Chemistry of Materials最新文献

{"title":"Deconvoluting\u0000the Convoluted: Structural Ramifications\u0000of Postsynthetic Linkage Modification in COF-366-Co Catalysts","authors":"Samuel Van Gele,Amelie Heilmaier,Fabian Heck,Kathrin Küster,Armin Schulz,Artem Shevchenko,Liang Yao,Bettina V. Lotsch","doi":"10.1021/acs.chemmater.6c01374","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01374","url":null,"abstract":"Abstract Postsynthetic modification (PSM) is a powerful strategy for modifying properties such as pore environment, stability and catalytic activity in covalent organic frameworks (COFs). While the chemical outcomes of PSMs are well documented, their impact on the underlying crystal lattice is rarely quantified. Yet, when translating modified COF systems toward catalytic applications, such structural changes can impact performance. In this work we interrogate precisely that blind spot for the benchmark electrocatalyst COF-366-Co. We apply three chemical PSM routes to the imine backbone: (i) quinoline cyclization (q-COF-366-Co), (ii) amine reduction (r-COF-366-Co), and (iii) nitrone oxidation (o-COF-366-Co) and investigate chemical as well as structural modifications induced by the functionalization. The catalysts are further investigated toward the electrochemical carbon dioxide reduction reaction in an attempt to decouple the multitude of convoluted aspects that affect catalytic activity, stability and selectivity such as particle size, disorder, strain, catalytic environment, and framework stability. Among the series, q-COF-366-Co showed a higher stability toward CO selectivity over time compared to the pristine COF-366-Co at −0.88 V vs reversible hydrogen electrode (RHE). Investigating q-COF-366-Co further showed, however, that higher functionalization concentrations led to simultaneous increase in disorder and a lower selectivity toward CO during catalysis. This indicates that a balance must be found between functionalization and preservation of crystalline lattice, offering insights into the design importance of maintaining structural coherence when comparing COF-based materials toward applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092272","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":"Cascade Thiol-Responsive Hydrogels Based on Poly(2-Isopropenyl-2-oxazoline)\u0000Cross-Linked with Ellman’s Reagent as Disulfide-Containing\u0000Cross-Linkers","authors":"Peitao Yu,Tomáš Sedlačík,Richard Hoogenboom","doi":"10.1021/acs.chemmater.6c01016","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01016","url":null,"abstract":"Abstract Thiol compounds play vital roles in environmental and biological systems, contributing to essential physiological processes, and there is a strong demand for methods to detect thiols and to design thiol-responsive materials. While stimuli-responsive hydrogels have been widely explored for biomedical and nonbiomedical applications, thiol-responsive hydrogels for thiol monitoring and detection remain scarcely reported. Herein, we present a straightforward strategy for synthesizing thiol-responsive hydrogels based on poly(2-isopropenyl-2-oxazoline) (PiPOx) bearing reactive 2-oxazoline side groups, cross-linked with Ellman’s reagent containing a disulfide linker. Disulfide bonds are incorporated into the hydrogel network through ester–amide junctions formed between the 2-oxazoline rings of PiPOx and the carboxylic acid groups of Ellman’s reagent. Upon exposure to thiols, the hydrogels undergo disulfide–thiol exchange reactions, releasing thiophenolate moieties and generating red coloration that enables rapid naked-eye colorimetric detection. Unexpectedly, the released thiophenolate groups further react with remaining 2-oxazoline groups of PiPOx, leading to decoloration accompanied by further evolution of the mechanical properties and enhancement of the hydrogel modulus. Consequently, a single thiol exposure induces a time-dependent cascade response involving swelling, softening, and coloration, followed by shrinking, stiffening, and decoloration. The timing of these events depends on thiol concentration, highlighting the potential of these hydrogels for time-programmable sensing and multilevel cascade-responsive materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090852","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":"Metal–Organic\u0000Cages as Porous Photosensitizers\u0000for Polyoxometalate Catalysts","authors":"Yuta Sueda,Masaya Yara,Kiyoshi Miyata,Ken Onda,Ryo Ohtani,Benjamin Le Ouay,Masaaki Ohba","doi":"10.1021/acs.chemmater.6c00734","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00734","url":null,"abstract":"Abstract Ionic metal–organic cages (MOCs) offer a unique platform to promote the reactivity of their functional counterions by forming “porous functional salts” (PFSs), but the role of MOCs has so far been limited to structuring and porogenic agent without strong coupling of properties. Herein, we report a new PFS, built from the assembly of the stable and noble-metal-free Keggin-type polyoxometalate (POM) SiW12O404– (SiW12) with a cationic Zr-based metal–organic cage (ZrT-NH2). While pristine SiW12 did not present any porosity or light absorption in the visible light region (above 400 nm), the PFS ZrT-NH2/SiW12 presented an appreciable surface area for a POM-based material (SBET(CO2) = 143 m2/g) as well as a