Assisting molybdenum trioxide catalysis by engineering oxygen vacancy for enhancing hydrogen storage performance of magnesium hydride.

Magnesium hydride (MgH2) as an ideal hydrogen storage carrier whose hydrogen storage performance can be effectively improved by transition metal-based catalysts. To construct highly active catalysts, much attention has been paid to the regulation of transition metal components while less attention has been paid to non-transition metal components especially oxygen, leading certain limitations. Herein, further improved hydrogen storage performance of MgH2 can be obtained by adjusting oxygen vacancy content in molybdenum trioxide (MoO3) catalyst. Specifically, compared with pure MgH2 (1.1 wt%) and MgH2-10 wt% MoO3 (4.5 wt%), more hydrogen (5.9 wt%) can be released by MgH2-10 wt% MoO3-x (MoO3 with abundant oxygen vacancies) at 300.0 °C within 499.0 s. Besides, superb capacity retention (6.1 wt%, 99.0 %) after 50 isothermal hydrogen ab/desorption cycles can be obtained for MgH2-10 wt% MoO3-x. Through rigorous comparative experiments and theoretical calculations, the excellent catalytic activity of MoO3-x is demonstrated to come from the abundant oxygen vacancies and the active substances (polyvalent Mo and nano-sized MgO) it assists to form during ball milling process. This work verifies the feasibility for further improving the catalytic activity of transition metal-based catalysts by tuning non-transition metal elements and thus provides a new strategy in catalyzed MgH2 system.

Poisoning Mechanism Map for Metal Hydride Hydrogen Storage Materials.

The effective utilization of hydrogen storage materials (HSMs) is hindered by impurity gas poisoning, posing a significant challenge for large-scale applications. This study elucidates the poisoning mechanisms of various impurities gases (CO, CO2, O2, Ar, He, CH4, N2) on ZrCo, Pd, U and LaNi5. Impurities gases are categorized into active and inactive types based on their effecting behaviors and mechanisms on the hydrogenation of HSMs. During the hydrogenation process, active impurities chemically poison the hydrogenation reaction by limiting hydrogen absorption at interface, while inactive impurities physically hinder hydrogenation reaction by impeding hydrogen diffusion in hydrogen-impurity mixed gas. In situ Scanning Tunneling Microscope clarifies these behaviors, and a novel criterion based on hydrogen spontaneous dissociation energy is introduced to explain and predict impurity-substrate interaction characteristics. The novel findings of this work provide a comprehensive framework for designing long-lived HSMs with poisoning resistance, guiding the development of more resilient hydrogen storage systems.

Investigating the Effects of Transition Metals and Activated Carbon on Hydrogenation Characteristics of Severely Deformed ZK60 Processed by High-Energy Ball Milling.

The synergic effects of activated carbon and transition metals on the hydrogenation characteristics of commercial ZK60 magnesium alloy were investigated. Severe plastic deformation was performed using equal-channel angular pressing with an internal die angle of 120° and preheating at 300 °C. The ZK60 alloy samples were processed for 12 passes using route BA. The deformed ZK60 alloy powder was blended with activated carbon and different concentrations of transition metals (Ag, Pd, Co, Ti, V, Ti) using high-energy ball milling for 20 h at a speed of 1725 rpm. The amount of hydrogen absorbed and its kinetics were calculated using Sievert's apparatus at the higher number of cycles at a 300 °C ab/desorption temperature. The microstructure of the powder was analyzed using an X-ray diffractometer and scanning electron microscope. The results indicated that 5 wt% activated carbon presented the maximum hydrogen absorption capacity of 6.2 wt%. The optimal hydrogen absorption capacities were 7.1 wt%, 6.8 wt%, 6.7 wt%, 6.64 wt%, 6.65 wt%, and 7.06 wt% for 0.5 Ag, 0.3 Co, 0.1 Al, 0.5 Pd, 2 Ti, and 0.5 V, respectively. The hydrogen absorption capacities were reduced by 35.21%, 26.47%, 41.79%, 21.68%, 26.31%, and 26.34% after 100 cycles for 5C0.5Ag, 5C0.3Co, 5C0.1Al, 5C0.5Pd, 2Ti, and 5C0.5V, respectively. Hydrogen absorption kinetics were significantly improved so that more than 90% of hydrogen was absorbed within five minutes.

