Developing efficient and durable electrocatalysts for the alkaline hydrogen evolution reaction (HER) is crucial for sustainable hydrogen production. Although heterointerfaces between transition metal phosphides (TMPs) and metal (hydro)oxides (MOs) offer promise, their performance is fundamentally limited by inherent bottlenecks: strong hydroxyl (OH & lowast;) binding poisons the water-dissociation sites, while suboptimal hydrogen (H) adsorption persists on the TMP regions. Herein, we report a universal dual-phase boron doping strategy to simultaneously modulate the electronic structures of both components in a model Ni2 P/V2 O3 heterostructure. Experimental and theoretical analyses reveal that boron doping induces localized electron enrichment at V and P sites, achieving three synergistic effects: weakened OH & lowast; binding on V sites to prevent poisoning, near-ideal H & lowast; adsorption strength on P sites, and enhanced interfacial electric fields that accelerate water dissociation. The resulting Ni2 Bx P1-x /V2 By O3-y catalyst requires ultralow overpotentials of 16 mV (alkaline freshwater) and 17 mV (alkaline seawater) at 10 mA cm-2 , with exceptional durability over 100 h at 10 0 0 mA cm-2 in corrosive seawater. The universality of this strategy is demonstrated across diverse TMP/MO systems, establishing a generalizable paradigm for designing high-performance, industry-relevant electrocatalysts. (c) 2026 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.

The alkaline hydrogen evolution reaction (HER) offers a practical pathway for large-scale green hydrogen production but suffers from sluggish kinetics due to an additional water dissociation step and hydroxyl poisoning at heterojunction interfaces. Here, we address these challenges by designing a Sn-doped Ni3N/NiO heterostructure (Ni3N/Sn-NiO) grown on nickel foam via a hydrothermal–annealing approach. Experimental characterizations confirm that Sn4+ ions are selectively incorporated into the NiO lattice, inducing lattice expansion and electronic modulation. This targeted doping weakens the excessively strong OH* binding on NiO, mitigating hydroxyl poisoning, while the electronic perturbation extends to adjacent Ni3N, optimizing H* adsorption. Consequently, the Ni3N/Sn-NiO catalyst delivers outstanding alkaline HER performance with overpotentials of only 37 and 139  mV at 10 and 100  mA cm−2, respectively, along with excellent stability for 100  h. Kinetic isotope effect, pH–dependent measurements, and underpotential deposition reveal synergistically enhanced water dissociation, OH− transfer, and H* adsorption/desorption. This work establishes a targeted doping strategy at heterojunction interfaces to alleviate hydroxyl poisoning, providing a new reference for designing high–performance, non–precious metal HER catalysts for practical alkaline water/seawater electrolysis.

Electrochemical nitrate reduction reaction (NO3-RR) offers a sustainable avenue for concurrent ammonia synthesis and wastewater remediation. However, it is severely impeded by the sluggish kinetics of nitrate activation and the parasitic hydrogen evolution reaction. Herein, we present a trimetallic spinel oxide nanoarray (CoNiCuO4/CC) designed via cationic substitution to bridge the intrinsic conductivity and adsorption gaps of cobalt-based spinels. Experimental and theoretical investigations demonstrate that the integration of Cu and Ni induces a dual-enhancement mechanism: boosting bulk electronic conductivity while optimizing the d-band center, ensuring rapid interfacial electron transfer and reducing the thermodynamic barrier for the potential-determining reduction of *NO to *NOH. Consequently, the CoNiCuO4/CC electrocatalyst presents a remarkable NH3 yield of 710.35 μmol h−1 cm−2 at −0.7 V vs. RHE, alongside with a peak Faradaic efficiency of 98.87 % at −0.6 V vs. RHE. This work establishes a precise compositional engineering protocol for multi-metallic spinels, offering a robust pathway for upgrading NO3– pollutants into value-added energy carriers under ambient conditions.

