The past decades have witnessed a significant increase in interest in inorganic luminescent materials that emit in the narrowband ultraviolet-B (NB-UVB; 310-313 nm) spectral region due to the growing need for applications in photochemistry and photomedicine. However, the majority of existing NB-UVB phosphors rely on photoluminescence that requires constant external excitation. This common but inconvenient photoluminescence style significantly slows down the progress of NB-UVB luminescence technology. Herein, we report the design and synthesis of a new Gd3+-doped NB-UVB-emitting persistent phosphor, LiCaPO4:Gd3+, which shows strong NB-UVB persistent luminescence peaking at 312 nm and a super-long persistence time of >100 h after ceasing X-ray excitation. Owing to the zero-background noise from the ambient light, a UVB camera can detect the NB-UVB light emission originating from the charged LiCaPO4:Gd3+ phosphor in a bright indoor environment. Through spectroscopic investigations and first-principles calculations, the nature of energy traps and the persistent luminescence mechanism of Gd3+ in LiCaPO4 host have been thoroughly studied. Besides, remarkable photochromic behavior when irradiating the phosphor with X-ray is also observed, and the possible intrinsic point defects that contribute to the colorization are proposed. This NB-UVB persistent phosphor shows great potentials in indoor optical tagging, optical information storage, and dermatological therapy.
{"title":"Narrowband ultraviolet-B-emitting LiCaPO4:Gd3+ phosphor with super-long persistent luminescence over 100 h","authors":"Xihui Shan, Xulong Lv, Dongxun Chen, Yi Zhang, Lixin Ning, Yanjie Liang","doi":"10.1039/d4qi02407a","DOIUrl":"https://doi.org/10.1039/d4qi02407a","url":null,"abstract":"The past decades have witnessed a significant increase in interest in inorganic luminescent materials that emit in the narrowband ultraviolet-B (NB-UVB; 310-313 nm) spectral region due to the growing need for applications in photochemistry and photomedicine. However, the majority of existing NB-UVB phosphors rely on photoluminescence that requires constant external excitation. This common but inconvenient photoluminescence style significantly slows down the progress of NB-UVB luminescence technology. Herein, we report the design and synthesis of a new Gd3+-doped NB-UVB-emitting persistent phosphor, LiCaPO4:Gd3+, which shows strong NB-UVB persistent luminescence peaking at 312 nm and a super-long persistence time of >100 h after ceasing X-ray excitation. Owing to the zero-background noise from the ambient light, a UVB camera can detect the NB-UVB light emission originating from the charged LiCaPO4:Gd3+ phosphor in a bright indoor environment. Through spectroscopic investigations and first-principles calculations, the nature of energy traps and the persistent luminescence mechanism of Gd3+ in LiCaPO4 host have been thoroughly studied. Besides, remarkable photochromic behavior when irradiating the phosphor with X-ray is also observed, and the possible intrinsic point defects that contribute to the colorization are proposed. This NB-UVB persistent phosphor shows great potentials in indoor optical tagging, optical information storage, and dermatological therapy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The first chlororuthenacyclopentatrienes have been realized by the reactions of RuCl2(PPh3)3 with o-phenyldiyne derivatives in the presence of excess HCl. The structures of the unique chlororuthenacycles were fully characterized by spectroscopic data and X-ray diffraction. In addition, computational studies provided the evidence for their aromatic character, making them as an important supplement to the rare aromatic ruthenacycle family.
