Chemistry of Materials最新文献

{"title":"Molecular Recognition Affords Ligand-Free Au Nanoparticle Catalysts on an Interfacially Inert Supramolecular Support","authors":"Kushaan Bahl,&nbsp;Gerald Siu Hang Poon Ho,&nbsp;Brandon C. Bukowski,&nbsp;Marcella Lusardi","doi":"10.1021/acs.chemmater.6c01997","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01997","url":null,"abstract":"<p>Decoupling supportand ligand contributions in supportedmetalnanoparticle (NP) catalysts remains an open challenge, and the challengeis synthetic: what makes a support interface inert is also what limitsits ability to bind and disperse NPs, requiring ligands that are themselvesactive participants in the catalytic cycle. Here, we address thischallenge using melamine cyanurate (MCA), whose supramolecular constructionexposes coordinatively saturated terminations of melamine and cyanuricacid (CA) subunits that are interfacially inert yet accessible forfunctionalization using molecular recognition. Under mild aqueousconditions, a Au-bound thiol-functionalized CA derivative uniformlydisperses onto the edges of MCA sheets via complementary hydrogen-bonddonor–acceptor pairs, as shown by X-ray photoelectron spectroscopy(XPS), transmission electron microscopy (TEM), and density functionaltheory (DFT). Thermal treatment yields 2.5 ± 0.5 nm, monodisperse(dispersity index = 1.1), ligand-free Au⁰ NPs. MCA’sinertness at both NP-support and reactant-pool-support interfacesis established by XPS and the Au-catalyzed aerobic oxidative dehydrogenationof <em>N</em>-methyl-4-piperidinone, respectively, and benchmarkedagainst conventional supports (graphite, silica, P25 TiO₂), with and without capping ligands. The interfacial inertness ofMCA, together with the bare, uniform NPs afforded by the recognition-basedsynthesis, enables quantitative decoupling of support and ligand contributionsto reactivity, revealing that carbonaceous deposit formation and overoxidationare direct consequences of support functionality, rather than intrinsicto the Au⁰ active site. Free of both contributions, AuNPs on MCA achieve 100% selectivity to the target enaminone and 90%yield, versus &lt;70% on conventional supported catalysts. More broadly,by resolving the usual trade-off between support inertness and ligand-freeNP functionalization, this strategy, rooted in supramolecular principles,expands the design space of noninterfering supports for metal NP catalysts.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10282–10297"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173816","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":"Particle Size Controls Phase Selectivity and Lattice Flexibility in Copper Triazolate Metal–Organic Framework Nanoparticles","authors":"Audrey M. Davenport,&nbsp;Erik Svensson Grape,&nbsp;Emma E. Mahady,&nbsp;Samuel J. Weiss,&nbsp;Kentaro Kadota,&nbsp;Satoshi Horike,&nbsp;Samuel G. Dunning,&nbsp;Audrey N. Boeschoten,&nbsp;Parker S. Brodale,&nbsp;Christopher H. Hendon,&nbsp;Carl K. Brozek","doi":"10.1021/acs.chemmater.6c01236","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01236","url":null,"abstract":"<p>Stabilizingdesirable polymorphs of solid-state materials has beenat the forefront of materials research for decades. While severaltheories exist for targeting specific polymorphs of conventional solids,few strategies are available for metal–organic frameworks (MOFs),despite the superior performance of certain structures in gas sorption,luminescence, and other applications. Here, we report that particlesize dictates the phase selectivity of the MOF Cu(1,2,3-triazolate)₂ (Cu(TA)₂). Whereas micron-sized crystals stabilizein a tetragonal space group at room temperature, preparing particlessmaller than 200 nm furnishes a previously unreported structure withorthorhombic symmetry. A suite of variable-temperature and variable-pressurespectroscopy and X-ray diffraction analysis indicates that metal-linkerbonding becomes more flexible in smaller particles, even within agiven crystallographic phase. These results suggest smaller particlesadopt phases impossible in bulk crystals because their softer latticesaccommodate distorted geometries─an explanation that complementsongoing debates about the mechanism of phase stabilization in conventionalsolids. These results therefore provide potential design strategiesfor phase selectivity of MOFs and broader classes of materials ingeneral.