Improved design of metal-organic frameworks for efficient hydrogen storage at ambient temperature: A multiscale theoretical investigation

A multiscale theoretical technique is used to examine the combination of different approaches for hydrogen storage enhancement in metal-organic frameworks at room temperature and high pressure by implementation lithium atoms in linkers. Accurate MP2 calculations are performed to obtain the hydrogen binding sites and parameters for the following grand canonical Monte Carlo (GCMC) simulations. GCMC calculations are employed to obtain the hydrogen uptake at different thermodynamic conditions. The results obtained demonstrate that the combination of different approaches can improve the hydrogen uptake significantly. The hydrogen content reaches 6.6 wt% at 300 K and 100 bar satisfying DOE storage targets (5.5 wt%).     

Catenated metal-organic frameworks: Promising hydrogen purification materials and high hydrogen storage medium with further lithium doping

Based on the first-principles derived force fields and grand canonical Monte Carlo simulations, we find that the catenated metal-organic frameworks outperform the noncatenated structures, in terms of H₂ separation from other gases (CH₄, CO and CO₂) and H₂ adsorption by Li doping. A system utilizing IRMOF-11 (or IRMOF-13) for hydrogen separation and Li-doped IRMOF-9 for hydrogen storage is therefore proposed, with hydrogen uptake of 4.91 wt% and 36.6 g/L at 243 K and 100 bar for Li-doped IRMOF-9, which is close to the 2017 DOE target. It is promising to find appropriate microporous materials for hydrogen purification and storage at ambient conditions with structure catenated.     

Simulation of hydrogen storage tank packed with metal-organic framework

Hydrogen adsorption in high surface metal-organic framework (MOF) has generated significant interest over the past decade. We studied hydrogen storage processes of MOF-5 hydrogen storage systems with adsorbents of both the MOF-5 powder (0.13 g/cm³) and its compacted tablet (0.30 g/cm³). The charge–discharge cycles of the two MOF-5 adsorbents were simulated and compared with activated carbon. The physical model is based on mass, momentum and energy conservation equations of the adsorbent-adsorbate system composed of gaseous and adsorbed hydrogen, adsorbent bed and tank wall. The adsorption process was modeled using a modified Dubinin–Astakov (D–A) adsorption isotherm and its associated variational heat of adsorption. The model was implemented by means of finite element analysis software Comsol Multiphysics™, and the system simulation platform Matlab/Simulink™. The thermal average temperature from Comsol simulation is used to fill the gap between the system model and the multi-dimensional models. The heat and mass transfer feature of the model was validated by the experiments of activated carbon, the simulated pressure and temperatures are in good agreement with the experimental results. The model was further validated by the metal-organic framework of Cu-BTC and is being extended its application to MOF-5 in this study. The maximum pressure in the powder MOF-5 tank is much higher than that in the activated carbon tank due to the lower adsorbent density of MOF-5 and resulting lower hydrogen adsorption. The maximum pressure in the compacted MOF-5 tank is a little bit lower than that in the activated carbon tank due to the higher adsorbent density and resulting higher hydrogen adsorption. The temperature swings during the charge–discharge cycle of both MOF-5 tanks are higher than that of the activated carbon tank. These are caused mainly by pressure work in the powder MOF-5 tank and by adsorption heat in the compacted MOF-5 tank. For both MOF-5 hydrogen storage systems, the lumped parameter models implemented by Simulink agree well with experimental pressures and with pressures and thermal average temperatures from Comsol simulation.     

Enhancement of hydrogen adsorption by alkali-metal cation doping of metal-organic framework-5

Over the past decade, metal-organic frameworks (MOFs) have been extensively studied as a novel approach to store hydrogen. The large surface area and volume of micropores that are intrinsic to MOFs make them ideal for gas adsorption. In addition, we chemically reduced MOF-5 by doping it with alkali metals (Li, Na, and K). We found that the H₂ uptake capacity of MOF-5 materials doped with Li, Na, and K exceeded that of a neutral framework by 24%, 68%, and 70%, respectively. Notably, at the same levels of doping, the Li⁺-doped framework exhibited the strongest H₂ binding, and the binding strength decreased sequentially in the order Li⁺ > Na⁺ > K⁺.     

