Chemistry of Materials最新文献

{"title":"Structural Role of Different MXenes in CoMnS Composites for High-Energy Ionic Liquid Supercapacitors","authors":"Shrabani De,&nbsp;Bishnu Prasad Bastakoti","doi":"10.1021/acs.chemmater.6c01800","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01800","url":null,"abstract":"<p>A systematic comparative study of three MXenes, Ti₃C₂ (TC), V₂C (VC), and Mo₂Ti₂C₃ (MTC), and their corresponding CoMnS(CMS) compositeswas conducted to elucidate the influence of MXene chemistry on electrochemicalperformance. The composites were synthesized via in situ growth ofCMS on MXene surfaces, promoting strong interfacial interactions anduniform dispersion of redox-active species. Structural characterizationrevealed that TC possesses the most ordered layered structure andhighest synthesis efficiency, whereas MTC exhibits a more disorderedmorphology. Despite this, MTC-based composites delivered superiorelectrochemical performance owing to enhanced interfacial activityand faster ion/electron transport. All MXene/CMS composites significantlyoutperformed their pristine counterparts when employed as positiveelectrodes in asymmetric supercapacitors. A maximum energy densityof 432.3 Wh kg^–1 and a specific capacitance of 1216F g^–1 were achieved by the MTC/CMS device at 0.5A g^–1. The highest power density of 8000 W kg^–1 was obtained from the MTC/CMS device at 5 A g^–1 current density. In addition, a capacitance retentionof ∼94% was observed after 10,000 continuous cycles in an ionicliquid electrolyte. These enhanced properties are credited to a mutualreinforcement between Co/Mn redox-active pseudocapacitance and MXene-derivedelectric double-layer capacitance. Overall, the electrochemical performancefollows the order: MTC/CMS &gt; VC/CMS &gt; TC/CMS &gt; MTC &gt; VC&gt; TC &gt; CMS,highlighting the importance of MXene-dependent interfacial engineeringfor advanced energy-storage systems.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10994–11004"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368640","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":"Predictive Inorganic Synthesis Based on Machine Learning Using Small Data Sets: A Case Study of Hydrodynamic Diameter-Controlled Copper Nanoparticles","authors":"Brent Motmans,&nbsp;Digvijay Ghogare,&nbsp;Thijs G. I. van Wijk,&nbsp;Joren Van Herck,&nbsp;Saba Heidarian,&nbsp;Pieter De Meyer,&nbsp;Berend Smit,&nbsp;An Hardy,&nbsp;Danny E. P. Vanpoucke","doi":"10.1021/acs.chemmater.6c01699","DOIUrl":"10.1021/acs.chemmater.6c01699","url":null,"abstract":"<p>Copper nanoparticles(Cu NPs) have a broad applicability,yet theirsynthesis is sensitive to subtle changes in reaction parameters. Thissensitivity, combined with the time- and resource-intensive natureof experimental optimization, poses a major challenge in achievingreproducible and size-controlled synthesis. While machine learning(ML) shows promise in materials research, its application is oftenlimited by scarcity of large high-quality experimental data sets.This study explores ML to predict the DLS-derived hydrodynamic diameterof Cu NPs from microwave-assisted polyol synthesis using a small dataset of 25 in-house performed syntheses. Latin hypercube sampling isused to efficiently cover the parameter space while creating the experimentaldata set. Ensemble regression models successfully predict hydrodynamicdiameters with good predictive performance given the limited dataset. Since quantitative regression requires a unique DLS-derived hydrodynamicdiameter, the regression model is restricted to monomodal DLS distributions,while a complementary classification model identifies synthesis conditionsfor which quantitative prediction is applicable. Using equivalentout-of-sample validation (OOB and LOOCV), the ML and DoE models showedcomparable generalization (MAE = 40.92 and 40.46 nm, respectively).The final ensemble model achieved an <em>R</em>² of 0.74, an MAE of 23.81 nm, compared to an <em>R</em>² of 0.60, an MAE of 33.54 nm for the DoE model, while retainingthe complete synthesis parameter space, making it better suited forsynthesis guidance. Additionally, classification models using bothrandom