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9875–9885"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173849","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":"Ultrafast Site-Selective Excitation Pathways Governing Short-Lived Photoinduced Spin States in a Cyanide-Bridged Fe–Cr Spin-Crossover System","authors":"Kazuki Nakamura,&nbsp;Valentin Spitale,&nbsp;Grégory Taupier,&nbsp;Nicolas Godin,&nbsp;Daiki Kobayashi,&nbsp;Shintaro Akagi,&nbsp;Shin-ichi Ohkoshi,&nbsp;Hiroko Tokoro,&nbsp;Eric Collet","doi":"10.1021/acs.chemmater.6c01993","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01993","url":null,"abstract":"<p>We study the ultrafast light-induced excited spin statetrapping(LIESST) process in a cyanide-bridged Fe–Cr spin-crossovermaterial CsFe^II[Cr^III(CN)₆]·1.3H₂O. This material consists of an original Fe^II–NC–Cr^III units, responsible for the thermal spin transition (ST)of the low ligand field Fe ST site from a low-spin (LS) Fe^II_LS to a high-spin (HS) Fe^II_HS states.Although electronic structures suggest that a metastable HS statecan be reached by photoexcitation, no LIESST to this HS state hasyet been observed using conventional techniques. In addition, partof the units exhibits a thermally driven cyanide flip toward the Fe^II_LS–CN–Cr^III sites, whereFe is always LS by the high ligand field. By combining optical andIR spectroscopic studies, we investigated whether light excitationis ineffective in inducing the LIESST or whether it causes the cyanideflip. Our results reveal that photoexcitation indeed generates theHS state, but its lifetime is limited to a few picoseconds by ultrafaststructural relaxation. Excitation at 800 nm predominantly triggersa Fe-centered d–d transition at the ST site, whereas excitationat 530 nm induces metal-to-metal charge transfer (MM’CT) atboth ST and flipped sites. For the ST site, both excitation pathwaysgenerate the HS state within less than 200 fs, which launches coherenttorsional motion of the cyanide-bridged network, and this HS statedecays to a LS state within 3.5 ps. In contrast, at the flipped site,530 nm excitation selectively populates a transient MM’CT Fe^III_LS–Cr^II*, which decays withoutinducing spin state switching nor cyanide flipping. Overall, the photoinducedHS state rapidly decays, due to the counteracting pressure of therigid cyanide-bridged lattice, preventing long-lived LIESST and cooperativeswitching.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10271–10281"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173934","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–Thermoelectric Property Relations of the Nowotny Chimney–Ladder Phase Fe2Ge3","authors":"Oleksandr Cherniushok,&nbsp;Illia Lukashchuk,&nbsp;Kacper Pryga,&nbsp;Raisa Tahiyah,&nbsp;Taras Parashchuk,&nbsp;Yaroslav Tokaychuk,&nbsp;Lev Akselrud,&nbsp;Bartlomiej Wiendlocha,&nbsp;Roman Gladyshevskii,&nbsp;Yuri Grin,&nbsp;Alexandra Zevalkink,&nbsp;Krzysztof T. Wojciechowski","doi":"10.1021/acs.chemmater.6c00878","DOIUrl":"10.1021/acs.chemmater.6c00878","url":null,"abstract":"<p>The Nowotny chimney–ladder (NCL) phase in theFe–Gesystem near Fe₂Ge₃ composition is a promisingthermoelectric material owing to its characteristic coexistence ofdegenerate electronic transport and strongly suppressed lattice thermalconductivity, yet the structural and compositional origins of thisbehavior remain incompletely understood. Synchrotron diffraction showsthat samples prepared with nominal Fe₂Ge₃ compositioncrystallize as an incommensurately modulated NCL phase close to FeGe_1.52. From the superspace description, we derive and refinefor the first time a three-dimensional commensurate approximant, Fe₂₇Ge₄₁ (<em>tP</em>272). Chemical-bondinganalysis based on the model of Fe₂Ge₃ revealsa three-dimensional framework of heteroatomic multiatomic Fe–Geinteractions without homoatomic Fe–Fe or Ge–Ge bonds.DFT calculations for the Fe₂₇Ge₄₁ approximantshow that slight Ge excess in comparison with Fe₂Ge₃ shifts the Fermi level into the conduction band, yieldinga nominal carrier concentration of ∼10²¹ cm^–3, consistent with Hall measurements, and explainingthe degenerate <em>n</em>-type behavior without extrinsicdonors. The electronic structure is characterized by a high density-of-stateseffective mass (∼11 <em>m</em>_e), arisingfrom convergence of flat conduction bands near the Fermi level. Despitehigh elastic moduli and a moderate Grüneisen parameter, thelattice thermal conductivity is low (∼1.8 W m^–1 K^–1 at 300 K), corresponding to an estimated phononmean free path of approximately 8 Å. The failure of the Debye–Callawaymodel to reproduce this value indicates additional phonon scattering,which may be related to the incommensurate structure and bonding inhomogeneity.Overall, the incommensurate Fe–Ge NCL phase combines degenerateelectronic transport with phonon-glass-like thermal behavior.