Chemistry of Materials最新文献

{"title":"Ultralow Pt-Loaded Pt/Fe2O3 with Pt−Fe Pair Sites for Efficient Seawater Hydrogen Production","authors":"Zhen-Jia Wu,Yu-Xuan Xiao,Quan-Wei Shi,Yi Wang,Jie Ying","doi":"10.1021/acs.chemmater.6c02607","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02607","url":null,"abstract":"Seawater electrolysis for green hydrogen production urgently demands high-performance electrocatalysts that simultaneously deliver fast reaction kinetics with robust chloride ion (Cl−) resistance. Herein, we report an ultralow Pt-loaded (<1 wt %) Pt/Fe2O3 catalyst rich in Pt−Fe atomic pairs synthesized via a photoreduction synthetic strategy. Photogenerated electrons drive the selective reduction of Pt precursors at low-coordinate Fe3+ sites on α-Fe2O3 (012) facets, constructing Pt−Fe pair interfaces that enable directional electron transfer from Fe-dz2 to Pt-dz2 orbitals. This electronic modulation optimizes the Gibbs free energy of hydrogen adsorption, weakens the intrinsic affinity of active sites toward Cl−, and accelerates water dissociation. The as-synthesized catalyst achieves ultralow overpotentials of 9 and 51 mV at 10 and 100 mA cm−2 respectively in alkaline simulated seawater, with a slight potential decay of only 0.08 mV h−1 over 1000 h of continuous operation, outperforming most state-of-the-art electrocatalysts. When integrated into an anion exchange membrane electrolyzer, it delivers a low cell voltage of 2.0 V at 500 mA cm−2 and maintains stable operation for 200 h at 100 mA cm−2.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360016","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":"Discovery of One-Dimensional Rare-Earth Hybrid Nitrate Double Perovskites","authors":"Meng-Jun Lin,Xiang-Rong Ye,Lei Pan,Lang Wang,Jun-Ying Li,Hao-Fei Ni,Gele Teri,Chang-Feng Wang,Da-Wei Fu,Yi Zhang","doi":"10.1021/acs.chemmater.6c02751","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02751","url":null,"abstract":"Rare-earth hybrid nitrate double perovskites (REHNDPs) have recently emerged as an intriguing subclass of functional materials, combining structural diversity with rich intrinsic optoelectronic, magnetic, piezoelectric, and ferroelectric properties. Although notable progress has been made in three-dimensional (3D) and 2D REHNDPs, 1D counterparts have yet to be discovered. Herein, by introducing the bulky organic cation 1-adamantyltrimethylammonium (TMAA+), we report a family of 1D REHNDPs with the general formula (TMAA)2LnCs(NO3)6 (Ln = La3+, Ce3+, Pr3+, Nd3+, Sm3+, and Eu3+). Distinct from the μ2-κ3(O,O′,O″) mode characteristic of 2D and 3D REHNDPs, the bridging NO3− ligands adopt a μ2-κ3(O,O′) coordination mode in 1D counterparts. Strikingly, (TMAA)2SmCs(NO3)6 possesses a step-like high-temperature dielectric switch at 431.7 K. (TMAA)2EuCs(NO3)6 shows brilliant photoluminescence with a quantum yield of 65.46% and a lifetime of 5.21 ms. The X-ray detector based on (TMAA)2EuCs(NO3)6 demonstrates high X-ray sensitivity of 560 μC Gyair−1 cm−2 and a low detection limit of 153 nGyair s−1 under a bias of 25 V. This work bridges a critical dimensional gap and significantly expands the structural and functional portfolio of the REHNDPs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360013","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":"Three-Dimensional Hollow Square Array SAPO-34 with Optimal Acidity Distribution Showing Excellent Methanol-to-Olefins Performance","authors":"Xuefeng Shen,Jiajia Ding,Jing Ai,Chuanming Wang,Yingchun Ye,Hongxing Liu,Zaiku Xie","doi":"10.1021/acs.chemmater.6c02712","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02712","url":null,"abstract":"SAPO-34 is an excellent catalyst for methanol-to-olefins (MTO) reaction. Simultaneously alleviating the diffusion limitations and optimizing the acidity of SAPO-34 is extremely challenging. Herein, a three-dimensional hollow square array SAPO-34 (SAPO-34-HSA) with a sinusoidal-like distribution of silicon was synthesized in a simple way. The role of triethylamine (TEA) switches between the etchant and structure-directing agent according to the reaction temperature. In the heating stage, the seed with high silicon content was etched by TEA; during the crystallization process, TEA guides the epitaxial growth of raw materials on the seed crystal, forming a hollow core−shell structure; after crystallization, the shell was partly leached to form a hollow square array structure. The sinusoidal-like distribution of silicon is conducive to promoting olefin cycling in the hydrocarbon pool mechanism and significantly improving the selectivity of ethylene. So the SAPO-34-HSA catalyst exhibits 70%−400% longer catalytic lifetime in MTO reaction compared with the seed under different reaction conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"5 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360014","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":"Microenvironment-Responsive Polyaniline− Gelatin Conductive Hydrogel