Magnesium-based materials are promising for solid-state hydrogen storage, yet their practical application is impeded by the high thermodynamic stability of MgH₂ and sluggish sorption kinetics. Here, we develop a targeted interfacial engineering strategy via d-band modulation to tailor the hydrogen storage performance of nano-Mg, by fabricating hexagonal boron nitride-supported PdNi bimetallic clusters (PdNi/BN) as an advanced catalytic additive. The nano-Mg@PdNi/BN composite delivers a drastically reduced onset dehydrogenation temperature of 173 °C (175 °C lower than pristine MgH₂), along with ∼95% capacity retention over 10 cycles. Kinetic and thermodynamic analyses confirm the composite exhibits remarkably lowered hydrogen absorption/desorption activation energies and reduced hydride formation enthalpy. Density functional theory calculations reveal that strong interfacial interactions at the PdNi/BN interface downshift the PdNi d-band center to −1.456 eV, which weakens Mg-H bonds, lowers hydrogen vacancy formation energy to −0.598 eV, and enhances H₂ absorption, enabling a bifunctional catalytic effect for both hydrogen sorption processes. This work provides a powerful strategy and atomic-level guidance for designing high-performance Mg-based hydrogen storage materials via d-band modulation.

ABSTRACT Transition metal diborides (TMB 2 ) possess excellent properties but suffer from rapid oxidation at elevated temperatures, severely limiting their applications. Here, we demonstrate crystal orientation engineering as an effective strategy to enhance oxidation resistance while retaining intrinsic characteristics. The polycrystalline TaB 2 films with strong (001) and (100) preferred orientations were synthesized via substrate‐bias‐controlled deposition. Air annealing revealed that (001)‐oriented TaB 2 films exhibit significantly improved oxidation resistance over (100)‐oriented films. First‐principles calculations show that the TaB 2 (001) surface has higher oxygen adsorption energy and a larger diffusion barrier, attributed to the alternating boron–metal layer stacking along [001]. Moreover, (001)‐oriented films maintain higher hardness and shear strength at both room temperature and 600°C. These findings establish orientation control as a promising pathway to simultaneously optimize oxidation resistance and mechanical robustness in TMB 2 , offering guidance for the design of protective coatings for high‐temperature applications.

HYPOTHESIS:In classical dropwise condensation, droplet transport is restricted by substrate-controlled pinning forces, which enforce a growth-to-detachment pathway. We hypothesize that externally guided sliding interfaces can decouple droplet motion from the nucleation surface and create a new interfacial dynamic regime governed by wettability-directed energy release rather than size-limited detachment. EXPERIMENTS:To test this hypothesis, we fabricated Ti/TiO2/PTFE hydrophobic tubes and wrapped them with superhydrophilic or hydrophobic stainless-steel wires to form heterogeneous sliding interfaces. High-speed imaging, droplet statistical analysis, and heat-flux measurements (ΔTlmtd = 8-76 K) were combined with purely two-dimensional phase-field simulations (without vapor condensation) to resolve film-wise wicking, coalescence-driven acceleration, and contact-line depinning along wire-guided pathways. FINDINGS:The sliding interfaces create a distinct interfacial state where droplet motion is dominated by wetting asymmetry and surface-energy conversion. This mechanism enables early-stage detachment that does not depend on classical critical-size constraints. Hydrophobic sliding channels provide strong decoupling, ensure continuous surface renewal, and achieve a 38.1% enhancement in heat flux, reaching 749 kW m-2 at ΔTlmtd ≈ 76 K. This study introduces an externally guided and structurally decoupled droplet transport mechanism that broadens the fundamental understanding of capillarity-driven dynamics and supports scalable, high-performance condensation interfaces.

Titanium diboride (TiB2), a representative transition metal diboride (TMB2) commonly utilized as a coating for high-speed cutting tools, is renowned for its remarkable hardness; nevertheless, its limited oxidation resistance and toughness remain prominent bottlenecks. Herein, by mapping the oxidative and mechanical characteristics based on ab initio and thermodynamic calculations, we propose a Cr-centered compositional optimization strategy that confers an exceptional synergy of oxidation resistance, hardness, and crack resistance to multicomponent transition metal diborides (MTMB2s). Theoretical analyses and oxidation experiments collectively reveal that the superior oxidation resistance of Ti0.50Cr0.50B2 over Ti0.50Al0.50B2 originates from sluggish surface oxygen diffusion, retarded oxidation kinetics, and the generation of dense oxides, specifically the novel Cr2TiO5. Mechanical evaluations further demonstrate that Ti0.50Cr0.50B2 exhibits superior hardness compared to Ti0.50Al0.50B2 and other ternary TiB2-based diborides, while concurrently retaining favorable crack resistance. This experimentally validated compositional optimization strategy, derived from the rapid screening of oxidative-mechanical properties, provides pivotal guidance for advancing high-performance MTMB2s.