Effect of platinum doping of activated carbon on hydrogen storage behaviors of metal-organic frameworks-5

In this work, we prepared platinum doped on activated carbons/metal-organic frameworks-5 hybrid composites (Pt-ACs-MOF-5) to obtain a high hydrogen storage capacity. The surface functional groups and surface charges were confirmed by Fourier transfer infrared spectroscopy (FT-IR) and zeta-potential measurement, respectively. The microstructures were characterized by X-ray diffraction (XRD). The sizes and morphological structures were also evaluated using a scanning electron microscopy (SEM). The pore structure and specific surface area were analyzed by N₂/77 K adsorption/desorption isotherms. The hydrogen storage capacity was studied by BEL-HP at 298 K and 100 bar. The results revealed that the hydrogen storage capacity of the Pt-ACs-MOF-5 was 2.3 wt.% at 298 K and 100 bar, which is remarkably enhanced by a factor of above five times and above three times compared with raw ACs and MOF-5, respectively. In conclusion, it was confirmed that Pt particles played a major role in improving the hydrogen storage capacity; MOF-5 would be a significantly encouraging material for a hydrogen storage medium as a receptor.     

Pd (II) decorated conductive two-dimensional chromium-pyrazine metal-organic framework for rapid detection of hydrogen

The utilization of H₂ for versatile application has demanded highly selective, low cost and rapid hydrogen sensors that are proficient in sensing H₂ near flammability limit. In this report, Cr^IIICl₂(pyrazine)₂ MOF with negatively charged pyrazine linkers in its structure is used for the stabilization of Pd (II) via charge transfer interactions. This material design turned an innocent MOF into selective hydrogen sensor that can respond (through decrease in resistance under dynamic sensing setup) to H₂ in 5–7 s with a detection range of 0.25%–1% H₂ concentration. A correlation of H₂ sensing characteristics and the structure-property relationship is established using density functional theory (DFT) calculations. The calculations suggested that near fermi level in Pd^II@CrPy, the bandwidth increases upon interaction with H₂ thereby the phase space for electron delocalization increases leading to better carrier mobility. This new approach not only yields novel sensing properties but also enables limited usage of precious metal to develop cost-effective sensors.     

Review of hydrogen storage techniques for on board vehicle applications

Hydrogen gas is increasingly studied as a potential replacement for fossil fuels because fossil fuel supplies are depleting rapidly and the devastating environmental impacts of their use can no longer be ignored. H₂ is a promising replacement energy storage molecule because it has the highest energy density of all common fuels by weight. One area in which replacing fossil fuels will have a large impact is in automobiles, which currently operate almost exclusively on gasoline. Due to the size and weight constraints in vehicles, on board hydrogen must be stored in a small, lightweight system. This is particularly challenging for hydrogen because it has the lowest energy density of common fuels by volume. Therefore, a lot of research is invested in finding a compact, safe, reliable, inexpensive and energy efficient method of H₂ storage. Mechanical compression as well as storage in chemical hydrides and absorption to carbon substrates has been investigated. An overview of all systems including the current research and potential benefits and issue are provided in the present paper.     

Metal-organic frameworks (MOFs) and MOFs-derived CuO@C for hydrogen generation from sodium borohydride

Hydrogen gas has been considered as one of the promising sources of energy. Thus, several strategies including the hydrolysis of hydrides have been reported for hydrogen production. However, effective catalysts are highly required to improve the hydrogen generation rate. Two dimensional metal-organic frameworks (copper-benzene-1,4-dicarboxylic, CuBDC), and CuBDC-derived CuO@C were synthesized, characterized and applied as catalysts for hydrogen production using the hydrolysis and methanolysis of sodium borohydride (NaBH₄). CuBDC, and CuO@C display hydrogen generation rate of 7620, and 7240 mlH₂·g_cat⁻¹· min⁻¹, respectively for hydrolysis. While, CuBDC offers hydrogen generation rate of 9060 mlH₂·g_cat⁻¹· min⁻¹ for methanolysis. Both catalysts required short reaction time, and showed good recyclability. The materials may open new venues for efficient catalyst for energy-based applications.     

