Lead-free bismuth ferrite–barium titanate (BF–BT) relaxor ferroelectrics have emerged as promising candidates for high-strain actuator applications, yet the fundamental link between their nanoscale structure and macroscopic electromechanical performance remains elusive. This study overcomes this challenge by demonstrating that controlled A-site La3+ doping in 0.7(Bi0.95La0.05)FeO3–0.3BaTiO3 (BLF–BT) directly engineers a local structural environment characterized by chemical disorder and localized stress fields. Through local structure analysis and simulations, we reveal that La doping introduces A-site chemical heterogeneity and lattice mismatch, enhancing FeO6 octahedral distortions and local structural fluctuations. This pronounced local disorder suppresses long-range rhombohedral order, fostering a pseudocubic matrix populated by interacting randomly oriented polar nanoregions. These structural modifications create a flattened energy landscape that facilitates nearly isotropic and low-barrier polarization reorientation under an electric field. The resultant cooperative switching of these highly responsive nanodomains, the inherent lattice strain from local distortions, yields substantial unipolar strain of 0.35%, representing a 200% enhancement over undoped BF–BT. This work provides a definitive structural mechanism for giant strain in lead-free relaxors and establishes a design principle for activating large electromechanical responses through targeted local disorder.
{"title":"Engineering Giant Strain in Bismuth Ferrite–Barium Titanate Relaxor Ferroelectrics via A-Site Driven Local Structural Disorder","authors":"Zhanpeng Li, Xiaoming Shi, Xianghong Zhou, Yuxuan Yang, Zhi Tan, Chao Wu, Qihang Tang, Yang Zhang, Haijun Wu, Ting Zheng, Shujun Zhang, Jiagang Wu","doi":"10.1021/acs.chemmater.5c03265","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03265","url":null,"abstract":"Lead-free bismuth ferrite–barium titanate (BF–BT) relaxor ferroelectrics have emerged as promising candidates for high-strain actuator applications, yet the fundamental link between their nanoscale structure and macroscopic electromechanical performance remains elusive. This study overcomes this challenge by demonstrating that controlled A-site La<sup>3+</sup> doping in 0.7(Bi<sub>0.95</sub>La<sub>0.05</sub>)FeO<sub>3</sub>–0.3BaTiO<sub>3</sub> (BLF–BT) directly engineers a local structural environment characterized by chemical disorder and localized stress fields. Through local structure analysis and simulations, we reveal that La doping introduces A-site chemical heterogeneity and lattice mismatch, enhancing FeO<sub>6</sub> octahedral distortions and local structural fluctuations. This pronounced local disorder suppresses long-range rhombohedral order, fostering a pseudocubic matrix populated by interacting randomly oriented polar nanoregions. These structural modifications create a flattened energy landscape that facilitates nearly isotropic and low-barrier polarization reorientation under an electric field. The resultant cooperative switching of these highly responsive nanodomains, the inherent lattice strain from local distortions, yields substantial unipolar strain of 0.35%, representing a 200% enhancement over undoped BF–BT. This work provides a definitive structural mechanism for giant strain in lead-free relaxors and establishes a design principle for activating large electromechanical responses through targeted local disorder.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"46 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116210","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}
Pub Date : 2026-02-04DOI: 10.1021/acs.chemmater.5c03128
Volkan Kilinc,Linawati Sutrisno,Joel Henzie,Emmanuel Picheau,Yusuke Yamauchi,Katsuhiko Ariga,Jonathan P. Hill
Controlling the large-scale assembly of charged biopolymers is a fundamental challenge in materials chemistry. Here, we report a chemical strategy that uses disulfide-linked single-stranded DNA (ssDNA) dimers as unique building blocks to drive the hierarchical self-assembly of functional DNA microstructures. Formed from short, random-sequence oligomers, these dimers first organize into DNA-salt composite nanobead condensates, which then serve as scaffolds for the assembly of uniform, microrod-shaped DNA condensates called DNA-pod condensates. The key innovation of this work is the material’s unique, cooperative structural transition. Upon thermal stimulation (>60 °C), dsDNA-pod condensates undergo a rapid exfoliation into an expanded ssDNA network, a process driven by significant gains in configurational entropy and the relief of electrostatic repulsion. This establishes an accessible strategy for creating stimuli-responsive DNA materials through a chemistry-driven, sequence-independent pathway. We further demonstrate that these materials act as robust host matrices for encapsulating guest molecules like doxorubicin.
