H2 Desorption Research Articles

DFT study of Pd4 and Pd3P supported on modified graphene for hydrogen storage

In this study, density functional theory (DFT) calculations were utilized to investigate the feasibility of using Pd4 and Pd3P clusters for hydrogen adsorption and spillover, with a focus on their potential as hydrogen storage materials. Four different modified graphene slabs were examined and the results showed that pristine graphene (PG), phosphorus-doped pristine graphene (PPG), and phosphorus-doped single vacancy graphene (PSVG) are not suitable surfaces for decorating Pd4 and Pd3P clusters for hydrogen adsorption and spillover. Our results showed that Pd4/SVG and Pd3P/SVG materials exhibited high binding energies of −5.37 eV and −4.49 eV respectively, which indicated their potential to prevent desorption of Pd–H hydrides with H2 desorption. The stability of Pd4/SVG and Pd3P/SVG was also confirmed by molecular dynamics at a temperature of 500 K. Moreover, the decoration of Pd3P on SVG resulted in hydrogen adsorption with an average energy of 0.25 eV/H2, falling within the ideal useable range. At full saturation, the energy barrier for spillover decreased from 0.86 eV to 0.75 eV, and the system could store up to 5.74 wt% of hydrogen. Furthermore, the spillover reaction occurred rapidly at room temperature within 0.68 s. Our findings suggest that Pd3P decorated single vacancy graphene represents a promising hydrogen storage material, providing valuable insights into the development of effective hydrogen storage technologies.

The Catalytic Effect of Vanadium on Sorption Properties of MgH2-Based Nanocomposites Obtained Using Low Milling Time.

The effects of catalysis using vanadium as an additive (2 and 5 wt.%) in a high-energy ball mill on composite desorption properties were examined. The influence of microstructure on the dehydration temperature and hydrogen desorption kinetics was monitored. Morphological and microstructural studies of the synthesized sample were performed by X-ray diffraction (XRD), laser particle size distribution (PSD), and scanning electron microscopy (SEM) methods, while differential scanning calorimetry (DSC) determined thermal properties. To further access amorph species in the milling blend, the absorption spectra were obtained by FTIR-ATR analysis (Fourier transform infrared spectroscopy attenuated total reflection). The results show lower apparent activation energy (Eapp) and H2 desorption temperature are obtained for milling bland with 5 wt.% added vanadium. The best explanation of hydrogen desorption reaction shows the Avrami-Erofeev model for parameter n = 4. Since the obtained value of apparent activation energy is close to the Mg-H bond-breaking energy, one can conclude that breaking this bond would be the rate-limiting step of the process.

Critical dehydrogenation steps of perhydro-[formula omitted]-ethylcarbazole on Ru(0001) surface

Understanding of the critical atomistic steps during the dehydrogenation process of liquid organic hydrogen carriers (LOHCs) is important to the design of cost-efficient, high-performance LOHC catalysts. Based on the density functional theory (DFT) we studied the thermodynamics and kinetics of the complete dehydrogenation path of perhydro-N-ethylcarbazole (12H-NEC) on Ru(0001) surface, involving the adsorption of 12H-NEC, the discharge of H ions onto Ru surface, and the desorption of H2 and hydrogen-lean NEC. It was found that the bonding of nH-NEC is significantly strengthened for n≤4 because of the flat aromatic ring. Although the whole dehydrogenation process is endothermic, the release of H from nH-NEC, with H adsorbed onto the Ru surface, was found to be exothermic. The desorption of flat, hydrogen-lean NEC, which costs ∼255 kJ/mol, was identified as the most energy demanding step. In addition, the effect of surface morphology on adsorption was studied based on an amorphous surface model. Overall, the results imply more efficient dehydrogenation could be achieved from relatively weak bonding of NEC to catalysts, either through engineering catalyst surface (such as surface defects or smaller catalyst particles) or different catalyst materials. Our calculations also revealed possible dealkylation at elevated temperatures.

