Chemistry of Materials最新文献

{"title":"Direct Colloidal\u0000Synthesis of High-Entropy Carbide\u0000Nanoparticles with Altered CO2 Hydrogenation Selectivity","authors":"Brendan Ward-O’Brien,Hyewon Lee,Frederick G. Baddour,Daniel A. Ruddy,Richard L. Brutchey","doi":"10.1021/acs.chemmater.6c01753","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01753","url":null,"abstract":"Abstract The controlled synthesis of refractory carbide nanoparticles remains a longstanding challenge in colloidal nanoscience because strong metal–carbon bonding and high formation energies complicate nucleation, growth, and compositional control. Here, we report the direct colloidal synthesis of single-phase high-entropy (HE) carbide nanoparticles, (CrMnMoW)C1–x, (TiCrMnMoW)C1–x, and (CrMnFeMoW)C1–x, via the simultaneous thermolysis of transition metal carbonyl precursors in oleylamine. Structural analysis reveals substantial local disorder and lattice distortion, including a ∼50% increase in the full width at half-maximum of the first M–C pair distribution function peak relative to α-MoC1–x nanoparticles. During CO2 hydrogenation (at 300 °C and either 20 or 30 bar), the HE carbides exhibit lower CO selectivity than the monometallic α-MoC1–x control, decreasing from 77% to 38–67%, while shifting selectivity toward oxygenates and C2+ products. The largest enhancement in methanol and dimethyl ether formation was observed for (TiCrMnMoW)C1–x, increasing from 0.5% for the control to 6.7%, while (CrMnFeMoW)C1–x exhibited a 50% increase in C2+ selectivity, from 6.8% to 10.2%. These findings demonstrate that direct colloidal access to HE carbide nanoparticles provides a route to catalytic behavior distinct from that of conventional carbide nanoparticles.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"88 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151513","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":"PEDOT with Sulfonated PVA and Choline Chloride Enables\u0000Printable and Stretchable Electronics","authors":"Mengke Liu,Wenyue Zhang,Xinyu Zhang,Linfa Li,Xiuqiang Li,Yuwei Qiu,Zhongming Zhao,Dongzhao Hao,Shamaila Manzoor,Fanglian Yao,Junjie Li,Hong Zhang","doi":"10.1021/acs.chemmater.6c01577","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01577","url":null,"abstract":"Abstract Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has become an important conductive polymer dispersion for constructing flexible electronic devices; however, its electrical and mechanical performance still falls short of practical application requirements. Herein, a highly conductive and stretchable PEDOT film is prepared through a molecular-level material design strategy, using sulfonated poly(vinyl alcohol) (SPVA) as the PEDOT dopant to replace PSS and subsequently blending PEDOT:SPVA with choline chloride (ChCl). This substitution addresses the intrinsic limitations of PSS through chemical structure design rather than physical post-treatment. SPVA is fully utilized, with its sulfonic acid groups effectively doping PEDOT and its hydroxyl groups forming abundant hydrogen bonds (H-bonds). The H-bonds between SPVA and ChCl build a stretchable network in which PEDOT and ChCl synergistically maintain electrical conductivity. The resulting PEDOT:SPVA/ChCl (PSPC) films exhibit a high ultimate tensile strain of 310% and a maximum electrical conductivity of 92.8 S m–1 under the tested conditions. Furthermore, organic-solvent-free inks with tunable viscosities can be readily obtained through a simple aqueous redispersion step, enabling compatibility with diverse electronic manufacturing coating and printing processes. By optimizing the dopant system, this work balances conductivity and stretchability, offering a promising fabrication route for flexible electronics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"53 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150813","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":"Grain Boundary-Confined\u0000Lead Halides Mitigate Post-Treatment\u0000Surface Lattice Distortion in Wide-Bandgap Perovskites for Efficient\u0000Tandem Solar Cells","authors":"Hongling Guan,Yingying Xu,Jixiang Li,Xiangzhi Liu,Jiahao Wang,Shun Zhou,Weijun Ke","doi":"10.1021/acs.chemmater.6c02136","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02136","url":null,"abstract":"Abstract Wide-bandgap (WBG) perovskite solar cells (PSCs) have attracted increasing attention due to their essential role in high-efficiency tandem architectures. Post-treatment strategies are commonly employed to improve WBG perovskite films by modifying surface states and enhancing device performance. However, such treatments risk simultaneously inducing surface lattice distortion, thereby undermining device efficiency. To address this issue, we strategically introduce lead thiocyanate into perovskite