{"title":"Hierarchical Self-Assembly of Disulfide-Linked Single-Stranded DNA into Stimuli-Responsive Pods","authors":"Volkan Kilinc,Linawati Sutrisno,Joel Henzie,Emmanuel Picheau,Yusuke Yamauchi,Katsuhiko Ariga,Jonathan P. Hill","doi":"10.1021/acs.chemmater.5c03128","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03128","url":null,"abstract":"Controlling the large-scale assembly of charged biopolymers is a fundamental challenge in materials chemistry. Here, we report a chemical strategy that uses disulfide-linked single-stranded DNA (ssDNA) dimers as unique building blocks to drive the hierarchical self-assembly of functional DNA microstructures. Formed from short, random-sequence oligomers, these dimers first organize into DNA-salt composite nanobead condensates, which then serve as scaffolds for the assembly of uniform, microrod-shaped DNA condensates called DNA-pod condensates. The key innovation of this work is the material’s unique, cooperative structural transition. Upon thermal stimulation (>60 °C), dsDNA-pod condensates undergo a rapid exfoliation into an expanded ssDNA network, a process driven by significant gains in configurational entropy and the relief of electrostatic repulsion. This establishes an accessible strategy for creating stimuli-responsive DNA materials through a chemistry-driven, sequence-independent pathway. We further demonstrate that these materials act as robust host matrices for encapsulating guest molecules like doxorubicin.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"215 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111130","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}
Pub Date : 2026-02-04DOI: 10.1021/acs.chemmater.5c02676
Jacquelyn Sundstrom,Akshaya Chemmangat,Prashant V. Kamat
Ternary I–III–VI semiconductor quantum dots (QDs) are being explored as nontoxic alternatives to Cd- and Pb-based QDs for light-harvesting applications. Incorporation of Ga into AgInS2 reduces the number of defect states and improves its photophysical properties. Growth of a GaSy shell on a Ga-doped AgInS2 core further suppresses donor–acceptor pair (DAP states) emission and restores band-edge emission. We synthesized the core–shell architecture of AgInxGa1–xS2–GaSy QDs to make a direct comparison of the photophysical properties with those of AgInS2 and AgInxGa1–xS2 QDs. The photocatalytic activity of these QD systems was evaluated by probing electron transfer to ethyl viologen (EV2+) as an acceptor molecule. In all three cases, ultrafast electron transfer to surface-bound EV2+ occurred with rate constants on the order of ∼1011 s–1. However, the steady-state yield of the reduced product (viz., EV+•) varied, reflecting the influence of both intrinsic semiconductor properties and competing back electron transfer processes. These findings highlight how incorporation of Ga into AgInS2 improves the photophysical and photocatalytic properties of ternary semiconductor QDs and exemplifies the role of a core–shell architecture to suppress back electron transfer.