Promotes Infected Diabetic Wound Healing by Modulating Skin-Resident Cells Behavior","authors":"Xiaxi Pan,Fufen Li,Garang Suoan,Qingsu Cheng,Xinying Li,Zhilang Xu,Jimin Guo,Changdao Mu,Defu Li,Liming Ge","doi":"10.1021/acs.chemmater.6c01991","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01991","url":null,"abstract":"Diabetic wound healing is severely impaired by persistent inflammation, bacterial infection, impaired angiogenesis, and especially disrupted bioelectrical signaling. Conductive hydrogels can help restore local bioelectrical signal transmission and provide an attractive strategy for intractable wound healing by modulating the behaviors of bioelectrically responsive skin-resident cells. Here, we developed a glucose/pH-responsive polyaniline− gelatin conductive hydrogel (HGP@D) based on double dynamic covalent crosslinking of the imine bond and boronic ester bond for promoting the Staphylococcus aureus-infected full-thickness diabetic wound healing. The HGP@D hydrogel had strong mechanical property, great tissue adhesive strength, glucose/pH dual-responsive drug release behavior, alongside robust broad-spectrum antibacterial activity, and potent intracellular antioxidation. The HGP@D hydrogel restored local bioelectrical signaling and created an anti-inflammatory wound microenvironment, thereby modulating the behaviors of skin-resident cells involved in diabetic wound repair, including fibroblast migration, macrophage M2-like polarization, and endothelial angiogenic activity. Mechanistic analyses suggested that the HGP@D hydrogel promoted infected diabetic wound healing through two Ca2+-associated regulatory axes: the Ca2+/CaMKKβ/AMPK/NF-κB axis for inflammatory regulation and the Ca2+/PI3K/Akt/mTOR/HIF-1α/VEGF axis for angiogenesis and tissue reconstruction. Overall, HGP@D provides a promising clinical therapeutic strategy for the advanced healing of diabetic wounds and other non-healing wounds by integrating glucose/pH-responsive microenvironment regulation with bioelectrical modulation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359507","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":"Electronic Structure Perspective on Cation and Anion Redox in Li2FeS2","authors":"Yi-Ting Cheng,Eshaan S. Patheria,Colin T. Morrell,Nathan J. Szymanski,Kimberly A. See,Christopher J. Bartel","doi":"10.1021/acs.chemmater.6c02216","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02216","url":null,"abstract":"Multielectron redox in Li2FeS2 involves both cation and anion contributions. While prior studies have investigated this process experimentally, questions remain about the Fe-to-S redox transition, persulfide formation, and incomplete delithiation. Here, we revisit the electrochemistry of Li2FeS2 using density functional theory (DFT) calculations. Initial Fe oxidation is shown to proceed via increased Fe−S covalency driven by ligand-to-metal rehybridization. This accounts for only ∼60% of the Fe capacity, after which phase separation into Li1.5FeS2 and Li0.5FeS2 induces a shift to S oxidation. We identify nonbonding S 3p orbitals as redox-active centers. To track their evolution during delithiation, we isolate the localized nonbonding states by subtracting the bonding and antibonding contributions from the total electronic densities of states. These orbitals undergo S-to-Fe rehybridization, progressive oxidation, and eventual reorganization into persulfide bonds. At high states of charge, Li vacancies enable FeS4 tilting and facilitate S−S bond formation. Further delithiation beyond Li0.5FeS2 would require unstable S hole formation or conversion to pyrite FeS2, explaining why it is challenging to fully delithiate this material. These findings offer insights into the interplay of cation and anion redox, guiding the design of high-capacity sulfide cathodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359506","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":"Atomic-Scale Origin of Spatially Heterogeneous Insertion in Hollandite-Type MnO2","authors":"Hongyi Li,Yue Qi,Shusuke Fukui,Yuichiro Hayasaka,Xiatong Ye,Kakeru Kobayashi,Tomoya Kawaguchi,Tetsu Ichitsubo","doi":"10.1021/acs.chemmater.6c02510","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02510","url":null,"abstract":"Hollandite-type α-MnO2 is a prototypical tunnel-structured host for rechargeable batteries, yet the atomic-scale mechanisms governing multivalent-ion insertion remain poorly understood. Here, we reveal how guest-ion species dictate electrochemical reaction pathways through distinct occupation modes within the one-dimensional tunnels of α-MnO2. By combining electrochemical analyses, atomic-resolution scanning transmission electron microscopy, and soft X-ray absorption spectroscopy, we directly correlate reaction kinetics with guest-ion configurations and the accompanying structural and electronic responses of the host framework. Electrochemical measurements reveal substantial diffusion-controlled contributions for both Na+ and Mg2+, whereas