A DFT study of H2 adsorption on lithium decorated 3D hybrid Boron-Nitride-Carbon frameworks

Based on density functional theory (DFT) and first-principles molecular dynamics (MD),a new 3D hybrid Boron-Nitride-Carbon–interconnected frameworks (BNCIFs) consisting of organic linkers with Li decoration is created and optimized. Firstly, Li adsorption behaviors on several BNC_xcomplexes are investigated and compared systematically. The results indicate C substitution of N atom in pure BN layer could improve the metal binding energy effectively. Secondly, the BNC layer (BNC_NN) is chosen to model the frameworks of BNCIFs. The average binding energy of adsorbed Li atoms on BNCIFs is 3.6 eV which is much higher than the cohesive energy of bulk Li and avoids the Li clustering problem. Finally, we study the H₂ adsorptions on the Li decorated BNCIFs by DFT. Every Li atom could adsorb four H₂ molecules with an average binding energy of 0.24 eV. The corresponding gravimetric and volumetric storage capacities are 14.09 wt% and 126.2 g/L respectively overpassing the published 2020 DOE target. The excellent thermal stability of 160H₂@40Li@BNCIFs is also proved by MD. This nanostructure could be served as a promising hydrogen storage medium at ambient conditions.     

Ultra-high capacity hydrogen storage of B6Be2 and B8Be2 clusters

The B₆Be₂ and B₈Be₂ clusters, adopting fascinating inverse sandwich-like geometries, were recently predicted with quantum chemical calculations. Both systems exhibit the high stability and double aromaticity with 4σ/6π or 6σ/6π delocalized electrons. The hydrogen storage of two systems is studied in the present paper. Our calculations show that B₆Be₂ and B₈Be₂ clusters have the ultra-high capacity hydrogen storage, each Be site can bound up with seven H₂ molecules, corresponding to a gravimetric density of 25.3 wt percentage (wt%) for B₆Be₂ and 21.1 wt% for B₈Be₂, respectively, which far exceeds the target (5.5 wt%) proposed by the US department of energy (DOE) in 2017. The average absorption energies of 0.10–0.45 eV/H₂ for B₆Be₂ and 0.11–0.50 eV/H₂ for B₈Be₂ at the wB97XD level suggest that both systems are ideal for reversible hydrogen storage and release. The reversibility of H₂ molecules on B₆Be₂ and B₈Be₂ complexes are faithfully demonstrated with the Born-Oppenheimer molecular dynamics (BOMD) simulations. The Be-doped boron nanostructure is a promising candidate for ultra-high hydrogen storage materials.     

Graphene pillared with hybrid fullerene and nanotube as a novel 3D framework for hydrogen storage: A DFT and GCMC study

A new-type 3D pillared graphene framework with hybrid fullerene and nanotube pillars (PGF-hFN) has been created depended on density functional theory (DFT) and first-principles molecular dynamics simulations (MD). It is proved to have excellent thermal structural stability. The average adsorption energy of Li is 2.77 eV much higher than the metal cohesive energy excluding lithium aggregation problem. From DFT calculations, for Li-decorated B-doped PGF-hFN, the hydrogen gravimetric density (HGD) is as high as 12.92 wt% and the according volumetric uptake is 96.4 g/L with an average adsorption energy of 0.195 eV per H₂. Further grand canonical Monte Carlo (GCMC) simulations predict 7.2 wt% in excess HGD and 53.8 g/L in excess volumetric hydrogen density at near ambient temperature (233 K) and 100 bars with the ideal adsorption enthalpy which have exceeded the 2020 the U.S. Department of Energy (DOE) ultimate target for mobile applications. Our multiscale theoretical simulations indicate this new pillared structure should be a promising carrier accessible for sorption of hydrogen molecules.     

