Chemistry of Materials最新文献

{"title":"Mechanistic\u0000Insights into the Colloidal Synthesis\u0000of Monodisperse CoF2 Nanorods","authors":"Liwei Dai,Henry McCollom,Albert Xiao,Mauro Pasta","doi":"10.1021/acs.chemmater.6c02062","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02062","url":null,"abstract":"Abstract Transition metal fluorides (TMFs) are promising conversion-type cathode materials for high-energy lithium–metal batteries owing to their exceptionally high theoretical energy density, making them attractive for demanding applications such as electric aviation. However, their practical implementation is hindered by sluggish conversion kinetics, pronounced voltage hysteresis, and poor electrochemical reversibility. Understanding the structural and chemical evolution of TMFs and the electrode–electrolyte interphase formed during cycling is essential for improving their performance. Monodisperse nanocrystalline TMFs are ideal model systems for high-resolution transmission electron microscopy because their uniform size, morphology, and electron transparency enable representative nanoscale characterization. Here, we investigate a reproducible colloidal synthesis of monodisperse, single-crystalline CoF2 nanorods and elucidate the mechanisms governing their formation to achieve precise control over particle size and aspect ratio. By independently varying reaction time, temperature, precursor composition, and ligand chemistry, we identify the key factors controlling precursor decomposition, burst nucleation, phase selection, and anisotropic crystal growth. These insights provide a transferable framework for the controlled synthesis of a broad range of transition metal fluoride nanocrystals.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Density Functional\u0000Theory and Data-Driven Insights\u0000into Hydrogen Incorporation and Transport in Ternary ABO3 Perovskites","authors":"Zhen Jiang,Christopher M. Wolverton","doi":"10.1021/acs.chemmater.6c02724","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02724","url":null,"abstract":"Abstract Hydrogen is a promising energy carrier due to its clean and versatile nature, offering opportunities for decarbonizing diverse sectors. Hydrogen utilization in many applications relies on identifying and understanding materials with exceptional hydrogen storage and transport properties. In this study, we conducted a comprehensive investigation of the thermodynamic and kinetic properties of hydrogenation reactions in ternary ABO3 perovskites using density functional theory (DFT) calculations and machine learning (ML) screening. We performed DFT simulations for a diverse range of perovskites featuring a variety of A-site cations (Ca, Sr, Ba) and B-site cations (Co, Fe, Mn, Ce, Ti, Zr) across various phases (cubic, tetragonal, orthorhombic, and hexagonal). By computing all data at the same theoretical level, we establish a consistent framework to compare how crystal phase, lattice-site chemistry, and host electronic structure govern hydrogen incorporation and diffusion. Therefore, we identify hexagonal SrMnO3, cubic SrFeO3, and hexagonal BaFeO3 as particularly promising candidates, combining favorable hydrogenation thermodynamics (ΔG < 1 eV) with low rotation and hopping barriers (<0.2 eV), while orthorhombic phases, although thermodynamically preferred, suffer from proton trapping, highlighting the importance of phase engineering toward cubic/hexagonal frameworks. Ab initio molecular dynamics further support this phase-dependent kinetic picture by showing relatively facile H diffusion in cubic SrFeO3 but much slower proton motion in orthorhombic BaCeO3 under the same conditions. By incorporating spatial and electronic descriptors with the DFT data into our ML models, we further develop a mechanistically motivated ML model based on structural and electronic descriptors to screen hydrogenation thermodynamics across 111 ternary ABO3 compositions. This model led to the identification of two additional promising candidates, hexagonal BaPdO3 and cubic BaSnO3, which were subsequently validated by DFT calculations. These findings provide a foundation for the rational design of ABO3 perovskites and demonstrate the potential of ML-driven frameworks