Chemistry of Materials最新文献

{"title":"Template-Guided Crystal Chemical Design of Eu2+-Activated La2Ca3[Si4N4O8] Oxonitridosilicate Phosphor","authors":"Hong-Wei Zheng,Xiao-Ming Wang,Leiming Fang,Tian-Hui Liu,Guang-Dong Xu,Jiang-Bo Lu,Zu-Pei Yang,Huan Jiao","doi":"10.1021/acs.chemmater.6c01957","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01957","url":null,"abstract":"Template-guided crystal-chemical design offers a route to oxonitridosilicates, but transfer of an oxide topology requires compatible cation coordination and charge balance. Here, we report the synthesis and structural characterization of the 6-ring host La2Ca3[Si4N4O8], designed by considering [SiN]+ for [AlO]+ substitution in the Ca3[Al2O6] template together with aliovalent La3+/Ca2+ substitution. The idealized structural description contains isolated rings of corner-sharing [SiN2O2] tetrahedra and partially occupied or vacant cation sites. The nominal substitution scheme, 3Ca2+ → 2La3+ + VCa, provides a charge-balanced crystal-chemical rationale for the cation deficiency. Theoretical calculations reveal that the aliovalent substitution induces cation vacancies accompanied by local charge redistribution and coordination rearrangement, which may alleviate the lattice strain arising from the cation-size mismatch. Eu2+ activation produces broadband orange emission centered near 600 nm, with a reported photoluminescence quantum yield of 29.3%. The phosphor was further applied to a white LED by combining it with multiple phosphors. This work illustrates how cation composition and occupancy can be considered alongside the topology in template-guided exploratory synthesis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"21 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360534","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":"Reactive Decaborane Initiates Low-Temperature Polymer Decomposition and Drives Ceramic Formation","authors":"Benjamin J. Stovall,Asma Ul Hosna,Tainara Coutinho de Carvalho,Kavindi Sabaratne,Kalana D. Halanayake,Nabankur Dasgupta,Nitish Baradwaj,Danielle Reifsnyder Hickey,Aiichiro Nakano,Priya Vashishta,Jon-Paul Maria,Adri C. T. van Duin,Robert J. Hickey","doi":"10.1021/acs.chemmater.6c02312","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02312","url":null,"abstract":"Boron carbide (B4C) is a ceramic of considerable interest due to its high hardness, elevated melting point, excellent thermal stability, low density, and chemical inertness. Decaborane-functionalized preceramic polymers (PCPs) prepared from ring-opening metathesis polymerization (ROMP) are excellent single-source precursors of B4C, but the mechanistic details for the decomposition and ceramic conversion during pyrolysis have been overlooked, preventing advances in redesigning preceramic polymers that have high char yields and desirable chemical compositions. Herein, we reveal insights into the role of decaborane during the polymer-to-ceramic transition of poly(cyclooctenyldecaborane) (PCD) to boron carbide. ROMP of the cyclooctenyldecaborane monomer enabled controllable molecular weight and produced a series of polymers with molecular weights up to 35 kg/mol and dispersities (D̵) in the range of 1.3-1.6. Thermogravimetric analysis coupled with infrared spectroscopy and mass spectrometry (TGA-IR and TGA-MS, respectively) of PCD revealed the evolution of small hydrocarbon species following an initial release of hydrogen at low decomposition temperatures around 250 °C, which is in stark contrast to the decomposition profile of unfunctionalized poly(cyclooctadiene) (PCOD) that transitions into volatile hydrocarbon species at approximately 450 °C. ReaxFF molecular dynamics (MD) simulations support the experimental findings that hydrogen release from decaborane initiates the polymer-to-ceramic conversion. MD simulations indicate that the release of H2 results in the exothermic formation of boron clusters, which promote the thermal decomposition of the hydrocarbon polymer backbone. These findings indicate that decaborane plays an active role in the polymer-to-ceramic conversion rather than serving solely as a boron source, providing mechanistic insight that will enable the rational design of next-generation PCPs with enhanced ceramic yields and tunable compositions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360532","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":"Vapor−Liquid−Solid Growth of Unconventional Nanowires","authors":"Thang Pham,Arindom Nag","doi":"10.1021/acs.chemmater.6c01372","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01372","url":null,"abstract":"Vapor−liquid−solid (VLS) growth has delivered a level of synthetic control in group IV and III−V semiconductor nanowires that remains unmatched in any other class of one-dimensional materials. For Si, Ge, and GaAs, decades of mechanistic study have made diameter, growth direction, crystal phase, and axial composition into design parameters. For oxides, carbides, and chalcogenides, including emerging van der Waals materials, which we refer to collectively as non-conventional nanowires, one-dimensional structures have been reported in abundance, but comparable deterministic control has not been achieved despite their predicted functional properties and broad application potential. This review examines where and why the two groups diverge. We survey and categorize the literature on VLS and VLS-related synthesis of non-conventional nanowires, following the sequence of the growth process itself, namely, precursor creation and delivery, seed particle formation and evolution, and nucleation and growth of one-dimensional structures. Each step is compared against the group IV and III−V baseline to locate shared behavior and genuine differences. From this comparison, we identify seed particles, spanning the choice of seed material, the chemical composition of the seed during and after growth, and its dynamics, as the principal bottleneck restricting deterministic synthesis, with precursor creation and delivery