Hydrogen trapping efficiency of Li decorated porous boron fullerene B38: The first-principles study

The demand for clean renewable energy is urgent in current. The hydrogen application is difficult mainly due to the ratively low capacity in the storage medium. In this work, the adsorption and desorption of the hydrogen molecules by the Li atoms decorated B₃₈ cage are studied by the density functional theory. The calculated largest binding energy of one Li atom (2.68 eV and 2.58 eV) is upon the hexagonal hole of the B₃₈ cage, which is much larger than the experimental cohesive energy of bulk Li (1.63 eV). Each Li atom in the outside of the B₃₈ cage can adsorb up to four H₂ molecules. The E_ad of B₃₈(Li-nH₂)₄ decreases from the 0.22 eV for n = 1 to the 0.11 eV for n = 4. The B₃₈(Li–4H₂)₄ structure achieves the 6.85 wt% hydrogen gravimetric density, which is higher than the goal of 5.5 wt% before 2017 set by the United States Department of Energy. The almost the same partial density of states for the fifth H₂ molecule as that of the isolated H₂ molecule, the longer 4.5 Å distance between the fifth H₂ molecule and the Li atom, together with the small NBO charges all reveal the weak electronic field around the Li⁺, which can interpret the weak H₂ adsorption mechanism. Finally, the B₃₈Li₄ structure can easily release 9H₂ molecules at 373 K known from the molecular dynamic simulation and practically trap about 1.08H₂ molecules at 373 K/3 atom condition calculated by the grand partition function. Thus, its reversible practical HGD of B₃₈Li₄-14.34H₂ is 6.18 wt%, which is almost the same value as the theoretical 6.85 wt% for B₃₈(Li–4H₂)₄. Our studies will be the strong theory basis for the future application in hydrogen storage material development.     

Li decorated C9N4 monolayer as a potential material for hydrogen storage

Based on first−principles calculations, we investigate the possibility of the two-dimensional porous C₉N₄ material as for hydrogen storage, and find that the adsorption energy of H₂ molecules on the pristine C₉N₄ is too weak to meet the requirements of hydrogen storage, whereas the adsorption on the Li−decorated sheet is relatively moderate. Each C₉N₄ unit cell can incorporate 6 Li atoms, of which 3 Li atoms are located above the intrinsic hole and the others are below. The unit cell can hold 14 hydrogen molecules with an average adsorption energy of −0.12 eV, which meets the reversible storage condition of hydrogen, and the gravity density reaches 7.04 wt%. Particularly, 6Li@C₉N₄ maintains excellent H₂ storage performance under a tensile strain within 2%. The ab initio MD simulations performed at 300 K show that all 14 H₂ molecules remained on the double sides of 6Li@C₉N₄ in the absence and presence of strain. Therefore, we predict that Li−modified C₉N₄ could be a potential material with excellent ductility for hydrogen storage at room temperature.     

Li-decorated double vacancy graphene for hydrogen storage application: A first principles study

Lithium decoration is an effective strategy for improving the hydrogen adsorption binding energy and the storage capacity in carbon nanostructures. Here, it is shown that Li-decorated double carbon vacancy graphene (DVG) can be used as an efficient hydrogen storage medium by means of Density Functional Theory (DFT) based calculations. The Li binding energy in DVG is 4.04 eV, which is much higher than that of pristine graphene. A maximum of four hydrogen molecules adsorb on Li decorated on one side of DVG and this leads to a gravimetric storage capacity of 3.89 wt% with an average adsorption binding energy of 0.23 eV/H₂. When Li is decorated on both sides of DVG, the gravimetric storage capacity reaches 7.26 wt% with a binding energy of 0.26 eV/H₂ which shows that desorption would take place at ambient conditions.     

Hydrogen storage capacity and reversibility of Li-decorated B4CN3 monolayer revealed by first-principles calculations

This work explored the feasibility of Li decoration on the B₄CN₃ monolayer for hydrogen (H₂) storage performance using first-principles calculations. The results of density functional theory (DFT) calculations showed that each Li atom decorated on the B₄CN₃ monolayer can physically adsorb four H₂ molecules with an average adsorption energy of ?0.23 eV/H₂, and the corresponding theoretical gravimetric density could reach as high as 12.7 wt%. Moreover, the H₂ desorption behaviors of Li-decorated B₄CN₃ monolayer at temperatures of 100, 200, 300 and 400 K were simulated via molecular dynamics (MD) methods. The results showed that the structure was stable within the prescribed temperature range, and a large amount of H₂ could be released at 300 K, indicative of the reversibility of hydrogen storage. The above findings demonstrate that the Li-decorated B₄CN₃ monolayer can serve as a favorable candidate material for high-capacity reversible hydrogen storage application.     