In-situ one-step synthesis of activated Carbon@MIL-101 (Cr) composites for hydrogen storage

Metal-organic frameworks (MOFs) unlocked new prospects of developing novel adsorbing materials for H₂ storage. However, MOF porosity is not yet fully utilized. To compensate for that disadvantage, we synthesized MIL-101(Cr) MOF-based activated carbon AC@MIL-101 (Cr) composites using in situ hydrothermal method. Different amounts of activated carbon (AC) derived from fir bark were added to adjust the pore structure of the resulting MOF-based composites. The pore number and their sizes increased and decreased, respectively, after pristine MIL-101(Cr) was combined with AC. The surface area and pore volume of pristine MIL-101(Cr) were equal to 2299 m²/g and 1.06 cm³/g, respectively. These values became equal to 3367 m²/g and 1.64 cm³/g after AC was combined with MIL-101(Cr) to form AC@MIL-101(Cr) composite. The highest H₂ uptake by AC@MIL-101(Cr) was equal to 6.93 wt % at 77 K and 40 bar. Such excellent hydrogen storage performance (a 32.3% increase than what was observed for unmodified MIL-101(Cr) material) was attributed to a synergy between AC and MIL-101(Cr).     

Co-pelletization of a zirconium-based metal-organic framework (UiO-66) with polymer nanofibers for improved useable capacity in hydrogen storage

We report on a concept of co-pelletization using mechanically robust hydroxylated UiO-66 to develop a metal-organic framework (MOF) monolith that contains 5 wt% electrospun polymer nanofibers, and consists of an architecture with alternating layers of MOF and nanofiber mats. The polymers of choice were the microporous Polymer of Intrinsic Microporosity (PIM-1) and non-porous polyacrylonitrile (PAN). Co-pelletized UiO-66/PIM-1 and UiO-66/PAN monoliths retain no less than 85% of the porosity obtained in pristine powder and pelletized UiO-66. The composition of the pore size distribution in co-pelletized UiO-66/PIM-1 and UiO-66/PAN monoliths is significantly different to that of pristine UiO-66 forms, with pristine UiO-66 forms showing 90% of the pore apertures in the micropore region and both UiO-66/nanofiber monoliths showing a composite micro-mesoporous pore size distribution. The co-pelletized UiO-66/nanofiber monoliths obtained improved useable H₂ capacities in comparison to pristine UiO-66 forms, under isothermal pressure swing conditions. The UiO-66/PIM-1 monolith constitutes the highest gravimetric (and volumetric) useable capacities at 2.3 wt% (32 g L^?1) in comparison to 1.8 wt% (12 g L^?1) and 1.9 wt% (29 g L^?1) obtainable in pristine UiO-66 powder and UiO-66 pellet, respectively. The co-pelletized UiO-66/PAN monolith, however, shows a significantly reduced surface area by up to 50% less in comparison to pristine UiO-66, but its pore volume only 13% less in comparison to pristine UiO-66. As a result, total gravimetric H₂ capacity of the co-pelletized UiO-66/PAN monolith is 50% less in comparison to that of pristine UiO-66, but crucially the useable volumetric H₂ capacity is 50% higher for the UiO-66/PAN monolith in comparison to pristine UiO-66 powder. The co-pelletization strategy provides a simple method for generating hierarchical porosity into an initially highly microporous MOF without changing the structure of the MOF through complex chemical modifications. The UiO-66/nanofiber monoliths offer improvements to the typically low H₂ useable capacities in highly microporous MOFs, and open new opportunities towards achieving system-level H₂ storage targets.     

Computational insights into the energy storage of ultraporous MOFs NU-1501-M (M = Al or Fe): Protonization revealing and performance improving by decoration of superalkali clusters

In 2020, Chen et al. reported the synthesis of a series of promising metal–organic frameworks (MOFs) based on Al/Fe trinuclear clusters, known as NU-1501-M (M = Al or Fe). Both the gravimetric and volumetric Brunauer-Emmett-Teller (BET) areas of this novel structure are in an ideal range, making it highly promising for hydrogen storage. However, the physical chemistry of its adsorption processes has not been investigated. In this work, we applied grand canonical Monte Carlo (GCMC), density functional theory (DFT), and ab initio molecular dynamics (AIMD) to study their adsorption behaviours in details. These simulations suggest that the balance between the chemical porosity and the electronic structure is critical in determining the quality of the designed MOFs materials in deliverable energy storage. Moreover, theoretical predictions reveal the possible protonization of oxygen atoms from M trinuclear nodes by hydrogen molecules. To protect MOFs from being protonized, we proposed to employ NAl₃ clusters to decorate the MOFs. Simulations reveal that this novel strategy can not only stablize the oxygen atoms, but also significantly improve the hydrogen storage performance by almost one order of magnitude. Our work proposes an important and promising way to improve the energy storage performance of these MOFs.     