Tutton salt (NH4)2Zn(SO4)2(H2O)6: thermostructural, spectroscopic, Hirshfeld surface, and DFT investigations.

CONTEXT: Ammonium Tutton salts have been widely studied in recent years due to their thermostructural properties, which make them promising compounds for application in thermochemical energy storage devices. In this work, a detailed experimental study of the Tutton salt with the formula (NH4)2Zn(SO4)2(H2O)6 is carried out. Its structural, vibrational, and thermal properties are analyzed and discussed. Powder X-ray diffraction (PXRD) studies confirm that the compound crystallizes in a structure of a Tutton salt, with monoclinic symmetry and P21/a space group. The Hirshfeld surface analysis results indicate that the main contacts stabilizing the material crystal lattice are H···O/O···H, H···H, and O···O. In addition, a typical behavior of an insulating material is confirmed based on the electronic bandgap calculated from the band structure and experimental absorption coefficient. The Raman and infrared spectra calculated using DFT are in a good agreement with the respective experimental spectroscopic results. Thermal analysis in the range from 300 to 773 K reveals one exothermic and several endothermic events that are investigated using PXRD measurements as a function of temperature. With increasing temperature, two new structural phases are identified, one of which is resolved using the Le Bail method. Our findings suggest that the salt (NH4)2Zn(SO4)2(H2O)6 is a promising thermochemical material suitable for the development of heat storage systems, due to its low dehydration temperature (≈ 330 K), high enthalpy of dehydration (122.43 kJ/mol of H2O), and hydration after 24 h. METHODS: Computational studies using Hirshfeld surfaces and void analysis are conducted to identify and quantify the intermolecular contacts occurring in the crystal structure. Furthermore, geometry optimization calculations are performed based on density functional theory (DFT) using the PBE functional and norm-conserving pseudopotentials implemented in the Cambridge Serial Total Energy Package (CASTEP). The primitive unit cell optimization was conducted using the Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm. The electronic properties of band structure and density of states, and vibrational modes of the optimized crystal lattice are calculated and analyzed.

Current insights and future prospects of graphene aerogel-enhanced supercapacitors: A systematic review.

Supercapacitors present a compelling alternative to conventional batteries, offering rapid energy storage and high power density. Despite their advantages, they typically fall short in energy density compared to traditional batteries, primarily due to limitations in electrode materials. Graphene Aerogels (GA) have emerged as a promising solution to enhance supercapacitor performance because of their unique properties, such as high surface area and excellent conductivity. This systematic review provides a comprehensive analysis of recent advancements in GA technology, focusing on their synthesis methods and applications in supercapacitors. It highlights significant improvements that GA can bring to Electric Double-Layer Capacitors (EDLCs), pseudocapacitors, and hybrid supercapacitors. Additionally, the review explores GA's potential for enhancing electric generators and integrating into flexible, wearable technologies. Future research directions are emphasised, particularly regarding GA's potential applications in waste management and environmental protection. The review was conducted through a thorough literature search, prioritising peer-reviewed sources related to GA synthesis and supercapacitor applications. Methodological quality and potential biases of the included studies were assessed using principles similar to the Cochrane Risk of Bias tool. Thematic analysis was employed to synthesise findings and identify key trends and challenges. Limitations such as potential biases and methodological variations are discussed. Overall, this review highlights the technological prospects of GA and provides guidance for future research in supercapacitor development and applications.

Investigation on hydrogenation performance of Mg17Al12 by adding Y.

The mechanism of Y on H/H2 adsorption performance of Mg17Al12 were studied by the density functional theory. We obtained that for the Y-adsorbed systems, Y tended to occupy on the bridge site between adjacent Mg atoms. For the Y-substituted surfaces, Y atoms inclined to replace Mg atoms on the surfaces. We found that hydrogen (H/H2) absorption on the Mg17Al12(110) systems were improved by adding Y, the order of adsorption energy was as follows: clean Mg17Al12(110) > the Y-substituted surfaces > the Y-adsorbed surfaces. In addition, H2 molecules could dissociate on the Y-containing systems without barrier energy. Electronic properties showed that for H2 adsorption, the s states of atomic H mainly hybridized with the d states of Y. The formations of the Y-H bonds and the interactions between Y and H atoms could expound the mechanism for the promoted hydrogenation performance of the Y-containing surfaces.