The properties of ultra-fine grained cemented carbide are highly dependent on the uniformity and grain size of its raw material powders. In this study, VC-modified WC-10Co-xVC composite powders were systematically fabricated via spray conversion combined with in-situ synthesis technology. The focus was placed on investigating the influence of the spray-drying–calcination process on the structure of precursors and oxide powders, optimizing the parameters of reduction–carburization processes, elucidating the reaction pathway and mechanism during the in-situ synthesis of WC–Co–VC composite powders, and analyzing the occurrence state of VC in the composite powders as well as its potential impact on the subsequent alloy performance. Results indicate that the precursors obtained by spray drying exhibit sphere-like concave structures, which are fully converted into oxides such as WO₃, CoWO₄, and V₂O₅ after calcination at 550°C for 30 minutes, with homogeneous elemental distribution. Short-duration ball milling effectively disrupts the spherical morphology of the precursors. Under a hydrogen atmosphere, complete conversion of oxides into WC and Co is achieved after reduction–carburization at 1150°C for 60 minutes, where the uniform distribution of carbon derived from glucose pyrolysis significantly promotes the low-temperature carburization process, while vanadium undergoes a transformation sequence of V₂O₅ → VO₂/V₂O₃ → VC. The addition of VC does not markedly alter the powder morphology but causes a shift of Co-phase diffraction peaks toward lower angles, indicating the dissolution of V atoms into the Co phase, thereby providing the microstructural basis for VC to inhibit WC grain growth during subsequent sintering. This study provides an efficient and reliable process route for producing ultra-fine WC-based composite powders with homogeneous composition and effective inhibitor doping.

Mitigating the poisoning effect of sulfur dioxide on catalysts remains a significant challenge for ammonia selective catalytic reduction (NH3-SCR) technology. To this end, this study prepared a co-doped CeFeMn-Ti catalyst via the sol-gel method. For comparison, Ce/FeMn-Ti catalyst with exposed Ce and FeMn/Ce-Ti catalyst with internally dispersed Ce were also synthesized. Experimental results demonstrate that the CeFeMn-Ti catalyst delivers optimal NH3-SCR performance, achieving 100% NOx conversion between 125 and 200 degrees C while exhibiting exceptional SO2 resistance. The co-doping strategy enhances synergistic interactions among the components, which significantly increases the population of surface acid sites and oxygen vacancies. Furthermore, co-doping preserved the catalyst's maximum specific surface area, endowing the CeFeMn-Ti catalyst with the highest number of active sites. Consequently, cerium doping effectively suppresses the sulfation of manganese, thereby markedly improving the catalyst's sulfur tolerance. This study provides crucial guidance for optimizing the performance and enhancing the water and sulfur resistance of composite oxide catalysts in NH3SCR systems.

Element doping modification strategies affect the surface catalytic process and reaction kinetics by altering the local structure and electronic states of catalytic sites. A thorough understanding of the microscopic atomic and electronic structures is conducive to uncovering the catalytic potential of materials. In this study, Mn-doped Co3O4 was synthesized and demonstrated significantly superior catalytic performance, water resistance, and long-term durability compared to pure Co3O4. Research indicates that Mn doping endows Co3O4 with a relatively high Co3+ content and oxygen vacancies, which are more conducive to CO catalytic oxidation. Additionally, Mn has fewer d electrons than Co, resulting in a higher d-band center, which could hinder the electron exchange between Mn and CO molecules. Such an effect weakened the CO adsorption, shifting it toward the optimal range defined by the Sabatier principle. This study revealed the controllability of the surface catalytic process of reactant molecules and provided theoretical guidance for the element doping strategy.

The design of catalysts with broad operational temperature window and strong poisoning resistance is a central challenge in NOx catalytic removal. Herein, we report a strategy to regulate CeZrOx electronic structure and surface properties via Mo doping. Moderate Mo doping not only increases specific surface area but, more importantly, induces strong electronic interactions within the CeZrOx lattice. These interactions markedly increase Ce3+ concentration and surface chemisorbed oxygen species, generating abundant oxygen vacancies and optimizing surface acid site distribution, which synergistically enhances redox performance and surface acidity. The optimized CeZrMo9 catalyst achieves >85% NO conversion at 225–400 °C while maintaining >90% N2 selectivity across 150–350 °C, with outstanding resistance to water and sulfur poisoning. In situ DRIFTS confirms the reaction proceeds via the Langmuir-Hinshelwood mechanism, whereby Mo doping modulates the electronic structure to promote reactant adsorption and reaction on adjacent active sites. This work reveals the crucial role of intermetallic electronic interactions in optimizing SCR catalysts, offering a new design strategy for highly efficient and poisoning-resistant NOx abatement catalysts.

The strategic design of heterostructured interfaces is a powerful avenue for optimizing electrocatalytic performance, yet leveraging crystalline-amorphous interactions for the CO2 reduction reaction (CO2RR) remains underexplored. Herein, an Ag/La(OH)3 crystalline-amorphous heterostructure was constructed by a facile synthesis. This unique configuration induces strong electronic coupling, optimizing intermediate adsorption. The optimized catalyst achieves exceptional CO selectivity with a 97.6% faradaic efficiency at -0.78 V vs. RHE. Furthermore, it enables a Zn-CO2 battery with a 16.71 mW cm-2 peak power density.