Ca2+ exhibits predominantly surface-controlled behavior. Atomic-resolution imaging demonstrates that, despite their comparable macroscopic kinetic contributions, Na+ and Mg2+ exhibit distinctly different microscopic insertion modes: Na+ homogeneously occupies the tunnel-center sites throughout the particles, whereas Mg2+ occupies both tunnel-center and off-center sites, with pronounced near-surface enrichment accompanied by local tunnel distortion. In contrast, the Ca2+ reaction is largely confined to the near-surface region, with no clearly detectable occupation of the internal tunnel sites. Soft X-ray absorption spectroscopy further reveals spatially heterogeneous Mn reduction, with more pronounced reduction near the structurally less constrained particle surface. These results establish a direct relationship between guest-ion occupation modes, electrochemical reaction pathways, and the resulting structural evolution, providing an atomic-scale design principle for engineering tunnel-type host materials for multivalent-ion insertion.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359517","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":"Donor−Acceptor Engineering in Porphyrin-Based Two-Dimensional Polymers for Ultrafast Nonlinear Optical Response","authors":"Lu Chen,Haozheng Li,Hongyi Lang,Lulu Fu,Zhipeng Huang,Mark G. Humphrey,Chi Zhang","doi":"10.1021/acs.chemmater.6c02410","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02410","url":null,"abstract":"Leveraging their extended π-conjugation, structurally tunable backbones, and superior film-forming processability, two-dimensional (2D) organic polymers have emerged as a highly promising class of materials for third-order nonlinear optical (NLO) applications. Herein, a series of porphyrin-based donor−acceptor (D−A) 2D polymer films, namely, TAPP-TAPZ, TAPP-BATD, TAPP-TDAT, and TAPP-BDTA, are successfully fabricated via a liquid−liquid interfacial polymerization approach. These films exhibit broad absorption profiles across the visible region alongside markedly narrowed optical bandgaps, underscoring the extensive π-electron delocalization inherent to the 2D polymeric frameworks. Femtosecond open-aperture Z-scan measurements conducted at 515 and 800 nm unambiguously reveal pronounced reverse saturable absorption in all samples. Strikingly, the TAPP-TAPZ film delivers exceptional nonlinear absorption coefficients (β) of 8.8 × 103 cm GW−1 at 800 nm and 5.2 × 103 cm GW−1 at 515 nm, values that not only substantially outperform the analogous TAPP-BATD, TAPP-TDAT, and TAPP-BDTA counterparts but also rival or surpass those of numerous reported covalent organic frameworks, 2D inorganic nanomaterials, and small-molecule NLO systems. Complementary density functional theory calculations ascribe this remarkable performance to the incorporation of benzothiadiazole units, which stabilize a donor−donor−acceptor (D−D−A) electronic configuration and facilitate efficient intramolecular charge transfer. Collectively, our findings establish interfacial polymerization as a robust and generalizable route for constructing ordered, defect-minimized 2D films, thereby offering actionable design principles for the development of next-generation ultrafast photonic devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149304818","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":"Synthesis of fcc/2H and fcc/4H Copper Nanodisks Towards Carbon Dioxide Reduction","authors":"Shutang Chen,Tong Zhang,Huairuo Zhang,Yi Rao,Albert V. Davydov,Gugang Chen","doi":"10.1021/acs.chemmater.6c01583","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01583","url":null,"abstract":"Two-dimensional Cu nanostructures containing noncanonical face-centered cubic/hexagonal close-packed (fcc/hcp) heterophase boundaries are attractive for CO2 electroreduction but remain difficult to prepare by wet-chemical methods. Here, we report a high-temperature solution reduction route to Cu nanodisks with a thickness of 26.5 ± 2.3 nm and a diameter of 85.6 ± 3.7 nm. Transmission electron microscopy reveals abundant fcc/2H and fcc/4H interfaces on the nanodisk side surfaces, where the 2H and 4H polytypes exhibit AB and ABCB stacking, respectively. In CO2-saturated 0.1 M KHCO3, the nanodisks achieve a methane Faradaic efficiency of 60.4% at −1.25 V vs the reversible hydrogen electrode and outperform fcc Cu nanoparticle and microsheet controls tested at the same catalyst loading. Density functional theory calculations indicate that the free-energy penalty for forming the *CHO intermediate is smaller on the fcc/2H and fcc/4H models than on fcc Cu. These results support a thermodynamic contribution of heterophase interfaces to the observed methane selectivity; the calculations do not establish a reduction in kinetic activation barriers. This solution-phase route therefore provides access to phase-engineered Cu nanodisks and enables structure−property relationships relevant to CO2-to-CH4 electrocatalysis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"84 