通过 RuCl2(PPh3)3 与邻苯基二炔衍生物在过量盐酸存在下的反应，首次实现了氯钌环五三烯。光谱数据和 X 射线衍射对这些独特的氯钌环的结构进行了全面表征。此外，计算研究还证明了它们的芳香特性，使它们成为稀有芳香钌环家族的重要补充。
{"title":"Synthesis and Structure of Chlororuthenacyclopentatriene","authors":"Zhenwei Chu, Zhishun Peng, Xu Cheng, Yuhui Hua, Guomei He, Jiangxi CHEN, Guochen Jia","doi":"10.1039/d4qi01833h","DOIUrl":"https://doi.org/10.1039/d4qi01833h","url":null,"abstract":"The first chlororuthenacyclopentatrienes have been realized by the reactions of RuCl2(PPh3)3 with o-phenyldiyne derivatives in the presence of excess HCl. The structures of the unique chlororuthenacycles were fully characterized by spectroscopic data and X-ray diffraction. In addition, computational studies provided the evidence for their aromatic character, making them as an important supplement to the rare aromatic ruthenacycle family.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Achieving multifunctional optimization of halide optical materials through the precise modulation of intermolecular interactions is highly significant, yet it faces considerable challenges. Here, we propose a strategy of π-π interactions microregulating to achieve the simultaneous optimization of multiple properties of halide optical materials. Using this strategy, we obtained a new lead-free zero-dimensional (0D) zinc halide [DPE]ZnCl4 (DPE = 1,2-di(4-pyridyl)ethylene), in which the protonated DPE cations are orderly arranged via π-π interactions, facilitating the ordered embedding and local regulation of [ZnCl4]2- units within long-range one-dimensional cationic π-π stacking. As a result of these modifications, [DPE]ZnCl4 exhibits efficient blue light emission with a high photoluminescent quantum yield (PLQY) of 18.55%, far exceeding that of corresponding organic salt halides. Furthermore, this compound demonstrates enhanced third-order nonlinear optical (NLO) response, with the modulation depth and the third-order NLO absorption coefficient reaching 0.70 and 3.81 × 10-10 m W-1, respectively, surpassing those of three-dimensional (3D) perovskite quantum dots and most organic-inorganic hybrid halides. Notably, the modulation of π-π interactions results in a significant breakthrough in water resistance, allowing [DPE]ZnCl4 to maintain excellent structural and performance stability in water for a week. This innovative strategy of π-π interaction modulation provides new avenues for the multifunctional regulation and waterproof design of halide optical materials, and it is expected to advance the development and functionalization of stable halide optical materials.
{"title":"Water-Stable Zero-Dimensional Hybrid Zinc Halide Modulated by π-π Interactions: Efficient Blue Light Emission and Third-Order Nonlinear Optical Response","authors":"Jia-Wei Li, Wenke Dong, Yanjie Liu, Yuhan Li, Lu-Yuan Qiao, Guang-Lu Liu, Hui Zhang, Chunjie Wang, Hui-Li Zheng, Jian-Qiang Zhao","doi":"10.1039/d4qi02194k","DOIUrl":"https://doi.org/10.1039/d4qi02194k","url":null,"abstract":"Achieving multifunctional optimization of halide optical materials through the precise modulation of intermolecular interactions is highly significant, yet it faces considerable challenges. Here, we propose a strategy of π-π interactions microregulating to achieve the simultaneous optimization of multiple properties of halide optical materials. Using this strategy, we obtained a new lead-free zero-dimensional (0D) zinc halide [DPE]ZnCl4 (DPE = 1,2-di(4-pyridyl)ethylene), in which the protonated DPE cations are orderly arranged via π-π interactions, facilitating the ordered embedding and local regulation of [ZnCl4]2- units within long-range one-dimensional cationic π-π stacking. As a result of these modifications, [DPE]ZnCl4 exhibits efficient blue light emission with a high photoluminescent quantum yield (PLQY) of 18.55%, far exceeding that of corresponding organic salt halides. Furthermore, this compound demonstrates enhanced third-order nonlinear optical (NLO) response, with the modulation depth and the third-order NLO absorption coefficient reaching 0.70 and 3.81 × 10-10 m W-1, respectively, surpassing those of three-dimensional (3D) perovskite quantum dots and most organic-inorganic hybrid halides. Notably, the modulation of π-π interactions results in a significant breakthrough in water resistance, allowing [DPE]ZnCl4 to maintain excellent structural and performance stability in water for a week. This innovative strategy of π-π interaction modulation provides new avenues for the multifunctional regulation and waterproof design of halide optical materials, and it is expected to advance the development and functionalization of stable halide optical materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