Hollow CuFe-CeO2 catalyst using carbon spheres (CS) as sacrificial templates was successfully designed for COSCR. Here, we achieve the precise control of the distribution of Cu2+ and Fe3+ in hollow CeO2 sphere and demonstrate the importance of synergistic effects among active components. The results indicate that both Cu2+ and Fe3+ are incorporated into the CeO2 sphere lattice, enhancing the synergistic effects between Cu-Ce and FeCe and generating a large number of reactive oxygen species and oxygen vacancies. This enables the catalyst to achieve approximately 100% NO conversion and 90% N2 selectivity at 225 degrees C. During the reaction, Cu species maintain a certain degree of cycling between Cu2+ and Cu+. The reaction mechanism further elucidates Cu species and Fe species serve as low-temperature and high-temperature active sites respectively, exhibiting a "dual switch effect": the former endows the catalyst with outstanding low-temperature reactivity, while the latter ensures its high-temperature stability. In summary, this research serves as a possible foundation for developing hollow CeO2-based catalysts.

Copper- and cobalt-based oxides are promising catalysts for sustainable NOX abatement. However, their practical application is severely limited by the unavoidable presence of water vapor in exhaust gases. Herein, we demonstrate that trace, frequently overlooked ethylene glycol (EG)-derived in situ carbon can be deliberately exploited as an effective electron donor to regulate the electronic structure of CuCo2O4. As a result, both water tolerance and high-temperature DeNOX efficiency are significantly improved. Integrated characterizations and DFT calculations demonstrate that synthesis temperature dictates metal-EG coordination, thereby regulating the in situ carbon content. Acting as an intrinsic electron donor, this residual carbon promotes the formation of low-valent Cu+ and Co2+ species and markedly increases the concentration of oxygen vacancies. In situ DRIFTS, NO-TPD-MS, and characterization of the control sample demonstrate that these oxygen vacancies facilitate the formation of abundant and thermally stable NOX species through the continuous generation of reactive oxygen. While abundant and stable NOX species limit low-temperature activity by suppressing Cu+-CO intermediates, they enable a direct reaction with CO at elevated temperatures, boosting catalytic performance. More importantly, these stable NOX species effectively inhibit the competitive adsorption of H2O on active sites, thereby significantly enhancing water resistance. Consequently, this work highlights the potential of EG-derived in situ carbon as an efficient electronic modulator for CuCo2O4, offering a simple, one-pot, and cost-effective pathway for developing water-resistant DeNOX catalysts.

The electrochemical reduction of nitrate (NO3- ) presents a sustainable approach for mitigating NO3 -contamination while generating value-added ammonia (NH3). However, achieving high efficiency and selectivity under ambient conditions remains a significant challenge. Here, we develop an enzyme-like CuO-Co3O4 heterojunction catalyst that efficiently facilitates NO3 -reduction to NH3 under neutral conditions, mimicking enzymatic active sites to boost activity. The enzyme-like catalyst exhibits an exceptional NO3 -conversion rate of 99.6 % and 100 % NH3 selectivity, achieved through the optimization of interfacial electronic interactions. In-situ Raman spectroscopy and density functional theory analyses reveal that cascade reactions facilitated by the CuO-Co3O4 interface significantly enhance the rate-determining step and lower the energy barrier, thereby improving NO3 - electroreduction efficiency. Furthermore, a continuous supply system suppling NH4+-N demonstrates its potential to promote plant growth and fruit production, highlighting its practical applicability. This study offers targeted strategies for addressing NO3 -contamination, synthesizing value-added NH3, and advancing sustainable agriculture practices.

Herein, a WO3 nanorod array photoanode is controllably synthesized via a urea-modulated hydrothermal process, after which iron phthalocyanines (FePcs) with tunable Fe centers (H-FePc) are in situ deposited onto the surface of WO3 nanorods through electrodeposition, followed by a hydrogen reduction treatment. The optimized H-FePc/WO3 photoanode exhibits a remarkable photocurrent density of 2.44 mA cm-2 at 1.23 VRHE while showing robust stability under AM 1.5 G irradiation, which is ∼10-fold enhancement in comparison with that of pristine WO3 nanorod arrays. The one-dimensional array structure of WO3 nanorods can enhance light harvesting by virtue of the light trapping effect, provide large surface area for electrolyte penetration and offer a short diffusion path for electrons. Moreover, the modified FePcs considerably facilitate charge transfer and separation by extracting holes to the electrode-electrolyte interface. In addition, the isolated Fe(II)/Fe(0) catalytic sites synergistically expedite water oxidation kinetics. This study offers a feasible route to designing and fabricating high-performance photoanodes for water oxidation.

