Pub Date : 2026-01-29DOI: 10.1021/acs.chemmater.5c02665
Sungwoo Jung, Liang Yan, Anthony Megret-Bonilla, Wei You
While p-type doping of conjugated polymers has been extensively studied, the development of efficient and stable n-type doping remains a significant challenge. Although the importance of the LUMO (lowest unoccupied molecular orbital) energy level of conjugated polymers on effective n-type doping has been widely recognized, there are few systematic studies to quantify the influence of the LUMO level on n-type doping of conjugated polymers. In this work, we synthesized a series of BDOPV-based conjugated polymers with tunable LUMO energy levels (− 4.05 to −4.37 eV) by incorporating fluorine atoms and cyano (−CN) groups onto an otherwise identical conjugated backbone. Our results revealed that a deeper LUMO level facilitates more efficient electron transfer and charge carrier generation, corresponding to the observed higher doping efficiency and conductivity. Our data suggest that polymers with LUMO levels below −4.3 eV exhibit substantially enhanced resistance to oxidative degradation by air. These results highlight the pivotal role of the LUMO energy level in determining the doping characteristics of n-type conjugated polymers and offer insights to further the development of high-performance, air-stable n-doped conjugated polymers.
{"title":"Impact of LUMO Energy Level on n-Type Doping Efficiency and Air Stability of Conjugated Polymers","authors":"Sungwoo Jung, Liang Yan, Anthony Megret-Bonilla, Wei You","doi":"10.1021/acs.chemmater.5c02665","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02665","url":null,"abstract":"While p-type doping of conjugated polymers has been extensively studied, the development of efficient and stable n-type doping remains a significant challenge. Although the importance of the LUMO (lowest unoccupied molecular orbital) energy level of conjugated polymers on effective n-type doping has been widely recognized, there are few systematic studies to quantify the influence of the LUMO level on n-type doping of conjugated polymers. In this work, we synthesized a series of BDOPV-based conjugated polymers with tunable LUMO energy levels (− 4.05 to −4.37 eV) by incorporating fluorine atoms and cyano (−CN) groups onto an otherwise identical conjugated backbone. Our results revealed that a deeper LUMO level facilitates more efficient electron transfer and charge carrier generation, corresponding to the observed higher doping efficiency and conductivity. Our data suggest that polymers with LUMO levels below −4.3 eV exhibit substantially enhanced resistance to oxidative degradation by air. These results highlight the pivotal role of the LUMO energy level in determining the doping characteristics of n-type conjugated polymers and offer insights to further the development of high-performance, air-stable n-doped conjugated polymers.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070673","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}
Defect-rich RuO2 catalysts, although possessing high electrocatalytic activity, are inherently unstable for the anode oxygen evolution reaction (OER) in proton exchange membrane water electrolysis (PEMWE) due to rapid lattice oxygen depletion. Here we report an atomically Ir-doped, grain-boundary-rich RuO2 catalyst (Ir-GB-RuO2) that suppresses overactivation of lattice oxygen by forming robust Ru–O–Ir bridging motifs at grain boundaries, achieving high-performance acidic OER electrocatalysis and ampere-level stable PEMWE. The induced electronic modulation shifts the catalytic mechanism from a pure lattice oxygen mechanism (LOM) to a balanced coexistence of LOM and the adsorbate evolution mechanism (AEM), thereby achieving robust stability while preserving high intrinsic activity. The primary Ir-GB-RuO2 catalyst requires only 191 mV overpotential to achieve 10 mA cm–2 and exhibits a prolonged durability exceeding 1000 h at 100 mA cm–2. In a PEM electrolyzer, it attains the current density of 1.0 A cm–2 at a notably low cell voltage (1.67 V) and exhibits a minimal potential decay rate of only 55.3 μV h–1 over 1500 h of continuous operation. This work overcomes the intrinsic activity–stability trade-off in defect-rich Ru-based catalysts for industrial PEMWE.