forests and large language models (LLMs) are evaluated to distinguishbetween large and small particles. These classification models exhibitedonly modest predictive performance, indicating that this small dataset is insufficient to fully exploit the capabilities of complex LLMs.Overall, this study demonstrates that carefully curated small datasets, paired with robust classical ML, can effectively support thesynthesis of Cu NPs and highlights that for lab-scale studies, complexmodels like LLMs may offer limited benefits. The validation experimentsfurther indicate the potential of ML guided synthesis to improve theefficiency of experimental optimization and reduce resource consumption.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10981–10993"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248741","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 Defect Formation Energies Limit Ionic Conductivity in Na3Ga2Li3F12 and Na3Al2Li3F12","authors":"Michael J. Brady,&nbsp;Hauke Glück,&nbsp;Jessica L. Andrews,&nbsp;Erica Truong,&nbsp;Alexander G. Squires,&nbsp;Ifeoluwa P. Oyekunle,&nbsp;Rachel C. Monger,&nbsp;Wolfgang G. Zeier,&nbsp;Yan-Yan Hu,&nbsp;David O. Scanlon,&nbsp;Benjamin J. Morgan,&nbsp;Brent C. Melot","doi":"10.1021/acs.chemmater.6c01542","DOIUrl":"10.1021/acs.chemmater.6c01542","url":null,"abstract":"<p>Lithium-conducting fluoride garnets exhibit ionic conductivitiesof ∼10^–10 S cm^–1, far belowthose of their oxide counterparts. Here, we investigate the originof this poor transport in Na₃Ga₂Li₃F₁₂ and Na₃Al₂Li₃F₁₂ through a combination of structural characterization andfirst-principles calculations. Both compounds are highly ordered,with no significant antisite disorder, and exhibit intrinsic ionicconductivities of ∼2 × 10^–11 S cm^–1 at 100 °C. Nudgedelastic band calculations reveal low Li-ion migration barriers (0.16to 0.29 eV), indicating that the fluoride garnet framework does notinherently restrict Li-ion diffusion. However, the formation energiesfor lithium Frenkel and Schottky defect pairs are high (1.9 to 2.4eV), indicating that the intrinsic concentrations of mobile Li-iondefects are negligibly small. These results establish that the lowconductivity of stoichiometric fluoride garnets arises from high defect-formationenergies, rather than high migration barriers.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10973–10980"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241560","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":"Revisiting 2-Isopropylthioxanthone: Direct and Reactivable Photopolymerization of Acrylates from Near-UV to Blue Light. Efficient 3D Printing and Surface Modification","authors":"Carlo Gonzato,&nbsp;Loïc Buchon,&nbsp;Jean-Louis Clément,&nbsp;Yohann Guillaneuf,&nbsp;Olivier Soppera","doi":"10.1021/acs.chemmater.6c02002","DOIUrl":"10.1021/acs.chemmater.6c02002","url":null,"abstract":"<p>Reversible-deactivation radical photopolymerization(photoRDRP)enables precise spatiotemporal control of polymer architectures. Becauseof embedded active chain ends, photoRDRP offers straightforward reactivationand chain extension, providing unmatched flexibility for fine-tuningstructural, mechanical, and physicochemical properties for targetedapplications. Nevertheless, its application to 3D printing remainslimited by the cost and synthetic effort of the control agent, aswell as by a limited reactivity under common near-UV and blue lightsources, which requires printers working in the visible range andresults in usually low printing rates. Herein, we show the unexpectedability of 2-isopropylthioxanthone (ITX) to promote both a directacrylate photopolymerization, (with no need for any conventional co-initiatorand a printing rate close to those of conventional photoinitiators)and a subsequent surface-initiated (SI) photopolymerization via reactivablesurface-bound species, yielding postfunctionalization results thatare equivalent to, or surpass, those of RAFT systems. Compared tobenzyldithiocarbamate (BDC) and <em>N</em>-(<em>tert</em>-butyl)-<em>N</em>-(2-methyl-1-(4-benzoylphenyl)propyl)-<em>O</em>-(1-phenylethyl) hydroxylamine (MBA), two model photoinitiatorsfor photoRDRP in the near-UV range, ITX enabled controlled SI photopolymerizationof neat acrylate monomers over thicknesses of several hundred micrometers,with higher molar reactivity and a broader spectral response. Thisallowed for direct photopolymerization and photostructuring usingwavelengths from 365 to 405 nm. This straightforward and scalableapproach opens promising avenues for the on-demand functionalizationand assembly of complex 3D-printed architectures and is expected tobridge the gap between academic precision and industrial accessibility.