, and therefore, electrostatic As discussed, the adsorption of H2 on NLi4 occurs via
attraction exists between Li and H2. In addition to the electrostatic interactions. The main mechanism is that when
electrostatic attraction between NLi4 and H2, H2 molecules H2 is close to NLi4 both ends carry a charge with polarity
also experience electrostatic repulsion between each other. opposite to that carried by Li, leading to H2 adsorption.
Thus, the adsorption energy difference between 7H2-NLi4-B12 Therefore, the degree of positive charge carried by the Li
and 7H2-NLi4-N11′ arises because of the competing electro- atoms greatly affects the H2 storage. Before studying the
static attraction and repulsion. hydrogen storage capacity of NLi4-GDY-A, the adsorption of
3.4. Structure and Hydrogen Storage Capacity of H2 at each adsorption site (Up and Down sites) of NLi4 was
NLi4-GDY-A. In addition to substitution, nonmetallic elements investigated. The optimized H2 adsorption configuration is
can be immobilized on two-dimensional nanosheets by shown in Figure S12.
adsorption.56 The nonmetallic atoms A (A = B, N, Si, P) are Figure S12a−d shows the structures of 3H2 adsorbed at the
adsorbed on the NLi4-GDY structure, and their most stable Up site on NLi4-GDY-B, NLi4-GDY-N, NLi4-GDY-Si, and
adsorption sites are determined based on the adsorption NLi4-GDY-P structures, respectively, and Figure S12e−h
energy. In Figure S9, the adsorption site of nonmetallic atom A shows the structures at the Down site. The average adsorption
on NLi4-GDY can be seen. The adsorption sites are the top site energy for H2 adsorption at the Up and Down sites of NLi4-
of the C atom (T1-T3), the top site of C−C (B1-B4), the GDY-A are shown in Table S6. The energy of H2 adsorption at
corner of the acetylenic ring (H1), the center of 18MR-hole the Up site of NLi4-GDY-B, NLi4-GDY-N, and NLi4-GDY-P
(H3), and the H2 site between H1 and H3. To locate the most structures is higher than that at the Down site, so the most
stable adsorption site for A on NLi4-GDY, the adsorption stable H2 adsorption site in the above structures is the Up site.
energy Eads was calculated according to the following equation However, when the NLi4-GDY-Si structure absorbs hydrogen,
Eads = E NLi4 E NLi4 EA the adsorption energy at the Down site is higher than that at
GDY A GDY (6) the Up site, so the most stable adsorption site of the structure
is the Down site.
where ENLi4‑GDY‑A represents the total energy of nonmetallic
d

The CDD maps of 3H2 at the Up and Down sites of the

atom A adsorbed on NLi4-GDY, and ENLi 4‑GDY and EA
d
NLi4-GDY-A (A = B, N, Si, P) structure are shown in Figure
represent the energies of NLi4-GDY and nonmetallic atom S13, and the corresponding Bader charge data are presented in
A, respectively. The adsorption energy results are shown in Table S8. Figure S13a−d shows the CDD of 3H2 adsorption at
Figure 7e. the Up site of NLi4-GDY-A structure: the charge transfer
The adsorption energy of the nonmetallic atom A at the H3 occurs mainly between the top Li atom and the H2 molecule.
site was higher than that at the other sites, so the H3 site was According to the Bader charge results, the positive charge of
considered to be the most stable adsorption site for A. The the top Li atom of NLi4 is significantly increased when the 3H2
geometric structure of NLi4-GDY-A(H3) after relaxation is molecule is adsorbed at the Up site of the NLi4-GDY-A
shown in Figure 7a−d. Compared with the original structure, structure, while the two end atoms of the H2 molecule also
the bond lengths inside the NLi4 cluster in the adsorbed carry a negative charge. This indicates that the top Li atom of
structure of A atoms change. The bottom N−Li bond lengths NLi4 transfers charge to the H2 molecule. Due to the mutual
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Figure 8. Optimized hydrogen storage structure of NLi4-GDY-A (A = B, N, Si, P): (a) 6H2-NLi4-GDY-B, (b) 3H2-NLi4-GDY-N, (c) 7H2-NLi4-
GDY-Si, (d) 6H2-NLi4-GDY-P.