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9802–9816"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148767195","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":"Mag4: An Automated First-Principles Workflow to Extract Magnetic Interactions, from Pair Couplings to Four-Spin Ring Exchange","authors":"Xavier Rocquefelte,&nbsp;Peter Blaha","doi":"10.1021/acs.chemmater.6c02203","DOIUrl":"10.1021/acs.chemmater.6c02203","url":null,"abstract":"<p>Chemists rationalize and design magnetic materials throughstructure-propertyrelationships built on pairwise exchange couplings <em>J</em>, which energy-mapping methods now extract routinely from first principles.Yet whenever four magnetic centers close a loop, as in the CuO₂ planes of the cuprates or the square nets of infinite-layeroxides, a four-spin ring (cyclic) exchange <em>J</em>_ring can arise, reshaping magnetic ground states and corruptingthe very <em>J</em> values used for design. What has beenmissing is a practical way to obtain it: a direct, local extractionof the kind the four-state method provides for <em>J</em>.We supply it by generalizing that method to a 16-state (2⁴) scheme, and we automate the complete workflow in the openly available <span>Mag4</span> package, a fully automatic implementation of the four-statefamily of methods: from a single cif file, <span>Mag4</span> proposesthe supercell that isolates the couplings, generates the density functionaltheory (DFT) inputs in the exchange-correlation flavour of the user’schoice, extracts <em>J</em> and <em>J</em>_ring with the band-gap and local-moment diagnostics that certify them,and predicts the magnetic order, its propagation vector, and the criticaltemperature. Symmetry reduces the 16 configurations to six or eightinequivalent energies, so the cost is modest. The derivation alsoshows that the conventional four-state magnetic coupling, <em>J</em>, is itself ring-renormalized, by ∓2<em>J</em>_ring<em>S</em>² with the sign set bythe reference state. T-La₂CuO₄ confirms thisquantitatively: three concordant routes agree on <em>J</em>_ring to 0.2%, giving <em>J</em>_ring/<em>J</em>₁ = 0.25, and a four-state <em>J</em>₁ quoted without naming its reference is wrongby 12% in this material. The direct 16-state extraction itself provesreference-dependent, the Néel and ferromagnetic baths bracketingthe mapping value: a fourth-order fingerprint of interactions beyondthe pair-plus-ring model, which additional reference baths resolveinto a bare <em>J</em>_ring and a converging towerof six- and eight-spin loop couplings. SrFeO₂ (<em>S</em> = 2), with the same plaquette yet <em>J</em>_ring/<em>J</em> = 0.006, provides the negative control:a plaquette is necessary for ring exchange, far from sufficient: astructure-property criterion that chemists can screen against whensearching for materials hosting strong multi-spin magnetism.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10351–10365"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973961","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-Site Cation Template-Induced N–H···O Hydrogen-Bond Orientations for Constructing Three-Dimensional Cesium-Based Energetic Molecular Perovskites","authors":"Zhenghang Luo,&nbsp;Ruibing Lv,&nbsp;Qi Zhang","doi":"10.1021/acs.chemmater.6c01921","DOIUrl":"10.1021/acs.chemmater.6c01921","url":null,"abstract":"<p>Energetic molecular perovskites (EMPs) are a high-energysubclassof molecular perovskites that integrate oxidizers and fuels withina single framework. However, the structures of reported EMPs remainrather limited, and the structural contribution and governing roleof their component ions remain elusive. Herein, we develop an A-sitecation-templated strategy to direct the spatial orientation of N–H···Ohydrogen bonds, enabling the rational engineering of two Cs-basedEMPs with distinct 3D frameworks: trigonal DCP-1 and tetragonal TCP-1.The inductive effect of the A-site cation in framework constructionis elucidated. Unlike H₂hmta²⁺, H₂dabco²⁺ features a unique parallel N–H vector field,which drives the connection of [Cs(ClO₄)₆] octahedrathrough a rare alternating face-sharing and corner-sharing mode. Thisassembly results in the first EMP crystallizing in the <em>R</em>3̅<em>c</em> space group. Such structural divergence,governed by the spatial orientation of hydrogen bonds, leads to asignificant differentiation in physicochemical properties. This worknot only introduces