Contact-electro-catalysis (CEC) offers a promising mechanochemical pathway for harvesting ubiquitous mechanical energy to drive hydrogen evolution. Bismuth oxyhalides are attractive CEC candidates owing to their layered polar structures and strong internal electric fields, yet their performance is limited by weak interactions between surface sites and adsorbates. Here, we combine density functional theory screening with experimental validation to investigate transition-metal-doped Bi5O7I as vibration-driven hydrogen evolution catalysts. Ten dopants (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) were systematically evaluated with respect to doping feasibility, water adsorption, and electronic characteristics. Among them, Fe-doped Bi5O7I was identified as a representative system offering a favorable balance of activity, abundance, and cost. Guided by theoretical insights, Fe/Bi5O7I nanorods were synthesized and demonstrated a hydrogen evolution rate of 2004.11 mu mol & sdot;g-1 & sdot;h-1 under ultrasonic stimuli. Mechanistic analyses further revealed that Fe doping enriches the electronic states near the Fermi level, enhances water adsorption, and reduces reaction barriers, while strain introduced by mechanical stimulation provides additional electronic modulation. This work establishes a theory-assisted framework for designing transition-metal-doped Bi5O7I catalysts and highlights the potential of CEC as a sustainable approach to hydrogen production.

Although chemical looping combustion (CLC) with solid fuels has reached the industrial demonstration stage, the utilization of oxygen carrier fines escaping from CLC reactors remains a critical bottleneck for its large-scale commercialization. This study proposes a novel strategy for preparing perovskite oxygen carriers using ilmenite fines from a 5MWth CLC pilot unit. The ilmenite fines, escaping from a 5MWth CLC pilot unit with biomass as fuel, are collected and used as the raw material for the perovskite oxygen carriers (CaMn0.5Ti0.375-Fe0.125O3-delta). A tonne-scale production of coarse-grained perovskite oxygen carriers with particle sizes larger than 450 mu m was achieved by a disc granulation method. The long-term cyclic performance of the optimized particles was evaluated using a micro-fluidized bed thermogravimetric analyzer (MFB-TGA). The prepared particles exhibit a superior combination of properties: a high single-particle crushing strength of 29 N (124 MPa), undiminished reactivity with no agglomeration after 150 redox cycles, and an attrition rate below 0.042%/h. The maximum oxygen capacity is 4.49 wt% for CLC, and the oxygen release amount is 0.12 wt% for CLOU. Furthermore, the oxidation rate is 7.835 & times; 10-4 wt%/s, the reduction rate is 1.668 & times; 10-4 wt%/s, and the performance of the perovskite prepared in this work is very similar to that of perovskite materials prepared from pure oxides. Additionally, XRD and EDS results indicate that no significant phase separation or elemental migration occurred in the particles after cycling. This work provides a feasible and scalable pathway to recover and reuse the ilmenite fines escaping from CLC reactors.

Alkaline aqueous zinc batteries (AZBs) are promising for high safety and high-energy density but are plagued by the poor reversibility of the zinc anode, manifesting as severe corrosion, hydrogen evolution, and passivation. While electrolyte additives can mitigate these issues, most of them fail to address the sluggish kinetics of the essential Zn/Zn(OH)42-/ZnO solid-liquid-solid conversion. Herein, we introduce cadmium selenide quantum dots (CdSe QDs) with tailored abundant Cd2+ dangling bonds as a multifunctional electrolyte additive. The QD species form a uniform dispersion across the electrode interface, significantly suppressing corrosion and hydrogen evolution. Simultaneously, the positively charged Cd dangling bonds act as active sites that adsorb OH-, which lowers the activation energy for the conversion reaction and enhances ion transport. As a result, Zn & Vert;Zn symmetric batteries with the QD additive exhibit longer cycle stability, lasting over 220 000 s at 5 mA cm-2, while that of KOH + ZnO is just around 30 000 s. This superiority is also validated in Zn-Ni full batteries, which demonstrate longer cycle life and higher capacity for the CdSe QD system. This work presents a novel strategy of using functional QDs as electrolyte additives to simultaneously stabilize the interface and promote reaction dynamics, paving the way for high-performance alkaline zinc-based batteries.