Physical Analysis and Mathematical Modeling of the Hydrogen Storage Process in the MmNi4.2Mn0.8 Compound.

The results of an experimental and mathematical study into the MmNi4.2Mn0.8 compound's hydrogen storage properties are presented in the present research. Plotting and discussion of the experimental isotherms (P-C-T) for different starting temperatures (288 K, 298 K, 308 K, and 318 K) were carried out first. Then, the enthalpy and entropy of formation (ΔH0, ΔS0) were deduced from the plot of van't Hoff. Following that, the P-C-T were contrasted with a mathematical model developed via statistical physics modeling. The steric and energetic parameters, such as the number of the receiving sites (n1, n2), their densities (Nm1, Nm2), and the energy parameters (P1, P2) of the system, were calculated thanks to the excellent agreement between the numerical and experimental results. Therefore, plotting and discussing these parameters in relation to temperature preceded their application in determining the amount of hydrogen in each type of site per unit of metal ([H/M]1, [H/M]2) as well as for the entire system [H/M] versus temperature and pressure besides the absorption energies associated with each kind of site (ΔE1, ΔE2) and the thermodynamic functions (free energy, Gibbs energy, and entropy) that control the absorption reaction.

Enhanced Energy Storage Performance through Controlled Composition and Synthesis of 3D Mixed Metal-Oxide Microspheres.

Binary transition metal oxide complexes (BTMOCs) in three-dimensional (3D) layered structures show great promise as electrodes for supercapacitors (SCs) due to their diverse oxidation states, which contribute to high specific capacitance. However, the synthesis of BTMOCs with 3D structures remains challenging yet crucial for their application. In this study, we present a novel approach utilizing a single-step hydrothermal technique to fabricate flower-shaped microspheres composed of a NiCo-based complex. Each microsphere consists of nanosheets with a mesoporous structure, enhancing the specific surface area to 23.66 m2 g-1 and facilitating efficient redox reactions. When employed as the working electrode for supercapacitors, the composite exhibits remarkable specific capacitance, achieving 888.8 F g-1 at 1 A g-1. Furthermore, it demonstrates notable electrochemical stability, retaining 52.08% capacitance after 10,000 cycles, and offers a high-power density of 225 W·kg-1, along with an energy density of 25 Wh·kg-1, showcasing its potential for energy storage applications. Additionally, an aqueous asymmetric supercapacitor (ASC) was assembled using NiCo microspheres-based complex and activated carbon (AC). Remarkably, the NiCo microspheres complex/AC configuration delivers a high specific capacitance of 250 F g-1 at 1 A g-1, with a high energy density of 88 Wh kg-1, for a power density of 800 W kg-1. The ASC also exhibits excellent long-term cyclability with 69% retention over 10,000 charge-discharge cycles. Furthermore, a series of two ASC devices demonstrated the capability to power commercial blue LEDs for a duration of at least 40 s. The simplicity of the synthesis process and the exceptional performance exhibited by the developed electrode materials hold considerable promise for applications in energy storage.

Powering the Future by Iron Sulfide Type Material (FexSy) Based Electrochemical Materials for Water Splitting and Energy Storage Applications: A Review.

Water electrolysis is among the recent alternatives for generating clean fuels (hydrogen). It is an efficient way to produce pure hydrogen at a rapid pace with no unwanted by-products. Effective and cheap water-splitting electrocatalysts with enhanced activity, specificity, and stability are currently widely studied. In this regard, noble metal-free transition metal-based catalysts are of high interest. Iron sulfide (FeS) is one of the essential electrocatalysts for water splitting because of its unique structural and electrochemical features. This article discusses the significance of FeS and its nanocomposites as efficient electrocatalysts for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and overall water splitting. FeS and its nanocomposites have been studied also for energy storage in the form of electrode materials in supercapacitors and lithium- (LIBs) and sodium-ion batteries (SIBs). The structural and electrochemical characteristics of FeS and its nanocomposites, as well as the synthesis processes, are discussed in this work. This discussion correlates these features with the requirements for electrocatalysts in overall water splitting and its associated reactions. As a result, this study provides a road map for researchers seeking economically viable, environmentally friendly, and efficient electrochemical materials in the fields of green energy production and storage.