cesium into EMPs for the first time but also expandsthe structural diversity of EMPs by introducing an unusual trigonalframework. The universal principle of tailoring crystal structuresand energetic properties by A-site hydrogen-bond vectors is revealed,providing insights into next-generation high-performance energeticmaterials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10202–10214"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010453","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 Ordering and Phase Stability Govern Optical Band Gaps in BaZrS3xSe3–3x","authors":"Erik Fransson,&nbsp;Michael Xu,&nbsp;Prakriti Kayastha,&nbsp;Kevin Ye,&nbsp;Ida Sadeghi,&nbsp;Rafael Jaramillo,&nbsp;James M. LeBeau,&nbsp;Lucy Whalley,&nbsp;Paul Erhart","doi":"10.1021/acs.chemmater.6c01949","DOIUrl":"10.1021/acs.chemmater.6c01949","url":null,"abstract":"<p>Chalcogenide perovskiteshave emerged as promising lead-free materialsfor photovoltaic and thermoelectric applications. Among them, BaZrS₃ has attracted particular attention due to its thermal andchemical stability, favorable optoelectronic properties, and low thermalconductivity. Here, we combine molecular dynamics and Monte Carlosimulations based on a machine-learned interatomic potential withscanning transmission electron microscopy to investigate mixing thermodynamicsand phase stability in the BaZrS_3<em>x</em>Se_{3–3<em>x</em>} system. We identify an unusualordered structure, with signatures of anion ordering persisting atroom temperature, most prominently at 33% S, where S and Se atomsform alternating layers within the crystal. Free-energy calculationsyield the temperature–composition phase diagram, includinga nonperovskite δ phase in the Se-rich limit and a perovskitephase in the S-rich limit, separated by a broad two-phase region.Analysis of the dielectric function and the absorption coefficientdemonstrates that composition, crystal structure, and anion orderingjointly control the optical band gap. Selenium alloying enables tuningbetween approximately 1.5 and 1.9 eV, while anion ordering withina given composition reduces the gap by about 0.2 eV. Lastly, variationsbetween structural polymorphs give rise to band gap differences ofup to 0.5 eV.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10251–10258"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019641","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":"Investigating Nonlinear Optical and Thermal Properties in Sr2SiSe4 through Noncentrosymmetric Crystal Structure Comparison with Sr2SnSe4","authors":"Tristan Licskai,&nbsp;Laura Mereweather,&nbsp;Abdeljalil Assoud,&nbsp;Ehsan Niknam,&nbsp;Yunseung Kuk,&nbsp;P. Shiv Halasyamani,&nbsp;Holger Kleinke","doi":"10.1021/acs.chemmater.6c02391","DOIUrl":"10.1021/acs.chemmater.6c02391","url":null,"abstract":"<p>An isovalent anion substitution approach allowed forthe discoveryof two noncentrosymmetric ternary selenides, Sr₂SiSe₄ and Sr₂SnSe₄. Sr₂SiSe₄ crystallizes in the α-Eu₂GeS₄ type, monoclinic space group <em>P</em>2₁, withlattice parameters <em>a</em> = 6.8866(19) Å, <em>b</em> = 7.0062(19) Å, <em>c</em> = 8.520(2) Å,β = 108.200(6)°, and <em>Z</em> = 2, while Sr₂SnSe₄ adopts the γ-Sr₂GeSe₄ type, orthorhombic space group <em>Ama</em>2, withlattice parameters <em>a</em> = 10.4802(10) Å, <em>b</em> = 10.6965(10) Å, <em>c</em> = 7.5411(7) Å,and <em>Z</em> = 4. Calculated PBE band gaps show that Sr₂SiSe₄ (<em>E</em>_g = 2.31 eV)and Sr₂SnSe₄ (<em>E</em>_g = 2.05 eV) both exhibit a broad transparency window in the infraredregion along with moderate band gaps, avoiding two-photon absorptionfrom 2090 nm lasers. The nonlinear optical response of Sr₂SiSe₄ was experimentally determined using AgGaS₂ as a reference, indicating that the material is phase-matchable,producing an intensity approximately 0.5 times that of AgGaS₂ using a 2090 nm laser. In addition to its promising nonlinear opticalproperties, Sr₂SiSe₄ exhibits ultralow thermalconductivity (0.46 W m^–1 K^–1 at523 K) despite being composed of rather light elements compared toBi₂Te₃ and PbTe, making it an interesting─andless toxic─potential candidate for thermoelectric energy conversionapplications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10388–10396"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019651","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":"Mixed Valence-Driven Phase Evolution and Property Tuning in PdSe2","authors":"Yao Abusa,&nbsp;Emma Ross,&nbsp;John Obeng,&nbsp;Genevieve Amobi,&nbsp;Gayatri Viswanathan,&nbsp;Samira Noor,&nbsp;Jemima Opare-Addo,&nbsp;Ajay