SrTiO 3 is a robust photocatalyst for overall water splitting, but its activity is limited by inefficient charge separation and sluggish surface redox kinetics.

The increasing adoption of lithium-ion batteries (LIBs) in electric vehicles, grid-scale energy storage, and emerging electric aviation is driving their development toward higher energy density and larger cell formats. This trend renders internal temperature gradients unavoidable, making it imperative to understand their effect on spatially inhomogeneous transport, electrochemical reactions, and lithium plating. Here, a high-fidelity threedimensional multiphysics model is developed to quantify the effects of cooling modes from the electrode to the cell scale. We show that temperature gradients amplify intrinsic transport and reaction heterogeneity, thereby governing the preferential initiation and evolution of lithium plating. Cell-scale simulations reveal that side cooling induces pronounced layer-to-layer electrochemical heterogeneity, while an inherent self-regulating mechanism emerges to mitigate state-of-charge (SOC) divergence among layers. More importantly, we uncover a counterintuitive layer-to-layer lithium plating behavior, whereby warmer electrode layers exhibit more severe lithium plating under high-rate charging despite their more favorable kinetics. Mechanistically, this behavior originates from the competition between current concentration and kinetic limitations, whereby faster kinetics in warmer layers drive secondary current redistribution and locally promote lithium plating when charging at high C-rates. These results provide mechanistic guidance for the synergistic design of next-generation batteries, thermal management strategies, and fast-charging protocols.

Supercapacitors (SCs) are fascinating energy storage devices due to their delivery of exceptional power density and long cycling stability. Unfortunately, their practical applications are still impeded by the inferior energy density derived from sluggish electrolyte transports. Herein, we demonstrate a strategy via the in situ electrochemically derived flexible metallopolymer electrode to precisely govern the directional migration of redox-active electrolytes. As a result, the assembled SC achieves a high areal capacitance of 2729 mF cm-2 at 1 mA cm-2, together with remarkable rate capability and cycling stability. Further fabrication of the solid-state device exhibits an ultrahigh areal capacitance of 1440 mF cm-2 and energy density of 0.5 mW h cm-2 at the power density of 0.8 mW cm-2. Systematic experimental characterizations combined with thermodynamic and kinetic simulations reveal that electrolytes are directionally guided to specific active sites on the electrode surface, where accelerated I-/I3 - faradaic reactions occur, highlighting a synergistic kinetic interplay between the electrode surface and electrolyte that enables high-performance flexible supercapacitors.

Electrochemical CO2 reduction (CO2R) offers a promising route to mitigate the pressing carbon emissions and facilitate renewable energy storage. Here, we report a facile electrolyte engineering strategy to modulate the electrical double layer (EDL) at the electrode/electrolyte interface, steering CO2R toward selective formate production on Cu. By introducing cationic surfactants (Dodecyltrimethylammonium bromide, DTAB) into the electrolyte, we achieve an 82% selectivity for formate on a Cu-based foam electrode at -0.9 V versus RHE. Through detailed kinetic analysis and in situ spectroscopy, we attribute this enhancement to the organic cation DTA+. Specifically, DTA+ reduces the interfacial charge-transfer resistance for CO2R, promotes the adsorption and stabilization of formate intermediates, and disrupts the hydrogenbond network by increasing the fraction of free interfacial water. We further demonstrate the practical relevance of this approach in a zero-gap cell and achieve a formate selectivity of 88% at a current density of 300 mA cm-2, with stable operation for 120 h at 100 mA cm-2. This organic-cation regulation strategy offers a feasible route to tune interfacial charge-transfer dynamics and intermediate adsorption, thereby enhancing CO2R reactivity toward a single product.

