Zengxin Lou, Kai Kang, Pingping Zhang, Qi Zhong, Yong Liu, Kaiqiang Liu, Wenzhuo Yuan, Yongchao Bao, Yongchao Bao, Juan Liu
Urea photosynthesis from CO₂ and nitrate presents a sustainable solution to mitigate carbon and nitrogen pollution. Nonetheless, simultaneously activating both substrates and directing selective C–N coupling remains challenging. In this study, we present the first construction of atomically coordinated Cu–Ti dual sites on a MXene-derived TiO₂/Ti₃C₂ heterostructure for direct urea synthesis. Asymmetric Cu–O–Ti dual sites are engineered by anchoring isolated Cu single atoms. HAADF-STEM and in-situ XPS/XAFS analyses confirm atomically dispersed Cu and light-induced, reversible Cu⁺/Cu²⁺ cycling. In-situ FTIR and DFT studies reveal that Cu sites convert CO2 to *CO, Ti sites catalyze the eight-electron nitrate reduction to *NH2, and the Cu-O-Ti bridge reduces the energy barrier for C-N coupling to urea intermediates, thereby suppressing CO and NH3 by-products. Under simulated sunlight, the optimized catalyst (0.5 wt% Cu) achieves a urea production rate of 11.57 μmol·gcat−1·h−1, which is 2.2 times higher than that of TiO2/Ti3C2, with excellent cycling stability. This MXene-enabled single-atom coordination strategy provides a general approach for renewable-energy-driven C-N coupling and pollutant valorization.
二氧化碳和硝酸盐的尿素光合作用是缓解碳和氮污染的可持续解决方案。然而，同时激活两种底物并指导选择性C-N偶联仍然具有挑战性。在这项研究中，我们首次在mxene衍生的TiO₂/Ti₃C₂异质结构上构建了原子配位的Cu-Ti双位点，用于直接合成尿素。不对称Cu - o - ti双位是通过锚定孤立的Cu单原子来设计的。HAADF-STEM和原位XPS/XAFS分析证实了原子分散的Cu和光诱导的、可逆的Cu + /Cu 2 +循环。原位FTIR和DFT研究表明，Cu位点将CO2转化为*CO， Ti位点催化8电子硝酸盐还原为*NH2， Cu- o -Ti桥降低了C-N偶联到尿素中间体的能垒，从而抑制了CO和NH3副产物。在模拟阳光下，优化后的催化剂（0.5 wt% Cu）的尿素产率为11.57 μmol·gcat−1·h−1，是TiO2/Ti3C2的2.2倍，且具有良好的循环稳定性。这种支持mxene的单原子配位策略为可再生能源驱动的碳氮耦合和污染物增值提供了一种通用方法。
{"title":"Atomically Anchored Cu on MXene-Derived TiO₂/Ti₃C₂ Enables Cu-Ti Dual Sites for Selective Urea Photosynthesis from CO₂ and Nitrate","authors":"Zengxin Lou, Kai Kang, Pingping Zhang, Qi Zhong, Yong Liu, Kaiqiang Liu, Wenzhuo Yuan, Yongchao Bao, Yongchao Bao, Juan Liu","doi":"10.1039/d6qi00180g","DOIUrl":"https://doi.org/10.1039/d6qi00180g","url":null,"abstract":"Urea photosynthesis from CO₂ and nitrate presents a sustainable solution to mitigate carbon and nitrogen pollution. Nonetheless, simultaneously activating both substrates and directing selective C–N coupling remains challenging. In this study, we present the first construction of atomically coordinated Cu–Ti dual sites on a MXene-derived TiO₂/Ti₃C₂ heterostructure for direct urea synthesis. Asymmetric Cu–O–Ti dual sites are engineered by anchoring isolated Cu single atoms. HAADF-STEM and in-situ XPS/XAFS analyses confirm atomically dispersed Cu and light-induced, reversible Cu⁺/Cu²⁺ cycling. In-situ FTIR and DFT studies reveal that Cu sites convert CO2 to *CO, Ti sites catalyze the eight-electron nitrate reduction to *NH2, and the Cu-O-Ti bridge reduces the energy barrier for C-N coupling to urea intermediates, thereby suppressing CO and NH3 by-products. Under simulated sunlight, the optimized catalyst (0.5 wt% Cu) achieves a urea production rate of 11.57 μmol·gcat−1·h−1, which is 2.2 times higher than that of TiO2/Ti3C2, with excellent cycling stability. This MXene-enabled single-atom coordination strategy provides a general approach for renewable-energy-driven C-N coupling and pollutant valorization.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489357","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}
Near-infrared (NIR) phosphors constitute a significant class of luminescent materials for light-emitting diodes (LEDs). Recently, considerable research efforts in this active field have been devoted to the development of Cr3+-doped oxide, fluoride, and chloride phosphors for NIR luminescence emission, in which the unique d-d transition enables their tunable luminescence properties suitable for diverse LED applications such as plant growth lighting, bioimaging, night vision, non-destructive testing, and compositional analysis. This review article provides a comprehensive overview of recent advances in Cr3+-doped NIR phosphors, with emphasis on their detailed preparation methods, luminescence properties, and application potential in LED devices. Additionally, significant research challenges are outlined to guide the development of Cr3+-activated NIR phosphors, supported by a comprehensive list of representative references.