Figure 9. Maximum hydrogen storage amounts and adsorption energies of NLi4-SGDY-A configurations: (a) NLi4-BGDY-Si, (b) NLi4-BGDY-P,
(c) NLi4-NGDY-Si, and (d) NLi4-NGDY-P.

attraction of opposite charges, 3H2 is electrostatically adsorbed adsorption energy and vice versa. The electropositivity of the
near the top Li atom. Interestingly, the adsorption energy of top Li atom and the adsorption energy follow the order NLi4-
3H2 at the Up site shown in Table S6 is positively correlated GDY-Si < NLi4-GDY-B < NLi4-GDY-P < NLi4-GDY-N. Figure
with the electropositivity of the top Li atom (Table S5); i.e., S13e−h shows the CDD of 3H2 adsorbed at the Down site on
the stronger the top Li electropositivity is, the higher the H2 the NLi4-GDY-A structure. Table S8 shows the corresponding
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Bader charge data. The results show that when 3H2 is adsorbed NGDY-P configurations. Figure 9a−d shows the average
at the Down site of the NLi4-GDY-A structure, the top Li atom adsorption energies of the four configurations NLi4-BGDY-Si,
of NLi4 transfers charge to H(Above) and the bottom Li atom NLi4-BGDY-P, NLi4-NGDY-Si, and NLi4-NGDY-P for the
gains charge from H(Lower). In this case, the top H atom of adsorption of nine hydrogen molecules. As mentioned in the
H2 points to Li(Up) and the bottom H atom points to Section 1, the ideal hydrogen adsorption energy should be
Li(Down), and thus, it is polarized and adsorbed between the between −0.15 and −0.60 eV. Therefore, in each panel of
top and bottom Li atoms. Figure 9, we added a dashed line (Eavg = −0.15 eV) as a
To further investigate the hydrogen absorption threshold of reference line for the reasonable adsorption energy. Structures
the NLi4-GDY-A structure, the addition of H2 molecules was with reasonable adsorption energy are above this dashed line,
continued until saturation was reached (Ecot below −0.1 eV). while structures with too low adsorption energy are below this
The relevant hydrogen storage parameters of the NLi4-GDY-A dashed line. In Figure 9a,b, we have marked with red circles the
structures are listed in Table S7. The results show that the H− average adsorption energy points of nine hydrogen molecules
H bond length of H2 on NLi4-GDY-A is longer than that in the adsorbed by the most desirable structures among the four
initial structure, and the H−H bond length and adsorption configurations (NLi4-B13′-Si, NLi4-B12-P, NLi4-N12′-Si, and
distance of different hydrogen storage structures are different NLi4-N1-P), and their structures are shown in the insets.
at the same amount of hydrogen storage. Based on the Ecot Table S10 lists the parameters related to the adsorption of
values, it is known that up to three H2 molecules can be nine H2 molecules by NLi4-B13′-Si, NLi4-B12-P, NLi4-N12′-Si,
adsorbed on the NLi4-GDY-N structure; further, NLi4-GDY-B and NLi4-N1-P structures. The results show that the distance
and NLi4-GDY-P structures can adsorb up to six H2 molecules, between Li and H is the shortest, and the H−H bond is the
and NLi4-GDY-Si can adsorb up to seven H2 molecules. The longest in the NLi4-N1-P structure, which indicates the
optimized configuration is shown in Figure 8. strongest adsorption of H2 by the NLi4-N1-P structure.