precursor solutions to induce the formation of excess lead halides at grain boundaries. These halide species act as protective buffers that react preferentially with post-treatment salts, effectively hindering the formation of post-treatment-induced surface lattice distortion. Consequently, the resulting single-junction PSCs with a 1.77 eV bandgap achieve an impressive power conversion efficiency (PCE) of 19.60%. Furthermore, by integrating these high-performance WBG subcells with a narrow-bandgap perovskite counterpart, we realize two-terminal all-perovskite tandem devices that deliver a remarkable PCE of 28.61%, highlighting their strong potential for next-generation multijunction photovoltaic systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151057","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":"Scalable Thermoset\u0000Informatics Integrated with Autonomous\u0000Experimentation for On-Demand Discovery","authors":"Marcus R. Fratarcangeli,Ayush Jain,Farzad Gholami,Jiaqi Nie,Anagha Savit,H. Jerry Qi,Rampi Ramprasad","doi":"10.1021/acs.chemmater.6c01600","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01600","url":null,"abstract":"Abstract As photopolymer additive manufacturing matures, there is an increasing need for on-demand, application-specific materials. A major bottleneck is the limited exploration of the vast design space for new thermoset polymer formulations, which must satisfy both material property requirements and processing constraints. This challenge arises from the combinatorial complexity of formulations and the high cost of experimental evaluation. In this work, we present an end-to-end pipeline that integrates a partial self-driving laboratory (p-SDL) with informatics-driven optimization to discover and validate thermoset acrylate formulations. The pipeline begins with a thermoset acrylate database that consolidates multiple data sources, including in-house experiments, molecular dynamics simulations, and literature data. These data sets are used to train single-task and multitask predictive models, which interface directly with the p-SDL to guide experiments and measure mechanical and processing-related properties. Each component is validated independently and then deployed together to optimize a target elastomeric material with over 90% reduction in human effort. The complete optimization required only ∼40 h of active experimental time, demonstrating rapid identification of formulations that satisfy multiple target properties without exhaustive screening. This work establishes a scalable framework for embedding multifidelity machine learning within laboratory workflows, enabling autonomous, data-driven thermoset formulation discovery.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150982","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":"Potassium Molybdenum Chalcogenides: Electronic Structure\u0000Modulation through Cluster Dimensionality","authors":"Rose E. Smiley,Konstantina G. Mason,Adway Gupta,Cocoro A. Nagasaka,Jessica C. Ortíz-Rodriguez,Rose A. Lam,Forrest P. Hyler,David Prendergast,Jesús M. Velázquez","doi":"10.1021/acs.chemmater.6c01424","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01424","url":null,"abstract":"Abstract Herein, we report a systematic structural and electronic investigation of potassium-inserted extended molybdenum chalcogenides synthesized via microwave-assisted solid-state routes, focusing on KMo6S8, K2Mo15S19, and K2Mo6S6. Using X-ray absorption spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy, we evaluate how systematic variations in Mo/S ratio modulate phase morphology and local electronic structure. Analysis of the S K-edge and Mo L3-edge XANES reveals distinct electronic environments across the extended clusters, demonstrating precise control over oxidation state and coordination as a function of Mo–Mo cluster extension. To probe the tunability of these materials, KxMo15S19 was employed as a platform to investigate the limits of potassium insertion. Synthesis of KxMo15S19, with a generalized product-phase thermodynamic model, indicates that compositions within the range of x = 2–2.5 demonstrate the highest stability, maintained through enthalpy and entropy effects. Finally, electrochemical studies demonstrate that stable KxMo15S19 phases enable modulation of proton adsorption and electron-transfer behavior during the hydrogen evolution reaction, establishing extended Mo–Mo chalcogenides as a versatile platform for studying electron density localization and reactivity. Altogether, this work uncovers design rules that are generalizable across multinary chalcogenides and that deepen our understanding of how compositional and structural variations govern functional properties in these solids.