The growing demand for sustainable hydrogen production has driven increasing interest in wastewater as a resource for simultaneous pollutant removal and energy recovery. However, most existing wastewater-to-hydrogen approaches rely on external electricity, light, or chemical agents, underutilizing mechanical energy and inherent charge complementarity. Here, a piezocatalytic upgrading strategy is developed to couple organic pollutant degradation with hydrogen evolution in a single mechanically driven system. Zinc oxide nanorods serve as the piezoelectric platform, while surface-engineered silver regulates interfacial charge extraction and directional utilization. Under mechanical excitation, piezoelectric polarization generates complementary charges that drive oxidative pollutant degradation and reductive hydrogen evolution. Using rhodamine B as a model contaminant, the Ag-modified ZnO nanorods deliver a 90.8% increase in hydrogen yield and a 339% enhancement in degradation kinetics compared to pristine ZnO. Notably, the system demonstrates versatile applicability across various classes of pollutants and real-water matrices, maintaining efficient upgrading performance under ambient atmosphere and low-intensity mechanical stirring. Combined experimental and theoretical results reveal that the Ag interface enhances charge separation, water activation, and hydrogen adsorption energetics. This work establishes a dual-functional piezocatalysis paradigm for scalable wastewater-to-hydrogen upgrading.

Electrochemical CO 2 reduction to multicarbon (C 2+ ) products with high selectivity at industrial current densities using a membrane electrode assembly (MEA) electrolyzer in neutral electrolytes holds a great promise for carbon neutrality. However, the complex reaction pathways and low selectivity for C 2+ products have hindered further development. Herein, an oxygen vacancy‐engineered CuO nanoflower catalyst was designed to construct stable Cu 0 /Cu + active interfaces and induce a localized alkaline microenvironment, effectively suppressing the competing hydrogen evolution reaction (HER) while enhancing ethylene (C 2 H 4 ) selectivity. In situ spectroscopic characterization confirmed the stability of the Cu 0 /Cu + active sites and their high *CO surface coverage. Multiphysics simulations combined with density functional theory (DFT) calculations revealed that the stable Cu 0 /Cu + interface coupled with the localized alkaline microenvironment reduces the energy barrier for asymmetric C─C coupling, thereby boosting C 2 H 4 selectivity. The optimized catalyst achieved remarkable C 2 H 4 Faradaic efficiencies of 66.8% in alkaline and 66.1% in neutral electrolyte at a current density of 200 mA cm – 2 . This strategy of stabilizing Cu 0 /Cu + interfaces coupled with microenvironment modulation offers novel insights for enabling highly selective CO 2 ‐to‐C 2 H 4 electrosynthesis at high current densities.

Electrochemical CO2 reduction to multicarbon (C2+) products with high selectivity at industrial current densities using a membrane electrode assembly (MEA) electrolyzer in neutral electrolytes holds a great promise for carbon neutrality. However, the complex reaction pathways and low selectivity for C2+ products have hindered further development. Herein, an oxygen vacancy-engineered CuO nanoflower catalyst was designed to construct stable Cu0/Cu+ active interfaces and induce a localized alkaline microenvironment, effectively suppressing the competing hydrogen evolution reaction (HER) while enhancing ethylene (C2H4) selectivity. In situ spectroscopic characterization confirmed the stability of the Cu0/Cu+ active sites and their high *CO surface coverage. Multiphysics simulations combined with density functional theory (DFT) calculations revealed that the stable Cu0/Cu+ interface coupled with the localized alkaline microenvironment reduces the energy barrier for asymmetric C & horbar;C coupling, thereby boosting C2H4 selectivity. The optimized catalyst achieved remarkable C2H4 Faradaic efficiencies of 66.8% in alkaline and 66.1% in neutral electrolyte at a current density of 200 mA cm- 2. This strategy of stabilizing Cu0/Cu+ interfaces coupled with microenvironment modulation offers novel insights for enabling highly selective CO2-to-C2H4 electrosynthesis at high current densities.