3.5. Structure and Hydrogen Storage Capacity of Notably, dLi−H is negatively correlated with Eavg, and dH−H is
NLi4-SGDY-A. A series of NLi4-SGDY and NLi4-GDY-A were positively correlated with Eavg. The average adsorption energy
constructed by B/N substitution and A (A = B, N, Si, P) increases when the H−H bond length increases and the Li−H
adsorption, and the electronic structure and hydrogen storage distance decreases.
capacity of each structure were investigated. The hydrogen The results show that in the NLi4-SGDY-A configuration,
storage capacity of the NLi4-SGDY structure after B/N NLi4-B13′-Si, NLi4-B12-P, and NLi4-N1-P can store up to 9H2
substitution increased substantially, and a maximum of seven molecules in each NLi4 with adsorption energies between
H2 molecules could be stored in a single NLi4 cluster. For the −0.15 and −0.60 eV. PDOS with electrostatic potential maps
NLi4-GDY-A structure, the hydrogen storage capacity also (EPM) was plotted to clarify the hydrogen storage mechanism
increased substantially after B, Si, and P atom adsorption; of these four structures. Figure S18a−d shows the PDOS of
further, the highest hydrogen storage capacity was realized 9H2-NLi4-B13′-Si, 9H2-NLi4-B12-P, 9H2-NLi4-N12′-Si, and
when Si atom was adsorbed, and a single NLi4 cluster could 9H2-NLi4-N1-P, respectively. The results show that when the
store up to seven H2 molecules. The 24 kinds of NLi4-SGDY- above structures adsorb nine H2 molecules, the density of
Si configurations were constructed by Si adsorption on NLi4- states of 1s orbitals of H undergoes splitting at −13 to −7 eV,
SGDY, and the maximum amount of hydrogen stored was which indicates the electrostatic repulsion between the
investigated. In addition, the 24 kinds of NLi4-SGDY-P adsorbed H2. At this time, the 1s orbital of the H2 molecule
configurations were constructed by P adsorption on NLi4- and the 2p orbital of the Li atom are weakly hybridized,
SGDY for comparison. The optimized configurations of 24 indicating that the H2 adsorption behavior originates from the
kinds of NLi4-SGDY-Si and 24 kinds of NLi4-SGDY-P are electrostatic force between H2 and Li atoms. Figure S19a−d
shown in Figures S14−S17: Figures S14 and S15 show the shows the electrostatic potential diagrams of 9H2-NLi4-B13′-
optimized structures of NLi4-BGDY-Si and NLi4-BGDY-P, Si, 9H2-NLi4-B12-P, 9H2-NLi4-N12′-Si, and 9H2-NLi4-N1-P.
respectively, and Figures S16 and S17 show the optimized The results show that, as described previously, H2 is adsorbed
structures of NLi4-NGDY-Si and NLi4-NGDY-P, respectively. on NLi4 when its two terminal H atoms carry negative charges
The energy of adsorption Eads of Si/P on NLi4-SGDY was with polarity opposite to that of charges carried by the Li
calculated according to the following equation atoms, resulting in electrostatic attraction between Li and H2,
Eads = E NLi4 E NLi4 EA and electrostatic repulsion between H2 molecules. The
SGDY A SGDY (7) electrostatic attraction and repulsion compete, resulting in a
difference in the adsorption energy between the different
where ENLi4‑SGDY‑A represents the total energy of NLi4-SGDY-A,
d

structures.
and ENLi4‑SGDY and EA represent the energies of NLi4-SGDY
d
Finally, we investigated the maximum hydrogen storage for
and the nonmetallic atom A, respectively. The adsorption various configurations of NLi4-GDY, NLi4-SGDY, NLi4-GDY-
energy results are shown in Table S9: The adsorption energies A, and NLi4-SGDY-A. The results show that 2NLi4-GDY,
of NLi4-BGDY-Si, NLi4-BGDY-P, NLi4-NGDY-Si, and NLi4- 2NLi4-N11′, 2NLi4-GDY-Si, and 2NLi4-N1-P are the optimal
NGDY-P ranged from −6.069 to −8.999 eV, −5.223 to hydrogen storage structures for the above configurations. As
−10.930 eV, −3.450 to −6.000 eV, and −3.432 to −7.899 eV, depicted in Figure S20, the maximum hydrogen storage
respectively. The structure shows that the B substitution capacities of 2NLi4-N11′, 2NLi4-GDY-Si, and 2NLi4-N1-P are
effectively increases the strength of the interaction between Si/ determined to be 14, 14, and 18H2 molecules, respectively.