Retarding anion migration for alleviating concentration polarization towards stable polymer lithium-metal batteries.

Traditional dual-ion lithium salts have been widely used in solid polymer lithium-metal batteries (LMBs). Nevertheless, concentration polarization caused by uncontrolled migration of free anions has severely caused the growth of lithium dendrites. Although single-ion conductor polymers (SICP) have been developed to reduce concentration polarization, the poor ionic conductivity caused by low carrier concentration limits their application. Herein, a dual-salt quasi-solid polymer electrolyte (QSPE), containing the SICP network as a salt and traditional dual-ion lithium salt, is designed for retarding the movement of free anions and simultaneously providing sufficient effective carriers to alleviate concentration polarization. The dual salt network of this designed QSPE is prepared through in-situ crosslinking copolymerization of SICP monomer, regular ionic conductor, crosslinker with the presence of the dual-ion lithium salt, delivering a high lithium-ion transference number (0.75) and satisfactory ionic conductivity (1.16 × 10-3 S cm-1 at 30 °C). Comprehensive characterizations combined with theoretical calculation demonstrate that polyanions from SICP exerts a potential repulsive effect on the transport of free anions to reduce concentration polarization inhibiting lithium dendrites. As a consequence, the Li||LiFePO4 cell achieves a long-cycle stability for 2000 cycles and a 90% capacity retention at 30 °C. This work provides a new perspective for reducing concentration polarization and simultaneously enabling enough lithium-ions migration for high-performance polymer LMBs.

Preparation and performance of solid thermal energy storage materials based on low-grade pyrophyllite minerals.

The new sensible thermal energy storage materials were prepared by the sintering method with low-grade pyrophyllite mineral powders as main raw materials, Suzhou clay as the sintering aid and sulfite liquors as the binder. Further, the performance of sensible thermal energy storage under different size distributions and sintering temperatures was investigated and analyzed. The results show that the optimum particle size distribution is 50:15:35, the bulk density, thermal conductivity, and specific heat capacity are the largest values, which are 1.97 g cm-3, 0.87 W m-1 K-1 and 0.63 kJ kg-1 K-1, respectively. Other properties including porosity, water absorption, flexural and compressive strength and so on are optimal under this size distribution. When the sintering temperature is 1200 °C, the material has a good thermal conductivity of 0.89 W m-1 K-1 and a high bulk density of 2.05 g cm-3. Meanwhile, the sample with the used temperature from 50 to 900 °C has the best thermal energy storage capacity of 306.29 kWh·m-3.

On the Use of Solomon Echoes in 27 Al NMR Studies of Complex Aluminium Hydrides.

The quadrupole coupling constant CQ and the asymmetry parameter η have been determined for two complex aluminium hydrides from 27 Al NMR spectra recorded for stationary samples by using the Solomon echo sequence. The thus obtained data for KAlH4 (CQ =(1.30±0.02) MHz, η=(0.64±0.02)) and NaAlH4 (CQ =(3.11±0.02) MHz, η<0.01) agree very well with data previously determined from MAS NMR spectra. The accuracy with which these parameters can be determined from static spectra turned out to be at least as good as via the MAS approach. The experimentally determined parameters (δiso , CQ and η) are compared with those obtained from DFT-GIPAW (density functional theory - gauge-including projected augmented wave) calculations. Except for the quadrupole coupling constant for KAlH4 , which is overestimated in the GIPAW calculations by about 30 %, the agreement is excellent. Advantages of the application of the Solomon echo sequence for the measurement of less stable materials or for in situ studies are discussed.

Double Carbon Networks Reinforce the Thermal Storage and Thermal Transfer Properties of 1-Octadecanol Phase Change Materials.