Basic tuning of hydrogen powered car and artificial intelligent prediction of hydrogen engine characteristics

Many studies of renewable energy have shown hydrogen is one of the major green energy in the future. This has lead to the development of many automotive application of using hydrogen as a fuel especially in internal combustion engine. Nonetheless, there has been a slow growth and less knowledge details in building up the prototype and control methodology of the hydrogen internal combustion engine [1]. In this paper, The Toyota Corolla 4 cylinder, 1.8l engine running on petrol was systematically modified in such a way that it could be operated on either gasoline or hydrogen at the choice of the driver. Within the scope of this project, several ancillary instruments such as a new inlet manifold, hydrogen fuel injection, storage system and leak detection safety system were implemented. Attention is directed towards special characteristics related to the basic tuning of hydrogen engine such as: air to fuel ratio operating conditions, ignition timing and injection timing in terms of different engine speed and throttle position. Based on the experimental data, a suite of neural network models were tested to accurately predict the effect of different engine operating conditions (speed and throttle position) on the hydrogen powered car engine characteristics. Predictions were found to be ±3% to the experimental values for all of case studies. This work provided better understanding of the effect of hydrogen engine characteristic parameters on different engine operating conditions.     

Enhancement of hydrogen storage properties of metal-organic framework-5 by substitution (Zn,Cd and Mg) and decoration (Li,Be and Na)

Two strategies of decoration by three elements Z = Li, Be and Na in cyclic site, and substitution of Zn by Mg and Cd in unit cell were used in the framework of functional density theory to tune the hydrogen storage properties of metal-organic framework-5 (MOF-5) based on Zn whose decomposition temperature and initial gravimetric capacity are 300 K and 1.57 wt% respectively.Based on the adsorption of hydrogen molecules in the crystal surface at three different adsorption sites with three orientations of H₂, we show that our system may reach a maximum gravimetric storage capacity of 4.09 wt% for multiple hydrogen molecules. Moreover, the functionalization of Z combined to the substitution, shows an exceptional improvement of hydrogen storage properties. For example, Mg-MOF-5 decorated with Li₂ has a capacity up to 5.41 wt% and 513 K as desorption temperature.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

A fast procedure for the estimation of the hydrogen storage capacity by cryoadsorption of metal-organic framework materials from their available porous properties

In order to identify the best porous materials for the cryogenic physisorption of hydrogen, high-throughput calculations are performed starting, i.e., from the collected information in crystallographic databases. However, these calculations, like molecular simulations, require specific training and significant computational cost. Herein, a relatively simple procedure is proposed to estimate and compare hydrogen uptakes at 77 K and pressure values from 40 bar starting from the porous properties of MOF materials, without involving simulation tools. This procedure uses definitions for adsorption and considers the adsorbed phase as an incompressible fluid whose pressure-density change is that for the liquid phase at 19 K. For the 7000 structures from the CoRE MOF database, the average error of the predictions is only of 1% from reference values at 100 bar, with an SD of ±8%. This accuracy is lower than that from simulation tools, but involving lower computational cost and training.     

Synthesis and characterization of porous HKUST-1 metal organic frameworks for hydrogen storage

Hydrogen storage capacity has been investigated on a copper-based metal organic framework named HKUST-1 with fine structural analyses. The crystalline structure of HKUST-1 MOF has been confirmed from the powder X-ray diffraction and the average particle diameter has been found about 15–20 μm identified by FE-SEM. Nitrogen adsorption isotherms show that HKUST-1 MOF has approximately type-I isotherm with a BET specific surface area of 1055 m²g⁻¹. Hydrogen adsorption study shows that this material can store 0.47 wt.% of H₂ at 303 K and 35 bar. The existence of Cu (II) in crystalline framework of HKUST-1 MOF has been confirmed by pre-edge XANES spectra. The sharp feature at 8985.8 eV in XANES spectra represents the dipole-allowed electron transition from 1s to 4p_xy. In addition, EXAFS spectra indicate that HKUST-1 MOF structure has the Cu–O bond distance of 1.95 Å with a coordination number of 4.2.     