富缺陷RuO2催化剂虽然具有较高的电催化活性，但由于晶格氧的快速耗竭，在质子交换膜电解（PEMWE）中阳极析氧反应（OER）中具有固有的不稳定性。在这里，我们报道了一种原子掺杂的、富含晶界的RuO2催化剂（Ir-GB-RuO2），它通过在晶界形成鲁棒的Ru-O-Ir桥接基序来抑制晶格氧的过度活化，实现了高性能的酸性OER电催化和安培级稳定的PEMWE。诱导电子调制将催化机制从纯晶格氧机制（LOM）转变为LOM和吸附质演化机制（AEM）的平衡共存，从而在保持高内在活性的同时实现了强大的稳定性。初级Ir-GB-RuO2催化剂只需要191 mV过电位就可以达到10 mA cm-2，并且在100 mA cm-2下表现出超过1000小时的延长耐久性。在PEM电解槽中，在极低的电池电压（1.67 V）下，它的电流密度可达1.0 a cm-2，在连续工作1500小时内，其电位衰减率仅为55.3 μV h - 1。这项工作克服了工业PEMWE中富含缺陷的钌基催化剂的固有活性与稳定性之间的权衡。
{"title":"Stabilizing Grain-Boundary-Rich RuO2 by Atomic Iridium-Doping To Achieve High-Performance Oxygen Evolution for Ampere-Level PEM Water Electrolysis","authors":"Junlin Cai, Pengfei Li, Hongpu Huang, Shupeng Wang, Yu Peng, Yuhang Peng, Qiuxiang Wang, Xiaohong Wang, Zhaoxiong Xie, Shuifen Xie","doi":"10.1021/acs.chemmater.5c03326","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03326","url":null,"abstract":"Defect-rich RuO<sub>2</sub> catalysts, although possessing high electrocatalytic activity, are inherently unstable for the anode oxygen evolution reaction (OER) in proton exchange membrane water electrolysis (PEMWE) due to rapid lattice oxygen depletion. Here we report an atomically Ir-doped, grain-boundary-rich RuO<sub>2</sub> catalyst (Ir-GB-RuO<sub>2</sub>) that suppresses overactivation of lattice oxygen by forming robust Ru–O–Ir bridging motifs at grain boundaries, achieving high-performance acidic OER electrocatalysis and ampere-level stable PEMWE. The induced electronic modulation shifts the catalytic mechanism from a pure lattice oxygen mechanism (LOM) to a balanced coexistence of LOM and the adsorbate evolution mechanism (AEM), thereby achieving robust stability while preserving high intrinsic activity. The primary Ir-GB-RuO<sub>2</sub> catalyst requires only 191 mV overpotential to achieve 10 mA cm<sup>–2</sup> and exhibits a prolonged durability exceeding 1000 h at 100 mA cm<sup>–2</sup>. In a PEM electrolyzer, it attains the current density of 1.0 A cm<sup>–2</sup> at a notably low cell voltage (1.67 V) and exhibits a minimal potential decay rate of only 55.3 μV h<sup>–1</sup> over 1500 h of continuous operation. This work overcomes the intrinsic activity–stability trade-off in defect-rich Ru-based catalysts for industrial PEMWE.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090124","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 : 2026-01-28DOI: 10.1021/acs.chemmater.5c02792
Zhuozhuo Tang, Jia Chen, Li Sheng, Zonglong Li, Da Zhu, Yang Yang, Jianlong Wang, Yaping Tang, Xiangming He, Hong Xu
Three-dimensional covalent organic frameworks (3D COFs) offer high surface areas and diverse microstructures for gas adsorption, yet their hydrogen storage is limited by weak host–guest interactions in physisorption. Here, we report a microstructural tuning strategy using an N–N-containing hydrazine monomer to simultaneously minimize pore size and enhance pore-surface interactions with hydrogen. The resulting HZ-Si-COF features ultramicropores of 0.8 nm and abundant nitrogen sites with excess charges, which induce H2 polarization and yield a high adsorption heat. Consequently, HZ-Si-COF achieves 2.22 wt % H2 uptake at 77 K and 1 bar and 5.00 wt % at 70 bar, with excellent cycling stability under high pressure. This study demonstrates that strengthening pore-surface induction via structural design is an effective route to improving gas adsorption, providing insights for the development of COFs with superior hydrogen storage capabilities.