The challenge in designing efficient reverse water-gas shift (RWGS) catalysts necessitates high CO selectivity and CO2 conversion while suppressing CH4 formation and ensuring thermal stability. In this study, entropy engineering was proposed to successfully synthesize the medium entropy encapsulated crystalline oxide catalyst La4(NiCoAlCu)Ox (MEO). The entropy-driven delayed diffusion promotes the formation of the Ni-Co-Cu alloy phase during the reduction process, while the simultaneous formation of the La2O3 support improves the dispersion of the active metal. It combined with the physical confinement effect of the hierarchical porosity structure, effectively stabilizing the Ni/Co/Cu nanoparticles against high temperature agglomeration. Entropy-induced lattice distortion generated abundant oxygen vacancies, providing strong adsorption sites for CO2 and promoting H2 dissociation into active H* species. These synergistic effects created a tripartite active configuration ("alloy-oxide interface-oxygen vacancies") within MEO, enabling an "efficient adsorption-activation-conversion" pathway. Consequently, MEO achieved outstanding catalytic performance and high thermal stability at 550 degrees C, maintaining >= 95% CO selectivity over 1000 hours. In contrast, enthalpy-dominated La5(NiCoAlCuZr)Ox (Zr-MEO) suffered from significantly reduced activity due to multiphase segregation and oxygen vacancy scarcity. This work elucidates entropy engineering's pivotal role in stabilizing the catalyst structure and modulating interfacial activity, proposing an "entropy-driven structural engineering" strategy for designing durable, highly active, and selective high-temperature CO2 hydrogenation catalysts.

MnOx exhibits excellent low temperature activity for degradation NOx, but its poor SO2 tolerance restrains its application. Herein, an in situ construction method for MnOx loading on Mn-doped ZrO2 carrier with carbon (MnOx/Mn-ZrO2-C) derived from Mn(NO3)2/UIO-66 by in situ doped pyrolysis-oxidation, in which Mn replaces Zr to modify the electronic structure of the ZrO2. The MnOx/Mn-ZrO2-C with abundant surface oxygen and acid sites showed excellent activity and better SO2 resistance. A series of characterization results indicated that Mn doping modulates the electron structure of carrier ZrO2 and enhances the interactions among MnOx, carbon, and Mn-ZrO2, resulting in increasing the electron cloud density around Mn and Zr, and consequently, the Mn and Zr on the MnOx/Mn-ZrO2-C exhibit poorer sulfiphilic. These findings emphasize the benefits of utilizing a multi-pronged effect to fabricate highly active and sulfur-resistant NH3-SCR catalysts.

Correction for ‘Amorphous heterojunction and fluoride-induced effects enable a F-Ni(OH)2/Ni–B electrocatalyst for efficient and stable alkaline freshwater/seawater hydrogen evolution at a high current density’ by Shenyi Chen et al., Inorg. Chem. Front., 2024, 11, 8212–8222, https://doi.org/10.1039/D4QI01853B.

To shed light on the rapid voltage degradation of anion exchange membrane water electrolyzers, this study examines the degradation mechanism of a cathode electrode prepared via spray coating. To circumvent this obstacle, a solution casting technique is suggested to enhance the stability of the membrane-electrode interface, thereby effectively mitigating the performance deterioration.

The SO2 resistance for Ce-based catalysts is a significant challenge for practical application in NH3-SCR. Herein, a series of the tungstophosphoric acid (HPW) modification Fe-Ce bimetal oxide catalysts are prepared by a one-pot sol-gol strategy. The 0.2H-Fe0.15Ce0.85 catalyst exhibits more than 90 % NO conversion at 225-375 degrees C and satisfactory SO2 resistance under a GHSV of 60000 h-1. The HPW increases abundant Br & Oslash;nsted acid sites on the catalyst surface while facilitating the adsorption and activation of NH3. The XPS and O2-TPD analysis showed that the HPW facilitates the redox cycle between Ce4+ and Ce3+, increasing oxygen vacancies and improving oxygen storage and release capacity. Additionally, in situ DRIFTS indicated that L-H and E-R mechanisms existed in the Fe0.15Ce0.85 and 0.2H-Fe0.15Ce0.85 catalysts. The adsorbed ammonia species on surface acid sites converted to bidentate nitrate species with the assistance of abundant surface adsorbed oxygen, which improved the reaction between NH3/NH4+ and NOx and followed by the L-H mechanism.