Transition metal stannates have emerged as promising candidates for efficient air purification owing to their remarkable activity in volatile organic compounds (VOCs) degradation under ambient conditions. However, the molecular-level origin of key active species and the fundamental mechanism underlying aromatic ring activation specifically, the steps of C-H bond cleavage and ring-opening oxidation remain elusive, hindering the rational design of catalysts toward complete toluene (C7H8) mineralization. Herein, an oxygen-vacancy-enriched S-scheme heterojunction, denoted as OV/SnO2@MSH (MSH = MgSn(OH)6), was constructed via a facile one-step hydrothermal strategy. The optimized heterostructure exhibits outstanding performance in C7H8 removal (96.65%), mineralization efficiency (101.8%), and long-term operational stability (>600 min). Combined experimental and theoretical analyses unveil the critical roles of OVs in modulating charge transfer and reactive oxygen species (ROSs) evolution. Specifically, (1) the incorporation of OVs induces a dual-electron transfer pathway centered on OV sites, greatly facilitating interfacial charge migration; (2) this enhanced charge transfer in turn promotes O2 adsorption and its activation into highly oxidative singlet oxygen; and (3) the optimized interface further accelerates intermediate conversion, enabling a smoother Gibbs free energy profile for efficient ring-opening oxidation. This work provides molecular-level insights into charge dynamics and ROSs modulation within S-scheme heterojunctions, offering a new paradigm for the rational design of advanced photocatalysts toward deep VOCs mineralization and sustainable air purification.

Solar-driven photocatalytic hydrogen evolution over TiO2 presents a sustainable solution to the global energy crisis and environmental issues. However, the practical application of TiO2 is currently hampered by its rapid electron-hole recombination and scarcity of active sites. Herein, a Cu-O-Ti asymmetric dual-site photocatalyst (Cu1-Ti/TiO2) was constructed by anchoring Cu single atoms onto TiO2. The electronic asymmetry between the introduced Cu atoms and the intrinsic Ti sites gives rise to a built-in electric field oriented from Cu to Ti. This interfacial polarization drives the migration of photogenerated electrons from Ti 3d orbitals to partially filled Cu 3d orbitals, where the Cu centers serve as electron-trapping sites, thereby promoting efficient charge separation and inhibiting electron-hole recombination. Moreover, Ti sites act as the primary centers for H2O adsorption and dissociation, whereas Cu sites preferentially mediate H adsorption and H2 formation, synergistically facilitating hydrogen evolution. Consequently, an extraordinary H2 evolution rate of 1.91mmol g-1h- 1 is achieved, which is 63.67 times higher than that of pristine TiO2 (Ti/TiO2) and ranks among the highest reported for TiO2-based photocatalysts. This work provides a novel strategy for the rational construction of asymmetric dual sites to advance solar-to-hydrogen energy conversion.

Photocatalytic conversion of CO2 to renewable hydrocarbon fuels provides a sustainable avenue for mitigating the global greenhouse effect and the energy shortage crisis. However, the development of highly efficient CO2 photoreduction catalysts remains a substantial challenge due to the weak light absorption, rapid carrier recombination, and inefficient active site. Herein, we suggest a plasmonic silver-deposited Bi5O7I photocatalyst synthesized via combination approaches of wet chemical and solid-state reaction methods, achieving an enhanced CO evolution rate of 23.01 μmol g-1 h-1 under simulated solar light without any sacrificial agents. Mechanism analysis indicated that the enhanced activity originates from the localized surface plasmon resonance effect and plasmonic metal/semiconductor junction, which can trigger stronger visible light absorption and facilitate the separation of photogenerated carriers. Moreover, the metal/semiconductor interface can provide highly efficient active sites to significantly enhance the adsorption capability of reaction intermediates and smooth the Gibbs free energy profiles, ultimately leading to superior photocatalytic CO2 reduction (PCR) activity. To summarize, this work delivers an efficient strategy to achieve the simultaneous improvement of light absorption, carrier dynamics, and surface reaction and ultimately promote the PCR performance.