{"title":"Modulating Pore-Surface Adsorption in Covalent Organic Frameworks for Superior Hydrogen Storage","authors":"Zhuozhuo Tang, Jia Chen, Li Sheng, Zonglong Li, Da Zhu, Yang Yang, Jianlong Wang, Yaping Tang, Xiangming He, Hong Xu","doi":"10.1021/acs.chemmater.5c02792","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02792","url":null,"abstract":"Three-dimensional covalent organic frameworks (3D COFs) offer high surface areas and diverse microstructures for gas adsorption, yet their hydrogen storage is limited by weak host–guest interactions in physisorption. Here, we report a microstructural tuning strategy using an N–N-containing hydrazine monomer to simultaneously minimize pore size and enhance pore-surface interactions with hydrogen. The resulting HZ-Si-COF features ultramicropores of 0.8 nm and abundant nitrogen sites with excess charges, which induce H<sub>2</sub> polarization and yield a high adsorption heat. Consequently, HZ-Si-COF achieves 2.22 wt % H<sub>2</sub> uptake at 77 K and 1 bar and 5.00 wt % at 70 bar, with excellent cycling stability under high pressure. This study demonstrates that strengthening pore-surface induction via structural design is an effective route to improving gas adsorption, providing insights for the development of COFs with superior hydrogen storage capabilities.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"8 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089811","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 : 2026-01-28DOI: 10.1021/acs.chemmater.5c02815
Chad D. Cruz, Karl J. Thorley, Zachary Knepp, Jared Wahlstrand, Gil M. Repa, John C. Stephenson, Sean Parkin, Lisa A. Fredin, John E. Anthony, Emily G. Bittle
The photophysics of organic semiconductors impacts their efficiency in optoelectronic devices where exciton transitions, including singlet fission, intersystem crossing and the formation of charge transfer states influence the ability to convert between bright and dark states and to dissociate into free charges. Unfortunately, photodegradation and spurious signals often confound the results of optical studies, especially of important triplet states. Here four asymmetric cyclopentannulated acenes are synthesized and studied. This system represents an extreme in photophysics achieved via molecular design to fully quench the photoluminescence and bypass triplet formation allowing for comparative studies with other highly absorbing acenes. Rapid molecular exciton decay that is unaffected by strong electronic coupling induced by the crystal packing is found. The quick return to the ground state inhibits the formation of triplets and leads to heating in the solid state. These aceacenes are photostable both in solution and as single crystals, likely because the short excited-state lifetime diminishes the chances for deleterious photoreactions. Density functional theory calculations highlight excited state twisting in the five-membered ring, indicating a key driver of rapid internal conversion.