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"11028–11037"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241809","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":"Alloy-Assisted Formation of Vanadium-Rich Thiophosphates with Enhanced Charge Transport and Glassy Magnetism","authors":"Patricia E. Meza,&nbsp;Tyler J. Slade,&nbsp;Adam Balvanz,&nbsp;Abishek K. Iyer,&nbsp;Hengdi Zhao,&nbsp;Andrew Kindseth,&nbsp;Yukun Liu,&nbsp;Roberto dos Reis,&nbsp;Jeremy Lee,&nbsp;Alexander A. High,&nbsp;Mercouri G. Kanatzidis,&nbsp;Vinayak P. Dravid","doi":"10.1021/acs.chemmater.6c00920","DOIUrl":"10.1021/acs.chemmater.6c00920","url":null,"abstract":"<p>Vanadium-based thiophosphates in the MPQ₃/M₂P₂Q₆ family provide an unusual platformforcoupling mixed-metal valence, metal vacancies, and 2D magnetism, butaccess to phase-pure multimetal solid solutions with verified chemicalhomogeneity remains limited. Here, we show that multication alloyingprovides a route to incorporating V into layered thiophosphates whileretaining the mixed-valent, vacancy-containing character of V_{2−<em>x</em>}P₂S₆. Thisapproach yields Fe_1.25V_0.6P₂S₆, Ni_1.25V_0.6P₂S₆, Co_1.25V_0.6P₂S₆, andhigh-entropy V-containing compositions. Single-crystal X-ray diffraction(scXRD) and electron energy-loss spectroscopy (EELS) mapping confirmformation of layered single-phase alloys and chemical uniformity bothacross the surface and through the flake thickness. Optical measurementsshow semiconducting band gaps spanning ∼1.33−1.66 eV,while temperature-dependent transport reveals markedly enhanced conductivityand low activation energies (∼0.2−0.3 eV) relative toconventional divalent TM₂P₂S₆ analogs.Oxidation-state mapping indicates robust mixed-valent V²⁺/V³⁺ character consistent with defect-assisted hoppingand self-doping linked to vanadium vacancies, likely causing enhancedconductivity. Magnetic measurements further show composition-dependentbehavior, consistent with magnetic frustration and glassy componentsin Fe_1.25V_0.6P₂S₆ and(VMnFeCoNi)₂P₂S₆, highlighting therole of multimetal disorder in shaping exchange interactions. Together,these results establish a route to phase-pure, conductive V-containingthiophosphate alloys and expand the tunable design space for coupledtransport and magnetism in layered chalcophosphates.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10934–10949"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248740","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":"Quantum Dot Superlattice: Formation, Properties, and Future Challenges","authors":"Tong Zhang,&nbsp;Qian Zhao,&nbsp;Youwen Xue,&nbsp;Yuxuan Wang,&nbsp;Jianyu Yuan,&nbsp;Huanqi Cao,&nbsp;Guoran Li,&nbsp;Shougen Yin","doi":"10.1021/acs.chemmater.6c01278","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01278","url":null,"abstract":"<p>Quantumdot superlattices (QDSLs) are composed of long-rangeorderedquantum dots (QDs), exhibiting both the ultrahigh structural precisioncharacteristic of single crystals and the quantum confinement effectsintrinsic to QDs, thereby bridging two extremes of crystal dimensionality.This unique integration endows QDSLs with remarkable multifunctionalproperties that transcend the limitations of conventional materials.In the era of the Fourth Industrial and Energy Revolutions, QDSLshold significant promise for enabling high-speed, high-efficiencyinformation transmission and energy conversion, addressing criticalbottlenecks in next-generation information technologies, supportingcarbon neutrality, and alleviating the global energy crisis. In thisreview, we summarize recent progress in QDSL research, including advancedsynthesis methods and investigations into their thermoelectric, optical,electronic, and optoelectronic properties. We also critically examinecurrent challenges and provide perspectives on large-area fabricationof QDSL films, precise assembly of defect-free superlattices, andelucidation of structure–property relationships. Notably, theemergence of perovskite QDs (PQDs) is anticipated to drive furtherperformance enhancements, guiding future research toward technologicalbreakthroughs and accelerating the transition of QDSLs from fundamentalstudies to real-world technologies.