High-capacity hydrogen storage in Li-decorated (AlN)n (n = 12, 24, 36) nanocages

The capability of Li-decorated (AlN)_n (n = 12, 24, 36) nanocages for hydrogen storage has been studied by using density functional theory (DFT) with the generalized gradient approximation (GGA). It is found that each Al atom is capable of binding one H₂ molecule up to a gravimetric density of hydrogen storage of 4.7 wt% with an average binding energy of 0.189, 0.154, and 0.144 eV/H₂ in the pristine (AlN)_n (n = 12, 24, 36) nanocages, respectively. Further, we find that Li atoms can be preferentially decorated on the top of N atoms in (AlN)_n (n = 12, 24, 36) nanocages without clustering, and up to two H₂ molecules can bind to each Li atom with an average binding energy of 0.145, 0.154, 0.102 eV/H₂ in the Li_n(AlN)_n (n = 12, 24, 36) nanocages, respectively. Both the polarization of the H₂ molecules and the hybridization of the Li-2p orbitals with the H-s orbitals contribute to the H₂ adsorption on the Li atoms. Thus, the Li-decorated (AlN)_n (n = 12, 24, 36) nanocages can store hydrogen up to 7.7 wt%, approaching the U.S. Department of Energy (DOE) target of 9 wt% by the year 2015, and the average binding energies of H₂ molecules lying in the range of 0.1–0.2 eV/H₂ are favorable for the reversible hydrogen adsorption/desorption at ambient conditions. It is also pointed out that when allowed to interact with each other, the agglomeration of Li-decorated (AlN)_n nanocages would lower the hydrogen storage capacity.     

A novel lithium decorated N-doped 4,6,8-biphenylene for reversible hydrogen storage: Insights from density functional theory

Two-dimensional (2D) carbon-based (C-based) and carbon-nitrogen (C–N) materials have great potential in the energy harvest and storage fields. We investigate a novel carbon biphenylene (C468) consisting of four-, six- and eight-membered rings of sp² carbon atoms (Fan et al., Science, 372:852-6 (2021)) for hydrogen storage. Using first-principles based Density functional theory calculations, we study the geometrical and electronic properties of C468 and N-doped C468. Lithium (Li) atoms were symmetrically adsorbed on both sides of the substrate, and their adsorption positions were determined. The maximum gravimetric density of hydrogen (H₂) adsorbed symmetrically on both sides of Li atom was studied within the scope of physical adsorption process (−0.2 eV/H₂ ∼ −0.6 eV/H₂). Li-decorated C468 can adsorb 8 upper hydrogen molecules and 8 lower hydrogen molecules, and Li-decorated N-doped C468 can adsorb 9 upper hydrogen molecules and 9 lower hydrogen molecules. The gravimetric densities of Li-decorated C468 and Li-decorated N-doped C468 can reach 9.581 wt% and 10.588 wt%, respectively. Our findings suggest significant insights for using Li-decorated C468 and Li-decorated N-doped C468 as hydrogen storage candidates and effectively expand the application scope of C-based materials and C–N materials.     

A DFT-D3 investigation on Li,Na, and K decorated C6O6Li6 cluster as a new promising hydrogen storage system

Because of the increasing demand for energy sources, searching for reversible and high-capacity hydrogen storage materials plays a vital role in the extensively utilizing of hydrogen as a clean energy source. In this study, dispersion-corrected density functional theory (DFT-D3) calculations are utilized to examine the possibility of storing H₂ molecules on Li, Na, and K alkali metals decorated C₆O₆Li₆ cluster. To evaluate H₂ adsorption capability, the adsorption energies, electron density difference iso-surfaces, and charge-transfers are calculated and discussed. The results indicate that a hydrogen molecule is physisorbed on the Li@C₆O₆Li₆, Na@C₆O₆Li₆, and K@C₆O₆Li₆ with average adsorption energies of −0.264, −0.150, and −0.109 eV, respectively. Double-sided alkali metal atoms decoration can lead to the maximum gravimetric density of 15.68, 14.49, and 13.79 wt% for 2Li@C₆O₆Li₆–8H₂, 2Na@C₆O₆Li₆–10H₂, and 2K@C₆O₆Li₆–12H₂ complexes, respectively. Finally, desorption temperatures reveal that the systems can operate as reversible hydrogen storage materials.     

