Floatable Termination-Vacant MXene Architecture for High-Performance and Cost-Effective Photothermal Dehydrogenation.

Liquid hydrogen carriers have garnered considerable interest in long-distance and large-scale hydrogen storage owing to their exceptional hydrogen storage density, safety, and compatibility. Nonetheless, their practical application is hampered by the low hydrogen production rate and high cost, stemming from poor thermal utilization and heavy reliance on noble metals in solar bulk dehydrogenation platforms. To conquer these challenges, we devise an economical all-in-one architecture comprising the photothermal catalytic termination-vacant MXene and a highly insulated melamine substrate. This design floats on the air-reactant interface to efficiently drive solar interfacial dehydrogenation. The melamine enables interfacial heat localization to improve the thermal utilization, providing a high reaction temperature. Meanwhile, the MXene with termination vacancies exposes rich active sites for formic acid dehydrogenation, and simultaneously high performance and cost-effectiveness can be realized. This work offers fresh perspectives on the design and application of photothermal catalytic MXene, broadening the prospects for hydrogen storage using liquid hydrogen carriers.

Electrolytic Hydrogen Release from Hydrogen Boride Sheets.

Solid-state hydrogen storage materials are safe and lightweight hydrogen carriers. Among the various solid-state hydrogen carriers, hydrogen boride (HB) sheets possess a high gravimetric hydrogen capacity (8.5 wt%). However, heating at high temperatures and/or strong ultraviolet illumination is required to release hydrogen (H2) from HB sheets. In this study, the electrochemical H2 release from HB sheets using a dispersion system in an organic solvent without other proton sources is investigated. H2 molecules are released from the HB sheets under the application of a cathodic potential. The Faradaic efficiency for H2 release from HB sheets reached >90%, and the onset potential for H2 release is -0.445 V versus Ag/Ag+, which is more positive than those from other proton sources, such as water or formic acid, under the same electrochemical conditions. The total electrochemically released H2 in a long-time experiment reached ≈100% of the hydrogen capacity of HB sheets. The H2 release from HB sheets is driven by a small bias; thus, they can be applied as safe and lightweight hydrogen carriers with economical hydrogen release properties.

Lithium Borohydride Nanorods: Self-Assembling Growth and Remarkable Hydrogen Cycling Properties.

Nanostructured metal hydrides with unique morphology and improved hydrogen storage properties have attracted intense interests. However, the study of the growth process of highly active borohydrides remains challenging. Herein, for the first time the synthesis of LiBH4 nanorods through a hydrogen-assisted one-pot solvothermal reaction is reported. Reaction of n-butyl lithium with triethylamine borane in n-hexane under 50 bar of H2 at 40-100 °C gives rise to the formation of the [100]-oriented LiBH4 nanorods with 500-800 nm in diameter, whose growth is driven by orientated attachment and ligand adsorption. The unique morphology enables the LiBH4 nanorods to release hydrogen from ≈184 °C, 94 °C lower than the commercial sample (≈278 °C). Hydrogen release amounts to 13 wt% within 40 min at 450 °C with a stable cyclability, remarkably superior to the commercial LiBH4 (≈9.1 wt%). More importantly, up to 180 °C reduction in the onset temperature of hydrogenation is successfully attained by the nanorod sample with respect to the commercial counterpart. The LiBH4 nanorods show no foaming during dehydrogenation, which improves the hydrogen cycling performance. The new approach will shed light on the preparation of nanostructured metal borohydrides as advanced functional materials.

Nanoencapsulated MgBu2@ZIF-67 to Construct High Loading Mg-Co@C Nanocomposites: Breaking Through the Barrier of Room Temperature Onset Dehydrogenation.