Kumar,&nbsp;Emily Smith,&nbsp;Takeshi Kobayashi,&nbsp;Joel Rosenthal,&nbsp;Yaroslav Mudryk,&nbsp;Kirill Kovnir","doi":"10.1021/acs.chemmater.6c01922","DOIUrl":"10.1021/acs.chemmater.6c01922","url":null,"abstract":"<p>Layered palladium diselenide (PdSe₂) is anemergingfunctional dichalcogenide whose structural flexibility enables tunableelectronic, magnetic, and transport properties. However, controlledaccess to compositionally substituted and metastable polymorphs remainschallenging using conventional synthetic approaches. Here, we reporta benchtop solution-phase route for the rapid and scalable synthesisof highly crystalline orthorhombic PdSe₂ (<em>o</em>-PdSe₂) and its polymorphs induced by aliovalent substitutions.This sustainable approach enables controlled phase evolution and yieldsmaterials suited for detailed structural, spectroscopic, magnetic,and transport studies. Using this platform, we achieve substitutionat the Pd site with both 3<em>d</em> and 5<em>d</em> transition metals, Mn and Pt, respectively. Approximately 10 at.% Mn substitution preserves the orthorhombic framework while inducinga complex magnetic ground state. In contrast, Pt substitution stronglymodifies Se–Se dimer stability and drives sequential structuraltransformations. Unlike Pd, Pt prefers a 4+ oxidation state, resultingin a partial destabilization of the Se–Se dumbbells and formationof monoclinic <em>I</em>2/<em>a</em> polymorph withmixed Pt²⁺/Pt⁴⁺ centers at low Pt content (∼12at. %). This structural reorganization induced by minute amounts ofPt drastically alter charge and heat transport properties, includinga carrier-type switch from <em>p</em>-type to <em>n</em>-type conduction, a narrowing of the bandgap, and ultralow thermalconductivity of 0.27 Wm^1–K^–1 at300 K. At higher Pt content (≥30 at. %), Pd is progressivelyforced to +4 oxidation state resulting in the complete destabilizationof the Se–Se dimers and structural transformation into a trigonalmetallic phase with [MSe₆] octahedra. These results establisha versatile soft chemical route to compositionally and structurallytunable PdSe₂-based materials with emergent magnetic andtransport properties, alluding to their promise for energy conversionand storage applications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10215–10230"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019654","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":"Semiautomated Synthesis and Interactive Visualization of Zeolitic Imidazolate Framework-Based Biocomposites","authors":"Xue Chen,&nbsp;Aleksandar Kondinski,&nbsp;Jing Yang,&nbsp;Helmar Wiltsche,&nbsp;Bernd Nidetzky,&nbsp;Francesco Carraro,&nbsp;Paolo Falcaro","doi":"10.1021/acs.chemmater.6c01702","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01702","url":null,"abstract":"<p>Zeolitic imidazolateframework (ZIF) biocomposites are widely studiedfor their potential in biocatalysis and biomedicine. However, theirpreparation is highly sensitive to precursor composition, concentration,washing conditions, and operator-dependent handling procedures. Here,we combine a semiautomated syringe-pump system, high-throughput samplepreparation, and digital data visualization to map synthesis–structure–propertyrelationships in ZIF biocomposites. A programmable four-syringe pumpplatform was used to systematically prepare 360 distinct samples intriplicate, yielding 1080 samples. The investigated synthetic parameterswere relative amounts of metal, ligand, protein, the total precursorconcentration, and the washing protocol. Structural, chemical, andfunctional characterization yielded a data set of ∼2250 entriescomprising crystalline-to-amorphous ratios, IR-based protein-to-frameworkratios, encapsulation efficiency, and loading capacity. We note thatexploring such a large data set manually can be challenging and thatcurrent static visualizations can hide meaningful trends. With theaim of enabling a customized and interactive exploration of the data,we designed the ZIF Biocomposite Explorer App (ZIF-BEA), which supportsuser-defined navigation in the space of the variables, providing directaccess to experimental data and material properties. We anticipatethat integrating large experimental data sets with interactive digitalplatforms may expedite the design of MOF-based biocomposites, whileproviding a transferable tool for the exploration of other classesof functional materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10135–10148"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173898","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}