Achieving optimal hydrogen storage performance in covalent organic frameworks (COFs) requires precise synthetic tuning to balance pore architecture, functionalization, and structural stability while ensuring scalability. However, significant challenges remain in translating laboratory-scale advancements into practical applications. This review critically examines the key challenges in COF synthesis, including the trade-off between porosity and functionalization, the need for precise control over hierarchical pore structures, and limitations in reproducibility and large-scale fabrication. We highlight the bottlenecks in current synthetic strategies, such as the difficulty in maintaining crystallinity while achieving high hydrogen binding affinity, and the challenges of integrating scalable synthesis techniques without compromising material performance. We explore emerging scalable synthesis approaches, including microwave-assisted, mechanochemical, and interfacial synthesis, which offer pathways toward industrial feasibility. Additionally, we discuss the future prospects of COF design, emphasizing the role of machine learning, high-throughput screening, and predictive modeling in accelerating material discovery and optimization. By integrating computational and experimental insights, we propose a data-driven roadmap for guiding the rational design of COFs, aiming to bridge the gap between fundamental research and practical hydrogen storage applications.

Transition metal diborides (TMB2) possess excellent properties but suffer from rapid oxidation at elevated temperatures, severely limiting their applications. Here, we demonstrate crystal orientation engineering as an effective strategy to enhance oxidation resistance while retaining intrinsic characteristics. The polycrystalline TaB2 films with strong (001) and (100) preferred orientations were synthesized via substrate-bias-controlled deposition. Air annealing revealed that (001)-oriented TaB2 films exhibit significantly improved oxidation resistance over (100)-oriented films. First-principles calculations show that the TaB2(001) surface has higher oxygen adsorption energy and a larger diffusion barrier, attributed to the alternating boron-metal layer stacking along [001]. Moreover, (001)-oriented films maintain higher hardness and shear strength at both room temperature and 600 degrees C. These findings establish orientation control as a promising pathway to simultaneously optimize oxidation resistance and mechanical robustness in TMB2, offering guidance for the design of protective coatings for high-temperature applications.

Electrocatalytic water splitting is a promising pathway for sustainable hydrogen production; however, its efficiency remains constrained by sluggish reaction kinetics and high overpotentials. Recently, the integration of multiple external physical fields has emerged as a powerful strategy to enhance catalytic activity by tuning charge transfer, adsorption behavior, and reaction energetics. This review comprehensively summarizes the synergistic effects of light and magnetic fields in electrocatalytic water splitting, covering both fundamental mechanisms and recent advances. The light field promotes charge separation, local photothermal heating, and plasmon‐induced hot‐carrier generation, thereby accelerating the hydrogen and oxygen evolution reactions. Meanwhile, the magnetic field modulates spin polarization, induces magnetohydrodynamic convection, and triggers magnetothermal effects to facilitate mass transport and optimize reaction pathways. We further highlight dual‐field coupling strategies, in which light and magnetic fields collaboratively reconfigure the electronic structure, regulate intermediate adsorption states, and jointly lower reaction barriers, leading to nonlinear catalytic enhancement. Finally, current challenges and future opportunities are discussed, emphasizing the integration of photonic, magnetic, and electronic effects in the rational design of next‐generation electrocatalytic systems for efficient and low‐carbon hydrogen production.

Developing efficient and durable electrocatalysts that minimize or eliminate Ir usage is essential for large-scale hydrogen production through proton exchange membrane water electrolysis. In this work, two IrO r -Co 3 O 4 catalysts with distinct interfacial configurations were constructed to clarify the effect of structural coupling on activity and stability. The embedded IrO r -Co 3 O 4 was prepared via a galvanic replacement-induced embedding process, while the surface-exposed IrO r -Co 3 O 4 was obtained through photo-reduction deposition. Structural analyses confirm the formation of strong Co-O-Ir linkages in embedded IrO r -Co 3 O 4 , in contrast to discrete surface IrO r nanoparticles in the exposed sample. Electrochemical measurements show that exposed-IrO r delivers a lower overpotential of approximate to 331 mV at 10 mA cm - 2 but suffers from fast Ir dissolution, whereas embedded IrO r maintains stable operation with a voltage of 1.78 V at 1 A cm - 2 for over 200 h in a PEM cell. In-situ Raman and DEMS results reveal that embedded IrO r follows a dominating classical adsorbate-evolution mechanism (AEM), while exposed IrO r -Co 3 O 4 involves a lattice-oxygen-mediated mechanism (LOM), leading to its inferior stability. This work highlights that strengthening Co-O-Ir interface effectively suppresses Ir loss and provides a general strategy for designing robust Ir-based catalysts for acidic water electrolysis.