The synergies of nanoconfinement and catalysis is an effective strategy to improve the kinetic and thermodynamic properties of Mg-based materials. However, obtaining Mg-based materials with high loading, anti-aggregation, and containing nanocatalysts to achieve dehydrogenation at room temperature remains a huge challenge. Herein, a novel and universal preparation strategy for Mg-Co@C nanocomposites with 9.5 nm Mg nanoparticles and 9.4 nm Co nanocatalysts embedded in carbon scaffold is reported. The 9.3 nm MgBu2 nanosheets precipitated by solvent displacement are encapsulated in ZIF-67 to prepare MgBu2@ZIF-67 precursors, then removing excess MgBu2 on the precursor surface and pyrolysis to obtain Mg-Co@C. It is worth noting that the Mg loading rate of Mg-Co@C is as high as rare 69.7%. Excitingly, the Mg-Co@C begins to dehydrogenate at room temperature with saturate capacity of 5.1 wt.%. Meanwhile, its dehydrogenation activation energy (Ea(des) = 68.8 kJ mol-1) and enthalpy (ΔH(des) = 61.6 kJ mol-1) significantly decrease compared to bulk Mg. First principles calculations indicate that the hydrogen adsorption energy on the Mg2CoH5 surface is only -0.681 eV. This work provides a universally applicable novel method for the preparation of nanoscale Mg-based materials with various nanocatalysts added, and provides new ideas for Mg-based materials to achieve room temperature hydrogen storage.

Leveraging Curvature on N-Doped Carbon Materials for Hydrogen Storage.

Carbon sorbent materials have shown great promise for solid-state hydrogen (H2) storage. Modification of these materials with nitrogen (N) dopants has been undertaken to develop materials that can store H2 at ambient temperatures. In this work density functional theory (DFT) calculations are used to systematically probe the influence of curvature on the stability and activity of undoped and N-doped carbon materials toward H binding. Specifically, four models of carbon materials are used: graphene, [5,5] carbon nanotube, [5,5] D5d-C120, and C60, to extract and correlate the thermodynamic properties of active sites with varying degrees of sp2 hybridization (curvature). From the calculations and analysis, it is found that graphitic N-doping is thermodynamically favored on more pyramidal sites with increased curvature. In contrast, it is found that the hydrogen binding energy is weakly affected by curvature and is dominated by electronic effects induced by N-doping. These findings highlight the importance of modulating the heteroatom doping configuration and the lattice topology when developing materials for H2 storage.

Optimization Strategy in Hydrogen Storage Performance of Ti─V─Cr─Mn Alloys via LiAlH4.

V-based solid solution materials hold a significant position in the realm of hydrogen storage materials because of its high hydrogen storage capacity. However, the current dehydrogenation temperature of V-based solid solution exceeds 350 °C, making it challenging to fulfill the appliance under moderate conditions. Here advancements in the hydrogen storage properties and related mechanisms of TiV1.1Cr0.3Mn0.6 + x LiAlH4 (x = 0, 5, 8, 10 wt.%) composites is presented. According to the first principle calculation analysis, the inclusion of Al and Li atoms will lower the binding energy of hydride, thus enhancing the hydrogen absorption reaction and significantly decreasing the activation difficulty. Furthermore, based on crystal orbital Hamilton population (COHP) analysis, the strength of the V─H and Ti─H bonds after doping LiAlH4 are reduced, leading to a decrease of the hydrogen release activation energy (Ea) for the V-based solid solution material, thus the hydrogen release process is easier to carry out. Additionally, the structure of doped LiAlH4 exhibits an outstanding hydrogen release rate of 2.001 wt.% at 323 K and remarkable cycling stability.

Ti3C2Tx MXene as Intriguing Material for Electrochemical Capacitor.

This study provides meaningful insight into the charge storage in Ti3C2Tx MXene (M-transition metal, X-carbon, T-Cl, F, O) for electrochemical capacitor (EC) application. The experiments show that this 2D material is especially adapted for the hydrogen electrosorption under negative polarization. It is found that hydrogen bonding to the Ti3C2Tx surface occurs through interactions of various strength. Different mechanisms are suggested to explain the nature of H stored at the electrode/electrolyte interface depending on pH and potential range. For the negative potentials, both capacitive and faradaic currents are involved, and the electrode can operate in a relatively wide range. On the other hand, the narrow range of positive potentials limits whole voltage of EC. Such charge disproportion has a major impact on the performance failure of symmetric MXene-based ECs. New design of MXene cells with a wide operating voltage is introduced. To equalize the charge storage of both electrodes, the positive Ti3C2Tx electrode is replaced by the porous carbon (BP2000) with a wide working potential and a good capacitive response. Thus, EC operating voltage is considerably expanded to 1.3, 1.4, 2 V in acidic, basic, neutral medium, respectively. During cycling tests at 1 A g-1, the asymmetric cell MXene/BP2000 maintains 80% of initial capacitance after 22 000 cycles.