CO2 radical anion (CO2-) is a powerful single electron reductant and an important intermediate in the CO2 involved reactions. Herein, we report an approach to engineer a pyrene MOF composite photocatalyst toward the formation of CO2- through regulating the charge transfer from type-II to Z-scheme via a chemical bond-modulated strategy. Through a post-synthetic modification, cysteamine (Cys) was rationally anchored onto the unsaturated Cd clusters of a pyrene-based MOF (namely WYU-11) via chemical bonds, giving rise to a modified MOF of WYU-11-Cys. This modification induced the growth of CdS nanoparticles (NPs) on the surfaces of WYU-11-Cys via the chemical bonds between CdS and Cys, resulting in the formation of MOF composite of CdS@WYU-11-Cys. The introduction of Cys could regulate the charge transfer between CdS and WYU-11, leading to the conversion from type II to Z scheme with a high redox potential of -1.93 V vs. normal hydrogen electrode. CdS@WYU-11-Cys could reduce CO2 to CO2-, which was confirmed by electron paramagnetic resonance (EPR) experiment, and promote the photocatalytic cyclization of CO2 and propargylic amines. This work provides useful inspirations on the rational design of Z-scheme MOF composites for the CO2 conversion.
二氧化碳自由基阴离子（CO2-）是一种强大的单电子还原剂，也是涉及二氧化碳反应的重要中间体。在此，我们报告了一种通过化学键调控策略调节电荷从 II 型向 Z 型转移，从而设计出一种芘 MOF 复合光催化剂以形成 CO2- 的方法。通过后合成修饰，半胱胺（Cys）被合理地通过化学键锚定到芘基MOF（即WYU-11）的不饱和镉簇上，从而产生了WYU-11-Cys修饰MOF。这种修饰通过 CdS 与 Cys 之间的化学键，诱导 CdS 纳米颗粒（NPs）在 WYU-11-Cys 表面生长，从而形成 CdS@WYU-11-Cys 的 MOF 复合材料。Cys 的引入可以调节 CdS 与 WYU-11 之间的电荷转移，从而实现从 II 型到 Z 型的转换，与普通氢电极相比，其氧化还原电位高达 -1.93 V。电子顺磁共振（EPR）实验证实，CdS@WYU-11-Cys 可将 CO2 还原为 CO2- 并促进 CO2 与丙炔胺的光催化环化。这项工作为合理设计用于二氧化碳转化的 Z 型 MOF 复合材料提供了有益的启示。
{"title":"Engineering a pyrene MOF composite photocatalyst toward the formation of carbon dioxide radical anion through regulating the charge transfer from type-II to Z-scheme via a chemical bond-modulated strategy","authors":"Xin Zhao, Yajun Zhao, Yuan-Peng Li, Pengbo Lyu, Chunying Chen, Zong-Wen Mo, Chao Peng, Jiewei Liu, Li Zhang","doi":"10.1039/d4qi02072c","DOIUrl":"https://doi.org/10.1039/d4qi02072c","url":null,"abstract":"CO2 radical anion (CO2-) is a powerful single electron reductant and an important intermediate in the CO2 involved reactions. Herein, we report an approach to engineer a pyrene MOF composite photocatalyst toward the formation of CO2- through regulating the charge transfer from type-II to Z-scheme via a chemical bond-modulated strategy. Through a post-synthetic modification, cysteamine (Cys) was rationally anchored onto the unsaturated Cd clusters of a pyrene-based MOF (namely WYU-11) via chemical bonds, giving rise to a modified MOF of WYU-11-Cys. This modification induced the growth of CdS nanoparticles (NPs) on the surfaces of WYU-11-Cys via the chemical bonds between CdS and Cys, resulting in the formation of MOF composite of CdS@WYU-11-Cys. The introduction of Cys could regulate the charge transfer between CdS and WYU-11, leading to the conversion from type II to Z scheme with a high redox potential of -1.93 V vs. normal hydrogen electrode. CdS@WYU-11-Cys could reduce CO2 to CO2-, which was confirmed by electron paramagnetic resonance (EPR) experiment, and promote the photocatalytic cyclization of CO2 and propargylic amines. This work provides useful inspirations on the rational design of Z-scheme MOF composites for the CO2 conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiao Xia, Xingxing Jiang, Lu Qi, Chao Wu, Zheshuai Lin, Zhipeng Huang, Mark G Humphrey, Kazuyuki Tatsumi, Chi Zhang