Li decorated penta-silicene as a high capacity hydrogen storage material: A density functional theory study

The H₂ adsorption characteristics of Li decorated single-sided and double-sided penta-silicene are predicted via density functional theory (DFT). The orbital hybridization results in Li atom strongly bind onto the surface of the penta-silicene with a large binding energy and it keeps the decorated Li atoms from aggregation. Moreover, Li decorated double-sided penta-silicene can store up to 12H₂ molecules with the average hydrogen adsorption energy of ?0.220 eV/H₂ and hydrogen uptake capacity of 6.42 wt%, respectively. The ab initio molecular dynamics (AIMD) simulations demonstrate the H₂ molecules are released gradually from the substrate material with the increasing simulation time and the calculated desorption temperature T_D is 281 K in the suitable operating temperature range. Our explorations confirm that Li decorated penta-silicene can be regarded as a promising hydrogen storage candidate for hydrogen storage applications.     

Density functional theory study of reversible hydrogen storage in monolayer beryllium hydride by decoration with boron and lithium

The hydrogen storage capacity of M-decorated (M = Li and B) 2D beryllium hydride is investigated using first-principles calculations based on density functional theory. The Li and B atoms were calculated to be successfully and chemically decorated on the Surface of the α-BeH₂ monolayer with a large binding energy of 2.41 and 4.45eV/atom. The absolute value was higher than the cohesive energy of Li and B bulk (1.68, 5.81eV/atom). Hence, the Li and B atoms are strongly bound on the beryllium hydride monolayer without clustering. Our findings show that the hydrogen molecule interacted weakly with B/α-BeH₂(B-decorated beryllium hydride monolayer) with a low adsorption energy of only 0.0226 eV/H₂ but was strongly adsorbed on the introduced active site of the Li atom in the decorated BeH₂ with an improved adsorption energy of 0.472 eV/H₂. Based on density functional theory, the gravimetric density of 28H₂/8li/α-BeH₂) could reach 14.5 wt.% higher than DOE's target of 6.5 wt. % (the criteria of the United States Department of Energy). Therefore, our research indicates that the Li-decorated beryllium hydride monolayer could be a candidate for further investigation as an alternative material for hydrogen storage.     

The theoretical research of hydrogen storage capacities of Cu3Bx (X=1–4) compounds under ambient conditions

The hydrogen adsorption and storage of Cu₃B_x (X = 1–4) compounds have been computationally investigated at B3LYP-D3/6-311G (3df, 3pd) level. The most stable compounds of Cu₃B_x (X = 1–4) can adsorb 16, 11, 15, and 9 hydrogen molecules with H₂ gravimetric densities of 13.80, 9.46, 11.94, 7.20 wt%, respective. Their average adsorption energies are in the range of 0.26–0.43 eV/H₂. The Gibbs free energy corrected adsorption energies indicate that the maximum adsorption of Cu₃B_x (X = 1–4) are energetically favorable under ambient conditions. Atom-centered density matrix propagation (ADMP) molecular dynamics simulations are used to analyzed the real time dynamics of H₂ and Cu₃B_x (X = 1–4). We can find that Cu₃B_x (X = 1–4) can bind with 4–5 H₂ within 1000 fs at 200 K.     

Hydrogen adsorption of Li functionalized Covalent Organic Framework-366: An ab initio study

This work deals with the investigations of hydrogen adsorption energies of the Li functionalized Covalent Organic Framework-366 (COF-366) by using the density functional theory method. Based on total energy calculations, it was found that Li atom is preferentially trapped at the center site of the tetra(p-amino-phenyl) porphyrin and the onN site of a terephthaldehyde chain. Moreover, hydrogen adsorption energies per H₂ for 1–3 H₂ loadings range from 0.03 to 0.22 eV. According to ab initio molecular dynamics simulations, our results found that hydrogen capacities of Li functionalized COF-366 at ambient pressure are 2.06, 1.58, and 1.05 wt% for 77, 150 and 298 K, respectively.     

A density functional theory and grand canonical Monte Carlo simulations study the hydrogen storage on the Li-decorated net-τ

To find ideal hydrogen storage media, hydrogen storage performance of Li decorated net-τ has been investigated by first-principles calculations. Maximum 6 Li atoms are adsorbed on net-τ, with the average binding energy of 2.15 eV for per Li atom. Based on 6Li-decorated net-τ, up to twenty H₂ molecules are adsorbed, with a high H₂ storage capacity of 12.52 wt% and an appropriate adsorption energy of 0.21 eV/H₂. Finally, H₂ uptake performance is measured by GCMC simulations. Our results suggest that Li-decorated net-τ may be a promising hydrogen storage medium under realistic conditions.     