{"title":"Enhanced Photostability through Rapid Exciton Decay in Desymmetrized Cyclopentannulated Acenes with Strong Face-to-Face pi Stacking","authors":"Chad D. Cruz, Karl J. Thorley, Zachary Knepp, Jared Wahlstrand, Gil M. Repa, John C. Stephenson, Sean Parkin, Lisa A. Fredin, John E. Anthony, Emily G. Bittle","doi":"10.1021/acs.chemmater.5c02815","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02815","url":null,"abstract":"The photophysics of organic semiconductors impacts their efficiency in optoelectronic devices where exciton transitions, including singlet fission, intersystem crossing and the formation of charge transfer states influence the ability to convert between bright and dark states and to dissociate into free charges. Unfortunately, photodegradation and spurious signals often confound the results of optical studies, especially of important triplet states. Here four asymmetric cyclopentannulated acenes are synthesized and studied. This system represents an extreme in photophysics achieved via molecular design to fully quench the photoluminescence and bypass triplet formation allowing for comparative studies with other highly absorbing acenes. Rapid molecular exciton decay that is unaffected by strong electronic coupling induced by the crystal packing is found. The quick return to the ground state inhibits the formation of triplets and leads to heating in the solid state. These aceacenes are photostable both in solution and as single crystals, likely because the short excited-state lifetime diminishes the chances for deleterious photoreactions. Density functional theory calculations highlight excited state twisting in the five-membered ring, indicating a key driver of rapid internal conversion.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"105 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070674","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 : 2026-01-28DOI: 10.1021/acs.chemmater.5c02861
Maarten Stam, Hua Chen, Yan B. Vogel, Irene Stavast, Mourijn van Leeuwen, Reinout F. Ubbink, Niels van Silfhout, Colin F. A. van der Made, Luca Giordano, Pieter Schiettecatte, Zeger Hens, Arjan J. Houtepen
Indium phosphide (InP) quantum dots (QDs) are promising heavy-metal-free materials for optoelectronics, but their redox stability, trap-state landscape, and charge carrier dynamics are not well understood. Here we investigate InP and InP/ZnSe/ZnS QD films with different ligands by using spectroelectrochemistry. For both core-only and core/shell/shell QD films, the absorption spectra remain unchanged during charging, indicating that injected charges do not populate the conduction or valence bands. InP/ZnSe/ZnS QD films with original ligands exhibit reversible photoluminescence (PL) modulation: an increase at modest cathodic potentials, followed by quenching at more negative potentials. Solid-state ligand exchange using ethylenediamine (2DA) and sodium sulfide (Na2S) enhances conductivity and induces stronger PL changes at both cathodic and anodic potentials. These results are in line with the population of electron traps at modest cathodic potentials (i.e., near the midbandgap), suppressing nonradiative recombination and increasing the PL. At more negative potentials, electrochemical reactions of surface species result in new trap states quenching the PL. Our findings provide insights into the stability and trap-state-mediated carrier dynamics during electrochemical charging of InP-based QDs.
{"title":"Electrochemical Stability and Trap-State-Mediated Photoluminescence Modulation of InP-Based Quantum Dots","authors":"Maarten Stam, Hua Chen, Yan B. Vogel, Irene Stavast, Mourijn van Leeuwen, Reinout F. Ubbink, Niels van Silfhout, Colin F. A. van der Made, Luca Giordano, Pieter Schiettecatte, Zeger Hens, Arjan J. Houtepen","doi":"10.1021/acs.chemmater.5c02861","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02861","url":null,"abstract":"Indium phosphide (InP) quantum dots (QDs) are promising heavy-metal-free materials for optoelectronics, but their redox stability, trap-state landscape, and charge carrier dynamics are not well understood. Here we investigate InP and InP/ZnSe/ZnS QD films with different ligands by using spectroelectrochemistry. For both core-only and core/shell/shell QD films, the absorption spectra remain unchanged during charging, indicating that injected charges do not populate the conduction or valence bands. InP/ZnSe/ZnS QD films with original ligands exhibit reversible photoluminescence (PL) modulation: an increase at modest cathodic potentials, followed by quenching at more negative potentials. Solid-state ligand exchange using ethylenediamine (2DA) and sodium sulfide (Na<sub>2</sub>S) enhances conductivity and induces stronger PL changes at both cathodic and anodic potentials. These results are in line with the population of electron traps at modest cathodic potentials (i.e., near the midbandgap), suppressing nonradiative recombination and increasing the PL. At more negative potentials, electrochemical reactions of surface species result in new trap states quenching the PL. Our findings provide insights into the stability and trap-state-mediated carrier dynamics during electrochemical charging of InP-based QDs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"16 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057052","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 : 2026-01-27DOI: 10.1021/acs.chemmater.5c03511
Paul D. Goring, and , Sara E. Skrabalak*,