with chemical insights to accelerate materials discovery in energetic and catalytic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"31 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Measurements\u0000and Analysis of Catalyst Diffusion\u0000and Reaction Fronts in Chemically Amplified Resists","authors":"Christopher M. Bottoms,Tanguy Terlier,Manolis Doxastakis,Gila E. Stein","doi":"10.1021/acs.chemmater.6c02591","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02591","url":null,"abstract":"Abstract The propagation of both catalyst diffusion and reaction fronts in a polymeric chemically amplified resist (CAR) is evaluated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling, and is compared with the propagation of catalyst diffusion fronts in inert resist analogues. We report that catalysts display accelerated and highly non-Fickian dynamics in the reactive CAR, even when located well behind the propagation front, while simple Fickian diffusion is observed for the same conditions in inert resist analogues. The complex catalyst dynamics of reactive systems is attributed to two key factors: (1) Transient free volume following deprotection events, which is a long-hypothesized acceleration mechanism acting on the diffusion front; and (2) a newly identified plasticization process induced by inert, nonvolatile byproducts of catalyst photoactivation. We propose a physics-informed model of enhanced catalyst diffusion due to the independent contributions of these two processes, and demonstrate that this model coupled to a first-order reaction provides a reasonable prediction of both the diffusion and reaction fronts. Our study presents a critical evaluation of mechanisms that control the spatial extent of reaction in CARs, and suggests that quantitative models of the patterning process should account for the impact of nonvolatile catalyst activation byproducts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure–Redox–Magnetism\u0000Dynamics Induced\u0000by Pd–Fe Interaction in Mixed Iron Oxide Nanoparticles","authors":"Elena Montejano-Nares,Esther Asedegbega-Nieto,Juan P. Holgado,Juan Rubio-Zuazo,Laura Cervera-Gabalda,Óscar Rodríguez de la Fuente,Pablo Carmona-López,Francisco J. Terán,Francisco Ivars-Barceló","doi":"10.1021/acs.chemmater.6c02139","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02139","url":null,"abstract":"Abstract The incorporation of noble metals into iron oxide nanomaterials represents an effective strategy to tailor their redox and structural properties through metal-oxide interactions. However, a detailed experimental understanding of these effects is limited. This work investigates the impact of Pd incorporation and Ag perturbation in mixed iron oxide nanoparticles by combining bulk- and surface-sensitive techniques. X-ray absorption spectroscopy (XAS) shows that Pd significantly enhances iron reducibility. Accordingly, wavelet transform analysis of the EXAFS region further provides evidence of Fe–Pd interactions, indicating nanoscale proximity between Pd and Fe atoms. These bulk-sensitive results are complemented by X-ray photoelectron spectroscopy (XPS), which reveals an increased fraction of reduced Fe species at the nanoparticle near surface upon Pd incorporation. In situ grazing-incidence X-ray diffraction (GI-XRD) during heat treatment under H2 provides insight into the evolution of these effects, showing (i) suppression of the hematite minor phase already after Pd impregnation and (ii) magnetite major phase lattice expansion during H2 treatment, both occurring exclusively in the presence of Pd. Complementary XPS analysis indicates partial migration of Pd into the iron oxide lattice under H2 treatment, contributing to the oxide lattice expansion beyond that of iron reduction alone. Magnetic measurements reveal an overall magnetization increase upon Pd incorporation, with a nonlinear dependence on Pd loading reflecting the balance between enhanced iron reducibility and lattice disorder. Finally, Ag incorporation slightly increases the fraction of reduced Fe species but strongly alters the magnetic response, consistent with an additional bimetallic perturbation arising from Pd–Ag coexistence.