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150812","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":"Noncentrosymmetric\u0000Manganese Bismuth Thiocyanate Perovskites","authors":"Madeleine Geers,Dominik J. Kubicki,Stephen P. Argent,Jeremiah P. Tidey,Elodie Salager,Benjamin B. Duff,Oscar Fabelo,Laura Cañadillas-Delgado,Matthew J. Cliffe","doi":"10.1021/acs.chemmater.6c02127","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02127","url":null,"abstract":"Abstract Symmetry-lowering orderings in perovskites can produce a wide range of functions. Thiocyanate based perovskites, AM(SCN)3, have orderings distinct from those of the atomic oxides, enabling new functional behavior. We report four new defect-ordered manganese thiocyanate perovskites K{Mn[Bi(SCN)6]},NH4{Mn[Bi(SCN)6]}·18H2O,Cs{Mn[Bi(SCN)6]}·18H2O, and Gua6{Mn9[Bi(SCN)6]8}·6H2O, and solve their structures using a combination of powder X-ray, single crystal X-ray, single crystal electron and single-crystal neutron diffraction combined with solid-state 1H, 13C, and 133Cs MAS NMR. These frameworks each adopt a structure distinct from both previously reported thiocyanates, and other molecular and atomic perovskites. These noncentrosymmetric thiocyanate perovskites demonstrate how frustration between octahedral tilts and A-site ordering can produce complex function.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"31 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150985","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":"SrZrO3 Polyhedra with Lattice Variations\u0000Showing Efficient Piezocatalytic Hydrogen Evolution","authors":"Po-Yen Yang,Yu-Chen Wei,Te-Jung Liao,Satyaranjan Jena,Yung-Jung Hsu,Michael H. Huang","doi":"10.1021/acs.chemmater.6c01859","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01859","url":null,"abstract":"Abstract SrZrO3 cubes with two different sizes as well as octahedra and rhombic dodecahedra have been solvothermally synthesized. Synchrotron X-ray diffraction (XRD) analysis indicates the possession of an orthorhombic crystal structure, with cubes and octahedra having greater cell constant changes. Lattice point images, derived from high-resolution transmission electron microscopy (HR-TEM) images of a single cube and octahedron after fast Fourier transform (FFT) treatment, reveal significant lattice point deviations near the surface region, proving the presence of both bulk and surface lattices. The crystals have ultralarge band gaps in the range of 6.5–7.4 eV. Octahedra exhibit the largest piezoelectric and ferroelectric behaviors among the different particle morphologies. They also deliver the highest piezocatalytic hydrogen evolution rate from pure water, surpassing commercial BaTiO3 powder and many reported materials for piezocatalytic hydrogen generation, demonstrating the value of crystal shape control to enhance piezocatalytic performance.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"69 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150987","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":"Increasing\u0000the (Re)Activity of MgO for Carbon Capture\u0000under Continuous Ball Milling","authors":"Emanuele Antico,Thibaud Aumond,Marc Meyer,Linfeng Li,Eko Budiyanto,Ferdi Schüth","doi":"10.1021/acs.chemmater.6c01597","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01597","url":null,"abstract":"Abstract Carbon capture and storage from point emission sources is a crucial technology able to mitigate the progress of climate change by slowing down the emission of greenhouse gases. Current technologies, such as amine scrubbing and calcium looping, face challenges including high energy consumption and limited efficiency under humid conditions. Magnesium oxide (MgO) is a promising CO2 sorbent due to its lower decarboxylation enthalpy compared to calcium oxide, but its practical use is hindered by slow CO2 uptake kinetics and the formation of a passivating carbonate layer that inhibits further CO2 diffusion. While synthetic methods have improved MgO surface area, scalability remains an issue. This study addresses the kinetic limitations of MgO by investigating how continuous ball milling can reduce the performance hindrance from the passivating-carbonate layer on MgO and enhance CO2 uptake under industrially relevant conditions. Here we show that continuous ball milling of MgO under a CO2 atmosphere significantly increases its CO2 uptake capacity. Unlike conventional approaches that rely on presynthesized high-surface-area MgO, our results demonstrate that ball milling during the sorption step does not only increase the specific surface area of MgO but also actively enhances its CO2 capture performance, with a 6-fold increase in adsorption capacity compared to static exposure. The addition of water further boosts performance, doubling uptake under simulated flue gas conditions (10% CO2, 40 °C), likely due to