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}
Pub Date : 2026-02-02DOI: 10.1021/acs.chemmater.5c02963
Luis Garay, Leah Borgsmiller, Duncan Zavanelli, G. Jeffrey Snyder, James C. Fettinger, Susan M. Kauzlarich
Polar intermetallics are an emerging class of thermoelectric materials whose electronic properties can be finely tuned by cation chemistry. Single crystals of Eu5–xYbxAl3Sb6 and Eu5–x–ySrxYbyAl3Sb6 were synthesized by flux methods and their structures determined by single-crystal X-ray diffraction, confirming monoclinic C2/m symmetry and an electron count near 3.5 e– per atom, consistent with polar intermetallic classification. The Al content in these phases can be increased from 3 to 4. A comparative study of polycrystalline synthesized Eu5Al4Sb6 and its Sr- and Yb-substituted solid solutions, along with the pseudoquinary phase Eu2.5Sr2Yb0.5Al4Sb6, is presented. Substituting Eu2+ with the more ionic Sr2+ enhances mobility and increases the magnitude of the Seebeck coefficient, while the more covalent Yb2+ drives the system metallic, lowering Seebeck values but improving zT to 0.8 at 873 K. The quinary phase further suppresses bipolar conduction, delaying the high-temperature downturn observed in both ternary solid solutions. Across all compositions, thermal conductivities remain exceptionally low (<1 W m–1 K–1), enabling promising figures of merit. These results highlight how ionic versus covalent A-site substitution can serve as a powerful lever to control scattering, band overlap, and transport in polar intermetallics, opening design pathways parallel to those of the benchmarked half-Heusler phases and PbTe.
极性金属间化合物是一类新兴的热电材料，其电子性能可以通过阳离子化学精细调节。用通量法合成了Eu5-xYbxAl3Sb6和Eu5-x-ySrxYbyAl3Sb6单晶，并用x -射线单晶衍射确定了它们的结构，证实了它们的单斜C2/m对称性，每个原子的电子计数接近3.5 e-，符合极性金属间分类。这些相中的Al含量可以从3增加到4。对合成的多晶Eu5Al4Sb6及其Sr取代固溶体和yb取代固溶体以及假五相Eu2.5Sr2Yb0.5Al4Sb6进行了比较研究。用离子含量较高的Sr2+取代Eu2+提高了迁移率，增加了塞贝克系数的大小，而更共价的Yb2+使体系呈金属化，降低了塞贝克值，但在873 K时将zT提高到0.8。五相进一步抑制双极传导，延缓了在这两种三元固溶体中观察到的高温下降。在所有成分中，导热系数仍然非常低（<1 W m-1 K-1），从而实现了有希望的性能数字。这些结果突出了离子与共价a位取代如何作为一个强大的杠杆来控制极性金属间化合物的散射、能带重叠和输运，打开了与基准半赫斯勒相和PbTe平行的设计途径。
{"title":"One Cation Makes a Difference: Structure–Thermoelectric Interplay in Pseudo–Rock Salt Intermetallic Eu5–xAxAl3Sb6 (A = Sr and Yb)","authors":"Luis Garay, Leah Borgsmiller, Duncan Zavanelli, G. Jeffrey Snyder, James C. Fettinger, Susan M. Kauzlarich","doi":"10.1021/acs.chemmater.5c02963","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02963","url":null,"abstract":"Polar intermetallics are an emerging class of thermoelectric materials whose electronic properties can be finely tuned by cation chemistry. Single crystals of Eu<sub>5–<i>x</i></sub>Yb<sub><i>x</i></sub>Al<sub>3</sub>Sb<sub>6</sub> and Eu<sub>5–<i>x–y</i></sub>Sr<sub><i>x</i></sub>Yb<sub><i>y</i></sub>Al<sub>3</sub>Sb<sub>6</sub> were synthesized by flux methods and their structures determined by single-crystal X-ray diffraction, confirming monoclinic <i>C</i>2/<i>m</i> symmetry and an electron count near 3.5 e<sup>–</sup> per atom, consistent with polar intermetallic classification. The Al content in these phases can be increased from 3 to 4. A comparative study of polycrystalline synthesized Eu<sub>5</sub>Al<sub>4</sub>Sb<sub>6</sub> and its Sr- and Yb-substituted solid solutions, along with the pseudoquinary phase Eu<sub>2.5</sub>Sr<sub>2</sub>Yb<sub>0.5</sub>Al<sub>4</sub>Sb<sub>6</sub>, is presented. Substituting Eu<sup>2+</sup> with the more ionic Sr<sup>2+</sup> enhances mobility and increases the magnitude of the Seebeck coefficient, while the more covalent Yb<sup>2+</sup> drives the system metallic, lowering Seebeck values but improving <i>zT</i> to 0.8 at 873 K. The quinary phase further suppresses bipolar conduction, delaying the high-temperature downturn observed in both ternary solid solutions. Across all compositions, thermal conductivities remain exceptionally low (<1 W m<sup>–1</sup> K<sup>–1</sup>), enabling promising figures of merit. These results highlight how ionic versus covalent A-site substitution can serve as a powerful lever to control scattering, band overlap, and transport in polar intermetallics, opening design pathways parallel to those of the benchmarked half-Heusler phases and PbTe.