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281895","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":"Frontier Orbital Engineering of the Oxide Photocatalyst K2Zn2Nb4O13 by Coupling Crystal Structure, Electronic Structure, and Chemical Bonding","authors":"Qubin Shi,Yongfeng Zhou,Zhiyuan Lei,Guangxiang Lu,Zien Cheng,Can Yang,Le Kang,Dexiang Gao,Pengfei Jiang,Rihong Cong,Tao Yang","doi":"10.1021/acs.chemmater.6c02831","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02831","url":null,"abstract":"Rational design of oxide photocatalysts with intrinsically efficient bulk carrier transport remains a major challenge because carrier migration is strongly governed by the complex interplay among crystal structure, electronic structure, and chemical bonding. Here, we propose a Frontier orbital engineering strategy to regulate intrinsic carrier transport by reconstructing the Frontier orbital composition within a structurally robust oxide framework. Based on the tunnel-type Na2Ti6O13 structure, the oxide semiconductor K2Zn2Nb4O13 was designed and synthesized through the cooperative substitution of Ti4+ by Zn2+/Nb5+. Combined high-resolution PXRD and NPD refinements confirm the successful realization of the designed tunnel framework with complete Zn/Nb ordering. Orbital-resolved electronic structure and chemical bonding analyses demonstrate that the valence band maximum (VBM) and conduction band minimum (CBM) are mainly derived from Zn 3d−O 2p and Nb1 4d−O 2p antibonding orbitals, respectively. Such orbital decoupling of Frontier orbital contributing units and the continuous covalent networks along the b-axis provide favorable pathways for bulk carrier migration and establish the structural and electronic basis for the proposed Frontier orbital engineering strategy. Experimentally, Pd-loaded K2Zn2Nb4O13 exhibits enhanced photocatalytic H2 generation activity, achieving a rate of 119(3) μmol/h. This work provides Frontier orbital engineering as a design paradigm for functional materials, enabling the rational manipulation of intrinsic charge transport properties through the synergistic regulation of crystal structure, electronic structure, and chemical bonding.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"87 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281896","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 Temperature Stable Pt Nanoclusters Formation in Alumina-Encapsulated Pt Catalysts","authors":"Gennaro Liccardo,Shyama C. Mandal,Jacob Smith,Tomás Vergara,Arik Beck,Miaofang Chi,Frank Abild-Pedersen,Stacey F. Bent,Matteo Cargnello","doi":"10.1021/acs.chemmater.6c02125","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c02125","url":null,"abstract":"Metal nanoparticle sintering in high-temperature oxidizing atmospheres remains a primary deactivation pathway for platinum-group metal catalysts on alumina supports. Here, atomic layer deposition (ALD) was used to deposit alumina on supported Pt catalysts and develop alumina-encapsulated Pt/Al2O3 catalysts that were aged at 800 °C under different atmospheres and characterized by time-resolved high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), CO-probe diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), and propene combustion kinetics. Within the alumina-encapsulated system, a sub-2 nm Pt cluster population formed under all oxidizing atmospheres tested but not under inert atmosphere, and this population persisted for at least 12 h at 800 °C under propene complete combustion (PCC) conditions. Unencapsulated Pt/Al2O3 controls, by contrast, developed only a transient sub-2 nm population, detected within 1 min of aging in air at 800 °C and no longer present afterward, consistent with the rapid disappearance of small particles predicted by Ostwald ripening theory. CO-DRIFTS confirmed the presence of undercoordinated Pt surface sites in all oxidatively aged samples, with no detectable signal when the sample was aged under inert atmosphere. Propene combustion rates measured after aging for an alumina-encapsulated catalyst were approximately two and five times higher than the fresh encapsulated catalyst for catalysts aged under inert atmosphere and under oxygen and steam, respectively. DFT calculations of Pt diffusion through defective Al2O3 identified kinetically accessible diffusion pathways at 800 °C, with activation barriers as low as 0.76 eV. Furthermore, Pt surface binding was calculated to be favored in the presence of O2. These results identify oxygen-driven surface segregation, mediated by defect-assisted diffusion through the ALD overcoat, as a possible mechanism responsible for nanocluster formation in this system. The persistence of the sub-2 nm cluster population for at least 12 h at 800 °C under PCC conditions demonstrates the thermal stability of these sites within the encapsulated architecture.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281939","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}