acting as an upstream constraint that narrows the accessible seed design space. We discuss potential solutions, including new precursor chemistries, improved reactor designs, and in situ characterization of growth, that would deepen the mechanistic understanding of nanowires already demonstrated by VLS and extend seeded growth to emerging quantum and functional materials, ultimately paving the way for deterministic synthesis and integration of complex one-dimensional nanomaterials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360533","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":"Anion-Templated Cu14 Nanoclusters Reveal Ligand-Controlled Stability and Catalytic Evolution During Electrochemical CO2 Reduction","authors":"Yihan Chen,Mandira Ghosh,Mohd Rashid,Maho Kamiyama,Sahla Sherin,Shahina Mekrakkunnan,Tokuhisa Kawawaki,Biswarup Pathak,Sourav Biswas,Yuichi Negishi","doi":"10.1021/acs.chemmater.6c02517","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02517","url":null,"abstract":"Two atomically precise sulfide-templated Cu14 nanoclusters (NCs), [S@Cu14(4MBT)12(PPh3)6] (S@Cu14-4MBT) and [S@Cu14(3MBT)12(PPh3)6] (S@Cu14-3MBT), were synthesized and structurally characterized to investigate the influence of ligand engineering on the stability and electrocatalytic performance of Cu NCs during the electrochemical CO2 reduction reaction (CO2RR). Single-crystal X-ray diffraction analysis revealed that both NCs possess a highly similar S@Cu14 core architecture stabilized by twelve positionally different methyl-substituted thiolate and six triphenylphosphine ligands, allowing direct evaluation of ligand effects without changes in core structure. Despite their structural similarity, positional variation of the methyl substituent generated distinct electronic environments, intermolecular interactions, and crystal-packing arrangements. The relatively electron-deficient Cu environment in S@Cu14-3MBT resulted in superior CO2RR performance, achieving highly selective Faradaic efficiencies of 52% for formate and 18% for CO at −1.4 V vs. RHE with suppressed hydrogen evolution, whereas S@Cu14-4MBT exhibited lower selectivity and stability. Theoretical calculations, together with comparison with structurally analogous metal NCs, reveal that precise modulation of the electronic configuration plays a critical role in promoting formate selectivity. Post-catalytic analyses revealed degradation and ligand loss in S@Cu14-4MBT, whereas S@Cu14-3MBT remained structurally intact. These results highlight ligand engineering and anion templation as key strategies for tuning the stability and CO2RR performance of atomically precise metal NCs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"22 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360530","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":"Cathode-Induced Stress Can Suppress Dendritic Failure in Thin Solid Electrolyte Separators","authors":"Dominic Spencer-Jolly,Guanchen Li,Bingkun Hu,Shengming Zhang,Jaimini J. Mistry,Mikkel Juelsholt,Sofia De Sousa Coutinho,Lechen Yang,James Le Houx,Shashidhara Marathe,Dominic L. R. Melvin,Peter G. Bruce","doi":"10.1021/acs.chemmater.6c02340","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02340","url":null,"abstract":"Solid-state batteries pairing lithium metal anodes with inorganic solid electrolytes promise a step change in energy density, but during charging at practical rates lithium dendrites penetrate the solid electrolyte, short-circuiting the cell. Our current understanding of dendrite propagation derives largely from symmetric Li−Li cells with millimetre-thick electrolyte pellets, whereas practical cells will employ solid electrolyte separators less than 100 μm in thickness. In this work, we use in situ synchrotron X-ray computed tomography to show that dendrites in a thin Li6PS5Cl separator, which generally propagate from the lithium anode to the cathode, can be made to propagate laterally by the cathode. Volume contraction of the NMC cathode during charge places the thin separator under lateral compressive stress, deflecting dendritic cracks to propagate laterally (parallel to the electrodes) rather than transversely (across the separator). The result is that the cell resists short circuit even after passing 3 mA h cm−2 capacity at a rate of 3 mA cm−2. Replacing NMC with zero-volume-change pre-lithiated Li4Ti5O12 removes this compressive stress, and the cell rapidly fails by transverse cracking. Chemomechanical modelling rationalises both behaviours, with cathode volume change emerging as a design parameter that can suppress or accelerate failure, with direct implications for cathode selection and cathode/separator interface engineering in practical solid-state batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360015","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":"Editorial: Celebrating the 80th Anniversary of Jilin University","authors":"Yulan Chen,Yi Li","doi":"10.1021/acs.chemmater.6c03047","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c03047","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359760","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":"Transition Metal Chalcogenides as Electrocatalysts for Anion Exchange Membrane Water Electrolysis","authors":"Priyadarshani Tamang,Rumana Sultana Parvin,Sk Riyajuddin","doi":"10.1021/acs.chemmater.6c02593","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02593","url":null,"abstract":"Amid escalating energy demand and severe environmental effects, green hydrogen production via water electrolysis has emerged as a cornerstone technology. Conventional alkaline water electrolysis (AWE) generally suffers from low hydrogen purity and current density, while proton exchange membrane water electrolysis (PEMWE) relies on high-cost noble-metal catalysts and harsh acidic conditions. To mitigate these limitations, researchers have turned to anion exchange membrane water electrolysis (AEMWE) as a promising alternative, offering an intermediate pathway that pairs the