Hydrogen storage in Na decorated heteroborospherene Si4B32: Insights from density functional study

This article investigates the structural stability and hydrogen adsorption performance of Na-decorated heteroborospherene Si4B32 using density functional theory (DFT) methods. DFT calculations demonstrate that six sodium (Na) atoms can successfully and chemically bind to the surface of heteroborospherene Si4B32, exhibiting a substantial average binding energy of 2.465 eV without clustering. Moreover, the resulting Na6Si4B32 structure retains its integrity even after absorbing up to 30 hydrogen (H2) molecules, with an average adsorption energy of 0.251 eV/H2. Utilizing DFT analysis, the gravimetric density of Na6Si4B32·(H2)30 can reach 9.143 wt%. Additionally, employing ab initio molecular dynamics (AIMD) simulations, we find that a significant fraction of the H2 molecules desorb from Na6Si4B32 at 300K within 1000 fs. These findings establish the potential of Na-decorated heteroborospherene Si4B32 as a promising candidate for reversible hydrogen storage. The successful binding of Na atoms without clustering and the substantial H2 adsorption capacity, coupled with the structural stability and facile H2 desorption observed at moderate temperatures, highlight the viability of this material for practical hydrogen storage applications.

Metal Hydride Hydrogen Storage (Compression) Units Operating at Near-Atmospheric Pressure of the Feed H2

Metal hydride (MH) hydrogen storage and compression systems with near-atmospheric H2 suction pressure are necessary for the utilization of the low-pressure H2 produced by solid oxide electrolyzers or released as a byproduct of chemical industries. Such systems should provide reasonably high productivity in the modes of both charge (H2 absorption at PL ≤ 1 atm) and discharge (H2 desorption at PH = 2–5 atm), which implies the provision of H2 equilibrium pressures Peq < PL at the available cooling temperature (TL = 15–20 °C) and, at the same time, Peq > PH when heated to TH = 90–150 °C. This work presents results of the development of such systems based on AB5-type intermetallics characterized by Peq of 0.1–0.3 atm and 3–8 atm for H2 absorption at TL = 15 °C and H2 desorption at TH = 100 °C, respectively. The MH powders mixed with 1 wt.% of Ni-doped graphene-like material or expanded natural graphite for the improvement of H2 charge dynamics were loaded in a cylindrical container equipped with internal and external heat exchangers. The developed units with a capacity of about 1 Nm3 H2 were shown to exhibit H2 flow rates above 10 NL/min during H2 charge at ≤1 atm when cooled to ≤20 °C with cold water and H2 release at a pressure above 2 and 5 atm when heated to 90 and 120 °C with hot water and steam, respectively.

Highly dispersed Pt boosts active FexN formation in ammonia decomposition

Ammonia decomposition plays an important role in hydrogen production, especially in the context of a hydrogen economy. Fe-based catalysts are a popular choice due to their affordability and moderate activity, making them attractive for large-scale applications. However, the transformation of Fe-based catalysts into more active FexN species can be slow, resulting in a prolonged induction period. To address this issue, we investigated the effects of Pt addition on FexN formation in ammonia decomposition. Our results show that even a slight Pt addition significantly enhances the FexN formation rate, increasing it over threefold. Pt aids in H2 desorption via reverse spillover, which, in turn, exposes more Fe surface sites where nitridation occurs, leading to the formation of iron nitride. Characterization via High-angle annular dark-field imaging scanning transmission electron microscopy, X-ray diffraction, and in situ X-ray absorption spectroscopy (XAS) revealed the formation of Fe2N as active species, whereas temperature-programmed hydrogen desorption, temperature-programmed reduction by hydrogen, and in situ XAS supported the existence of H reverse spillover and spillover effects. Overall, our study provides an improved understanding of the active species formation mechanism of Fe catalysts in ammonia decomposition and offers a simple strategy for improving their catalytic performance.