{"title":"Engineering Excited-State Dynamics in AgInS2 Quantum Dots by Gallium Incorporation and GaSy Shell Passivation","authors":"Jacquelyn Sundstrom,Akshaya Chemmangat,Prashant V. Kamat","doi":"10.1021/acs.chemmater.5c02676","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02676","url":null,"abstract":"Ternary I–III–VI semiconductor quantum dots (QDs) are being explored as nontoxic alternatives to Cd- and Pb-based QDs for light-harvesting applications. Incorporation of Ga into AgInS2 reduces the number of defect states and improves its photophysical properties. Growth of a GaSy shell on a Ga-doped AgInS2 core further suppresses donor–acceptor pair (DAP states) emission and restores band-edge emission. We synthesized the core–shell architecture of AgInxGa1–xS2–GaSy QDs to make a direct comparison of the photophysical properties with those of AgInS2 and AgInxGa1–xS2 QDs. The photocatalytic activity of these QD systems was evaluated by probing electron transfer to ethyl viologen (EV2+) as an acceptor molecule. In all three cases, ultrafast electron transfer to surface-bound EV2+ occurred with rate constants on the order of ∼1011 s–1. However, the steady-state yield of the reduced product (viz., EV+•) varied, reflecting the influence of both intrinsic semiconductor properties and competing back electron transfer processes. These findings highlight how incorporation of Ga into AgInS2 improves the photophysical and photocatalytic properties of ternary semiconductor QDs and exemplifies the role of a core–shell architecture to suppress back electron transfer.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111131","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}
Graphene nanoribbons (GNRs) have emerged as promising materials for next-generation electronic, optoelectronic, and quantum devices due to their tunable bandgaps and edge-dependent properties. A critical challenge in their integration lies in the ability to precisely control their length and ensure structural uniformity. This review highlights three major synthetic strategies developed to address this challenge: living polymerization, conventional iterative synthesis, and protecting group-aided iterative synthesis (PAIS). Living polymerization approaches enable scalable access to GNRs with narrow length distributions, although they rely on specialized monomers and catalyst design to maintain a living character. The conventional iterative synthesis strategy provides a pathway for the preparation of specific GNRs with precise length, but it is still not possible to synthesize general GNRs with a desired length or a well-defined heterogeneous monomer sequence. The PAIS strategy stands out, allowing atomic-level control over GNR length, width, edge structure, and heterojunction placement. Iterative methods offer unparalleled atomic precision and architectural flexibility but are labor-intensive and limited by solubility constraints. Each method presents complementary advantages and trade-offs. Future advancements are expected to stem from hybrid synthetic platforms, catalyst innovations, and programmable template design, ultimately enabling deterministic control over GNR structures and properties for device applications.
{"title":"Length-Controlled Synthesis of Graphene Nanoribbons","authors":"Daniel Pyle, Yutong Xiang, Xingchen Li, Ruohai Wang, Guangbin Dong, Jiangliang Yin","doi":"10.1021/acs.chemmater.5c02756","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02756","url":null,"abstract":"Graphene nanoribbons (GNRs) have emerged as promising materials for next-generation electronic, optoelectronic, and quantum devices due to their tunable bandgaps and edge-dependent properties. A critical challenge in their integration lies in the ability to precisely control their length and ensure structural uniformity. This review highlights three major synthetic strategies developed to address this challenge: living polymerization, conventional iterative synthesis, and protecting group-aided iterative synthesis (PAIS). Living polymerization approaches enable scalable access to GNRs with narrow length distributions, although they rely on specialized monomers and catalyst design to maintain a living character. The conventional iterative synthesis strategy provides a pathway for the preparation of specific GNRs with precise length, but it is still not possible to synthesize general GNRs with a desired length or a well-defined heterogeneous monomer sequence. The PAIS strategy stands out, allowing atomic-level control over GNR length, width, edge structure, and heterojunction placement. Iterative methods offer unparalleled atomic precision and architectural flexibility but are labor-intensive and limited by solubility constraints. Each method presents complementary advantages and trade-offs. Future advancements are expected to stem from hybrid synthetic platforms, catalyst innovations, and programmable template design, ultimately enabling deterministic control over GNR structures and properties for device applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"87 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102028","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}
Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlOx infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnOx infiltration, especially one that is initiated by AlOx priming, has not received much attention because highly reactive hydroxyl groups generated by AlOx-priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnOx VPI. Here, we interrogate the ZnOx infiltration mechanism in AlOx-primed poly(methyl methacrylate) (PMMA) in comparison to the control AlOx-only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlOx network can quickly saturate the AlOx infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnOx infiltration using divalent DEZ precursor, once activated via AlOx-priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlOx-priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnOx.