{"title":"Chemistry of Materials: Highlights from 2025─A Community Effort","authors":"Paul D. Goring, and , Sara E. Skrabalak*, ","doi":"10.1021/acs.chemmater.5c03511","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03511","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 2","pages":"557–558"},"PeriodicalIF":7.0,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045120","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 : 2026-01-27DOI: 10.1021/acs.chemmater.5c02820
Yuxing Fei, Matthew J. McDermott, Christopher L. Rom, Shilong Wang, Gerbrand Ceder
Powder X-ray diffraction (XRD) is a foundational technique for characterizing crystalline materials. However, the reliable interpretation of XRD patterns, particularly in multiphase systems, remains a manual and expertise-demanding task. As a characterization method that only provides structural information, multiple reference phases can often be fit to a single pattern, leading to potential misinterpretation when alternative solutions are overlooked. To ease humans’ efforts and address the challenge, we introduce Dara (data-driven automated Rietveld analysis), a framework designed to automate the robust identification and refinement of multiple phases from powder XRD data. Dara performs an exhaustive tree search over all plausible phase combinations within a given chemical space and validates each hypothesis using the BGMN Rietveld refinement routine. Key features include structural database filtering, automatic clustering of isostructural phases during tree expansion, and peak-matching-based scoring to identify promising phases for refinement. When ambiguity exists, Dara generates multiple hypothesis which can then be decided between by human experts or with further characterization tools. By enhancing the reliability and accuracy of phase identification, Dara enables scalable analysis of realistic complex XRD patterns and provides a foundation for integration into multimodal characterization workflows, moving toward fully self-driving materials discovery.
{"title":"Dara: Automated Multiple-Hypothesis Phase Identification and Refinement from Powder X-ray Diffraction","authors":"Yuxing Fei, Matthew J. McDermott, Christopher L. Rom, Shilong Wang, Gerbrand Ceder","doi":"10.1021/acs.chemmater.5c02820","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02820","url":null,"abstract":"Powder X-ray diffraction (XRD) is a foundational technique for characterizing crystalline materials. However, the reliable interpretation of XRD patterns, particularly in multiphase systems, remains a manual and expertise-demanding task. As a characterization method that only provides structural information, multiple reference phases can often be fit to a single pattern, leading to potential misinterpretation when alternative solutions are overlooked. To ease humans’ efforts and address the challenge, we introduce Dara (data-driven automated Rietveld analysis), a framework designed to automate the robust identification and refinement of multiple phases from powder XRD data. Dara performs an exhaustive tree search over all plausible phase combinations within a given chemical space and validates each hypothesis using the BGMN Rietveld refinement routine. Key features include structural database filtering, automatic clustering of isostructural phases during tree expansion, and peak-matching-based scoring to identify promising phases for refinement. When ambiguity exists, Dara generates multiple hypothesis which can then be decided between by human experts or with further characterization tools. By enhancing the reliability and accuracy of phase identification, Dara enables scalable analysis of realistic complex XRD patterns and provides a foundation for integration into multimodal characterization workflows, moving toward fully self-driving materials discovery.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"46 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070722","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 : 2026-01-27DOI: 10.1021/acs.chemmater.5c02655
Fang Yuan, Jiaze Xie, Ratnadwip Singha, Christie S. Koay, Sigalit Aharon, Guangming Cheng, Brianna L. Hoff, Vojtech Kundrat, Xiaoyu Song, Sudipta Chatterjee, Lothar Houben, Jakub Zalesak, Nan Yao, Leslie M. Schoop
Core–shell nanomaterials provide a versatile platform for tuning physical properties and integrating complementary functionalities in nanoscale systems, but their synthesis often requires multistep procedures and precise control over composition, morphology, and interfaces. Achieving core–shell architectures in nanosheets is particularly challenging due to the difficulty of controlling growth direction and interfacial formation. Here, we describe a one-step chemical exfoliation process that produces core–shell nanosheets from the highly air-sensitive compound Li1+xMnTe2. Brief sonication in Milli-Q water under ambient conditions yields a dark gray suspension of nanosheets within 10 min, which remains stable in air for at least 31 days. Powder X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, inductively coupled plasma–optical emission spectrometry, and transmission electron microscopy indicate the formation of few-layer crystalline Mn(OH)2 cores encapsulated by amorphous Te–O shells. Magnetic measurements show antiferromagnetic ordering in the restacked nanosheets. The suspension can be readily deposited onto coated glass, polyethylene terephthalate, and Si/SiO2 substrates to form uniform films, with electrical transport measurements indicating resistances on the order of megaohms at room temperature. These results demonstrate chemical exfoliation as an effective approach for producing core–shell nanosheets with magnetic and electronic functionality.