Temperature-dependent ethylene dissociative adsorption on ruthenium

The dissociative adsorption of ethylene onto Ru(111) at different temperatures was computed systematically at the first time. At 105 K, ethylene dissociative adsorption has the co-adsorbed CH2C*+2H* and CH3C*+H* as the first and second stable surface intermediates. At over 330 K, CH3C*+H* is converted back into CH2C* accompanied by H2 desorption and the subsequent dissociation of CH2C* into HCC*, HC*+C* and 2C*. The computed Arrhenius activation barriers of the dissociation of CH2CH2 (0.18 vs. 0.22 ± 0.04 eV) and CH3C (0.54 vs. 0.52 ± 0.04 eV) agree perfectly with the available experimental values, and CH3C* represents the most stable surface species. Under CO co-adsorption, the most stable surface species are the co-adsorbed CH3C*+H*+3CO*. It is found that CO co-adsorption promotes H2 desorption and stabilizes CH3C* by blocking the surface sites for dissociation and raises the dissociation barrier compared to the clean surface (0.78 vs 0.54 eV). Brønsted–Evans–Polanyi relationship between the activation Gibbs free energy barrier and reaction Gibbs free energy is found for CH2C*+2H*+nCO* = CH3C*+H*+nCO* and CH2C*+2H*+nCO* = HCC*+3H*+nCO* (n = 0–3). Ethylene adsorption has di-σ and π adsorption configurations in very close energy, and H2 has adsorption energy of about 0.90 eV.

Tailoring hydrogen adsorption and desorption properties of Li-doped SV (single vacancy) monolayer h-BN systems using ab initio calculations

This study uses density functional theory (DFT) technique to examine the hydrogen molecules (H2) storage on Li-decorated h-BN monolayer. The results of DFT have proven that Li-doped h-BN system can hold up to 9H2 with the adsorption energy lying in between −0.31 eV and −0.24 eV/H2 at ambient condition. However, the calculated average adsorption energy for 9H2 is −0.240 eV/H2 with hydrogen storage capacity of 5.96 wt.%, which is according to the United States Department of Energy. Partial density of state was computed for each configuration to provide additional justifications for the H2 storage on Li-doped h-BN monolayer. The hybridization shows a significant interaction between H2 and Li atom, and most of their hybrid peaks were observed in the energy range from −7.5 to −1 eV. Moreover, the H2 desorption simulations achieved via the ab initio molecular dynamics. The computed desorption temperature TD is 306 °K, which is a suitable operating temperature. Hence, our research demonstrates that Li-doped h-BN is a thermally stable and viable hydrogen storage material for hydrogen storage systems.

Hydrangea-like NiO@KNbO3 as catalyst doping for MgH2: Boosting hydrogen storage performance

MgH2 is regarded as one of the most favorable materials for hydrogen storage caused by its safety, high efficiency, considerable capacity for storing hydrogen, and low cost. However, the application of this material is limited owing to subpar thermodynamics and kinetics, which can be improved via combination with other materials. A hydrangea-like NiO@KNbO3 was prepared by solvent thermal, hydrothermal, and calcination methods. Then, different amounts of NiO@KNbO3 (3, 5, 7, and 10 wt %) were added to MgH2 using ball-milling. MgH2 composite material doped with 5 wt % NiO@KNbO3 exhibits the most superior hydrogen storage performance, with a hydrogen absorption capacity of 4.95 wt % H2 within 5 min at 150 ℃ and 1.5 MPa H2 pressure. Furthermore, H2 release started approximately at 175 °C with 5.96 wt % H2 at 300 °C. The composite's H2 desorption activation energy was decreased to 71.75 kJ/mol. The Mg2NiH4/Mg2Ni generated in situ can serve as a "hydrogen pump" by creating numerous activation sites and pathways for hydrogen diffusion, thereby facilitating H2 dissociation during the process of hydrogen absorption. Additionally, the NiO@KNbO3-doped MgH2 samples exhibited excellent integrated hydrogen storage properties due to the combined effect of KNbO3 and the in situ formed NbO. The study provides clear evidence that NiO@KNbO3, a bimetallic oxide, can effectively enhance the hydrogen storage performance of MgH2 as an additive. Furthermore, the straightforward synthesis of NiO@KNbO3 offers guidance for the development of high-performance oxide catalysts that can improve the properties of MgH2.