In GaAs/InAs core/shell nanowires, comprising a tubular conducting shell, interference phenomena observed under an axial field and originating from closed-loop states encircling the insulating core, provide an ideal platform for superconducting quantum devices that utilize effects such as Aharonov–Bohm or Altshuler–Aronov–Spivak-type conductance oscillations. Both effects are different in nature with respect to phase rigidity because of interference of non-time-reversed or time-reversed paths, respectively. Since their occurrence is largely governed by averaging effects, which depend on sample dimensions and the transport regime, we present a systematic study of flux-periodic oscillations of phase-pure zinc-blende GaAs/InAs core/shell nanowires as a function of gate voltage for samples with different contact separation lengths. Our analysis shows that with increasing contact separation length, averaging effects result in gradual reduction of h/e-periodic Aharonov–Bohm-type oscillations, while the h/2e-periodic Altshuler–Aronov–Spivak oscillations and its h/4e-periodic higher harmonics are enhanced. The additional phase rigidity seen in the h/3e-periodic oscillations is attributed to phase rigidity propagating from the neighbouring lower harmonics. Our tight-binding transport simulations on nanowires of different lengths which contain only a few scattering centers confirm the experimental observations regarding the different harmonics and their phase rigidity. Together, our experimental and simulation findings indicate quasi-ballistic transport with persistent Aharonov–Bohm-, and phase-rigid Altshuler–Aronov–Spivak-type oscillations despite few scattering centers.

Charge and proton transfer in photocatalytic CO2 reduction reaction (CO2RR) are considered primary steps for effectively utilizing sustainable solar energy to meet environmental and renewable energy demands. The rational design of active sites is crucial for accelerating charge and proton transfer. In this study, we develop a ligandcoordinated single site strategy to improve photocatalytic CO2 efficiency by anchoring homogeneously single strontium (Sr) atom and its coordinated hydroxyl-terminal glycol on TiO2. The ligands can not only induce Sr to precisely anchor on the surface of TiO2, but also interact with Sr to boost photocatalytic efficiency, achieving a CO production of 25.37 mu mol g-1 h-1-about 14.7 times higher than that of pristine TiO2(1.73 mu mol g-1 h-1). Furthermore, Raman experiments reveal the durability of ligand sites on inorganic substrate surfaces. The enhanced mechanism relies on single sites to increase photocarrier transfer and suppress the recombination. The introduction of the Sr1 site and the ligand site facilitates CO2 adsorption and lowers the energy barrier, thereby accelerating the CO2 reduction reaction. Therefore, constructing and understanding multi-sites provides insights for rational design of catalytic sites for numerous important chemical and biological reactions.

Photothermal catalytic reduction of carbon dioxide (CO2) into valuable chemical feedstocks represents a sustainable approach for storing intermittent renewable energy and reducing CO2 emissions. However, this process is still impeded by the inherent inertness of CO2 and the production of multiple intermediates. Herein, we propose a strategy that facilitates the direct cleavage of carbonate intermediates to boost photothermal catalytic CO2 conversion. A highly efficient catalyst featuring active sites designed to improve the carbonate coverage was successfully constructed, composed of atomically dispersed praseodymium-modified ceria loaded with highly dispersed nickel species (Ni/Pr-CeO2). The fine structure of the prepared catalysts was revealed by high-resolution, high-angle annular dark-field scanning transmission electron microscopy, and X-ray absorption fine structure. Multiple in situ/operando spectroscopy techniques confirmed the active participation of interface oxygen species from Ni/Pr-CeO2 in enhancing carbonate (CO3*) and bicarbonate (HCO3*) intermediates coverage and transformation. In particular, under light irradiation, the C═O bonds within these intermediates are effectively weakened and cleaved, overcoming the high energy barrier associated with CO2 activation and enabling efficient CO production. As a result, the Ni/Pr-CeO2 catalyst demonstrates a high CO yield of 27.2 mol molNi-1 min-1, which is nearly three times higher than that of the Ni/CeO2 catalyst and maintains exceptional stability over 110 h without deactivation. Our findings contribute to the development of efficient catalytic systems that not only recycle greenhouse gases but also facilitate the integration of intermittent renewable energy sources into the chemical production landscape.