Using thermal storage materials with excellent thermal properties in the energy utilization system enables efficient use of renewable energy sources. Organic phase change materials (PCMs) have the advantages of high heat storage density, no corrosion, and low cost, but low thermal conductivity and insufficient heat transfer capacity have always been the bottlenecks in their application. In this paper, melamine foam@ reduction graphene oxide (MF@rGO) and carbon foam@ reduction graphene oxide (CF@rGO) composite foams with double carbon networks were prepared by self-assembly method and further employed in 1-octadecinal (OD) PCMs. The microstructure, chemical composition, phase change behavior, thermal conductivity, and photothermal conversion performance of MF@rGO/OD and CF@rGO/OD were studied in detail using SEM, FTIR, Raman DSC, and LFA. The melting and solidification enthalpies of CF@rGO/OD composite PCMs were 208.3 J/g and 191.4 J/g, respectively, its thermal conductivity increased to 1.54 W/m·K, which is 6.42 times that of pure OD. The porous structure and high thermal conductivity of the double carbon network substantially enhance the efficiency of energy storage and release in composite PCMs. CF@rGO/OD composite PCMs have excellent heat storage performance and heat transfer capacity, and a wide range of application prospects in the fields of low-temperature solar heat storage, precision instrument temperature control, and intelligent buildings.

Utilizing Nanostructured Materials for Hydrogen Generation, Storage, and Diverse Applications.

The rapid advancement of refined nanostructures and nanotechnologies offers significant potential to boost research activities in hydrogen storage. Recent innovations in hydrogen storage have centered on nanostructured materials, highlighting their effectiveness in molecular hydrogen storage, chemical storage, and as nanoconfined hydride supports. Emphasizing the importance of exploring ultra-high-surface-area nanoporous materials and metals, we advocate for their mechanical stability, rigidity, and high hydride loading capacities to enhance hydrogen storage efficiency. Despite the evident benefits of nanostructured materials in hydrogen storage, we also address the existing challenges and future research directions in this domain. Recent progress in creating intricate nanostructures has had a notable positive impact on the field of hydrogen storage, particularly in the realm of storing molecular hydrogen, where these nanostructured materials are primarily utilized.

Oxidation Kinetics of Nanocrystalline Hexagonal RMn1-xTixO3 (R = Ho, Dy).

Hexagonal manganites, RMnO3 (R = Sc, Y, Ho-Lu), are potential oxygen storage materials for air separation due to their reversible oxygen storage and release properties. Their outstanding ability to absorb and release oxygen at relatively low temperatures of 250-400 °C holds promise of saving energy compared to current industrial methods. Unfortunately, the low temperature of operation also implies slow kinetics of oxygen exchange in these materials, which would make them inefficient in applications such as chemical looping air separation. Here, we show that the oxidation kinetics of RMnO3 can be improved through Ti4+-doping as well as by increasing the rare earth cation size. The rate of oxygen absorption of nanocrystalline RMn1-xTixO3 (R = Ho, Dy; x = 0, 0.15) was investigated by thermogravimetric analysis, X-ray absorption near-edge structure, and high-temperature X-ray diffraction (HT-XRD) with in situ switching of atmosphere from N2 to O2. The kinetics of oxidation increases for larger R and even more with Ti4+ donor doping, as both induce expansion of the ab-plane, which reduces the electrostatic repulsion between oxygen in the lattice upon oxygen ion migration. Surface exchange rates and activation energies of oxidation were determined from changes in lattice parameters observed through HT-XRD upon in situ switching of atmosphere.

Solid-solution MAX phase TiVAlC assisted with impurity for enhancing hydrogen storage performance of magnesium hydride.

Although MXene catalysts etched from precursor MAX have greatly improved the hydrogen storage performance of magnesium hydride (MgH2), the use of dangerous and polluting etchers (such as hydrofluoric acid) and the direct removal of potentially catalytically active A-layer substances (such as Al) present certain limitations. Here, solid-solution MAX phase TiVAlC catalyst without etching treatment has been directly introduced into MgH2 system to improve the hydrogen storage performance. The optimal MgH2-10 wt% TiVAlC can release about 6.00 wt% hydrogen at 300 °C within 378 s and absorb about 4.82 wt% hydrogen at 175 °C within 900 s. After 50 isothermal hydrogen ab/desorption cycles, the excellent cyclic stability and capacity retention (6.4 wt%, 99.6%) can be found for MgH2-10 wt% TiVAlC. The superb catalytic activity of TiVAlC catalyst can be explained by abundant electron transfer at external interfaces with MgH2/Mg, which can be further enhanced by impurity phase Ti3AlC2 due to strong H affinity brought from abundant electron transfer at internal interfaces (Ti3AlC2/TiVAlC). The influence of impurity phase which is common in MAX phase on the overall activity of catalysts has been firstly studied here, providing a unique method for designing composite catalyst to improve hydrogen storage performance of MgH2.

Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials.

New energy storage materials are an object of study within the framework of the global energy transition. The development of renewable sources is being boosted thanks to stationary energy storage systems such as redox flow batteries (RFBs). This work reports the synthesis of the cobalt-containing Keggin-type polyoxometalates [CoW12O40]6- (CoW12) and [Co(H2O)SiW11O39]6- (CoSiW11), which have previously been shown to have applicability in RFBs. These procedures were reassessed to meet the strict requirements associated with the further implementation of RFBs, including fast and affordable synthetic procedures with high reaction yields. In contrast to the lengthy and complicated synthetic approaches published to date, the optimized synthesis reported in this work enables the isolation of the pure crystalline salt of the CoW12 anion with a 75% reduction of the time of the whole reaction procedure, eliminating tedious steps such as the recrystallization and including a 20% increased yield. The control of the stoichiometry, fine-tuning of reaction conditions, and the identification of intermediate species, as well as the acidic equilibria taking place during the process, were monitored via thermal, spectroscopic, and structural analyses. In the case of the CoSiW11 anion, its preparation was based on a simple and highly efficient procedure. Moreover, promising electrochemical properties were observed with the use of the one-pot synthetic approach, in which the stoichiometric amounts of the starting reagents are dissolved in the supporting electrolyte to be directly implemented as the electrolyte for a RFB.

PdNi Biatomic Clusters from Metallene Unlock Record-Low Onset Dehydrogenation Temperature for Bulk-MgH2.

Hydrogen storage has long been a priority on the renewable energy research agenda. Due to its high volumetric and gravimetric hydrogen density, MgH2 is a desirable candidate for solid-state hydrogen storage. However, its practical use is constrained by high thermal stability and sluggish kinetics. Here, PdNi bilayer metallenes are reported as catalysts for hydrogen storage of bulk-MgH2 near ambient temperature. Unprecedented 422 K beginning dehydrogenation temperature and up to 6.36 wt.% reliable hydrogen storage capacity are achieved. Fast hydrogen desorption is also provided by the system (5.49 wt.% in 1 h, 523 K). The in situ generated PdNi alloy clusters with suitable d-band centers are identified as the main active sites during the de/re-hydrogenation process by aberration-corrected transmission electron microscopy and theoretical simulations, while other active species including Pd/Ni pure phase clusters and Pd/Ni single atoms obtained via metallene ball milling, also enhance the reaction. These findings present fundamental insights into active species identification and rational design of highly efficient hydrogen storage materials.

Room-Temperature Transient Hydrogen Uptake of MgH2 Induced by Nb-Doped TiO2 Solid-Solution Catalysts.

The practical applications of MgH2 as a high-density hydrogen carrier depend heavily on efficient and low-cost catalysts to accelerate the dehydriding/hydriding reactions at moderate temperatures. In the present work, this issue is addressed by synthesizing Nb-doped TiO2 solid-solution-type catalysts that dramatically improve the hydrogen sorption performances of MgH2. The catalyzed MgH2 can absorb 5 wt % of H2 even at room temperature for 20 s, release 6 wt % of H2 at 225 °C within 12 min, and the complete dehydrogenation can be achieved at 150 °C under a dynamic vacuum atmosphere. Density functional theory calculations reveal that Nb doping introduces Nb 4d orbitals with stronger interaction with H 1s into the density of states of TiO2. This considerably enhances both the adsorption and dissociation ability of the H2 molecule on the catalysts surface and the hydrogen diffusion across the specific Mg/Ti(Nb)O2 interface. The successful implementation of solid solution-type catalysts in MgH2 offers a demonstration and inspiration for the development of high-performance catalysts and solid-state hydrogen storage materials.