Calcium-Decorated Polygon-Graphenes for Hydrogen Storage

We performed first-principles calculations to investigate hydrogen (H2) storage properties of bare and calcium (Ca)-decorated polygon-graphenes, i.e., biphenylene and ψ-graphene monolayers consisting of polygons, from tetragons to octagons. In pristine forms, both biphenylene and ψ-graphene bind H2 weakly. However, upon Ca doping, biphenylene adsorbed up to five H2 molecules regardless of polygonal sites, whereas ψ-graphene anchored up to six and five H2 molecules to pentagonal and heptagonal sites, respectively. In all the cases, the H2 binding energy was ∼0.30 eV, enabling reversible room-temperature H2 storage. The H2 storage capacity can reach ∼6.8 and ∼4.2 wt % for Ca-decorated biphenylene and ψ-graphene, respectively. Using equilibrium thermodynamics, we showed the adsorption and desorption of H2 at 300 and 380 K under ambient pressure, respectively. This clearly indicates that Ca-decorated 2D sp2 carbon sheets with polygons (biphenylene, ψ-graphene) could be used as promising H2 storage materials.

Cascade Anchoring Strategy for Fabricating High-Loading Pt Single Atoms as Bifunctional Catalysts for Electrocatalytic Hydrogen Evolution and Oxygen Reduction Reactions.

Carbon supports containing single-atomically dispersed metal-Nx (denoted as MSAC-NxCy, x, y: coordination number) have attracted increasing attention due to their superb performance in heterogeneous catalysis. However, large-scale controllable preparation of single-atom catalysts (SACs) with high concentration of supported metal-Nx is still a big challenge because of the metal atom agglomeration during synthesis at high density and temperatures. Herein, we report a stepwise anchoring strategy from a 1,10-o-phenanthroline Pt chelate to an Nx-doped carbon (NxCy) with isolated Pt single-atom catalysts (PtSAC-NxCy) containing Pt loadings up to 5.31 wt % measured via energy-dispersive X-ray spectroscopy (EDS). The results show that 1,10-o-phenanthroline Pt chelate predominantly contributes to the formation of chelate single metal sites that bind tightly to platinum ions to prevent metal atoms from aggregating, resulting in high metal loading. The high-loading PtSAC-NxCy exhibits a low hydrogen evolution (HER) overpotential of 24 mV at 0.010 A cm-2 current density with a relatively small Tafel gradient of 60.25 mV dec-1 and excellent stable performance. In addition, the PtSAC-NxCy catalyst shows excellent oxygen reduction reaction (ORR) catalytic activity with good stability, represented by the fast ORR kinetics under high-potential conditions. Theoretical calculations show that PtSAC-NC3 (x = 1, y = 3) offers a lower H2O activation energy barrier than Pt nanoparticles. The adsorption free energy of a H atom on a Pt single-atom site is lower than that on a Pt cluster, which is easier for H2 desorption. This study provides a potentially powerful cascade anchoring strategy in the design of other stable MSAC-NxCy catalysts with high-density metal-Nx sites for the HER and ORR.