P atoms and NLi4-SGDY, while the N substitution produces Notably, these structures exhibit enhanced hydrogen storage
the opposite effect. capacity compared with their initial configurations (2NLi4-
To identify the structure with the best hydrogen storage GDY). Specifically, the structures of 2NLi4-N11′, 2NLi4-GDY-
performance, we investigated the hydrogen storage capacity of Si, and 2NLi4-N1-P demonstrate improved hydrogen storage
NLi4-BGDY-Si, NLi4-BGDY-P, NLi4-NGDY-Si, and NLi4- capacity with values of up to approximately 8.09, 7.29, and 8.91
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wt %, respectively. Additionally, all structures demonstrate

adsorption energies between −0.15 and −0.60 eV. Notably,
■
*
ASSOCIATED CONTENT
sı Supporting Information
the wt % of H2 in 2NLi4-N11′, 2NLi4-GDY-Si, and 2NLi4-N1- The Supporting Information is available free of charge at
P are highly competitive with experimentally synthesized https://pubs.acs.org/doi/10.1021/acsanm.3c01948.
MWCNTs + Pd (6.0wt %),58 Graphene + Ni + Al (5.7 wt
%),59 and Graphene-Ni Nanocomposites (>6.5 wt %).60 Band structures for γ-GDY (1 × 1) at the PBE level; top
After obtaining the optimal hydrogen storage structures, we and side views of the optimized 12 NLi4-NGDY
expanded the cell size of 2NLi4-GDY, 2NLi4-N11′, 2NLi4- structures; potential adsorption sites of nonmetallic
GDY-Si, and 2NLi4-N1-P(1 × 1) to (2 × 2) to investigate the atoms A (A = B, N, P, Si) on NLi4-GDY; electrostatic
structural configuration and hydrogen storage capacity at potential maps (EPM) of 9H2-NLi4-B13’-Si, 9H2-NLi4-
different cell sizes. The optimized structures of 8NLi4-GDY, B12-P, 9H2-NLi4-N12’-Si, and 9H2-NLi4-N1-P struc-
8NLi4-N11′, 8NLi4-GDY-Si, and 8NLi4-N1-P are shown in tures; cohesion energy Ecoh(eV) of 12 BGDY structures
Figure S21, and the results show that the optimized structures and the charges carried by B atoms and adjacent C
are highly similar to the unit cell structures. We then atoms; and adsorption energy Eads (eV) of Si/P atoms
investigated the hydrogen storage performance of 8NLi4- during adsorption on NLi4-SGDY structure (PDF)
GDY, 8NLi4-N11′, 8NLi4-GDY-Si, and 8NLi4-N1-P structures,
and the results are shown in Figure S22. The structures 8NLi4-
GDY, 8NLi4-N11′, 8NLi4-GDY-Si, and 8NLi4-N1-P can store
a maximum of 24, 56, 56, and 72 hydrogen molecules,
■ AUTHOR INFORMATION
Corresponding Author
Hong Cui − School of Mechanical Engineering, Shaanxi
respectively, and the average adsorption energy of hydrogen is
University of Technology, Hanzhong, Shaanxi 723001,
highly similar to that in the (1 × 1) structure.