{"title":"Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration","authors":"Nikhil Tiwale, Ashwanth Subramanian, Sayantani Sikder, Xiaohui Qu, Guillaume Freychet, Eliot Gann, Cherno Jaye, Kim Kisslinger, Jorge Anibal Boscoboinik, Chang-Yong Nam","doi":"10.1021/acs.chemmater.5c02584","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02584","url":null,"abstract":"Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO<sub><i>x</i></sub> infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO<sub><i>x</i></sub> infiltration, especially one that is initiated by AlO<sub><i>x</i></sub> priming, has not received much attention because highly reactive hydroxyl groups generated by AlO<sub><i>x</i></sub>-priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO<sub><i>x</i></sub> VPI. Here, we interrogate the ZnO<sub><i>x</i></sub> infiltration mechanism in AlO<sub><i>x</i></sub>-primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO<sub><i>x</i></sub>-only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO<sub><i>x</i></sub> network can quickly saturate the AlO<sub><i>x</i></sub> infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO<sub><i>x</i></sub> infiltration using divalent DEZ precursor, once activated via AlO<sub><i>x</i></sub>-priming, can lead to accelerated ZnO<sub><i>x</i></sub> infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO<sub><i>x</i></sub>-priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO<sub><i>x</i></sub>.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122368","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}
Perovskite single-crystal (SC) heterojunctions have sparked great interest in enhancing the performance of optoelectronic devices due to their diverse structures and tunable compositions that benefit the low defect density and higher stability. The latest progress and future perspectives of perovskite SC heterojunctions are reviewed herein. First, we briefly introduce the fundamentals of perovskite SC heterostructures. Then, the preparation methods and the classification of perovskite SC heterostructures are discussed. Moreover, the physical mechanism and the progress in X-ray detection application of perovskite SC heterojunctions are systematically summarized. Finally, we propose a global perspective on the challenges and development of perovskite SC heterojunctions. This review summarizes the achievements of halide perovskite SC heterojunctions over the past decade, identifies their existing limitations, and offers valuable insights to guide the future development of SC heterojunctions.
{"title":"Advances of Perovskite Single-Crystal Heterojunctions for High-Performance X-ray Detectors","authors":"Hongjie Liu, Wenjun Ma, Jiaxin Liu, Xue Sun, Xutang Tao, Guodong Zhang","doi":"10.1021/acs.chemmater.5c02807","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02807","url":null,"abstract":"Perovskite single-crystal (SC) heterojunctions have sparked great interest in enhancing the performance of optoelectronic devices due to their diverse structures and tunable compositions that benefit the low defect density and higher stability. The latest progress and future perspectives of perovskite SC heterojunctions are reviewed herein. First, we briefly introduce the fundamentals of perovskite SC heterostructures. Then, the preparation methods and the classification of perovskite SC heterostructures are discussed. Moreover, the physical mechanism and the progress in X-ray detection application of perovskite SC heterojunctions are systematically summarized. Finally, we propose a global perspective on the challenges and development of perovskite SC heterojunctions. This review summarizes the achievements of halide perovskite SC heterojunctions over the past decade, identifies their existing limitations, and offers valuable insights to guide the future development of SC heterojunctions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"3 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116211","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}
Pub Date : 2026-02-02DOI: 10.1021/acs.chemmater.5c02491
Javad Esmaeili, Reza Jafari Aminabadi
Wounds can occur in extreme environments, including subzero temperatures, where conventional wound dressings lose flexibility and functionality. Given these circumstances, specific wound care products that function effectively in cold environments must be developed. Recently, antifreeze hydrogels (AFHs) have garnered attention as viable options due to their ability to withstand ice crystallization, maintain biocompatibility, facilitate drug delivery, exhibit antibacterial activity, and retain flexibility. This review summarizes recent findings and provides a comprehensive overview of key advancements in AFH. Also, AFH-based wound dressings (AFHWDs) were discussed with a focus on the primary design objectives and functional aspects guiding their development. Various AFHWDs have been developed using strategies, such as the incorporation of antifreeze agents (e.g., glycerol, polyethylene glycol), the utilization of natural biomaterials (e.g., bacterial cellulose, gelatin), and the design of highly cross-linked polymer networks, each illustrating distinct antifreezing mechanisms like thermal hysteresis and ice recrystallization inhibition. This study also explores the main challenges and future scientific potential of AFHWDs. Finally, this review concludes by emphasizing the potential of alternative fabrication techniques such as 3D printing and electrospinning, and the need to explore more effective and naturally derived antifreeze agents for the development of next-generation AFHs.