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10914–10933"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Measurements and Analysis of Catalyst Diffusion and Reaction Fronts in Chemically Amplified Resists","authors":"Christopher M. Bottoms,&nbsp;Tanguy Terlier,&nbsp;Manolis Doxastakis,&nbsp;Gila E. Stein","doi":"10.1021/acs.chemmater.6c02591","DOIUrl":"10.1021/acs.chemmater.6c02591","url":null,"abstract":"<p>The propagation ofboth catalyst diffusion and reactionfrontsin a polymeric chemically amplified resist (CAR) is evaluated by time-of-flightsecondary ion mass spectrometry (TOF-SIMS) depth profiling, and iscompared with the propagation of catalyst diffusion fronts in inertresist analogues. We report that catalysts display accelerated andhighly non-Fickian dynamics in the reactive CAR, even when locatedwell behind the propagation front, while simple Fickian diffusionis observed for the same conditions in inert resist analogues. Thecomplex catalyst dynamics of reactive systems is attributed to twokey factors: (1) Transient free volume following deprotection events,which is a long-hypothesized acceleration mechanism acting on thediffusion front; and (2) a newly identified plasticization processinduced by inert, nonvolatile byproducts of catalyst photoactivation.We propose a physics-informed model of enhanced catalyst diffusiondue to the independent contributions of these two processes, and demonstratethat this model coupled to a first-order reaction provides a reasonableprediction of both the diffusion and reaction fronts. Our study presentsa critical evaluation of mechanisms that control the spatial extentof reaction in CARs, and suggests that quantitative models of thepatterning process should account for the impact of nonvolatile catalystactivation byproducts.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"11038–11050"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Alcohol-Mediated Area-Selective Atomic Layer Deposition through Surface Chemical States Modulation","authors":"Weizhen Wang,&nbsp;Boxuan Li,&nbsp;Kun Cao,&nbsp;Zilian Qi,&nbsp;Eryan Gu,&nbsp;Yanwei Wen,&nbsp;Bin Shan,&nbsp;Rong Chen","doi":"10.1021/acs.chemmater.6c01198","DOIUrl":"10.1021/acs.chemmater.6c01198","url":null,"abstract":"<p>Area-selective atomic layer deposition (AS-ALD) fundamentallyrelieson a distinct disparity in surface chemical states between growthand nongrowth area. For SiO₂/Cu patterned architectures,the oxidation of the Cu surface serves as a primary driver for theloss of selectivity as the ALD process proceeds. Herein, an alcohol-mediatedAS-ALD process is proposed, utilizing alcohols with varying carbonchain lengths to precisely modulate surface chemical states to enhanceselectivity of AS-ALD WO_<em>x</em> film. A competitive-synergisticmechanism involving surface reductive capability and steric hindranceis identified as the governing factor for process selectivity. Resultsdemonstrate that while the reducing ability of alcohols on oxidizedCu surfaces diminishes with increasing carbon chain length, theirsteric hindrance increases. EtOH was identified as the optimal pretreatmentagent, yielding an exceptional selectivity exceeding 99.9% on SiO₂/Cu patterned surface. Moreover, the alcohol-mediated AS-ALDprocess is successfully extended to other oxide systems with precursorsbearing analogous ligands, demonstrating the generality of the proposedstrategy. This work provides a versatile methodology for modulatingsurface reductive capability and steric hindrance to achieve high-selectivityAS-ALD.