non-noble metal-based catalysts of AWE with the high purity and compact architecture of PEMWE. However, AEMWE technology remains comparatively underdeveloped. Herein, we have summarized transition metal chalcogenides (TMCs) as a low-cost catalyst platform for AEMWE devices. The current review focuses on a comparative analysis across the chalcogen family and discusses how variations in their physicochemical properties influence the overall catalytic performance of anion exchange membrane devices. In addition, the underlying mechanisms of AEMWE, the membrane-electrode assembly, and cell configurations have also been explored in detail. The review critically examines the intrinsic activity of the transition metal chalcogenide-based catalyst layer against device-level performance metrics and further highlights emerging future directions. The review aims to provide a clear roadmap toward the development of highly efficient and commercially competitive AEMWE systems for next-generation green hydrogen production.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360012","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":"Emergent Structural Prototypes of Stable Inorganic Materials","authors":"Roee Asher,Nadav Moav,Lee A. Burton","doi":"10.1021/acs.chemmater.6c02175","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02175","url":null,"abstract":"The number of possible crystal structures vastly exceeds the number realized among thermodynamically stable inorganic materials, suggesting that experimentally accessible structure space is organized around a limited set of preferred structural frameworks. Analysis of 23,160 structures on the thermodynamic convex hull identifies 6820 distinct structural frameworks, of which 2382 recur across multiple chemically distinct materials and are therefore classified as structural prototypes. Within a filtered dataset, metallic systems exhibit particularly strong structural recurrence, with 6270 materials grouped into 535 frameworks and 327 prototypes, while 5557 ionic compounds occupy 1704 frameworks and 696 prototypes. These results demonstrate that stable inorganic materials naturally coalesce into recurrent structural prototypes and do not require any a priori definition through manual curation. The resulting recurrence-based catalog also provides an empirical measure of framework prevalence, enabling the relative likelihood of structural frameworks in future materials to be estimated from their recurrence among known compounds.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360017","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":"Multicenter Bonding in Periodic Solids through the Lens of Atomic- and Molecular-Orbital Partitioning","authors":"Peter C. Müller,Linda S. Reitz,Richard Dronskowski,Simon Steinberg","doi":"10.1021/acs.chemmater.6c01845","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01845","url":null,"abstract":"To understand the nature of multicenter interactions in periodic solids and their associated materials (transport) properties, we investigate and quantify multicenter bonding on the basis of the underlying wave function, namely by a combination of quantum-chemical tools for a diverse series of functional materials. First, we probe all compounds by projected force constants based on plane-wave phonon calculations, followed by a projection from plane waves onto a local-orbital framework and its thorough quantum-chemical analysis. While the three-center crystal orbital bond index is used to quantify multicenter bonding between atomic orbitals, the linear combination of fragment orbitals provides a molecular-orbital lens. Eventually, both approaches are fused into the molecular orbital contribution index that directly attributes the contributions of a single molecular orbital to a multicenter bond.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"15 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360018","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":"Dopant-Dependent Surface Interaction Modulation by Pt with Hexagonal Perovskites for Robust Bifunctional Oxygen Electrocatalysts in Rechargeable Zn−Air Batteries","authors":"Boyean Kim,Heesu Kim,Yuri Ko,Kyuwook Ihm,Yukwon Jeon","doi":"10.1021/acs.chemmater.6c01685","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01685","url":null,"abstract":"Rechargeable Zn−air batteries (ZABs) have attracted considerable attention as promising energy storage systems owing to their high theoretical energy density and environmental compatibility. However, their practical application is hindered by the sluggish ORR/OER kinetics at the air cathode. This study investigates low Pt-modified Fe- and Ni-doped hexagonal perovskites (BaTi0.8M0.2O3−δ, M = Fe and Ni) as robust bifunctional oxygen electrocatalysts, focusing on the modulation of their participating metal and electronic structures. Structural analysis confirms the formation of stable hexagonal phases, while Pt deposition induces distinct electronic reconstruction depending on the dopant species. With a higher ORR catalytic behavior than the Pt/BTO-Ni catalyst, the Pt/BTO-Fe catalyst demonstrates remarkable bifunctionality driven through dopant-dependent surface interaction modulation by Pt with optimized surface/lattice oxygen distribution. Notably, in full-cell ZAB tests, the optimized Pt/BTO-Fe catalyst achieved a comparable peak power density of 124.8 mW cm−2 with a remarkably low round-trip efficiency decay rate of 0.41%/h under stable operation for 60 h, compared to the commercial IrO2 + Pt/C benchmark (125.2 mW cm−2 and 1.39%/h) even at lower Pt content. These findings highlight the critical role of Pt2+-mediated interfacial interactions in governing catalytic durability, providing a rational strategy for designing highly durable bifunctional electrocatalysts for next-generation energy storage systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"19 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359759","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}