On account of the high Td symmetry of the optically active [PO4] motif, the birefringence of ultraviolet (UV) nonlinear optical (NLO) phosphates is extremely small. Here, two UV-transparent phosphates (C4H7N2)(H2PO4) and (C3H5N2)(H2PO4) exhibiting pseudo two-dimensional (2D) intercalated layers were successfully synthesized by simultaneously introducing the planar and tetrahedral motifs. The arrangements of (C3H5N2)+ and (H2PO4)− motifs within the pseudo 2D intercalated layers change from the inverse pairing mode to the uniform pairing mode, resulting in the structural evolution from centrosymmetric (CS) (C4H7N2)(H2PO4) to noncentrosymmetric (NCS) (C3H5N2)(H2PO4). Compared with the CS phosphate (C4H7N2)(H2PO4) (0.12 at 546 nm, 5.21 eV), the NCS (C3H5N2)(H2PO4) exhibits larger birefringence (0.15 at 546 nm), a blue-shifted band gap (5.41 eV), and a phase-matching second harmonic generation. Structural analysis and first-principles calculations indicate that the large birefringence in the (C3H5N2)(H2PO4) crystal is caused by the closely antiparallel arrangement between adjacent pseudo 2D intercalated layers, in which the planar (C3H5N2)+ motifs play a dominant role in optical properties.
{"title":"Large Optical Anisotropy in Noncentrosymmetric Phosphate with Pseudo 2D Intercalated Layer","authors":"Qiao Xia, Xingxing Jiang, Lu Qi, Chao Wu, Zheshuai Lin, Zhipeng Huang, Mark G Humphrey, Kazuyuki Tatsumi, Chi Zhang","doi":"10.1039/d4qi02245a","DOIUrl":"https://doi.org/10.1039/d4qi02245a","url":null,"abstract":"On account of the high Td symmetry of the optically active [PO4] motif, the birefringence of ultraviolet (UV) nonlinear optical (NLO) phosphates is extremely small. Here, two UV-transparent phosphates (C4H7N2)(H2PO4) and (C3H5N2)(H2PO4) exhibiting pseudo two-dimensional (2D) intercalated layers were successfully synthesized by simultaneously introducing the planar and tetrahedral motifs. The arrangements of (C3H5N2)+ and (H2PO4)− motifs within the pseudo 2D intercalated layers change from the inverse pairing mode to the uniform pairing mode, resulting in the structural evolution from centrosymmetric (CS) (C4H7N2)(H2PO4) to noncentrosymmetric (NCS) (C3H5N2)(H2PO4). Compared with the CS phosphate (C4H7N2)(H2PO4) (0.12 at 546 nm, 5.21 eV), the NCS (C3H5N2)(H2PO4) exhibits larger birefringence (0.15 at 546 nm), a blue-shifted band gap (5.41 eV), and a phase-matching second harmonic generation. Structural analysis and first-principles calculations indicate that the large birefringence in the (C3H5N2)(H2PO4) crystal is caused by the closely antiparallel arrangement between adjacent pseudo 2D intercalated layers, in which the planar (C3H5N2)+ motifs play a dominant role in optical properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Radical-metal compounds as functional materials could apply to multiple fields such as solar-thermal conversion and ultra-high density data storage. However, reactivity and instability of organic radicals usually hamper the development and application of radical-metal compounds. Herein, we utilized persistent nitronyl nitroxide to construct two categories of nitronyl nitroxide-Ln compounds involving a rare [4f-2p-4f-2p-4f] multi-spin motif with electron donor-acceptor pattern. Significantly, the introduction of nitronyl nitroxide effectively recedes radiative transition process and facilitates bathochromic shift of absorption spectrum to endow Dy compounds with precious NIR-II photothermal conversion function. Furthermore, synergistic action of rad-Dy/rad magnetic interactions and strong magnetic anisotropy of DyIII ions bestows single-molecule magnets (SMMs) behavior upon the system. Notably, thanks to rigidity modification of nitronyl nitroxide, prominent enhancement of photothermal conversion efficiency from 56.9% to 74.0% and magnetic switching phenomenon have been observed with molecular structure transformation from flexibility to stiffness, offering an avenue in synchronous control of photothermal effect and magnetic dynamic for the first time.