Al-decorated carbon nanotube as the molecular hydrogen storage medium

Al-decorated, single-walled carbon nanotube has been investigated for hydrogen storage applications by using Density Functional Theory (DFT) based calculations. Single Al atom-decorated on (8,0) CNT adsorbs upto six H₂ molecules with a binding energy of 0.201 eV/H₂. Uniform decoration of Al atom is considered for hydrogen adsorption. The first Al atom has a binding energy of 1.98 eV on (8,0) CNT and it decreases to 1.33 eV/Al and 0.922 eV/Al respectively, when the number of Al atoms is increased to four and eight. Each Al atom in (8,0) CNT-8Al adsorbs four H₂ molecules, without clustering of Al atoms, and the storage capacity reaches to 6.15 wt%. This gravimetric storage capacity is higher than the revised 2015 target of U.S Department of Energy (DOE). The average adsorption binding energy of H₂ in (8,0) CNT-8(Al+4H₂), i.e. 0.214 eV/H₂, lies between 0.20 and 0.60 eV/H₂ which is required for adsorbing and desorbing H₂ molecules at near ambient conditions. Thus, Al-decorated (8,0) CNT is proposed as a good hydrogen storage medium which could be useful for onboard automobile applications, at near ambient conditions.     

Hydrogen adsorption on Li decorated graphyne-like carbon nanosheet: A density functional theory study

Motivated by novel graphyne-like carbon nanostructure C₆₈-GY, spin-polarized DFT calculations with dispersion-correction were performed to investigate the hydrogen adsorption capacity of Li decorated C₆₈-GY nanosheet. The binding energy between Li and C₆₈-GY was larger than the cohesive energy of bulk metal, indicating Li atoms would prefer to separately attached on C₆₈-GY. The ab initio molecular dynamics simulation has been performed to confirm the stability of Li/C complex. When five Li atoms decorated on C₆₈-GY, 14H₂ molecules were captured. The maximum hydrogen storage density was 8.04 wt% with an average hydrogen adsorption energy of −0.227 eV per H₂. The positively charged Li atoms aroused electrostatic field and induced the polarization of H₂. It was notable to observe strong hybridization between the main peak of H-1s orbitals with Li below Fermi level, which was responsible for the enhancement of hydrogen binding energy, indicating its potential application on hydrogen storage.     

Y-decorated MoS2 monolayer for promising hydrogen storage: A DFT study

The potential hydrogen storage performance of the constructed Y-decorated MoS₂ was investigated via first-principles density functional theory (DFT) calculations. The Y could be stably decorated on the MoS₂ monolayer with adsorption energy being ?4.82 eV, the absolute value of which was higher than the cohesive energy of bulk Y. The introduced H₂ interacted strongly with the Y-decorated MoS₂ with an elongated bond length and reasonable adsorption energy being 0.792 Å and ?0.904 eV, respectively. There would be four H₂ in maximum adsorbed and stored on the Y-decorated MoS₂ with average adsorption energy being ?0.387 eV. Moreover, the hydrogen gravimetric capacity of the MoS₂ with full Y coverage on each side could be improved to be 4.56 wt% with average adsorption energy being ?0.295 eV. Our study revealed that the MoS₂ decorated with Y could be a potential material to effectively store H₂ with promising gravimetric density.     

A first-principles study of Li and Na co-decorated T4,4,4-graphyne for hydrogen storage

To obtain high hydrogen storage performance, Li and Na co-decorated T4,4,4-graphyne have been studied by the method of first-principles calculations in this paper. Li and Na atoms are bound on hexagonal ring and acetylenic ring included in T4,4,4-graphyne, with the average adsorption energy of 1.73 and 2.38 eV, respectively. Our calculations show that the maximum gravimetric density of H₂ uptake is 10.46 wt%, and an appropriate adsorption energy is reached. Moreover, by plotting charge density differences, it is found that the induced electric field between Li/Na and T4,4,4-graphyne can enhance the adsorption for hydrogen molecule. Furthermore, this complex is thermodynamic stable at room temperature, which is certificated by molecule dynamics simulation. Our results demonstrate that Li and Na co-decorated T4,4,4-graphyne is an alternative material for hydrogen storage.