{"title":"Advances in Antifreeze Hydrogel-Based Wound Dressings","authors":"Javad Esmaeili, Reza Jafari Aminabadi","doi":"10.1021/acs.chemmater.5c02491","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02491","url":null,"abstract":"Wounds can occur in extreme environments, including subzero temperatures, where conventional wound dressings lose flexibility and functionality. Given these circumstances, specific wound care products that function effectively in cold environments must be developed. Recently, antifreeze hydrogels (AFHs) have garnered attention as viable options due to their ability to withstand ice crystallization, maintain biocompatibility, facilitate drug delivery, exhibit antibacterial activity, and retain flexibility. This review summarizes recent findings and provides a comprehensive overview of key advancements in AFH. Also, AFH-based wound dressings (AFHWDs) were discussed with a focus on the primary design objectives and functional aspects guiding their development. Various AFHWDs have been developed using strategies, such as the incorporation of antifreeze agents (e.g., glycerol, polyethylene glycol), the utilization of natural biomaterials (e.g., bacterial cellulose, gelatin), and the design of highly cross-linked polymer networks, each illustrating distinct antifreezing mechanisms like thermal hysteresis and ice recrystallization inhibition. This study also explores the main challenges and future scientific potential of AFHWDs. Finally, this review concludes by emphasizing the potential of alternative fabrication techniques such as 3D printing and electrospinning, and the need to explore more effective and naturally derived antifreeze agents for the development of next-generation AFHs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"28 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098016","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}
Pub Date : 2026-02-02DOI: 10.1021/acs.chemmater.5c02930
Niklas Ruser, Anastasia Yu. Molokova, Kirill A. Lomachenko, Zheting Chu, Xiaodong Zou, Felix Steinke, Diletta Morelli Venturi, Christoph Meier, Bastian Achenbach, Azat Khadiev, Jonas Gosch, Norbert Stock
The Ce(NO3)3·6H2O/H2TDC/CH3COOH/CH3CN (H2TDC = 2,5-thiophenedicarboxylic acid) chemical system was studied under solvothermal reaction conditions. Four different phases that successively crystallized as a function of time were observed. Three coordination networks, [CeIV(TDC)(CH3COO)2] (1), [CeIII4(TDC)3(CH3COO)6] (2a), and [CeIII(TDC)(CH3COO)] (3), could be isolated as orange, beige, and white phase pure products, respectively, and their crystal structures were resolved from powder X-ray diffraction data. Another crystalline compound (2b) was observed in situ, which seems to be structurally related to compound 2a. Compound 2a is a metal–organic framework (MOF) with a pore size of ∼3 Å. The use of CeIII(NO3)3 as the starting material, the different colors of the products, and the crystal structures indicated a peculiar redox behavior with a Ce(III)–Ce(IV)–Ce(III) redox transformation during product formation of 1, 2a, and 3. The oxidation states of 1 and 3 were confirmed by ex situ X-ray absorption near-edge structure (XANES) measurements, and the crystallization process was followed using quasi-simultaneous in situ powder X-ray diffraction (PXRD) and X-ray absorption spectroscopy (XAS) measurements. During the reaction, the consecutive crystallization in the order 1–2b–3 was clearly observed. Linear combination fitting (LCF) of the in situ XAS data also affirmed the formation of the title compounds.