the formation of bicarbonates and hydroxycarbonates. The performance stability of MgO under continuous milling and moisture conditions was evaluated in several sorption-regeneration cycles, showing consistent CO2 uptake over ten cycles with an average sorption capacity of 17.4 wt %. Structural analyses reveal that carbonation proceeds via magnesium hydroxycarbonate species, which fully decompose upon regeneration, preserving sorbent stability over ten cycles. This study underscores the practical relevance of mechanochemical activation for enhancing the capture capacity of MgO, offering a promising approach for industrial point-source CO2 capture applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150986","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":"Facet Selectivity\u0000Enables Near-Unity External Quantum\u0000Yields in Shell-free Silicon Quantum Dots","authors":"Yuito Oba,Honoka Ueda,Ken-ichi Saitow","doi":"10.1021/acs.chemmater.6c01903","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01903","url":null,"abstract":"Abstract Core–shell quantum dots (QDs) such as epitaxially passivated CdSe, InP, and lead-halide perovskite QDs, which are often used in solar cells and as photocatalysts, are highly luminescence-efficient and tunable. However, concerns surrounding sustainability, toxicity, and material availability have spurred interest in heavy-metal-free QDs derived from Earth-abundant elements. Ensuring that shell-free colloidal QDs emit efficiently and stably─a long-standing goal that is expected to simplify syntheses and broaden technological applicability─remains particularly challenging for silicon, an indirect-bandgap semiconductor traditionally regarded as emitting light inefficiently. Herein, we synthesized shell-free silicon QDs (SiQDs) with controlled crystal sizes (1.8–2.5 nm) via a hydrogen-silsesquioxane-polymer route and created a quantitative structure–property framework. The photoluminescence quantum yields (PLQYs) of fresh SiQDs were found to be determined by quantum confinement, exciton tunneling, crystallinity, and tensile strain, with volcano-type size dependences observed. Beyond this intrinsic behavior, long-term aging was found to distinctly enhance efficiency, with PLQYs of up to 99% sustained over extended periods of time (200–450 d) in solution under ambient conditions. This enhancement is attributable to the slow, facet-selective oxidation of Si–Si back bonds on Si(111) facets. These findings identify facet-selective back-bond chemistry in the subsurface region as a critical design feature for highly efficient, shell-free SiQDs and provide a general framework for sustainable, heavy-metal-free photonic nanomaterials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150984","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":"Spectrally\u0000Tunable Zero-Dimensional Manganese–Antimony-Based\u0000Halide Solid-Solution Glasses for X-ray Imaging and Information\u0000Encryption","authors":"Guangcheng Cui,Yebo Cai,Xuyan Wang,Weijia Wei,Mingtai Chen,Libo Li,Guangbao Wu,Ligang Xu,Runfeng Chen,Wenzhen Lv","doi":"10.1021/acs.chemmater.6c01437","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01437","url":null,"abstract":"Abstract Despite significant advances in high-performance X-ray scintillators based on organic–inorganic hybrid metal halides (OIHMHs), realizing spectrally tunable luminescence within a single OIHMH system remains a formidable challenge for next-generation multifunctional photonics. Herein, a series of Mn/Sb solid-solution OIHMH (denoted as M-MxSy) glasses were synthesized via a melt-quenching method using methyltriphenylphosphonium (MTP) as the organic ligand. These solid-solution glasses exhibit excellent glass-forming ability, thermal stability, and high optical transparency (>85%) in the range of 500–800 nm. The stable coexistence of Mn2+ and Sb3+ luminescent centers is observed, which display distinct, excitation-dependent competitive emissions including a 528 nm green emission from Mn2+ under 450 nm excitation and a 648 nm orange-red emission from self-trapped excitons (STEs) of Sb3+ under 396 nm excitation. Conversely, X-ray excitation can simultaneously activate both centers, enabling comprehensive color tuning depending on the Mn/Sb ratio. Notably, the optimized M-M3S1 glass demonstrates superior scintillation performance, with a high light yield of ∼35,300 photons M eV–1 and a spatial resolution of 20 lp mm–1. By leveraging these differentiated multimode luminescent responses, a high-quality X-ray imaging and a multilevel information encryption scheme were developed, highlighting the synergistic potential of these materials for advanced radiation imaging and anticounterfeiting applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150988","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}