photoinduced electron transfer from ZrT-NH2 to SiW12, which then enabled the formation of reactive species from dissolved dioxygen molecules. This combination made the PFS ZrT-NH2/SiW12 highly potent as a photocatalyst for environmental remediation (evaluated with the model pollutant rhodamine B), as porosity led to a pollutant preconcentration and improved accessibility to the SiW12 catalytic centers, while the photosensitizing effect enabled visible light photodegradation without the need for sacrificial reagents. This method of integrating POMs and functional MOCs offers a promising strategy for the development of functional materials with enhanced porosity and activity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"54 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090853","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":"Ultrathin\u0000SiO2 Nanofibrous Membranes with\u0000Voronoi-like Nanonets for High-Flux Water Filtration and Elution-Free\u0000Microplastics Analysis","authors":"Xiaoxi Li,Yucheng Tian,Xiaoyan Liu,Jianyong Yu,Yujang Cho,Minsoo Kim,Il-Doo Kim,Bin Ding","doi":"10.1021/acs.chemmater.6c01616","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01616","url":null,"abstract":"Abstract Inorganic microfiltration membranes are essential for water purification and microplastics detection; however, achieving high-flux water treatment and enabling straightforward microplastics analysis remain global challenges due to the limitations in the self-supporting nature and structural tunability of inorganic materials. Here, inspired by Voronoi-like natural structures, we report a route to create silicon dioxide (SiO2) nanofibrous membranes with a Voronoi-like nanonet structure (SiO2 VNMs), in which humidity-regulated phase separation and curing generate organosilicon-derived nanonets from silicone oil solution on electrospun and calcined SiO2 fibrous scaffolds. Subsequent calcination converts the organosilicon-derived nanonets into SiO2 nanonets. Benefiting from the self-organized Voronoi-like nanonet architecture, the resulting SiO2 VNMs simultaneously exhibit small pore sizes (≈150 nm), high porosity (≥80%), and an ultrathin thickness (≈1 μm). Consequently, the SiO2 VNMs deliver high filtration flux at low pressure (>6600 L m –2 h–1 at 15 kPa), and even under gravity-driven conditions (>900 L m–2 h–1 at 0.1 m H2O), exceeding that of existing inorganic membranes (6200 L m–2 h–1 at 70 kPa), rivaling the best state-of-the-art organic membranes. Moreover, the ultrathin inorganic structure enables direct on-membrane microscopic and spectroscopic identification of microplastics without elution. This work establishes a new pathway for designing inorganic filtration membranes that integrate efficient water purification with streamlined on-membrane microplastics detection.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"92 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090849","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":"Impact of\u0000Fluorine Content on Structure, Redox, and\u0000Electrochemical Performance of Disordered Rock-Salt Li1.25Mn0.5+\u0000 y\u0000 /2Nb0.25–\u0000 y\u0000 /2O2–\u0000 y\u0000 F\u0000 y\u0000 Electrode Materials","authors":"Quentin Deville,Valérie Dillay,Benoit Mortemard de Boisse,Stéphanie Belin,Matthew R. Suchomel,Mathieu Duttine,François Weill,Marie Guignard,Dany Carlier","doi":"10.1021/acs.chemmater.6c02082","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02082","url":null,"abstract":"Abstract Disordered rocksalt (DRS) oxides are highly promising positive electrode materials for next-generation Li-ion batteries, yet their practical application is severely bottlenecked by the irreversibility of oxygen-redox processes. Fluorination (O2– by F– substitution) represents a powerful strategy to mitigate these drawbacks, but achieving and characterizing high-content fluorine incorporation remains a significant challenge. In this work, we demonstrate the successful mechanochemical synthesis of an extended series of Mn- and Nb-based DRS oxyfluorides, Li1.25Mn0.5+y/2Nb0.25–y/2O2–yFy (0 ≤ y ≤ 0.5). While average structure analysis via powder XRD indicates the formation of a well-disordered solid solution across the entire series, local-structure probes reveal that the ideal cubic NaCl-type model with mixed occupation of the cation and anion sites fails to fully describe the materials. Pair distribution function (PDF) and XANES analyses unveil significant local deviations, highlighted by strongly distorted Mn3+ octahedra induced by the Jahn–Teller effect, while solid-state 7Li and 19F MAS NMR spectroscopies reveal a short-range clustering tendency. Bridging the local and macroscopic scales, dark-field TEM imaging demonstrates that these local arrangements assemble into coherent crystalline nanodomains (1–5 nm), in excellent agreement with the PDF analysis. Regarding the electrochemical properties, this progressive fluorination successfully shifts the redox mechanism from irreversible oxygen oxidation toward more reversible cationic Mn3+/Mn4+ redox, reducing the irreversible capacity and substantially enhancing the average discharge voltage. However, a persistent irreversible capacity loss remains regardless of the fluorine content. This study highlights the critical role of multiscale characterization in understanding the complex local