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Engineering Excited-State Dynamics in AgInS2 Quantum Dots by Gallium Incorporation and GaSy Shell Passivation 镓掺杂和GaSy壳钝化AgInS2量子点的工程激发态动力学
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-04 DOI: 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.
三元I-III-VI半导体量子点(QDs)正在被探索作为无毒的Cd和pb基量子点的光捕获应用替代品。在AgInS2中掺入Ga可以减少缺陷态的数量,提高其光物理性能。在ga掺杂的AgInS2核上生长GaSy壳层进一步抑制了供体-受体对(DAP态)发射,恢复了带边发射。我们合成了AgInxGa1-xS2 - gasy量子点的核壳结构,并与AgInS2和AgInxGa1-xS2量子点的光物理性质进行了直接比较。通过探测电子向紫乙酯(EV2+)作为受体分子的转移,评价了这些QD体系的光催化活性。在这三种情况下,超快电子转移到表面结合的EV2+,速率常数约为1011 s-1。然而,还原产物(即EV+•)的稳态产率发生了变化,反映了半导体固有特性和竞争电子转移过程的影响。这些发现强调了将Ga掺入AgInS2中如何改善三元半导体量子点的光物理和光催化性能,并举例说明了核壳结构在抑制反向电子转移中的作用。
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引用次数: 0
Length-Controlled Synthesis of Graphene Nanoribbons 石墨烯纳米带的长度控制合成
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-03 DOI: 10.1021/acs.chemmater.5c02756
Daniel Pyle, Yutong Xiang, Xingchen Li, Ruohai Wang, Guangbin Dong, Jiangliang Yin
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.
石墨烯纳米带(gnr)由于其可调谐的带隙和边缘依赖特性,已成为下一代电子、光电和量子器件的有前途的材料。其集成的关键挑战在于精确控制其长度和确保结构均匀性的能力。本文综述了为应对这一挑战而开发的三种主要合成策略:活聚合、常规迭代合成和保护基团辅助迭代合成(PAIS)。活性聚合方法可以扩展到具有窄长度分布的gnr,尽管它们依赖于专门的单体和催化剂设计来保持活性特性。传统的迭代合成策略为制备具有精确长度的特定gnr提供了途径,但仍无法合成具有理想长度或定义良好的异构单体序列的通用gnr。PAIS策略脱颖而出,允许对GNR长度、宽度、边缘结构和异质结放置进行原子级控制。迭代方法提供了无与伦比的原子精度和架构灵活性,但需要大量的劳动,并且受溶解度约束的限制。每种方法都有互补的优点和优缺点。未来的进展预计将源于混合合成平台、催化剂创新和可编程模板设计,最终实现对GNR结构和设备应用性能的确定性控制。
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引用次数: 0
Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration 气相渗透过程中氧化铝引发增强二乙基锌与聚甲基丙烯酸甲酯中羰基的结合
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-03 DOI: 10.1021/acs.chemmater.5c02584
Nikhil Tiwale, Ashwanth Subramanian, Sayantani Sikder, Xiaohui Qu, Guillaume Freychet, Eliot Gann, Cherno Jaye, Kim Kisslinger, Jorge Anibal Boscoboinik, Chang-Yong Nam
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.
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引用次数: 0
Advances of Perovskite Single-Crystal Heterojunctions for High-Performance X-ray Detectors 高性能x射线探测器用钙钛矿单晶异质结研究进展
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-03 DOI: 10.1021/acs.chemmater.5c02807
Hongjie Liu, Wenjun Ma, Jiaxin Liu, Xue Sun, Xutang Tao, Guodong Zhang
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.