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"50 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Kinetic Pathway Selection in Supramolecular Polymerization via Transient Helical Inversion","authors":"Hyeon Min Han,&nbsp;Solme Ji,&nbsp;Soeun Jo,&nbsp;Min Joo Kim,&nbsp;Jong Hwa Jung,&nbsp;Sung Ho Jung","doi":"10.1021/acs.chemmater.6c01511","DOIUrl":"10.1021/acs.chemmater.6c01511","url":null,"abstract":"<p>Designing the organization of supramolecular systemswith high-precisionself-assembly along diverse pathways is a crucial strategy for optimizingfunctional properties. However, achieving such control remains a significantchallenge in the field. Here, we report the selective pathway dynamicsof platinum(II) terpyridine-based complexes with (<em>R</em>)-chiral side chains, which exhibit three distinct states (Agg-A,-DH, and -SH) in different pathways during the self-assembly process.The assembly is initiated by the formation of metastable helical structures(Agg-A) with concentration-dependent handedness, which subsequentlyundergo a transient helical inversion. Kinetic evaluations revealthat Agg-A diverges into two distinct pathways governed by the thermalenergy landscape. At 308 K, Agg-A acts as an on-pathway intermediate,forming a kinetically trapped superhelix (Agg-DH) via interfiber interactions.Conversely, at 333 K, Agg-A serves as an off-pathway intermediate,directly transforming into a thermodynamically stable single helix(Agg-SH). Ultimately, all metastable and kinetically trapped statesconverge toward the thermodynamically favored Agg-SH. Notably, thisstructural divergence enables the selective regulation of chiropticalfunctions. Specifically, the thermodynamically stable Agg-SH stateexhibits a distinct circularly polarized luminescence (CPL) signal,whereas the kinetically trapped Agg-DH state displays a negligibleCPL response. Furthermore, we successfully demonstrated precise pathwaycontrol utilizing seeded living supramolecular polymerization. Thisstudy highlights how morphological evolution driven by transient helicalinversion and intermolecular Pt–Pt interactions can be utilizedas a rational design strategy to program the specific optical functionsof chiral supramolecular materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10024–10035"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Self-Sufficient Photocatalytic CO2 Reduction over Ionic Liquid-Modified Three-Dimensional-Printed Pt Single-Atom TiO2 Nanosheets","authors":"Hamza Majeed Ansari,&nbsp;Kaleem Ullah,&nbsp;Sana Karamat,&nbsp;Yu-Peng Han,&nbsp;Dhandapani Kuzhandaivel,&nbsp;Zul Qarnain,&nbsp;Sohail Mumtaz,&nbsp;Ateeq Ur Rehman Baloch,&nbsp;Amir Said","doi":"10.1021/acs.chemmater.6c01235","DOIUrl":"10.1021/acs.chemmater.6c01235","url":null,"abstract":"<p>Thephotocatalytic carbon dioxide reduction reaction (CO₂RR)offers a promising route to convert waste CO₂ intovaluable synthetic fuels and chemicals using solar energy. However,practical application is hindered by insufficient charge separation,weak CO₂ activation, and poor catalyst recoverability.Herein, we systematically synthesized a self-sufficient photocatalystcomprising ionic liquid (IL)-modified Pt single atoms on TiO₂ nanosheets, fabricated in both powder (IL-Pt/TiO₂) and3D-printed monolithic (3D-IL-Pt/TiO₂) forms. In the photocatalyticCO₂RR, the 3D-IL-Pt/TiO₂ exhibits a significantlyenhanced CO evolution rate of 2051.46 μmol g^–1 h^–1, significantly higher than that of the powdersample (1598.79 μmol g^–1 h^–1) and far exceeding the sum of the individual constituents withoutadditional cocatalysts. The spectroscopic analysis reveals that whilethe IL alone does not perturb the TiO₂ lattice, its combinationwith atomically dispersed Pt induces a strong interfacial electronicredistribution. This synergistic interaction of IL and Pt atoms stabilizessurface Ti³⁺ species and electron-rich Pt sites and modifiesthe surface oxygen environment without degrading the bulk structureof TiO₂. Notably, the system functions most effectivelywithout external photosensitizers, which otherwise compete for lightabsorption and promote charge recombination. Long-term stability testsreveal that the 3D-printed monolith retained stable performance overextended cycling, whereas the powder material gradually deactivated.These findings demonstrate that optimized interfacial electronic regulation,rather than extreme band-edge position, governs photocatalytic efficiency,offering a strategy for scalable solar-driven CO₂ conversion.