作为功能材料的自由基-金属化合物可应用于太阳能-热转换和超高密度数据存储等多个领域。然而，有机自由基的反应性和不稳定性通常会阻碍自由基金属化合物的开发和应用。在此，我们利用持久性亚硝基氮氧化物构建了两类亚硝基氮氧化物-锰化合物，其中涉及具有电子供体-受体模式的罕见[4f-2p-4f-2p-4f]多自旋基团。值得注意的是，硝基亚硝基的引入有效地减弱了辐射转变过程，促进了吸收光谱的浴色偏移，从而使 Dy 化合物具有珍贵的近红外-II 光热转换功能。此外，镭射-镝/镭射磁相互作用的协同作用和 DyIII 离子的强磁各向异性赋予了该体系单分子磁体（SMMs）特性。值得注意的是，由于对硝化亚硝基进行了刚性修饰，光热转换效率从 56.9% 显著提高到 74.0%，而且随着分子结构从柔性到刚性的转变，还观察到了磁性切换现象，首次为同步控制光热效应和磁性动态提供了途径。
{"title":"Near-Infrared-II Photothermal Conversion and Magnetic Dynamic Synchronous Control in [Ln3Rad2] Aggregate by Rigidity Modification of Nitronyl Nitroxide","authors":"Hongdao Li, Chaoyi Jin, Jing Han, Jianke Tang, Xiao-Feng Han, Zhenjun Song","doi":"10.1039/d4qi01952k","DOIUrl":"https://doi.org/10.1039/d4qi01952k","url":null,"abstract":"Radical-metal compounds as functional materials could apply to multiple fields such as solar-thermal conversion and ultra-high density data storage. However, reactivity and instability of organic radicals usually hamper the development and application of radical-metal compounds. Herein, we utilized persistent nitronyl nitroxide to construct two categories of nitronyl nitroxide-Ln compounds involving a rare [4f-2p-4f-2p-4f] multi-spin motif with electron donor-acceptor pattern. Significantly, the introduction of nitronyl nitroxide effectively recedes radiative transition process and facilitates bathochromic shift of absorption spectrum to endow Dy compounds with precious NIR-II photothermal conversion function. Furthermore, synergistic action of rad-Dy/rad magnetic interactions and strong magnetic anisotropy of DyIII ions bestows single-molecule magnets (SMMs) behavior upon the system. Notably, thanks to rigidity modification of nitronyl nitroxide, prominent enhancement of photothermal conversion efficiency from 56.9% to 74.0% and magnetic switching phenomenon have been observed with molecular structure transformation from flexibility to stiffness, offering an avenue in synchronous control of photothermal effect and magnetic dynamic for the first time.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Correction for ‘BaSc2(HPO3)4(H2O)2: a new nonlinear optical phosphite exhibiting a 3D {[Sc2(HPO3)4]2−}∞ anionic framework and phase-matchable SHG effect’ by Ru-Ling Tang, et al., Inorg. Chem. Front., 2022, 9, 5377–5385, https://doi.org/10.1039/D2QI01549H.