{"title":"Printable and Antiferromagnetic Mn(OH)2@Te–O Core–Shell Nanosheets","authors":"Fang Yuan, Jiaze Xie, Ratnadwip Singha, Christie S. Koay, Sigalit Aharon, Guangming Cheng, Brianna L. Hoff, Vojtech Kundrat, Xiaoyu Song, Sudipta Chatterjee, Lothar Houben, Jakub Zalesak, Nan Yao, Leslie M. Schoop","doi":"10.1021/acs.chemmater.5c02655","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02655","url":null,"abstract":"Core–shell nanomaterials provide a versatile platform for tuning physical properties and integrating complementary functionalities in nanoscale systems, but their synthesis often requires multistep procedures and precise control over composition, morphology, and interfaces. Achieving core–shell architectures in nanosheets is particularly challenging due to the difficulty of controlling growth direction and interfacial formation. Here, we describe a one-step chemical exfoliation process that produces core–shell nanosheets from the highly air-sensitive compound Li<sub>1+<i>x</i></sub>MnTe<sub>2</sub>. Brief sonication in Milli-Q water under ambient conditions yields a dark gray suspension of nanosheets within 10 min, which remains stable in air for at least 31 days. Powder X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, inductively coupled plasma–optical emission spectrometry, and transmission electron microscopy indicate the formation of few-layer crystalline Mn(OH)<sub>2</sub> cores encapsulated by amorphous Te–O shells. Magnetic measurements show antiferromagnetic ordering in the restacked nanosheets. The suspension can be readily deposited onto coated glass, polyethylene terephthalate, and Si/SiO<sub>2</sub> substrates to form uniform films, with electrical transport measurements indicating resistances on the order of megaohms at room temperature. These results demonstrate chemical exfoliation as an effective approach for producing core–shell nanosheets with magnetic and electronic functionality.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"2 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070675","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 : 2026-01-27DOI: 10.1021/acs.chemmater.5c02904
Vidyanshu Mishra, Jinseong Kim, Jong-Hoon Lim, Manya Rishi, Joon Jang, Abishek K. Iyer
Chalcoarsenates are a family of compounds that have shown promise as nonlinear optical materials. The varying oxidizing powers of chalcogens result in chalcoarsenates containing either As3+ or As5+, which exhibit different crystal structures. Two noncentrosymmetric chalcoarsenates, Sr3As2S7 and Sr3As2Se2.5S4.5, have been synthesized, and their structures consist of both As3+ centered trigonal pyramids and As5+ centered tetrahedra. These are the first reported chalcoarsenates made up of both As-units. Single-crystal X-ray diffraction reveals that they adopt their own crystal structure types. Sr3As2S7 crystallizes in trigonal space group P3 (a = 17.6283 (3), c = 7.1236 (1) Å, Z = 4), and Sr3As2Se2.5S4.5 crystallizes in hexagonal P63mc space group (a = 10.1997(3) Å, c = 6.8443(4) Å, Z = 1). Consistent with their colors, diffuse reflectance measurements confirm the band gaps of 1.6 eV for Sr3As2Se2.5S4.5 (dark brown) and 2.1 eV for Sr3As2S7 (yellow). Second harmonic generation (SHG) measurements show that Sr3As2S4.5Se2.5 has a strong SHG response of χeff(2) = 90 pm/V, which is the highest among alkaline earth containing chalcoarsenates and 1.6 × AgGaSe2. Sr3As2S7 shows a high laser-induced damage threshold of 2.11 GW/cm2. The promising SHG results highlight the need to study the Sr-containing chalcoarsenates, which are significantly underexplored.