Metallized HOT-graphene: A novel reversible hydrogen storage medium with ultrahigh capacity

By performing first-principles calculations, we have researched the hydrogen storage capability of the alkali metals (Li, Na, K) and alkali-earth metal (Ca) decorated HOT graphene, a novel excellent Dirac semimetal which consists of hexagon, octagon and tetragon carbon rings. Metal Li, Na, K and Ca can be strongly bonded on HOT graphene with very large binding energy instead of forming clusters. Each metal can absorb maximum of 3, 5, 5 and 6 H2, respectively, and the average adsorption energy are all in the reversible hydrogen storage range. In the case of double-sided adsorption, 16 metals can be loaded on 2 × 2 × 1 supercell of HOT graphene and then come into being gravimetric H2 uptake of 12.34 wt%, 14.59 wt%, 11.83 wt% and 13.71 wt% for Li, Na, K and Ca decorated HOT graphene, separately, which significantly exceeds the DoE standard (6.5 wt%). The analysis of the calculated electronic density of states and charge transfer indicates that the strong bonding between metal atoms and HOT graphene is derived from orbital interaction concerning charge transfer, while the adsorption of hydrogen molecule attributes to the polarization of hydrogen molecule near ionized metal atoms and thus electrostatic and van der Waals interactions render H2 to adsorb in the metal atoms. Finally, the integrity of metal decorated HOT graphene based on ab-initio molecular dynamics (AIMD) calculation at corresponding H2 desorption temperatures indicates that the feasibility of practical application of metallized HOT-graphene system as reversible hydrogen storage medium with ultrahigh capacity. And these findings could be expected to facilitate experimental studies.

Theoretical insights into the methane catalytic decomposition on graphene nanoribbons edges.

Catalytic methane decomposition (CMD) is receiving much attention as a promising application for hydrogen production. Due to the high energy required for breaking the C-H bonds of methane, the choice of catalyst is crucial to the viability of this process. However, atomistic insights for the CMD mechanism on carbon-based materials are still limited. Here, we investigate the viability of CMD under reaction conditions on the zigzag (12-ZGNR) and armchair (AGRN) edges of graphene nanoribbons employing dispersion-corrected density functional theory (DFT). First, we investigated the desorption of H and H2 at 1200K on the passivated 12-ZGNR and 12-AGNR edges. The diffusion of hydrogen atom on the passivated edges is the rate determinant step for the most favourable H2 desorption pathway, with a activation free energy of 4.17eV and 3.45eV on 12-ZGNR and 12-AGNR, respectively. The most favourable H2 desorption occurs on the 12-AGNR edges with a free energy barrier of 1.56eV, reflecting the availability of bare carbon active sites on the catalytic application. The direct dissociative chemisorption of CH4 is the preferred pathway on the non-passivated 12-ZGNR edges, with an activation free energy of 0.56eV. We also present the reaction steps for the complete catalytic dehydrogenation of methane on 12-ZGNR and 12-AGNR edges, proposing a mechanism in which the solid carbon formed on the edges act as new active sites. The active sites on the 12-AGNR edges show more propensity to be regenerated due lower free energy barrier of 2.71eV for the H2 desorption from the newly grown active site. Comparison is made between the results obtained here and experimental and computational data available in the literature. We provide fundamental insights for the engineering of carbon-based catalysts for the CMD, showing that the bare carbon edges of graphene nanoribbons have performance comparable to commonly used metallic and bi-metallic catalysts for methane decomposition.

Molecular-level understanding of carbon materials by temperature-programmed desorption

A wide variety of surface functional groups, such as oxygen-containing ones and hydrogen, exist at the graphene edge sites of carbon materials. Because the presence of these functional groups greatly affects the chemical properties of carbon-based materials produced from them, knowledge of the edge site state is essential to understand carbon chemistry. This review describes the analyses of edge sites and carbon-material structures by temperature-programmed desorption (TPD). Deuterium labeling of the protonic hydrogen of oxygen-containing functional groups enables the precise identification of the chemical structure of edge sites. Furthermore, the spatial distribution of edge sites in the carbon structure can be determined by the kinetic analysis of H2 desorption spectra collected at temperatures above 1000 °C. The average size of graphene sheets forming the carbon can be estimated from the number of edge sites. The TPD-based analytical approaches described in this paper help provide a better understanding of the carbon structure at the molecular level.