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9859–9874"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interlocked Regulation of Surface Poisoning and Ion Diffusion Enabled by Tungsten Integration and Holey Graphene Oxide Support for Ammonia Oxidation","authors":"Kirti Dahiya,&nbsp;Sidharth Barik,&nbsp;Nikhil S. Samudre,&nbsp;Swapnil Jadhav,&nbsp;Sailaja Krishnamurty,&nbsp;Chathakudath P. Vinod,&nbsp;Sreekumar Kurungot","doi":"10.1021/acs.chemmater.6c01697","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01697","url":null,"abstract":"<p>Therising consideration of ammonia as a viable fuelhas propelledthe research on exploring the feasibility of commercializing directammonia fuel cells (DAFCs). However, DAFCs at present have poor efficiencycaused by the sluggish ammonia oxidation reaction (AOR) kinetics andsurface poisoning of the catalyst. This work is tackling the issuesassociated with the anodic part of the DAFCs by developing an electrocatalyst,i.e., Pt_0.76Ir_0.21W_0.03/HGO-13. Theintrinsic pores of Holey Graphene Oxide (HGO) play a decisive rolein enhancing the metal–support interactions, along with effectivelymitigating flooding and mass-transport limitations during device testing.The oxyphilic W acts as a competitive OH^– reservoir,reducing OH^– poisoning on the PtIr active sites,which further boosts the AOR activity through OH^– mobilization by the spillover mechanism. The theoretical investigationof Pt_0.76Ir_0.21W_0.03/HGO-13 revealsthe electron redistribution among Pt, Ir, and W, thereby modulatingthe NH_<em>x</em> and N adsorption and mitigatingactive-site poisoning. Also, the 2–3 atomic % of the W incorporationcreates better nanointerface formation with PtIr than bulk W. Electrochemicalhalf-cell analysis shows a better onset potential of 0.37 V and asuperior peak current density of 76.1 A g^–1 (Pt_0.76Ir_0.21W_0.03/HGO-13) compared to thebenchmark systems (Pt/C and PtIr/C). When employed in DAFCs, the Pt_0.76Ir_0.21W_0.03/HGO-13-based electrodeexhibits a peak power density (PPD) of 90 mW cm^–2, outperforming the standard PtIr/C (54.8 mW cm^–2), clearly augmenting the synergistic modulations between the activesites and engineered porous support achieved in the present system.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10118–10134"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystal Engineering by Tuning Intermolecular CH−π Interactions Enables Processable and Highly Emissive Organic Crystals as Laser Media","authors":"Takumi Matsuo,&nbsp;Takuya Ogaki,&nbsp;Yuto Hino,&nbsp;Keigo Yano,&nbsp;Hiroshi Ikeda,&nbsp;Shotaro Hayashi","doi":"10.1021/acs.chemmater.6c01004","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01004","url":null,"abstract":"<p>In contrast to conventional inorganic laser media, organicsingle-crystal(OSC) laser media are emerging as next-generation light sources owingto their intrinsic high processability. To achieve practical OSC lasermaterials, candidate compounds must satisfy three key requirements:(1) processability, (2) crystallinity, and (3) high luminescence performance.However, fulfilling these criteria concurrently remains challenging.Processability and crystallinity are typically in a trade-off relationship,and luminescence performance is often difficult to control becauseit depends not only on molecular structure but also on the aggregationmotifs present in the crystal state. Here, we present a crystal engineeringstrategy that enables the simultaneous realization of these threeproperties in π-conjugated organic compounds. Our approach focuseson disrupting intermolecular CH−π interactions throughthe strategic introduction of methoxy substituents. Appropriate substitutionsites induce controlled disruption of CH−π contacts,promoting the formation of a rigid crystal framework while retaininghigh processability, effectively overcoming the conventional trade-offbetween these parameters. Moreover, the resulting changes in crystalpacking are accompanied by enhanced luminescence performance, includingan increased radiative decay rate. This methodology provides a molecular-designstrategy for OSC laser media integrating processability, crystallinity,and high optical performance, offering a promising route toward next-generationlaser technologies.