structure–property relationships of highly fluorinated DRS cathodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090851","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":"Circumventing\u0000the Piezoelectric Performance Bottleneck\u0000in Bi0.5Na0.5TiO3–Based Ceramics\u0000by Designing Multilayer Piezoelectric Ceramics with Local Phase Transition","authors":"Jun Chen,Yiping Wang,Huihui Liu,Ying Yang","doi":"10.1021/acs.chemmater.6c01394","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01394","url":null,"abstract":"Abstract Bi0.5Na0.5TiO3-based piezoceramics are attractive for their excellent electrical properties, but their industrial application is constrained by the difficulty in simultaneously achieving a high piezoelectric coefficient (d33 > 300 pC/N), a high ferroelectric-relaxor phase transition temperature (TF–R > 200 °C), and a low d33 variation (<20%). Herein, the aforementioned performance bottleneck is circumvented by designing the multilayer piezoelectric ceramics (MLPC) with a local phase transition from ferroelectric to relaxor state. The local phase transition is achieved by grinding sintered 0.93Bi0.5Na0.5TiO3–0.07BaTiO3 ceramic into a powder and then incorporating it into the 0.85Bi0.5Na0.5TiO3–0.15BaTiO3 ceramic. By this strategy, a five-layer piezoelectric ceramic possesses a high apparent d33 of 480 pC/N and a high TF–R of 220 °C. Furthermore, the d33 variation in the MLPC is less than 17% over the temperature range of 30–170 °C. The excellent temperature stability is associated with an appropriate reduction in remanent polarization, which is primarily attributed to the local temperature-sensitive rhombohedral and tetragonal distortions. These distortions then trigger a local phase transition from the ferroelectric R3c and P4mm phases to the relaxor P4bm phase. This work offers an alternative paradigm for designing high-performance MLPC.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"21 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090857","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":"High-Quality\u0000Semiconductor Nanocrystals through Eutectic\u0000Processing","authors":"Divesh Nazar,Bhanuka Thennakoon,Siddhartha Kalpa Samadhi Thennakoon,Amelia Waters,Kosgoda Somarathne,Keston Walleman,Ryan Liebowitz,Renown Shrestha,Lydia Boeding,Pavel Anzenbacher,Mikhail Zamkov","doi":"10.1021/acs.chemmater.6c02191","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02191","url":null,"abstract":"Abstract The use of eutectic reactions in colloidal semiconductor nanocrystal (NC) synthesis has recently opened a route to materials with exceptional structural and optical quality. Unlike conventional hot-injection and ripening methods, eutectic-like NC-halide mixtures can promote thermodynamically driven shape evolution through transient, halide-induced recrystallization of semiconductor nanoparticles. This mechanism has proven remarkably versatile, producing a broad range of metal chalcogenide NCs, including alloys and core/shell heterostructures with reduced defect densities and improved photostability. Despite these advances, the chemical pathways governing eutectic-like reconstruction in NCs remain poorly understood, leaving the field in an early stage of development. This Perspective examines the evolving picture of NC growth through halide-induced reconstruction, highlights representative examples of shape and line width control, and discusses the emerging theoretical insights into the underlying mechanisms. We further review evolving applications of eutectic processing in NC light-emitting devices, optical gain media, photovoltaics, and scintillators. Finally, we discuss future opportunities for the field, including broader adoption of eutectic conditions as a general synthetic strategy for colloidal nanomaterials, its extension to challenging compositions such as III–V semiconductors, and eutectic processing of NC films to create epitaxially connected nanoparticle assemblies.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"71 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090875","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":"Incommensurate\u0000Structural and Magnetic Modulations\u0000in Potassium-Rich Cryptomelane, K\u0000 x\u0000 Mn8O16 (\u0000 x\u0000 ≈ 1.45)","authors":"Liam A. V. Nagle-Cocco,Joshua D. Bocarsly,Krishnakanth Sada,Nicola D. Kelly,Mathias A. Kiefer,Emmanuelle Suard,Sarah J. Day,Cheng Liu,Clare P. Grey,Prabeer Barpanda,Clemens Ritter,Siân E. Dutton","doi":"10.1021/acs.chemmater.6c01980","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01980","url":null,"abstract":"Abstract Cryptomelane is a hollandite-like material consisting of K+ cations in an α-MnO2 tunnel-like crystallographic motif. Cryptomelane with stoichiometry KxMn8O16 (x ≈ 1.45) has been synthesized and its magnetic properties investigated using variable-temperature magnetic susceptibility, heat capacity, and neutron powder diffraction. Three distinct transitions at T1 = 184 K, T2 = 54.5 K, and T3 = 24 K are observed. At T1 there is a subtle tetragonal → monoclinic transition associated with emergence of a set of nonmagnetic superstructure peaks indexable to a k→struc≈0.74c*→ incommensurate modulation parallel to the α-MnO2 tunnels. Our findings are consistent with a relation previously reported in titanate hollandites, that x≈2|k→struc|. Magnetic Bragg peaks emerge below T2 = 54.5 K, and their positions indicate an incommensurate modulated magnetic structure. The model consistent with the data is a dual- k→mag structure with a ferromagnetic |k→mag|=0 component and an incommensurate k→mag≈0.37c*→, with the latter most likely to be helical. The period of oscillation of the incommensurate magnetic component is in line with predictions based on a Heisenberg spin Hamiltonian [Mandal et al. Phys. Rev. B 2014, 90, 104420]. Below T3 = 24 K, there is a magnetic transition, which gives rise to a different set of magnetic Bragg peaks indicative of a highly complex magnetic structure.