Bayesian Optimization for Efficient Prediction of Gas Uptake in Nanoporous Materials.

The discovery and optimization of novel nanoporous materials (NPMs) such as Metal-Organic Frameworks (MOFs) and Covalent Organic Frameworks (COFs) are crucial for addressing global challenges like climate change, energy security, and environmental degradation. Traditional experimental approaches for optimizing these materials are time-consuming and resource-intensive. This research paper presents a strategy using Bayesian optimization (BO) to efficiently navigate the complex design spaces of NPMs for gas storage applications. For a MOF dataset drawn from 19 different sources, we present a quantitative evaluation of BO using a curated set of surrogate model and acquisition function couples. In our study, we employed machine learning (ML) techniques to conduct regression analysis on many models. Following this, we identified the three ML models that exhibited the highest accuracy, which were subsequently chosen as surrogates in our investigation, including the conventional Gaussian Process (GP) model. We found that GP with expected improvement (EI) as the acquisition function but without a gamma prior which is standard in Bayesian Optimisation python library (BO Torch) outperforms other surrogate models. Additionally, it should be noted that while the machine learning model that exhibits superior performance in predicting the target variable may be considered the best choice, it may not necessarily serve as the most suitable surrogate model for BO. This observation has significant importance and warrants further investigation. This comprehensive framework accelerates the pace of materials discovery and addresses urgent needs in energy storage and environmental sustainability. It is to be noted that rather than identifying new MOFs, BO primarily enhances computational efficiency by reducing the reliance on more demanding calculations, such as those involved in Grand Canonical Monte Carlo (GCMC) or Density Functional Theory (DFT).

Establishing ZIF-8 as a reference material for hydrogen cryoadsorption: An interlaboratory study.

Hydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3-4 % between pressures of 10-100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material.

Adsorption and storage of hydrogen- A computational model approach.

Due to the imperative global energy transition crisis, hydrogen storage and adsorption technologies are becoming popular with the growing hydrogen economy. Recently, complex hydrides have been one of the most reliable materials for storing and transporting hydrogen gas to various fuel cells to generate clean energy with zero carbon emissions. With the ever-increasing carbon emissions, it is necessary to substitute the current energy sources with green hydrogen-based efficient energy-integrated systems. Herein, we propose an input-output model that comprehends complex hydrides such as lithium and magnesium alanates, amides and borohydrides to predict, estimate, and directly analyse hydrogen storage and adsorption. A critical and thorough comparative analysis of the respective complex hydrides for hydrogen adsorption and storage is discussed, elucidating the storage applications in water bodies. Several industrial scale-up processes, economic analysis, and plant design of hydrogen storage and adsorption approaches are suggested through volumetric and gravimetric calculations.

Epitaxial Hexagonal Boron Nitride for Hydrogen Generation by Radiolysis of Interfacial Water.

Hydrogen is an important building block in global strategies toward a future green energy system. To make this transition possible, intense scientific efforts are needed, also in the field of materials science. Two-dimensional crystals, such as hexagonal boron nitride (hBN), are very promising in this regard, as it has been demonstrated that micrometer-sized flakes are excellent barriers to molecular hydrogen. However, it remains an open question whether large-area layers fabricated by industrially relevant methods preserve such promising properties. In this work, we show that electron-beam-induced splitting of water creates hBN bubbles that effectively store molecular hydrogen for weeks and under extreme mechanical deformation. We demonstrate that epitaxial hBN allows direct visualization and monitoring of the process of hydrogen generation by radiolysis of interfacial water. Our findings show that hBN is not only a potential candidate for hydrogen storage but also holds promise for the development of unconventional hydrogen production schemes.