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10962–10972"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152041","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":"Metastable Inorganic Materials through Reactive Molten-Salt Ion Exchange","authors":"Sarah L. Ko,&nbsp;A. Elena Sjoblom,&nbsp;Kent J. Griffith","doi":"10.1021/acs.chemmater.6c01779","DOIUrl":"10.1021/acs.chemmater.6c01779","url":null,"abstract":"<p>Material discovery is the foundational process for fundamentalinvestigations and useful applications of functional and structuralmaterials. It is the prerequisite for all downstream processes includingproperty determination, synthetic optimization and scale-up, doping,defect engineering, morphology control, and surface and interfacialtuning. Through extensive experimental and, more recently, computationalexploration, the number of yet-to-be-discovered thermodynamicallystable compounds in low-order phase spaces has rapidly shrunk. However,new materials are needed to foster advances in established and emergingapplications, particularly those related to energy storage, conversion,and efficiency. Thinking beyond equilibrium phase diagrams, a muchlarger phase space of metastable compounds exists if such phases canbe synthetically accessed. This Perspective highlights the role ofreactive molten-salt ion exchange (MSIX) as a technique for metastableinorganic material discovery. We discuss the thermodynamics, kinetics,crystal chemistry, and atomic-scale characterization of reactive molten-saltion exchange. Emergent phenomena in ion exchange such as interdiffusionand the mixed-ion effect and challenges associated with characterizingmixed-ion and heterogeneous systems receive extra attention. In considerationof the breadth of MSIX, fundamental principles and general reactionschemes are used where possible with specific examples extensivelyreferenced. MSIX is contextualized by comparisons to adjacent fieldsthat involve molten salts, ion transport, and metastable materials.Opportunities and missed opportunities associated with computationalapproaches to molten-salt reactions and metastable materials are discussed.Unique prospects for in situ diffraction and NMR crystallography arehighlighted along with future directions, including extensions tosolid-state ion exchange (SSIX).</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 21","pages":"10897–10913"},"PeriodicalIF":7.1,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209749","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":"ZnO Vacancy Homojunction for Phonon-Enhanced Directional Charge Transfer","authors":"Yi-Tian Wang,Shi-Tian Xiao,Jia-Jie Zhou,Si-Ming Wu,Kang-Jun Wu,Xiu-Shuo Yuan,Li-Ying Wang,Yi Lu,Wei Geng,Jie Ying,Ling Shen,Guo-Qiang Luo,Ge Tian,Matthias Driess,Ion Tiginyanu,Xiao-Yu Yang","doi":"10.1021/acs.chemmater.6c02534","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02534","url":null,"abstract":"Directional charge transport is essential for efficient photocatalysis, yet carrier transfer in semiconductor nanocrystals is often random and limited by recombination. Although electron−phonon coupling strongly influences carrier dynamics, phonons are more commonly associated with energy dissipation than with enhanced charge transport. Here, we construct a ZnO vacancy homojunction composed of donor-type oxygen vacancies and acceptor-type zinc vacancies, establishing an intrinsic pathway for directional charge transfer. The resulting n−p junction introduces both an internal electric field and asymmetric lattice distortion, enabling phonon-assisted directional carrier transport under ultrasonication and leading to significantly enhanced photocatalytic performance in methylene blue degradation compared with conventional ZnO. Combined spectroscopic measurements, radical-trapping experiments, and density functional theory calculations reveal a phonon-enhanced directional charge-transfer mechanism. These findings provide a general strategy for regulating directional charge transport through lattice dynamics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"114 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374666","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}