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9817–9828"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Two-Photon Excited Fluorescence of Tetraphenylethylene-Based Metal–Organic Frameworks under Pressure with Different Ligand Arm Lengths","authors":"Jun-Zhe Dong,&nbsp;Qiang-Sheng Zhang,&nbsp;Shi-Cheng Wang,&nbsp;Rui-Qi Huang,&nbsp;Lin Zheng,&nbsp;Xue-Cui Jiang,&nbsp;Ya-Nan Fan,&nbsp;Zheng Wang,&nbsp;Mei Pan","doi":"10.1021/acs.chemmater.6c01120","DOIUrl":"10.1021/acs.chemmater.6c01120","url":null,"abstract":"<p>Metal–organic frameworks (MOFs) with excellenttwo-photonexcited fluorescence (TPEF) properties have shown great potentialin multiple fields. While numerous pressure-responsive TPEF MOFs havebeen reported, the precise modulation of their optical performancevia structural design remains a critical challenge. In this study,the impact of ligand coordination arm length on the TPEF propertiesof tetraphenylethylene-based MOFs (TPE-MOFs) was systematically explored.By designing two TPE-MOFs with varying coordination arm lengths, itwas demonstrated that LIFM-DJZ-1, based on L1 with long coordinationarms, exhibited superior PLQY and TPA action cross sections comparedto LIFM-DJZ-2 with shortened L2. Notably, pressure stimulation furtherenhanced the TPEF performance of LIFM-DJZ-1, highlighting the potentialof structural modulation in designing high-performance piezofluorochromicmaterials. This study not only offers fresh insights into the structure-propertyrelationship in TPE-MOFs but also establishes a crucial foundationand practical guideline for advancing the development of high-performanceTPE-MOF materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9839–9849"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solid-Solution Engineering of Earth-Abundant Metal Borides of Y(TM1TM2)B4-Type as Durable High-Current-Density Electrocatalysts for HER","authors":"MD Ali Hossain,&nbsp;Lesly Delgado,&nbsp;Pelumi Adanigbo,&nbsp;Weiyi Xia,&nbsp;Cai-Zhuang Wang,&nbsp;Sylvie Rangan,&nbsp;Benish Fatima,&nbsp;Yun Yu,&nbsp;Georgiy Akopov","doi":"10.1021/acs.chemmater.6c02150","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02150","url":null,"abstract":"<p>Earth-abundant transition-metalborides are promisingalternativesto noble-metal catalysts for the hydrogen evolution reaction (HER),but achieving high activity and durability under industrially relevantoperating conditions remains challenging. Herein, we develop a seriesof arc-melted solid-solution transition-metal borides, YCr_{1–<em>x</em>}Mo_<em>x</em>B₄, YCr_{1–<em>x</em>}W_<em>x</em>B₄, and YMo_{1–<em>x</em>}W_<em>x</em>B₄ (<em>x</em> = 0.25, 0.5, and0.75), as robust HER electrocatalysts for acidic media. Through solid-solutionengineering, the catalytic performance of the parent borides is significantlyimproved, with each composition outperforming commercial 20 wt % Pt/Cat high current density. Notably, YCr_0.25W_0.75B₄ exhibits the best overall HER performance, requiringonly 0.449 V overpotential to reach 1000 mA/cm², comparedwith 0.742 V for 20 wt % Pt/C. The enhanced activity is further supportedby a high double-layer capacitance of 54 mF/cm², reflectingincreased electrochemically accessible surface area and abundant exposedHER-active sites. The catalyst also shows excellent acid stability,retaining 92% of its activity after 5000 cycles and 24 h of continuousoperation. Scanning electrochemical cell microscopy (SECCM) analysisreveals heterogeneous, composition-dependent local HER behavior, withYMo_0.25W_0.75B₄ exhibiting the leastnegative onset potential, followed closely by YCr_0.25W_0.75B₄, highlighting the importance of surface compositionin controlling catalytic activity. These findings establish solid-solutiontransition-metal borides as a versatile platform for designing inexpensive,durable, and high current electrocatalysts for sustainable hydrogenproduction.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10319–10329"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}