钙钛矿单晶(SC)异质结由于其不同的结构和可调的成分,有利于低缺陷密度和更高的稳定性,在提高光电器件的性能方面引起了人们的极大兴趣。本文综述了钙钛矿SC异质结的最新研究进展和未来发展趋势。首先,我们简要介绍了钙钛矿SC异质结构的基本原理。然后,讨论了钙钛矿SC异质结构的制备方法和分类。系统总结了钙钛矿SC异质结的物理机理及其在x射线检测中的应用进展。最后,我们提出了钙钛矿SC异质结的挑战和发展的全球视角。本文综述了卤化物钙钛矿SC异质结在过去十年中的研究成果,指出了其存在的局限性,并为指导SC异质结的未来发展提供了有价值的见解。
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引用次数: 0
Advances in Antifreeze Hydrogel-Based Wound Dressings 抗冻水凝胶伤口敷料的研究进展
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 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.
伤口可能发生在极端环境中,包括零度以下的温度,在这种环境中,传统的伤口敷料会失去灵活性和功能。鉴于这些情况,必须开发在寒冷环境中有效发挥作用的特殊伤口护理产品。最近,由于抗冻水凝胶(AFHs)具有抗冰结晶、保持生物相容性、促进药物输送、抗菌活性和保持灵活性的能力,因此作为一种可行的选择,引起了人们的关注。这篇综述总结了最近的发现,并提供了AFH关键进展的全面概述。此外,还讨论了基于afh的伤口敷料(afhwd),重点讨论了其主要设计目标和指导其发展的功能方面。不同的afhwd采用不同的策略,如抗冻剂(如甘油、聚乙二醇)的掺入,天然生物材料(如细菌纤维素、明胶)的利用,以及高交联聚合物网络的设计,每种都有不同的抗冻机制,如热滞后和冰重结晶抑制。本研究还探讨了afhwd的主要挑战和未来的科学潜力。最后,本文强调了3D打印和静电纺丝等替代制造技术的潜力,以及为开发下一代afh而探索更有效和天然衍生的防冻剂的必要性。
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引用次数: 0
Cerium-Based Coordination Network Formation: An In Situ X-ray Absorption Spectroscopy and Powder X-ray Diffraction Study 铈基配位网络的形成:原位x射线吸收光谱和粉末x射线衍射研究
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 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 12b3 was clearly observed. Linear combination fitting (LCF) of the in situ XAS data also affirmed the formation of the title compounds.
在溶剂热反应条件下,研究了Ce(NO3)3·6H2O/H2TDC/CH3COOH/CH3CN (H2TDC = 2,5-噻吩二羧酸)化学体系。观察到四种不同的相随时间先后结晶。[CeIV(TDC)(CH3COO)2](1)、[CeIII4(TDC)3(CH3COO)6] (2a)和[CeIII(TDC)(CH3COO)](3)三个配位网络分别分离为橙色、米色和白色相纯产物,并通过粉末x射线衍射数据解析出它们的晶体结构。原位观察到另一种晶体化合物(2b),其结构似乎与化合物2a相关。化合物2a是一种孔径为~ 3 Å的金属有机骨架(MOF)。以CeIII(NO3)3为起始原料,产物的不同颜色和晶体结构表明,在1、2a和3的产物形成过程中发生了Ce(III) -Ce (IV) -Ce (III)氧化还原转变,表现出特殊的氧化还原行为。采用非原位x射线吸收近边结构(XANES)测定了1和3的氧化态,采用准同步原位粉末x射线衍射(PXRD)和x射线吸收光谱(XAS)测定了结晶过程。在反应过程中,可以清楚地观察到1-2b-3顺序连续结晶。原位XAS数据的线性组合拟合(LCF)也证实了标题化合物的形成。
{"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}
引用次数: 0
Tuning Catalytic Activity in Nitride Perovskite Through Strain-Induced Rashba Spin Splitting Manipulation 通过应变诱导Rashba自旋分裂操纵调整氮化钙钛矿的催化活性
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 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.