Sc-Modified C3N4 Nanotubes for High-Capacity Hydrogen Storage: A Theoretical Prediction.

Utilizing hydrogen as a viable substitute for fossil fuels requires the exploration of hydrogen storage materials with high capacity, high quality, and effective reversibility at room temperature. In this study, the stability and capacity for hydrogen storage in the Sc-modified C3N4 nanotube are thoroughly examined through the application of density functional theory (DFT). Our finding indicates that a strong coupling between the Sc-3d orbitals and N-2p orbitals stabilizes the Sc-modified C3N4 nanotube at a high temperature (500 K), and the high migration barrier (5.10 eV) between adjacent Sc atoms prevents the creation of metal clusters. Particularly, it has been found that each Sc-modified C3N4 nanotube is capable of adsorbing up to nine H2 molecules, and the gravimetric hydrogen storage density is calculated to be 7.29 wt%. It reveals an average adsorption energy of -0.20 eV, with an estimated average desorption temperature of 258 K. This shows that a Sc-modified C3N4 nanotube can store hydrogen at low temperatures and harness it at room temperature, which will reduce energy consumption and protect the system from high desorption temperatures. Moreover, charge donation and reverse transfer from the Sc-3d orbital to the H-1s orbital suggest the presence of the Kubas effect between the Sc-modified C3N4 nanotube and H2 molecules. We draw the conclusion that a Sc-modified C3N4 nanotube exhibits exceptional potential as a stable and efficient hydrogen storage substrate.

Recent Advances in the Preparation Methods of Magnesium-Based Hydrogen Storage Materials.

Magnesium-based hydrogen storage materials have garnered significant attention due to their high hydrogen storage capacity, abundance, and low cost. However, the slow kinetics and high desorption temperature of magnesium hydride hinder its practical application. Various preparation methods have been developed to improve the hydrogen storage properties of magnesium-based materials. This review comprehensively summarizes the recent advances in the preparation methods of magnesium-based hydrogen storage materials, including mechanical ball milling, methanol-wrapped chemical vapor deposition, plasma-assisted ball milling, organic ligand-assisted synthesis, and other emerging methods. The principles, processes, key parameters, and modification strategies of each method are discussed in detail, along with representative research cases. Furthermore, the advantages and disadvantages of different preparation methods are compared and evaluated, and their influence on hydrogen storage properties is analyzed. The practical application potential of these methods is also assessed, considering factors such as hydrogen storage performance, scalability, and cost-effectiveness. Finally, the existing challenges and future research directions in this field are outlined, emphasizing the need for further development of high-performance and cost-effective magnesium-based hydrogen storage materials for clean energy applications. This review provides valuable insights and references for researchers working on the development of advanced magnesium-based hydrogen storage technologies.

Magnesium-Based Hydrogen Storage Alloys: Advances, Strategies, and Future Outlook for Clean Energy Applications.

Magnesium-based hydrogen storage alloys have attracted significant attention as promising materials for solid-state hydrogen storage due to their high hydrogen storage capacity, abundant reserves, low cost, and reversibility. However, the widespread application of these alloys is hindered by several challenges, including slow hydrogen absorption/desorption kinetics, high thermodynamic stability of magnesium hydride, and limited cycle life. This comprehensive review provides an in-depth overview of the recent advances in magnesium-based hydrogen storage alloys, covering their fundamental properties, synthesis methods, modification strategies, hydrogen storage performance, and potential applications. The review discusses the thermodynamic and kinetic properties of magnesium-based alloys, as well as the effects of alloying, nanostructuring, and surface modification on their hydrogen storage performance. The hydrogen absorption/desorption properties of different magnesium-based alloy systems are compared, and the influence of various modification strategies on these properties is examined. The review also explores the potential applications of magnesium-based hydrogen storage alloys, including mobile and stationary hydrogen storage, rechargeable batteries, and thermal energy storage. Finally, the current challenges and future research directions in this field are discussed, highlighting the need for fundamental understanding of hydrogen storage mechanisms, development of novel alloy compositions, optimization of modification strategies, integration of magnesium-based alloys into hydrogen storage systems, and collaboration between academia and industry.