Carbon dioxide electroreduction reaction (CO 2 RR) offers a pathway to convert CO 2 into valuable multicarbon products (C 2+ ), potential clean energy, and chemical vectors, using renewable electricity. Copper catalysts are, so far, the most selective in this process, but still face challenges such as high overpotentials and insufficient selectivity and stability when used alone. One strategy to tackle these is the use of Cu-based tandem structures, which incorporate tailored reaction sites to drive a segment of the CO 2 RR reaction, in a more favorable way, within the same electrode. Recent examples have shown how Cu-tandem catalysts can lead to voltage savings and improvements in selectivity. This review analyses various Cu-based tandem catalysts, focusing on alloys, heterostructures (especially highlighting the role of polymer coatings in achieving tandem effects through environmental control), and metal–organic frameworks (MOFs). It covers synthetic strategies to achieve tandem-enabling configurations and their suggested impact on reaction mechanisms and performance improvement toward C 2+ electrosynthesis. The review concludes by offering a roadmap toward the design of more efficient Cu-based tandem electrodes for CO₂RR and beyond.

Tool protective films operate under extreme service conditions, requiring exceptional hardness. Transition metal diborides (TMB2), with strong covalent TM–B and B–B bonds, are promising candidates, but achieving superhardness while preserving their simple binary structure remains challenging. Here, we use HfB2 as a model system to reveal how boron vacancy filling and in-plane compressive stress synergistically enhance hardness, through combined experimental synthesis and first-principles calculations. (001)-oriented HfB2 thin films were fabricated, including sub-stoichiometric HfB2−x, stoichiometric HfB2, and stoichiometric HfB2 under compressive stress. Nanoindentation shows the hardness increases from 33.0 ± 1.1 GPa in HfB1.90 to 40.5 ± 0.4 GPa in stoichiometric HfB2, and further to 45.7 ± 1.1 GPa under −3.67 GPa stress. Calculations reveal that vacancy filling increases the number of load-bearing bonds and strengthens B–B bonding via charge accumulation, while compressive stress shortens B–B bonds to further enhance their strength. These findings clarify the atomic-scale mechanisms of vacancy and stress engineering in TMB2, and propose a simple, scalable pathway to superhard protective films without alloying or doping, addressing a long-standing challenge in coatings for extreme environments.

The photocatalytic reduction of CO2 presents a promising avenue for carbon fuel conversion. However, the efficiency of charge utilization remains a critical barrier to industrial applications. In this study, we introduce a tandem design of Bi2WO6-BiOCl with an atomically matched interface, achieving highly efficient photoreduction of CO2 to CO. By incorporating WO42-ions and tuning coordination environment, the (110) facet of BiOCl was in-situ grown on the (200) facet of Bi2WO6. Compared to single phases and ball-milling samples, Bi2WO6-BiOCl exhibits a remarkable CO yield of 68.03 mu mol g-1 h-1 with a selectivity of 98 %. Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport. Density functional theory (DFT) calculations and in-situ Fourier transform infrared (FTIR) spectroscopy provide insights into the intrinsic active sites and reaction mechanisms. The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Electrocatalysts support crucial industrial processes and emerging decarbonization technologies, but their design is hindered by structural and compositional changes during operation, especially at application-relevant current densities. Here we use operando X-ray spectroscopy and modelling to track, and eventually direct, the reconstruction of iron sulfides and oxides for the oxygen evolution reaction. We show that inappropriate activation protocols lead to uncontrollable Fe oxidation and irreversible catalyst degradation, compromising stability and reliability and precluding predictive design. Based on these, we develop activation programming strategies that, considering the thermodynamics and kinetics of surface reconstruction, offer control over precatalyst oxidation. This enables reliable predictions and the design of active and stable electrocatalysts. In a NixFe1-xS2 model system, this leads to a threefold improvement in durability after programmed activation, with a cell degradation rate of 0.12 mV h-1 over 550 h (standard operation: 0.29 mV h-1, constrained to 200 h), in an anion exchange membrane water electrolyser operating at 1 A cm-2. This work bridges predictive modelling and experimental design, improving the electrocatalyst reliability for industrial water electrolysis and beyond at high current densities.