硫砷酸盐是一类有希望作为非线性光学材料的化合物。不同的硫原的氧化能力导致含As3+或As5+的硫砷酸盐具有不同的晶体结构。合成了两种非中心对称的硫砷酸盐Sr3As2S7和Sr3As2Se2.5S4.5，它们的结构既有以As3+为中心的三角金字塔，也有以As5+为中心的四面体。这是首次报道的由两个as单元组成的硫砷酸盐。单晶x射线衍射表明，它们采用各自的晶体结构类型。Sr3As2S7结晶于三角形空间群P3 (a = 17.6283 (3), c = 7.1236 (1) Å， Z = 4), Sr3As2Se2.5S4.5结晶于六角形空间群P63mc (a = 10.1997（3) Å， c = 6.8443(4) Å， Z = 1）。与它们的颜色一致，漫反射测量证实了Sr3As2Se2.5S4.5（深棕色）的带隙为1.6 eV, Sr3As2S7（黄色）的带隙为2.1 eV。二次谐波产生（SHG）测量结果表明，Sr3As2S4.5Se2.5具有较强的二次谐波响应，χeff(2) = 90 pm/V，在含硫砷酸盐碱土和1.6 × AgGaSe2碱土中最高。Sr3As2S7的激光损伤阈值高达2.11 GW/cm2。有希望的SHG结果强调了研究含锶的硫砷酸盐的必要性，这方面的研究明显不足。
{"title":"Discovery of Noncentrosymmetric Sr3As2S7 and Sr3As2Se2.5S4.5 Featuring As3+/As5+ Coordination and Their Strong Nonlinear Optical Response","authors":"Vidyanshu Mishra, Jinseong Kim, Jong-Hoon Lim, Manya Rishi, Joon Jang, Abishek K. Iyer","doi":"10.1021/acs.chemmater.5c02904","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02904","url":null,"abstract":"Chalcoarsenates are a family of compounds that have shown promise as nonlinear optical materials. The varying oxidizing powers of chalcogens result in chalcoarsenates containing either As<sup>3+</sup> or As<sup>5+</sup>, which exhibit different crystal structures. Two noncentrosymmetric chalcoarsenates, Sr<sub>3</sub>As<sub>2</sub>S<sub>7</sub> and Sr<sub>3</sub>As<sub>2</sub>Se<sub>2.5</sub>S<sub>4.5</sub>, have been synthesized, and their structures consist of both As<sup>3+</sup> centered trigonal pyramids and As<sup>5+</sup> centered tetrahedra. These are the first reported chalcoarsenates made up of both As-units. Single-crystal X-ray diffraction reveals that they adopt their own crystal structure types. Sr<sub>3</sub>As<sub>2</sub>S<sub>7</sub> crystallizes in trigonal space group <i>P</i>3 (<i>a</i> = 17.6283 (3), <i>c</i> = 7.1236 (1) Å, <i>Z</i> = 4), and Sr<sub>3</sub>As<sub>2</sub>Se<sub>2.5</sub>S<sub>4.5</sub> crystallizes in hexagonal <i>P</i>6<sub>3</sub><i>mc</i> space group (<i>a</i> = 10.1997(3) Å, <i>c</i> = 6.8443(4) Å, <i>Z</i> = 1). Consistent with their colors, diffuse reflectance measurements confirm the band gaps of 1.6 eV for Sr<sub>3</sub>As<sub>2</sub>Se<sub>2.5</sub>S<sub>4.5</sub> (dark brown) and 2.1 eV for Sr<sub>3</sub>As<sub>2</sub>S<sub>7</sub> (yellow). Second harmonic generation (SHG) measurements show that Sr<sub>3</sub>As<sub>2</sub>S<sub>4.5</sub>Se<sub>2.5</sub> has a strong SHG response of χ<sub><i>eff</i></sub><sup>(2)</sup> = 90 pm/V, which is the highest among alkaline earth containing chalcoarsenates and 1.6 × AgGaSe<sub>2</sub>. Sr<sub>3</sub>As<sub>2</sub>S<sub>7</sub> shows a high laser-induced damage threshold of 2.11 GW/cm<sup>2</sup>. The promising SHG results highlight the need to study the Sr-containing chalcoarsenates, which are significantly underexplored.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"30 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057055","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 : 2026-01-27DOI: 10.1021/acs.chemmater.5c02868
Sai-Nan Guo, Si-Wen Zhang, Meng Qiao, Jie-Xin Wang