Research Progress and Application Prospects of Solid-State Hydrogen Storage Technology.

Solid-state hydrogen storage technology has emerged as a disruptive solution to the "last mile" challenge in large-scale hydrogen energy applications, garnering significant global research attention. This paper systematically reviews the Chinese research progress in solid-state hydrogen storage material systems, thermodynamic mechanisms, and system integration. It also quantitatively assesses the market potential of solid-state hydrogen storage across four major application scenarios: on-board hydrogen storage, hydrogen refueling stations, backup power supplies, and power grid peak shaving. Furthermore, it analyzes the bottlenecks and challenges in industrialization related to key materials, testing standards, and innovation platforms. While acknowledging that the cost and performance of solid-state hydrogen storage are not yet fully competitive, the paper highlights its unique advantages of high safety, energy density, and potentially lower costs, showing promise in new energy vehicles and distributed energy fields. Breakthroughs in new hydrogen storage materials like magnesium-based and vanadium-based materials, coupled with improved standards, specifications, and innovation mechanisms, are expected to propel solid-state hydrogen storage into a mainstream technology within 10-15 years, with a market scale exceeding USD 14.3 billion. To accelerate the leapfrog development of China's solid-state hydrogen storage industry, increased investment in basic research, focused efforts on key core technologies, and streamlining the industry chain from materials to systems are recommended. This includes addressing challenges in passenger vehicles, commercial vehicles, and hydrogen refueling stations, and building a collaborative innovation ecosystem involving government, industry, academia, research, finance, and intermediary entities to support the achievement of carbon peak and neutrality goals and foster a clean, low-carbon, safe, and efficient modern energy system.

Zr-Porphyrin Metal-Organic Framework as nanoreactor for boosting the formation of hydrogen clathrates.

We report the first experimental evidence for rapid formation of hydrogen clathrates under mild pressure and temperature conditions within the cavities of a zirconium-metalloporphyrin framework, specifically PCN-222. PCN-222 has been selected for its 1D mesoporous channels, high water-stability, and proper hydrophilic behavior. Firstly, we optimize a microwave (MW)-assisted method for the synthesis of nanosized PCN-222 particles with precise structure control (exceptional homogeneity in morphology and crystalline phase purity), taking advantage of MW in terms of rapid/homogeneous heating, time and energy savings, as well as potential scalability of the synthetic method. Second, we explore the relevance of the large mesoporous 1D open channels within the PCN-222 to promote the nucleation and growth of confined hydrogen clathrates. Experimental results show that PCN-222 drives the nucleation process at a lower pressure than the bulk system (1.35 kbar vs 2 kbar), with fast kinetics (minutes), using pure water, and with a nearly complete water-to-hydrate conversion. Unfortunately, PCN-222 cannot withstand these high pressures, which lead to a significant alteration of the mesoporous structure while the microporous network remains mainly unchanged.

Rechargeable Zn-H2O hydrolysis battery for hydrogen storage and production.

Reactive metals hydrolysis offers significant advantages for hydrogen storage and production. However, the regeneration of common reactive metals (e.g., Mg, Al, etc.) is energy-intensive and produces unwanted byproducts such as CO2 and Cl2. Herein, we employ Zn as a reactive mediator that can be easily regenerated by electrolysis of ZnO in an alkaline solution with a Faradaic efficiency of >99.9 %. H2 is produced in the same electrolyte by constructing a Zn-H2O hydrolysis battery consisting of a Zn anode and a Raney-Ni cathode to unlock the Zn-H2O reaction. The entire two-step water splitting reaction with a net energy efficiency of 70.4 % at 80 °C and 50 mA cm-2. Additionally, the Zn-H2O system can be charged using renewable energy to produce H2 on demand and runs for 600 cycles only sacrificing 3.76 % energy efficiency. DFT calculations reveal that the desorption of H* on Raney-Ni (-0.30 eV) is closer to zero compared with that on Zn (-0.87 eV), indicating a faster desorption of H* at low overpotential. Further, a 24 Ah electrolyzer is demonstrated to produce H2 with a net energy efficiency of 65.5 %, which holds promise for its real application.