Targeted Modulation of Competitive Active Sites toward Nitrogen Fixation via Sulfur Vacancy Engineering Over MoS2

AbstractElectrocatalytic nitrogen reduction reaction (NRR) offers an environmentally benign and sustainable alternative for NH3 synthesis. However, developing NRR electrocatalysts with both high activity and selectivity remains a significant challenge. Guided by the density functional theory (DFT) calculations and further verified by the experiment, a modulated MoS2 with well‐controlled S vacancies (MoS2‐Vs) is prepared as an excellent electrocatalyst for NRR, where both the activity and selectivity of NRR mightily rely on the S‐vacancy concentration. The optimized catalyst (MoS2‐7H) in a suitable S‐vacancy concentration (17.5%) is empowered with an excellent NRR activity (NH3 yield rate: 66.74 µg h−1 mg−1 at −0.6 V) and selectivity (Faradic efficiency (FE): 14.68% at −0.5 V). Further mechanistic study reveals that the NRR performance is powerfully concentration‐dependent since its activity is enhanced due to the S‐vacancy‐strengthened N2 adsorption and reduced reaction energy barrier. Simultaneously, its selectivity is synchronously improved by the steadily enhanced NRR activity and inversely suppressed hydrogen evolution reaction through limiting H2 desorption kinetics, which sets it markedly apart from other reported defective MoS2‐based catalysts.

Effet of hematite (Fe2O3) from natural iron ore as a catalyst in MgH2 as hydrogen storage materials

The main obstacle that hinders the application of fuel cell fuels for vehicles today is the hydrogen storage tube. Therefore, this paper will report the results of a study on MgH2-based hydrogen storage materials with Fe2O3 catalyst inserted (5 wt%, 10 wt%, 15wt%) and prepared by mechanical alloying technique for 10 hours. Fe2O3 samples were obtained from the Lhoong Setia Mining site in Jantang Village, Lhoong, Aceh Besar. The initial sample separation process was carried out manually using a bar magnet. Furthermore, hematite extraction was carried out with the addition of 1M HCL and NaOH each. Then the milling process of MgH2-Fe2O3 samples was carried out using a planetary ball mill. The results of the X-ray diffraction test showed that the MgH2 phase was the most dominant/mainstream phase. Thermal testing with DSC showed that the H2 desorption process experienced a decrease in temperature from 194.56 °C with a milling time variation of 7 hours.

Lithium and phosphorus-functionalized graphitic carbon nitride monolayer for efficient hydrogen storage: A DFT study

We have explored the consequence of lithium and phosphorous functionalization on the graphitic carbon nitride (g-C3N4) monolayer for hydrogen storage using density functional theory. Both pristine and Li and P decorated g-C3N4 show a semiconductor nature. The substantial overlap between the s orbital of Li and the p orbital of nitrogen near the Fermi level shows the binding between Li and the g-C3N4. The repositioning of HOMO and LUMO is noticed in the Li and P decorated g-C3N4. The Bader charge analysis indicates the charge allocation from the Li and P atom to the g-C3N4, which results in the adsorption of H2 by electrostatic interaction. The hydrogen storage capacity of 5.78 wt% is obtained after functionalizing Li and P into the g-C3N4. The obtained adsorption energies for the H2 adsorption and the H2 desorption temperature confirm that Li and P functionalized g-C3N4 is a fascinating candidate for the reversible loading of H2 at ambient conditions.