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090854","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 Design Strategy for Next-Generation Low-Dielectric\u0000Polyimide Materials: Regulating Aggregated Structures via Flexible\u0000Biphenyl Side Chains","authors":"Shi Liu,Mingyang Li,Hongxiang Li,Linman Li,Miao Wang,Xutao Zhang,Pengjian Gong,Rui Shi,Hujun Qian,Jiayu Wang,Pei Cheng,Jiaqiang Qin","doi":"10.1021/acs.chemmater.6c02357","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02357","url":null,"abstract":"Abstract The advancement of 5G and 6G communication technologies has introduced stringent requirements for the dielectric properties of the base materials employed in communication devices. Materials exhibiting a low dielectric constant (Dk) and low dielectric loss (Df) are particularly beneficial for signal transmission, as they reduce signal loss and latency. Modulating the molecular structure represents an effective approach to tailoring the dielectric characteristics of polymers. In this study, to concurrently decrease the Dk and Df values of polyimide (PI), we incorporate side chains comprising flexibly linked biphenyl liquid crystal (LC) units. These side chains increase the interchain spacing, thereby enhancing the free volume and reducing PI density, which contribute to lowering Dk. Concurrently, the flexible biphenyl LC moieties spontaneously organize into ordered stacks, promoting the ordered packing of the main polymer chains and effectively diminishing the Df. A series of PI films were synthesized to investigate the influence of side chains on the dielectric behavior. At a frequency of 17.4 GHz, the BPDA/6MPD film demonstrated a Dk value of 2.73 and a Df value of 0.0040, in contrast to values of 3.36 and 0.0318, respectively, for the BPDA/PDA film lacking side chains. This simultaneous reduction in dielectric parameters was further corroborated in the homopolymers. TAHQ/6MPD exhibited a Dk value of 2.79 and a Df value of 0.0029, while 6FDA/6MPD achieved values of 2.42 and 0.0036, respectively. The presented molecular design strategy thus offers a promising pathway for the development of high-performance, low-dielectric materials suitable for high-frequency-communication applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"147 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090855","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":"Chemical Characteristics\u0000Driving Formability in Li-Excess\u0000Disordered Rocksalt Cathodes","authors":"John D. Langhout,Jennifer A. Perez,Adam A. Corrao,Joyce Kim,Nicole Vlahos,Jason Jaquith,Kyle Schipf,Ella Rigdon,Ayden Israel,Juan C. Nino,Daniel Olds,Megan M. Butala","doi":"10.1021/acs.chemmater.6c02034","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02034","url":null,"abstract":"Abstract Li-excess disordered rocksalts are promising next-generation Li-ion battery cathode materials that feature a flexible, site-disordered cation sublattice. Understanding how different cations and their respective ratios can be adjusted is crucial to the further development of these materials. Here, we conceive a large, systematic set of potential disordered rocksalt formulations in which the redox-inactive charge compensator site has been substituted with a variety of cation species in varying ratios. From the phase purity of the 69 target formulations, we derive how the features of substituent charge compensator species impact the formability of disordered rocksalts. We find that cation size, cation tendencies to be in a distorted octahedron, and formation enthalpy of competing impurity phases are the primary drivers of amenability to form a locally disordered, single-phase product. We also find correlations of cation species with average structure lattice parameters and short-range order. A subset of rocksalt formulations is tested as Li-ion battery cathodes. We find that structural (crystallinity, short-range order, microstates of redox-active species) and chemical (surface chemistry) differences attributed to charge compensator substitution schemes impact performance metrics, such as capacity and capacity retention, highlighting the robust design space of this exciting class of materials. Insights reported here can inform the development of rocksalt oxides with targeted behavior, possibly including for favorable formation and performance of “δ” phases in Mn-rich rocksalts. In addition, we expect these findings about how cation features affect formability and structure translate to other compositionally complex oxide systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"84 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090858","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}