Construction of Highly Porous and Robust Hydrogen-Bonded Organic Framework for High-Capacity Clean Energy Gas Storage.

Development of highly porous and robust HOFs for high-pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing double-walled framework to target highly porous and robust HOF (ZJU-HOF-5a) for extraordinary CH4 and H2 storage. ZJU-HOF-5a features a minimized twofold interpenetration with double-walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls. This structural configuration can notably enhance the framework robustness while maintaining its high porosity, affording one of the highest gravimetric and volumetric surface areas of 3102 m2 g-1 and 1976 m2 cm-3 among the reported HOFs so far. ZJU-HOF-5a exhibits an extremely high volumetric H2 uptake of 43.6 g L-1 at 77 K/100 bar and working capacity of 41.3 g L-1 under combined swing conditions, and also impressive methane storage performance with a 5-100 bar working capacity of 187 (or 159) cm3 cm-3 at 270 K (or 296 K). SCXRD studies on CH4-loaded ZJU-HOF-5a reveal that abundant supramolecular binding sites combined with ultrahigh porosities account for its high CH4 storage capacities. Combined with high stability, super-hydrophobicity, and easy-recovery, ZJU-HOF-5a is placed among the most promising materials for H2 and CH4 storage applications.

Picturing the Gap Between the Performance and US-DOE's Hydrogen Storage Target: A Data-Driven Model for MgH2 Dehydrogenation.

Developing solid-state hydrogen storage materials is as pressing as ever, which requires a comprehensive understanding of the dehydrogenation chemistry of a solid-state hydride. Transition state search and kinetics calculations are essential to understanding and designing high-performance solid-state hydrogen storage materials by filling in the knowledge gap that current experimental techniques cannot measure. However, the ab initio analysis of these processes is computationally expensive and time-consuming. Searching for descriptors to accurately predict the energy barrier is urgently needed, to accelerate the prediction of hydrogen storage material properties and identify the opportunities and challenges in this field. Herein, we develop a data-driven model to describe and predict the dehydrogenation barriers of a typical solid-state hydrogen storage material, magnesium hydride (MgH2), based on the combination of the crystal Hamilton population orbital of Mg-H bond and the distance between atomic hydrogen. By deriving the distance energy ratio, this model elucidates the key chemistry of the reaction kinetics. All the parameters in this model can be directly calculated with significantly less computational cost than conventional transition state search, so that the dehydrogenation performance of hydrogen storage materials can be predicted efficiently. Finally, we found that this model leads to excellent agreement with typical experimental measurements reported to date and provides clear design guidelines on how to propel the performance of MgH2 closer to the target set by the United States Department of Energy (US-DOE).

Interfacial Engineering of Fluorinated TiO2 Nanosheets with Abundant Oxygen Vacancies for Boosting the Hydrogen Storage Performance of MgH2.

The interaction between fluorinated surface in the partially reduced nano-crystallite titanium dioxide (TiO2-x (F)) and MgH2 is studied for the first time. Compared with pristine MgH2 (416 °C), the onset desorption temperature of MgH2 +5 wt.% TiO2-x (F) composite can be dramatically lowered to 189 °C. In addition, the composite exhibits remarkable dehydrogenation kinetics, which can release 6.0 wt.% hydrogen thoroughly within 6 min at 250 °C. The apparent activation energy for dehydriding is decreased from 268.42 to 119.96 kJ mol-1 . Structural characterization and theoretical calculations indicate that the synergistic effect between multivalent Ti species, and the in situ formed MgF2 and MgF2-x Hx is beneficial for improving the hydrogen storage performance of MgH2 . Moreover, oxygen vacancies can accelerate the electron transportation and facilitate hydrogen diffusion. The study provides a novel perspective on the modification of MgH2 by fluorinated transition metal oxide catalyst.