{"title":"Cerium-Based Coordination Network Formation: An In Situ X-ray Absorption Spectroscopy and Powder X-ray Diffraction Study","authors":"Niklas Ruser, Anastasia Yu. Molokova, Kirill A. Lomachenko, Zheting Chu, Xiaodong Zou, Felix Steinke, Diletta Morelli Venturi, Christoph Meier, Bastian Achenbach, Azat Khadiev, Jonas Gosch, Norbert Stock","doi":"10.1021/acs.chemmater.5c02930","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02930","url":null,"abstract":"The Ce(NO<sub>3</sub>)<sub>3</sub>·6H<sub>2</sub>O/H<sub>2</sub>TDC/CH<sub>3</sub>COOH/CH<sub>3</sub>CN (H<sub>2</sub>TDC = 2,5-thiophenedicarboxylic acid) chemical system was studied under solvothermal reaction conditions. Four different phases that successively crystallized as a function of time were observed. Three coordination networks, [Ce<sup>IV</sup>(TDC)(CH<sub>3</sub>COO)<sub>2</sub>] (<b>1</b>), [Ce<sup>III</sup><sub>4</sub>(TDC)<sub>3</sub>(CH<sub>3</sub>COO)<sub>6</sub>] (<b>2a</b>), and [Ce<sup>III</sup>(TDC)(CH<sub>3</sub>COO)] (<b>3</b>), could be isolated as orange, beige, and white phase pure products, respectively, and their crystal structures were resolved from powder X-ray diffraction data. Another crystalline compound (<b>2b</b>) was observed in situ, which seems to be structurally related to compound <b>2a</b>. Compound <b>2a</b> is a metal–organic framework (MOF) with a pore size of ∼3 Å. The use of Ce<sup>III</sup>(NO<sub>3</sub>)<sub>3</sub> as the starting material, the different colors of the products, and the crystal structures indicated a peculiar redox behavior with a Ce(III)–Ce(IV)–Ce(III) redox transformation during product formation of <b>1</b>, <b>2a</b>, and <b>3</b>. The oxidation states of <b>1</b> and <b>3</b> were confirmed by ex situ X-ray absorption near-edge structure (XANES) measurements, and the crystallization process was followed using quasi-simultaneous in situ powder X-ray diffraction (PXRD) and X-ray absorption spectroscopy (XAS) measurements. During the reaction, the consecutive crystallization in the order <b>1</b>–<b>2b</b>–<b>3</b> was clearly observed. Linear combination fitting (LCF) of the in situ XAS data also affirmed the formation of the title compounds.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"30 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098014","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}
Pub Date : 2026-02-02DOI: 10.1021/acs.chemmater.5c02220
Prajna Parimita Mohanty, Showkat H. Mir, Rajeev Ahuja, Sudip Chakraborty
Rashba spin splitting is an emerging phenomenon originating from the synergistic effect of relativistic spin–orbit coupling (SOC) due to the presence of a heavy constituent element and the noncentrosymmetric crystal structure. We recently observed Rashba spin splitting in the rare nitride perovskite CeNbN3. This work explores how tuning the Rashba spin splitting strength can enhance photocatalytic water splitting and hydrogen evolution reaction (HER) activity. Based on our electronic structure calculations, we have observed the fine-tuning of Rashba spin splitting in CeNbN3 under the influence of compressive strain and the corresponding impact on HER activity. The evolution of electronic band structure, Rashba spin splitting strength, and spin texture under compressive strain corresponds well with the hydrogen adsorption free energy determined from the constructed reaction coordinate mapping of the HER mechanism. The strength of spin splitting shows a correlation with improved HER activity, which is in line with the influence of the Rashba effect.