The electrocatalytic CO2 reduction reaction (CO2RR) to obtain valuable chemicals is an appealing way to ease the energy and environmental crises, but the development of efficient catalysts remains challenging. Herein, we report a novel Ag-MnOx heterostructured catalyst and its high activity for the CO2RR to CO. The obtained Ag-MnOx exhibits a CO faradaic efficiency (FECO) of up to 97.5% at -0.8 V vs. reversible hydrogen electrode (RHE) and especially maintains an FECO above 90% within a broad potential window of 500 mV (-0.6 to -1.1 V vs. RHE). In addition, the CO2RR performance was optimized using a flow cell, and the Ag-MnOx catalyst reached a total current density of -255 mA cm-2 at -2.0 V vs. RHE. Our designed in situ experiments and density functional theory (DFT) calculations reveal that the heterojunction interface formed between O-defect-rich MnOx and active Ag enhances CO2 adsorption and activation and simultaneously stabilizes the *COOH intermediate, thus leading to its superior catalytic performance. Furthermore, the Ag-MnOx catalyst used as the cathode to assemble a Zn-CO2 cell exhibited an ultimate power density of 13.63 mW cm-2 and recharge time of over 65 h.

Single-atom catalysts (SACs) with MN4 active sites are a promising type of electrocatalyst for CO2 reduction reactions (CO2RR). Here, we designed a novel corrole-based CO2RR single-atom catalyst Cr-N4-Cz with a metal center supported by conjugated N4-macrocyclic ligand of corrole, which can serve as an excellent model for regulating the active center microenvironment, thereby achieving the goal of regulating the catalytic activity and selectivity. Density functional theory (DFT) calculations are performed to investigate the stability of Cr-N3X-Cz (X = N, C, O, S, P) and the mechanism of local coordination microenvironment regulating catalytic selectivity. The calculation results show that Cr-N4-Cz demonstrates high electrocatalytic activity for CO2RR with a limiting potential of -0.25 V, and the main product is CO. However, the selectivity of CO2RR is compromised due to the low limiting potential (-0.28 V) of the competitive hydrogen evolution reaction (HER). By substituting one N atom of Cr-N4-Cz with C, O, S and P, the corresponding main products become HCOOH, CO, CO, and CH3OH (or CH4). Moreover, the competing HER reaction is suppressed, thus remarkably increasing the selectivity of electrocatalytic CO2RR. Further mechanism investigation reveals different atomic substitution alters local coordination microenvironment of Cr metal center, resulting in the rising of d-orbital center and stabilizing the key intermediates of the potential determining step (PDS) by enhancing the integrated crystal orbital Hamilton population (ICOHP) between Cr and adsorbed intermediates, thereby regulating the CO2RR process. Especially, P substitution improves charge transfer, thus facilitating hydrogenation CO2 to form CH3OH (or CH4) in CO2RR.

The utilization of crop hybrids plays an important role in crop breeding and production, and the innovation of the male sterile germplasm is the basis for this utilization. Cotton has a very clear hybrid advantage, and the hybrid advantage in yield and quality has been widely utilized in cotton breeding. However, the exploitation of heterosis in cotton is currently dominated by cytoplasmic male sterility (CMS) lines. These CMS lines are found only in Harknessi cotton. They have a single cytoplasmic origin. Additionally, they exhibit a significant negative effect of cytoplasmic-nuclear interactions. To minimize this effect, it is necessary to select and breed CMS lines. In these CMS lines, both the cytoplasm and nucleus should originate from the same variety. However, no homologous cytoplasmic-nuclear CMS germplasm has been created, and its mechanism of occurrence has not been determined. In this study, two homologous cytoplasmic-nuclear CMS lines and two heterologous cytoplasmic-nuclear CMS lines were utilized, and the heterologous cytoplasmic-nuclear CMS lines were aborted at a relatively early stage. The physiological indexes related to reactive oxygen species ROS-mediated metabolic processes in the heterologous cytoplasmic-nuclear CMS lines were lower than those of the homologous cytoplasmic-nuclear CMS lines, including the enzyme activities of POD and CAT from tetrad to mature pollen grain, and the metabolite content of malondialdehyde (MDA) was inversely correlated with the enzyme activities of the heterologous cytoplasmic-nuclear CMS lines. Resequencing analysis of four cotton mitochondrial genomes (mt genomes) revealed that the heterologous cytoplasmic-nuclear CMS lines were more complex than the homologous cytoplasmic-nuclear CMS lines, and the homologous CMS lines showed a higher degree of collinearity with the maintainer lines. This indicates that heterologous cytoplasmic-nuclear interactions are more likely to lead to mtDNA structural variation. Taken together, the results showed that the cytoplasmic-nuclear homologous system was less affected by the cytoplasmic-nuclear interaction and was the best combination for the study of male sterility.