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"92 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097973","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.5c02922
Zhe Wang, Jie Zhu, Jiongzhao Li, Xudong Qian, Xiaogang Peng
Alkylnitriles, N≡CR with R as a long alkyl chain with 11–17 carbons, are introduced for synthesizing and stabilizing Ag2Se nanocrystals (NCs). Their intermediate bonding strength─stronger than alkylamines yet weaker than thiols─enables synthesis of monodisperse monoclinic Ag2Se NCs in a large size range (3–20 nm) at 120–140 °C. AgNO3 dissolved in N≡CR and Se-trioctylphosphine dissolved in NH2Ol are respectively introduced as the silver and selenium precursors, which effectively avoid formation of the Ag0 phase. Given the large excess of alkylamines in the synthesis, the native surface ligands on the as-synthesized NCs are dominated by dynamic and weak NH2Ol ligands, which can be readily replaced by relatively strong and stable N≡CR ligands at ambient temperatures. Unlike NH2Ol-coated Ag2Se NCs, N≡CR-coated ones have high phase (monoclinic) and electronic (either doped or undoped) stabilities, offering two series of Ag2Se NCs for either the short-wavelength or middle infrared window. The findings here indicate that specifically designed surface ligands not only ensure colloidal stability during synthesis and processing but also confer the desired phase and electronic stability to NCs, which may otherwise remain metastable when inappropriate ligands are used.
{"title":"Alkylnitrile Ligands Enable Stable Phase and Electronic Structures of Monodisperse Ag2Se Nanocrystals","authors":"Zhe Wang, Jie Zhu, Jiongzhao Li, Xudong Qian, Xiaogang Peng","doi":"10.1021/acs.chemmater.5c02922","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02922","url":null,"abstract":"Alkylnitriles, N≡CR with R as a long alkyl chain with 11–17 carbons, are introduced for synthesizing and stabilizing Ag<sub>2</sub>Se nanocrystals (NCs). Their intermediate bonding strength─stronger than alkylamines yet weaker than thiols─enables synthesis of monodisperse monoclinic Ag<sub>2</sub>Se NCs in a large size range (3–20 nm) at 120–140 °C. AgNO<sub>3</sub> dissolved in N≡CR and Se-trioctylphosphine dissolved in NH<sub>2</sub>Ol are respectively introduced as the silver and selenium precursors, which effectively avoid formation of the Ag<sup>0</sup> phase. Given the large excess of alkylamines in the synthesis, the native surface ligands on the as-synthesized NCs are dominated by dynamic and weak NH<sub>2</sub>Ol ligands, which can be readily replaced by relatively strong and stable N≡CR ligands at ambient temperatures. Unlike NH<sub>2</sub>Ol-coated Ag<sub>2</sub>Se NCs, N≡CR-coated ones have high phase (monoclinic) and electronic (either doped or undoped) stabilities, offering two series of Ag<sub>2</sub>Se NCs for either the short-wavelength or middle infrared window. The findings here indicate that specifically designed surface ligands not only ensure colloidal stability during synthesis and processing but also confer the desired phase and electronic stability to NCs, which may otherwise remain metastable when inappropriate ligands are used.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"62 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098015","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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