China; Shaanxi Key Laboratory of Industrial Automation,
In summary, the hydrogen storage performance of NLi4 in
Shaanxi University of Technology, Hanzhong, Shaanxi
GDY-based materials can be significantly improved by B/N
723001, China; orcid.org/0000-0003-0537-5533;
substitution or A (A = B, N, Si, P) adsorption, and we hope
Email: [email protected]
that this work can inspire the development of more promising
hydrogen storage materials. Authors
Qi Jiang − School of Mechanical Engineering, Shaanxi
4. CONCLUSIONS University of Technology, Hanzhong, Shaanxi 723001,
In this study, the hydrogen storage structure NLi4-GDY was China; Shaanxi Key Laboratory of Industrial Automation,
constructed using the DFT, and B/N substitution and A (A = Shaanxi University of Technology, Hanzhong, Shaanxi
B, N, Si, P) adsorption were used to build the hydrogen 723001, China
storage configurations NLi4-SGDY, NLi4-GDY-A, and NLi4- Xue Bai − School of Mechanical Engineering, Shaanxi
SGDY-A. The electronic structures of the various config- University of Technology, Hanzhong, Shaanxi 723001,
urations were investigated, and structures with high hydrogen China; Shaanxi Key Laboratory of Industrial Automation,
storage capacities were explored. The electronic structure Shaanxi University of Technology, Hanzhong, Shaanxi
analysis showed that the B/N substitution changes the charge 723001, China
distribution of the adjacent C atoms at the substitution site, Zepeng Jia − School of Mechanical Engineering, Shaanxi
and the B/N atoms also lose or gain charge from the nearby C University of Technology, Hanzhong, Shaanxi 723001,
atoms. The uneven charge distribution of the 24 SGDY China; Shaanxi Key Laboratory of Industrial Automation,
structures affected the charge transfer between NLi4 and the Shaanxi University of Technology, Hanzhong, Shaanxi
substrate resulting in varying stability and hydrogen storage 723001, China
capacity of NLi4 on different SGDY. A (A = B, N, Si, P) Sen Lu − School of Mechanical Engineering, Shaanxi
adsorption directly regulates the charge distribution of the University of Technology, Hanzhong, Shaanxi 723001,
NLi4 cluster, with different charges of Li atoms in the case of China; Shaanxi Key Laboratory of Industrial Automation,
different A atom adsorption. Thus, H2 adsorption near NLi4 Shaanxi University of Technology, Hanzhong, Shaanxi
was subject to different electrostatic attraction and electrostatic 723001, China
repulsion forces; further, the competition between electrostatic Pei Song − School of Mechanical Engineering, Shaanxi
attraction and repulsion forces led to the difference in the University of Technology, Hanzhong, Shaanxi 723001,
hydrogen storage capacities and adsorption energies between China; Shaanxi Key Laboratory of Industrial Automation,
different configurations. Compared with the initial hydrogen Shaanxi University of Technology, Hanzhong, Shaanxi
storage configurations 2NLi4-GDY(3.85 wt %), the NLi4- 723001, China
SGDY, NLi4-GDY-A, and NLi4-SGDY-A configurations had a Yunjian Chen − School of Mechanical Engineering, Shaanxi
higher hydrogen storage capacity, the optimal hydrogen University of Technology, Hanzhong, Shaanxi 723001,
storage structures for NLi4-SGDY, NLi4-GDY-A, and NLi4- China; Shaanxi Key Laboratory of Industrial Automation,
SGDY-A were 14H2-2NLi4-N11′, 14H2-2NLi4-GDY-Si, and Shaanxi University of Technology, Hanzhong, Shaanxi
18H2-2NLi4-N1-P, respectively, with gravimetric densities of 723001, China
8.09, 7.29, and 8.91 wt %, respectively, and the adsorption Pengyue Shan − School of Mechanical Engineering, Shaanxi
energies of all structures are in the range of −0.15 to −0.60 eV. University of Technology, Hanzhong, Shaanxi 723001,
As such, the hydrogen storage performance of NLi4 in GDY- China; Shaanxi Key Laboratory of Industrial Automation,
based materials could be considerably improved by B/N Shaanxi University of Technology, Hanzhong, Shaanxi
substitution or A (A = B, N, Si, P) adsorption. In this way, we 723001, China
propose a new concept for developing new hydrogen storage Rong Feng − School of Mechanical Engineering, Shaanxi
materials. University of Technology, Hanzhong, Shaanxi 723001,
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inappropriately influence their work. There is no professional decorated boron-doped carbon nanotube for hydrogen storage: A
or other personal interest of any nature or kind in any product, first-principle study. Int. J. Hydrogen Energy 2019, 44, 27853−27861.
service and/or company that could be construed as influencing (21) Samantaray, S. S.; Sangeetha, V.; Abinaya, S.; Ramaprabhu, S.
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■ ACKNOWLEDGMENTS
This research was funded by the National Natural Science
(22) Sathe, R. Y.; Bae, H.; Lee, H.; Kumar, T. J. D. Hydrogen
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Research Plan of Natural Science in Shaanxi Province (no. porous hydrogen substituted graphyne: A new member of promising
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