Rashba自旋分裂是由于重组成元素的存在和非中心对称晶体结构引起的相对论性自旋轨道耦合(SOC)的协同效应而产生的一种新兴现象。我们最近在稀有氮化钙钛矿CeNbN3中观察到Rashba自旋分裂。本研究探讨了调节Rashba自旋分裂强度如何提高光催化水裂解和析氢反应(HER)活性。基于我们的电子结构计算,我们观察到了压缩应变影响下CeNbN3中Rashba自旋分裂的微调以及相应的对HER活性的影响。压缩应变下的电子能带结构、Rashba自旋分裂强度和自旋织构的演变与根据构建的HER机制的反应坐标映射确定的氢吸附自由能相吻合。自旋分裂的强度与HER活性的提高有相关性,这与Rashba效应的影响是一致的。
{"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}
引用次数: 0
KHg4Ga5S12: A Diamond-like Tetrahedral Chalcogenide Exhibiting Giant Phase-Matching Second Harmonic Generation 具有巨大相位匹配二次谐波产生的类金刚石四面体硫属化合物KHg4Ga5S12
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 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.
基于四面体的硫族化合物是中红外(IR)非线性光学(NLO)晶体中最丰富的类型。同时,四面体的不同连接方式将决定中红外NLO特性,如双折射(Δn)和二次谐波产生(SHG)响应。在本研究中,我们系统地研究了四面体基化合物与中红外NLO性能之间的结构-性能调制关系。本文通过中温固相反应,成功合成了由四面体单元组成的kg4ga5s12、K2CdSi4S10和KCd4Ga3S9三个化合物。具体而言,具有相反极性的t2超四面体和随机取向螺旋四面体链的K2CdSi4S10和KCd4Ga3S9表现出较小的Δn和非相匹配(非pm) SHG响应。值得注意的是,具有畸变类金刚石(DL)结构的KHg4Ga5S12具有3.5 × AgGaS2 (AGS)的大PM SHG响应,Δn为0.042@2050 nm,激光诱导损伤阈值(LIDT)为4.1 × AGS。因此,结果表明KHg4Ga5S12具有作为高性能中红外NLO晶体的应用潜力。中红外NLO晶体的设计应优先考虑排列一致和畸变的DL结构。
{"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}
引用次数: 0
One Cation Makes a Difference: Structure–Thermoelectric Interplay in Pseudo–Rock Salt Intermetallic Eu5–xAxAl3Sb6 (A = Sr and Yb) 一种阳离子起作用:伪岩盐金属间化合物Eu5-xAxAl3Sb6 (a = Sr和Yb)的结构-热电相互作用
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 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 (&lt;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}
引用次数: 0
Alkylnitrile Ligands Enable Stable Phase and Electronic Structures of Monodisperse Ag2Se Nanocrystals 烷基腈配体使单分散Ag2Se纳米晶的相和电子结构稳定
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-02 DOI: 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.
烷基腈N≡CR,其中R为11-17个碳的长烷基链,用于合成和稳定Ag2Se纳米晶(NCs)。它们的中间键强度──比烷基胺强,但比硫醇弱──使在120-140℃下合成大尺寸范围(3-20 nm)的单分散单斜Ag2Se NCs成为可能。分别引入溶解在N≡CR中的AgNO3和溶解在nh2o中的se -三辛基膦作为银和硒的前驱体,有效地避免了Ag0相的形成。由于在合成过程中烷基胺的大量过量,合成的纳米碳上的天然表面配体主要是动态的弱nh2o配体,在环境温度下,这些配体很容易被相对强且稳定的N≡CR配体取代。与nh2o包覆的Ag2Se NCs不同,N≡cr包覆的Ag2Se NCs具有高的相位(单斜)和电子(掺杂或未掺杂)稳定性,为短波长或中红外窗口提供了两个系列的Ag2Se NCs。本文的研究结果表明,专门设计的表面配体不仅确保了合成和加工过程中的胶体稳定性,而且还赋予了纳米碳化合物所需的相和电子稳定性,否则当使用不合适的配体时,纳米碳化合物可能会保持亚稳态。
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Chemistry of Materials
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