{"title":"Correction: BaSc2(HPO3)4(H2O)2: a new nonlinear optical phosphite exhibiting a 3D {[Sc2(HPO3)4]2−}∞ anionic framework and phase-matchable SHG effect","authors":"Ru-Ling Tang, Gang-Xiang Liu, Wen-Dong Yao, Li-Nan Zhang, Wenlong Liu, Sheng-Ping Guo","doi":"10.1039/d4qi90072c","DOIUrl":"https://doi.org/10.1039/d4qi90072c","url":null,"abstract":"Correction for ‘BaSc<small><sub>2</sub></small>(HPO<small><sub>3</sub></small>)<small><sub>4</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>: a new nonlinear optical phosphite exhibiting a 3D {[Sc<small><sub>2</sub></small>(HPO<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sup>2−</sup></small>}<small><sub>∞</sub></small> anionic framework and phase-matchable SHG effect’ by Ru-Ling Tang, <em>et al.</em>, <em>Inorg. Chem. Front.</em>, 2022, <strong>9</strong>, 5377–5385, https://doi.org/10.1039/D2QI01549H.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sn-based compounds are emerging as a promising category of alkali metal ion storage materials due to their relatively high theoretical specific capacity and natural abundance. However, inadequate ion diffusion, poor electron transfer, and significant volume fluctuations during prolonged charge and discharge cycles lead to severe structural deterioration and capacity loss, hindering their further practical application. Heterostructure engineering can not only alleviate the internal stresses and dramatic volume alterations induced by ion deintercalation, but also enhance the dynamics of ion transport. Adopting a dual-optimization strategy that incorporates heterogeneous structure construction and doping, we successfully synthesized ultra-thin Co doped SnS2/SnO2 heterostructure nanosheets on carbon cloth substrates via a co-nucleation growth process. After rigorous investigation into its lithium-ion storage performance and mechanisms, it exhibited excellent lithium storage capabilities (1518 mA h g−1 at 330 mA g−1, with 81% of the initial capacity retained after 100 cycles). Pleasingly, when incorporated into next-generation sodium-ion batteries, Co-doped SnS2/SnO2 anodes exhibit highly competitive sodium storage capabilities (1250 mA h g−1 at 220 mA g−1, with 97.8% of the initial capacity retained after 200 cycles). The incorporation of Co ions and the formation of heterostructures have been confirmed to enhance ion diffusion and reaction kinetics. This study presents a novel approach for the facile preparation of multifunctional Li and Na ion storage materials featuring element-doped heterogeneous compositions.
锡基化合物因其相对较高的理论比容量和天然丰度，正在成为一类前景广阔的碱金属离子存储材料。然而，在长时间的充放电循环过程中，离子扩散不足、电子传递不畅以及显著的体积波动会导致严重的结构退化和容量损失，从而阻碍其进一步的实际应用。异质结构工程不仅能缓解离子脱插引起的内应力和剧烈体积变化，还能增强离子传输的动态性。我们采用异质结构构建和掺杂的双重优化策略，通过共核生长工艺在碳布基底上成功合成了超薄的钴掺杂 SnS2/SnO2 异质结构纳米片。经过对其锂离子存储性能和机理的严格研究，它表现出了卓越的锂存储能力（在 330 mA g-1 的条件下可存储 1518 mA h g-1，循环 100 次后可保留 81% 的初始容量）。令人欣喜的是，当将掺钴的 SnS2/SnO2 阳极应用到下一代钠离子电池中时，它表现出了极具竞争力的钠存储能力（在 220 mA g-1 的条件下可达到 1250 mA h g-1，循环 200 次后可保留初始容量的 97.8%）。Co 离子的加入和异质结构的形成已被证实能增强离子扩散和反应动力学。本研究提出了一种新方法，可用于轻松制备具有元素掺杂异质成分的多功能锂离子和钠离子存储材料。