The shift to sustainable energy requires efficient hydrogen production through water electrolysis. However, alkaline hydrogen evolution reaction (alkaline HER) technologies suffer from slow kinetics, high overpotential (>200 mV), and dependence on expensive Pt/Ru catalysts. High-entropy alloys (HEAs) offer promising tunability but suffer from oxidative deactivation, disordered active sites, and limited surface area. Herein, we first synthesize PtRuCoNiCu HEA nanodendrites (HEA-NDs) via a one-pot hydrothermal method, featuring a defect-rich 3D branching structure. The shortened Pt–Pt bond (2.61 Å) induces tensile strain, optimizing the hydrogen adsorption energy (ΔG*H = – 0.06 eV). The HEA-NDs achieve an ultralow overpotential of 10 mV at 10 mA cm–2 (82% lower than Pt/C), a Tafel slope of 23.4 mV dec–1, and greater than 95% stability over 100 h. Notably, they also exhibit exceptional mass activity in the methanol oxidation reaction (MOR) (4830 mA mg–1) and CO antipoisoning capability, demonstrating multifunctional catalytic superiority. The excellent catalytic performance of HEA-NDs is further elucidated by density functional theory-based mechanistic studies of HER and MOR pathways. The synergy between lattice strain and high-entropy effects in these dendritic nanostructures establishes a new paradigm for designing next-generation electrocatalysts for water electrolysis.
{"title":"PtRuCoNiCu High-Entropy Alloy Nanodendrites for Efficient Electrocatalytic Reactions","authors":"Sai-Nan Guo, Si-Wen Zhang, Meng Qiao, Jie-Xin Wang","doi":"10.1021/acs.chemmater.5c02868","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02868","url":null,"abstract":"The shift to sustainable energy requires efficient hydrogen production through water electrolysis. However, alkaline hydrogen evolution reaction (alkaline HER) technologies suffer from slow kinetics, high overpotential (>200 mV), and dependence on expensive Pt/Ru catalysts. High-entropy alloys (HEAs) offer promising tunability but suffer from oxidative deactivation, disordered active sites, and limited surface area. Herein, we first synthesize PtRuCoNiCu HEA nanodendrites (HEA-NDs) via a one-pot hydrothermal method, featuring a defect-rich 3D branching structure. The shortened Pt–Pt bond (2.61 Å) induces tensile strain, optimizing the hydrogen adsorption energy (Δ<i>G</i><sub><i>*</i></sub><sub>H</sub> = – 0.06 eV). The HEA-NDs achieve an ultralow overpotential of 10 mV at 10 mA cm<sup>–2</sup> (82% lower than Pt/C), a Tafel slope of 23.4 mV dec<sup>–1</sup>, and greater than 95% stability over 100 h. Notably, they also exhibit exceptional mass activity in the methanol oxidation reaction (MOR) (4830 mA mg<sup>–1</sup>) and CO antipoisoning capability, demonstrating multifunctional catalytic superiority. The excellent catalytic performance of HEA-NDs is further elucidated by density functional theory-based mechanistic studies of HER and MOR pathways. The synergy between lattice strain and high-entropy effects in these dendritic nanostructures establishes a new paradigm for designing next-generation electrocatalysts for water electrolysis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"42 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057054","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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