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.

Transition metal stannates are promising for efficient air purification due to their remarkable activity in volatile organic compounds (VOCs) degradation. However, the interfacial charge-transfer behavior and the fundamental mechanism of aromatic ring activation, specifically, C-H bond cleavage and ring-opening oxidation remain elusive, hindering rational catalyst design for toluene (C7H8) mineralization. Herein, an oxygen-vacancy-enriched S-scheme heterojunction (SMSH-30) is constructed via a facile one-step hydrothermal strategy. The optimized heterostructure exhibits outstanding toluene removal (96.65%), mineralization efficiency (101.8%), and long-term stability (>600 min). Combined experimental and theoretical analyses unveil that oxygen vacancies (OVs) modulate charge transfer and reactive oxygen species (ROS) evolution: (1) OVs induce dual-channel electron migration, greatly facilitating interfacial charge transfer; (2) this enhanced transfer promotes O-2 activation into highly oxidative singlet oxygen (O-1(2)); and (3) the optimized interface accelerates intermediate conversion with a favorable Gibbs free energy profile. This work provides molecular-level insights into charge dynamics and ROS modulation within S-scheme heterojunctions, offering a new paradigm for rational design of advanced photocatalysts toward deep VOC mineralization and sustainable air purification.

Sensitive and selective detection of nitrogen oxides (NOx) is increasingly critical for both environmental protection and human health. However, current detecting methods are based on metal oxide sensors, which are greatly limited by issues of high energy consumption, low selectivity, and poor environmental compatibility. Herein, we systematically explore the potential of eleven experimentally available transition metal single atoms (M = Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in nitrogen-doped graphene (M–N–C) for NOx detection. It is revealed that Ni–N–C exhibits exceptional selectivity and sensitivity toward NOx, as evidenced by the preferable and moderate adsorption strength and significant changes in microscopic electronic structures and macroscopic current–voltage characteristics. Furthermore, applying proper external electric fields or strains enables to accelerate the recovery of Ni–N–C. This work highlights the promising potential of Ni–N–C for real-time NOx monitoring and offers valuable insight into the application of single-atom catalysts in sensing.

We present a comprehensive first-principles study on a series of isostructural Cr3+-doped garnets with varying chemical compositions. The study aims to explore the effect of host properties and local coordination environments on the optical properties of the Cr3+ impurity ion. Specifically, we calculated the energies of the excitation and emission band maxima, as well as the zero-phonon line energies, for the 4A2-2E and 4A2-4T2 optical transitions of Cr3+ ions in A 3 B 5O12 garnets (A = Lu, Y, Gd, La; B = Al, Ga, Sc). The calculated optical transition energies are in good agreement with experimental measurements. Our results reveal that the position of the 4T2 energy level, governed by the crystal-field (CF) strength, is primarily determined by variations in the Cr3+-O2- bond lengths. Longer Cr3+-O2- bond lengths reduce the CF strength, placing the 4T2 energy level below the 2E energy level, which results in the broadband 4T2 -> 4A2 emission. In contrast, shorter Cr3+-O2- bond lengths increase the CF strength, raising the 4T2 energy level above the 2E energy level and producing only the R-line (2E -> 4A2) and its vibronic sideband in the Cr3+ emission spectrum at room temperature. In garnet compounds where the 4T2 and 2E energy levels are close in energy, the emission spectrum is composed of the R-line superimposed on the broadband 4T2 -> 4A2 emission. These findings enhance our understanding of the relationship between chemical composition and optical properties in Cr3+-doped garnets. Moreover, they hold significant scientific and technological importance, paving the way for the discovery of efficient phosphors for near-infrared phosphor-converted light-emitting diode devices using high-throughput design methodologies.

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.