Molybdenum disulfide (MoS2) is a potential material for capacitive deionization (CDI) electrodes due to its large surface area and theoretical capacitance. However, its low electrical conductivity and limited spacing between layers hinder the improvement of the desalination performance. In our research, we combined phase modulation and interlayer engineering methodologies to create a CDI electrode material made of metallic phase MoS2 with expanded interlayer spacing. The high conductivity of the metallic phase facilitates rapid charge transport, while the expanded interlayer spacing (increased from 6.2 & Aring; to 9.8 & Aring;) promotes effective utilization of active sites and reduces the barriers for ion diffusion. The created electrode showcases a notable specific capacitance (131.1 F g- 1 high desalination capacity of 47.1 mg g- 1 and a fast desalination rate of 2.4 mg g- 1 min- 1 in a 200 mg L- 1 NaCl solution. Furthermore, our density functional theory (DFT) calculations validate the essential role played by enlarged interlayer spacing in promoting Na+ insertion and accelerating its diffusion kinetics. at 10 mV s- 1 ) and an elevated capacitive contribution percentage (81 %). Additionally, it demonstrate

Equal-period modulated metal/ceramic multilayers have shown promise in enhancing the toughness of ceramic thin films. However, this toughness enhancement typically comes at the sacrifice of hardness, limiting their potential applications. To tackle this issue, this study designed and fabricated two gradient-structured multilayer variations using Ta/TaB2: one with a higher ceramic layer fraction near the surface (M2) and the other with a converse structure (M3). A conventional equal modulation period Ta/TaB2 multilayer film (M1) served as a reference. M2 exhibited superior performance, with a 30% hardness increase and significant toughness enhancement compared to M1. Conversely, M3 experienced failure due to excessive thermal stress from its unique gradient structure. Finite element simulations revealed that M2's structure could alleviate in-plane stress and enhance loading uniformity, thus enhancing the film's toughness. These findings suggest that a well-designed gradient structure holds promise for concurrently improving the hardness and toughness of metal/ceramic multilayer films. Gradient structure solves the hardness-toughness trade-off dilemma. image

Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolyte, renowned for its high ionic conductivity and robust safety profile at room-temperature, holds tremendous promise for diverse applications. However, it faces significant challenges, including high interface impedance with lithium and a propensity for lithium dendrite formation. To address these issues, a novel Li4(BH4)3I/2(d-BN) (LBHIbn) composite buffer layer - exhibiting high ionic conductivity and critical current density - is introduced at the LLZTO|Li interface. Theoretical calculations reveal that LBHIbn, serving as a protective layer of LLZTO, possesses a lower interface energy (0.366 J m-2) against lithium metal compared to LiBH4 (0.434 J m-2). Consequently, at 30 degrees C, the interface impedance of the LLZTO | LBHIbn | Li system is significantly reduced to 4 Omega cm-2. Simultaneously, the critical current density increases from 0.93 mA cm-2 of LLZTO | Li to 5.29 mA cm-2 (for LLZTO-LBHIbn | Li) with stable lithium-ion plating/stripping cycling demonstrated over 1000 h. Unlike conventional metal-based buffer layers that suffer from limited ionic conductivity, LBHIbn uniquely integrates high ionic conductivity (4.0 x 10-(4) S cm-1) with superior electronic insulation (1.9 x 10-(9) S cm-1), achieving simultaneous reduction of interfacial resistance (4 Omega cm2 at 30 degrees C) and effective suppression of lithium dendrite growth. This study demonstrates that the LBHIbn interface treatment effectively mitigates the interfacial issues between the LLZTO electrolyte and lithium anode, thereby expanding the potential applicability of hydride and oxide electrolyte materials in all-solid-state batteries

Methane dry reforming not only utilizes two potent greenhouse gases of methane and carbon dioxide, but also provides a valuable feedstock for the production of chemicals. However, this process has been heavily hindered by high operating temperature and coke formation with catalyst deactivation over the last century. Herein, we propose an approach whereby concentrated-solar catalytic methane dry reforming addresses these longstanding issues. By leveraging focused light as the sole energy source and utilizing a well-designed catalyst, the catalyst with Ni-O4 coordination active center achieves high conversion rates of 93.6% for CH4 and 93.7% for CO2, meanwhile sustaining stability for over 800 hours. Particularly noteworthy is the light-to-chemical energy conversion efficiency reaching 25.9%. This research represents a significant leap forward in integrating renewable energy sources with chemical production, offering a viable and sustainable alternative to traditional thermochemical processes for generating valuable chemicals.