{"title":"Co-nucleated Co doped SnO2/SnS2 heterostructures to facilitate diffusion towards high-performance Li and Na ion storage","authors":"Kunyu Hao, Ruixiao Zhang, Mingyue Chen, Yu Lu, Pengcheng Qi, Yanxin Wang, Hao Wu, Yiwen Tang","doi":"10.1039/d4qi01941e","DOIUrl":"https://doi.org/10.1039/d4qi01941e","url":null,"abstract":"Sn-based compounds are emerging as a promising category of alkali metal ion storage materials due to their relatively high theoretical specific capacity and natural abundance. However, inadequate ion diffusion, poor electron transfer, and significant volume fluctuations during prolonged charge and discharge cycles lead to severe structural deterioration and capacity loss, hindering their further practical application. Heterostructure engineering can not only alleviate the internal stresses and dramatic volume alterations induced by ion deintercalation, but also enhance the dynamics of ion transport. Adopting a dual-optimization strategy that incorporates heterogeneous structure construction and doping, we successfully synthesized ultra-thin Co doped SnS<small><sub>2</sub></small>/SnO<small><sub>2</sub></small> heterostructure nanosheets on carbon cloth substrates <em>via</em> a co-nucleation growth process. After rigorous investigation into its lithium-ion storage performance and mechanisms, it exhibited excellent lithium storage capabilities (1518 mA h g<small><sup>−1</sup></small> at 330 mA g<small><sup>−1</sup></small>, with 81% of the initial capacity retained after 100 cycles). Pleasingly, when incorporated into next-generation sodium-ion batteries, Co-doped SnS<small><sub>2</sub></small>/SnO<small><sub>2</sub></small> anodes exhibit highly competitive sodium storage capabilities (1250 mA h g<small><sup>−1</sup></small> at 220 mA g<small><sup>−1</sup></small>, with 97.8% of the initial capacity retained after 200 cycles). The incorporation of Co ions and the formation of heterostructures have been confirmed to enhance ion diffusion and reaction kinetics. This study presents a novel approach for the facile preparation of multifunctional Li and Na ion storage materials featuring element-doped heterogeneous compositions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448159","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianshu Zhang, Yijun Qian, Changyong Zhang, Tao Qian, Chenglin Yan
Accompanied by the ever-increasing demand for lithium-ion batteries (LIBs) worldwide, the recovery of spent LIBs, for both environmental concerns and social needs, is considered an efficient way to tackle the coming retirement tide of LIBs. Although hydrometallurgy is highly recognized for realizing the high-value recycling of critical metal elements from leaching solutions via chemical purification methods, its associated complex operations, large chemical consumption, and low efficiency fail to meet sustainability and eco-friendliness considerations, requiring an innovative separation approach to achieve these aims. Electrodialysis (ED) has emerged as an advanced membrane separation technology offering continuous operation and scalability advantages but has yet to be widely applied in recycling critical metals from the leaching solutions of spent LIBs. In this review, we introduce the fundamentals and evaluation indicators of the ED technique. Besides, the challenges of ED in metal extraction from the leaching solution are discussed. In addition, strategies for improving the separation performance of ED are provided and highlighted. Finally, we present the opportunities and challenges for the use of ED techniques in metal extraction from the leaching solution of spent LIBs.