Interaction of H2 with fragments of MOF-5 and its implications for the design and development of new MOFs: A computational study

The interaction energies (IEs) of H₂ and various organic ligands have been computed using coupled-cluster method with singles, doubles, and noniterative triples (CCSD(T)) at the complete basis set (CBS) limit. The density fitting-density functional theory-symmetry adapted perturbation theory (DF-DFT-SAPT) approach has been used to probe the nature of interaction between H₂ and organic linkers. It has been found that dispersive interaction predominantly stabilizes the intermolecular complex formation of H₂ on a variety of organic linkers. Furthermore, H₂ binding affinity of inorganic connectors is improved by partial isomorphic substitution of Zn by different metal ions such as Fe, Co, Ni and Cu. A new modified metal-organic framework (MOF-5 M) has been designed based upon the insight from the organic and inorganic fragments. The present study provides valuable information required for the design of novel MOFs with improved affinity for H₂ adsorption.     

An investigation of engine performance parameters and artificial intelligent emission prediction of hydrogen powered car

With the depletion of fossil fuel resources and the potential consequences of climate change due to fossil fuel use, much effort has been put into the search for alternative fuels for transportation. Although there are several potential alternative fuels, which have low impact on the environment, none of these fuels have the ability to be used as the sole “fuel of the future”. One fuel which is likely to become a part of the over all solution to the transportation fuel dilemma is hydrogen. In this paper, The Toyota Corolla four cylinder, 1.8 l engine running on petrol is systematically converted to run on hydrogen. Several ancillary instruments for measuring various engine operating parameters and emissions are fitted to appraise the performance of the hydrogen car. The effect of hydrogen as a fuel compares with gasoline on engine operating parameters and effect of engine operating parameters on emission characteristics is discussed. Based on the experimental setup, a suite of neural network models were tested to accurately predict the effect of major engine operating conditions on the hydrogen car emissions. Predictions were found to be ±4% to the experimental values. This work provided better understanding of the effect of engine process parameters on emissions.     

Modeling interfacial tension of the hydrogen-brine system using robust machine learning techniques: Implication for underground hydrogen storage

During the last years, there has been a surge of interest in cleaner ways for producing energy in order to successfully handle the climate issues caused by the consumption of fossil fuels. The production of hydrogen (H₂) is among the techniques which have grown up as attractive strategies towards energy transition. In this context, underground hydrogen storage (UHS) in saline aquifers has turned into one of the greatest challenges in the context of conserving energy for later use. The interfacial tension (IFT) of the H₂-brine system is a paramount parameter which affects greatly the successful design and implementation of UHS. In this study, robust machine learning (ML) techniques, viz., genetic programming (GP), gradient boosting regressor (GBR), and multilayer perceptron (MLP) optimized with Levenberg-Marquardt (LMA) and Adaptive Moment Estimation (Adam) algorithms were implemented for establishing accurate paradigms to predict the IFT of the H₂-brine system. The obtained results exhibited that the proposed models and correlation provide excellent estimations of the IFT. In addition, it was deduced that MLP-LMA outperforms the other models and the existing correlation in the literature. MLP-LMA yielded R² and AAPRE values of 0.9997 and 0.1907%, respectively. Lastly, the trend analysis demonstrated the physical coherence and tendency of the predictions of MLP-LMA.     

Ab initio study of hydrogen adsorption on Zn2(NDC)2(diPyTz) metal-organic framework decorated with alkali and alkaline earth metal cations

We have studied effect of alkali and alkaline earth metal cations (Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺) decoration on hydrogen adsorption of the organic linker of Zn₂(NDC)₂(diPyTz) by employing three cluster models: diPyTz:mLi⁺ (m = 1–4), diPyTz:mLi⁺:nH₂ (m = 0,1,2 and n = 1–5) and diPyTz:1M⁺:1H₂ (M⁺ = Na⁺, K⁺, Be²⁺, Mg²⁺) complexes, using density functional theory (DFT) and second-order Moller–Plesset perturbation theory (MP2). The calculated binding energies show that decoration of the organic linker with alkali and alkaline earth metal cations enhanced H₂ interaction with diPyTz when compared with the pristine diPyTz. The atomic charges were derived by Mulliken, ChelpG and ESP methods. Finally, the atoms in molecules theory (AIM) were also applied to get more insight into the nature of the interaction of diPyTz and Li⁺. Results of AIM analysis show that N–Li⁺ bond in diPyTz organic linker's complex appears as shared electron interaction.