Metal Hydride Composite Structures for Improved Heat Transfer and Stability for Hydrogen Storage and Compression Applications

Metal alloys and intermetallic compounds offer an attractive method for safely storing hydrogen (H2). The metal alloys absorb H2 into their structure, often swelling and fracturing as a result of phase transformation during hydride formation/decomposition cycles. The absorption of H2 is an exothermic process, requiring the effective and efficient removal of heat. This can be challenging as heat transfer to/from powdered beds is notoriously difficult, and often limited by poor thermal conductivity. Hence, the observed reaction kinetics for absorption and desorption of H2 is dominated by heat flow. The most common method for improving the thermal conductivity of the alloy powders is to prepare them into composite structures with other high thermal conductivity materials, such as carbons and expanded natural graphite. Such composite structures, some also combined with polymers/resins, can also mitigate safety issues related to swelling and improve cyclic durability. This paper reviews the methods that have been used to prepare such composite structures and evaluates the observed impact on thermal conductivity.

In situ diffraction studies of phase-structural transformations in hydrogen and energy storage materials: An overview

The paper presents an overview of advanced in situ diffraction studies as a highly valuable tool to probe the structure and reacting mechanisms of hydrogen and energy storage materials. These studies offer benefits from the use of a high flux diffraction beam in combination with high resolution measurements, and allow, even when using very small samples, establishing the mechanism of the phase-structural transformations and their kinetics based on a rapid data collection for the various charge-discharge states at variable test conditions. The applied conditions include a broad range of hydrogen/deuterium pressures, from vacuum to high pressures reaching 1000 bar H2/D2, and temperatures, from cryocooling (2 K) to as high as 1273 K (1000 °C). Simultaneously, various state-of-charge and discharge are probed when studying metal-H/D systems for hydrogen/deuterium gas storage and as anode electrodes of metal hydride batteries. The range of the studied systems includes but is not limited to the AB5, AB2 Laves type, AB, equiatomic ternary ABC intermetallics and Mg-containing layered AB3 structures and composites. Prospects on Li-ion full cells are considered as well. Interrelations between the structure and hydrogen storage performance, including maximum and reversible H storage capacity, hysteresis of hydrogen absorption and desorption, H2 absorption and desorption in dynamic equilibrium conditions, are considered and related to the ultimate goal of optimisation of the H storage behaviours of the advanced H storage materials. Numerous contributions of Dr. Michel Latroche to the field are highlighted, particularly in in situ studies during electrochemical transformations. The paper summarises a long-standing collaboration of the co-authors in the field, which also included 29 joint topical publications with Dr. Michel Latroche, and references 163 original publications.

Reversible hydrogen storage in Li‐functionalized [2,2,2]paracyclophane at cryogenic to room temperatures: A computational quest

AbstractIn this work, we have studied the H2 adsorption‐desorption properties and storage capacities of [2,2,2]paracyclophane (PCP222) functionalized with Li atoms, using dispersion‐corrected density functional theory and molecular dynamic simulation. The Li atom was found to bond strongly with the benzene ring of PCP222 via Dewar interaction. Subsequently, the calculation of the diffusion energy barrier revealed a significantly high energy barrier of 1.38 eV, preventing the Li clustering on PCP222. The host material, PCP222‐3Li, adsorbed up to 15H2 molecules via charge polarization mechanism with an average adsorption energy of 0.145 eV/5H2, suggesting physisorption type of adsorption. The PCP222 functionalized with three Li atoms showed a maximum hydrogen uptake capacity of up to 8.32 wt%, which was fairly above the US‐DOE criterion. The practical H2 storage estimation revealed that the PCP222‐3Li desorbed 100% of adsorbed H2 molecules at the temperature range of 260 K to 300 K and pressure range of 1 bar to 10 bar. The maximum H2 desorption temperature estimated by the Vant‐Hoff relation was found to be 219 K and 266 K at 1 bar and 5 bar, respectively. The ADMP molecular dynamics simulations assured the reversibility of adsorbed H2 and the structural integrity of the host material at sufficiently above the desorption temperature (300 K and 500 K). Therefore, the Li‐functionalized PCP222 can be considered as a thermodynamically viable and potentially reversible H2 storage material below room temperature.