{"title":"Tuning Catalytic Activity in Nitride Perovskite Through Strain-Induced Rashba Spin Splitting Manipulation","authors":"Prajna Parimita Mohanty, Showkat H. Mir, Rajeev Ahuja, Sudip Chakraborty","doi":"10.1021/acs.chemmater.5c02220","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02220","url":null,"abstract":"Rashba spin splitting is an emerging phenomenon originating from the synergistic effect of relativistic spin–orbit coupling (SOC) due to the presence of a heavy constituent element and the noncentrosymmetric crystal structure. We recently observed Rashba spin splitting in the rare nitride perovskite CeNbN<sub>3</sub>. This work explores how tuning the Rashba spin splitting strength can enhance photocatalytic water splitting and hydrogen evolution reaction (HER) activity. Based on our electronic structure calculations, we have observed the fine-tuning of Rashba spin splitting in CeNbN<sub>3</sub> under the influence of compressive strain and the corresponding impact on HER activity. The evolution of electronic band structure, Rashba spin splitting strength, and spin texture under compressive strain corresponds well with the hydrogen adsorption free energy determined from the constructed reaction coordinate mapping of the HER mechanism. The strength of spin splitting shows a correlation with improved HER activity, which is in line with the influence of the Rashba effect.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"58 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098054","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}
Pub Date : 2026-02-02DOI: 10.1021/acs.chemmater.5c03230
Weiping Guo, Chao Yang, Bingxuan Li, Hong-Hua Cui, Lingyun Li, Yan Yu, Zhong-Zhen Luo, Zhigang Zou
Tetrahedra-based chalcogenides constitute the most abundant type for mid-infrared (IR) nonlinear optical (NLO) crystals. Meanwhile, different connection modes of tetrahedra will determine the mid-IR NLO properties, such as birefringence (Δn) and the second harmonic generation (SHG) response. In this research, we systematically investigate the structure–property modulated relationship between tetrahedra-based compounds and mid-IR NLO properties. Herein, three compounds, KHg4Ga5S12, K2CdSi4S10, and KCd4Ga3S9, consisting of the tetrahedral units, have been successfully synthesized through a moderate-temperature solid-state reaction. Specifically, K2CdSi4S10 and KCd4Ga3S9 with the opposite polarity T2-supertetrahedra and random orientation helix tetrahedral chains exhibit a small Δn and non-phase-matching (non-PM) SHG response. Notably, KHg4Ga5S12 with the distorted diamond-like (DL) structure shows a large PM SHG response of 3.5 × AgGaS2 (AGS), moderate Δn of 0.042@2050 nm, and high laser-induced damage threshold (LIDT) of 4.1 × AGS. Therefore, the results indicate that KHg4Ga5S12 has potential for application as a high-performance mid-IR NLO crystal. The consistent arrangement and distorted DL structure can be prioritized for the design of mid-IR NLO crystals.
{"title":"KHg4Ga5S12: A Diamond-like Tetrahedral Chalcogenide Exhibiting Giant Phase-Matching Second Harmonic Generation","authors":"Weiping Guo, Chao Yang, Bingxuan Li, Hong-Hua Cui, Lingyun Li, Yan Yu, Zhong-Zhen Luo, Zhigang Zou","doi":"10.1021/acs.chemmater.5c03230","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03230","url":null,"abstract":"Tetrahedra-based chalcogenides constitute the most abundant type for mid-infrared (IR) nonlinear optical (NLO) crystals. Meanwhile, different connection modes of tetrahedra will determine the mid-IR NLO properties, such as birefringence (Δ<i>n</i>) and the second harmonic generation (SHG) response. In this research, we systematically investigate the structure–property modulated relationship between tetrahedra-based compounds and mid-IR NLO properties. Herein, three compounds, KHg<sub>4</sub>Ga<sub>5</sub>S<sub>12</sub>, K<sub>2</sub>CdSi<sub>4</sub>S<sub>10</sub>, and KCd<sub>4</sub>Ga<sub>3</sub>S<sub>9</sub>, consisting of the tetrahedral units, have been successfully synthesized through a moderate-temperature solid-state reaction. Specifically, K<sub>2</sub>CdSi<sub>4</sub>S<sub>10</sub> and KCd<sub>4</sub>Ga<sub>3</sub>S<sub>9</sub> with the opposite polarity T2-supertetrahedra and random orientation helix tetrahedral chains exhibit a small Δ<i>n</i> and non-phase-matching (non-PM) SHG response. Notably, KHg<sub>4</sub>Ga<sub>5</sub>S<sub>12</sub> with the distorted diamond-like (DL) structure shows a large PM SHG response of 3.5 × AgGaS<sub>2</sub> (AGS), moderate Δ<i>n</i> of 0.042@2050 nm, and high laser-induced damage threshold (LIDT) of 4.1 × AGS. Therefore, the results indicate that KHg<sub>4</sub>Ga<sub>5</sub>S<sub>12</sub> has potential for application as a high-performance mid-IR NLO crystal. The consistent arrangement and distorted DL structure can be prioritized for the design of mid-IR NLO crystals.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102029","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}
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