随着全球对锂离子电池（LIB）需求的不断增长，出于对环境和社会需求的考虑，回收废旧锂离子电池被认为是应对即将到来的锂离子电池退役潮的有效方法。尽管湿法冶金在通过化学纯化方法从浸出液中实现关键金属元素的高价值回收方面得到了高度认可，但其相关的复杂操作、大量化学消耗和低效率无法满足可持续发展和生态友好的要求，因此需要一种创新的分离方法来实现这些目标。电渗析（ED）是一种先进的膜分离技术，具有连续操作和可扩展性的优势，但尚未广泛应用于从废锂电池浸出液中回收关键金属。在本综述中，我们将介绍 ED 技术的基本原理和评估指标。此外，还讨论了从浸出液中提取金属的 ED 所面临的挑战。此外，还提供并强调了提高 ED 分离性能的策略。最后，我们介绍了在从废 LIB 的浸出液中提取金属时使用 ED 技术所面临的机遇和挑战。
{"title":"Critical metal recovery from spent lithium-ion batteries’ leaching solution using electrodialysis technologies: strategies and challenges","authors":"Tianshu Zhang, Yijun Qian, Changyong Zhang, Tao Qian, Chenglin Yan","doi":"10.1039/d4qi01978d","DOIUrl":"https://doi.org/10.1039/d4qi01978d","url":null,"abstract":"Accompanied by the ever-increasing demand for lithium-ion batteries (LIBs) worldwide, the recovery of spent LIBs, for both environmental concerns and social needs, is considered an efficient way to tackle the coming retirement tide of LIBs. Although hydrometallurgy is highly recognized for realizing the high-value recycling of critical metal elements from leaching solutions <em>via</em> chemical purification methods, its associated complex operations, large chemical consumption, and low efficiency fail to meet sustainability and eco-friendliness considerations, requiring an innovative separation approach to achieve these aims. Electrodialysis (ED) has emerged as an advanced membrane separation technology offering continuous operation and scalability advantages but has yet to be widely applied in recycling critical metals from the leaching solutions of spent LIBs. In this review, we introduce the fundamentals and evaluation indicators of the ED technique. Besides, the challenges of ED in metal extraction from the leaching solution are discussed. In addition, strategies for improving the separation performance of ED are provided and highlighted. Finally, we present the opportunities and challenges for the use of ED techniques in metal extraction from the leaching solution of spent LIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As global resource and environmental issues become increasingly severe, photocatalytic technology for efficiently and cleanly degrading pollutants has become a trend in development. Radical degradation pathways are highly regarded due to their wide application and efficiency in handling pollutants. Comparatively, direct oxidation by holes exhibits unique advantages in dealing with specific types of pollutants, and both degradation pathways have their own characteristics and strengths. However, past research on pollutant degradation has mainly focused on radical degradation, with little recognition of the role of direct hole oxidation in pollutant degradation, and there has been a lack of attention to the transition between the two pathways. This has made it difficult to select the most effective degradation strategy for different types of pollutants. To fill the cognitive gap in photocatalytic degradation pathways and break the predicament of blindly dealing with pollutants, the characteristics of these two oxidation pathways and their transition mechanisms are systematically explored. Additionally, this study provides the first summary of which types of pollutants are suitable for degradation by holes and radicals, respectively. This paper offers a clear basis for selecting the most appropriate photocatalytic strategy according to the characteristics of different pollutants and reaction conditions, aiming to enhance researchers' understanding of pollutant degradation and promote the development of environmental management technology towards higher efficiency and precision.
{"title":"Strategic Pathway Selection in Photocatalytic Degradation: Roles of Holes and Radicals","authors":"Yuxin Li, Xu Gao, Yixuan Li","doi":"10.1039/d4qi01635a","DOIUrl":"https://doi.org/10.1039/d4qi01635a","url":null,"abstract":"As global resource and environmental issues become increasingly severe, photocatalytic technology for efficiently and cleanly degrading pollutants has become a trend in development. Radical degradation pathways are highly regarded due to their wide application and efficiency in handling pollutants. Comparatively, direct oxidation by holes exhibits unique advantages in dealing with specific types of pollutants, and both degradation pathways have their own characteristics and strengths. However, past research on pollutant degradation has mainly focused on radical degradation, with little recognition of the role of direct hole oxidation in pollutant degradation, and there has been a lack of attention to the transition between the two pathways. This has made it difficult to select the most effective degradation strategy for different types of pollutants. To fill the cognitive gap in photocatalytic degradation pathways and break the predicament of blindly dealing with pollutants, the characteristics of these two oxidation pathways and their transition mechanisms are systematically explored. Additionally, this study provides the first summary of which types of pollutants are suitable for degradation by holes and radicals, respectively. This paper offers a clear basis for selecting the most appropriate photocatalytic strategy according to the characteristics of different pollutants and reaction conditions, aiming to enhance researchers' understanding of pollutant degradation and promote the development of environmental management technology towards higher efficiency and precision.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443929","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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