{"title":"Recent advances in Cr3+-doped near-infrared phosphors: preparation, luminescence, and LED applications","authors":"Qingmei Fan, Jing Wan, Zhengliang Wang, Zhong Lei, Chunyan Jiang, Qiang Zhou, Lei Zhou, Mingmei Wu","doi":"10.1039/d6qi00195e","DOIUrl":"https://doi.org/10.1039/d6qi00195e","url":null,"abstract":"Near-infrared (NIR) phosphors constitute a significant class of luminescent materials for light-emitting diodes (LEDs). Recently, considerable research efforts in this active field have been devoted to the development of Cr3+-doped oxide, fluoride, and chloride phosphors for NIR luminescence emission, in which the unique d-d transition enables their tunable luminescence properties suitable for diverse LED applications such as plant growth lighting, bioimaging, night vision, non-destructive testing, and compositional analysis. This review article provides a comprehensive overview of recent advances in Cr3+-doped NIR phosphors, with emphasis on their detailed preparation methods, luminescence properties, and application potential in LED devices. Additionally, significant research challenges are outlined to guide the development of Cr3+-activated NIR phosphors, supported by a comprehensive list of representative references.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478623","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}
Mariya Grudova, Alexey Galushko, Vladimir Skuratovich, Anastasiya Nakhatova, Valentina Ilyushenkova, Victor Chernyshev, Valentine P. Ananikov
Catalytic systems derived from Au(I) and Cu(I) precatalysts bearing phosphine and N-heterocyclic carbene (NHC) ligands are traditionally considered homogeneous. However, we demonstrate that under catalytically relevant conditions these systems undergo rapid and reversible metal–ligand bond cleavage, generating complex cocktails of molecular complexes, clusters, and nanoparticulate species. Using a combination of TEM analyses and poisoning experiments, we reveal that the identity of the dominant active species is not intrinsic to the metal/ligand pair but is critically reaction-dependent. For example, ligand-free nanoparticulate Cu species govern the Chan–Evans–Lam coupling, while molecular copper complexes dominate the Cu-AAC click reaction. In Au catalysis, ligandless nanoparticles are prevalent in A³-coupling and alkyne hydration, whereas in hydroamination the IMes ligand plays a striking promoting role within the cocktail, outperforming both phosphine-based and ligand-free systems. Inspired by this insight, we developed a simple, solvent- and silver-free Au/IMes protocol for alkyne hydroamination using bench-stable precursors. This study establishes the "cocktail of catalysts" paradigm as a fundamental concept in Au and Cu catalysis and highlights the need to reconsider traditional ligand design strategies when nanoparticulate species dynamically contribute to catalysis.
{"title":"When Ligands Promote, Inhibit, or Disappear: Reaction-Dependent Roles in Au and Cu Catalysis","authors":"Mariya Grudova, Alexey Galushko, Vladimir Skuratovich, Anastasiya Nakhatova, Valentina Ilyushenkova, Victor Chernyshev, Valentine P. Ananikov","doi":"10.1039/d5qi02569a","DOIUrl":"https://doi.org/10.1039/d5qi02569a","url":null,"abstract":"Catalytic systems derived from Au(I) and Cu(I) precatalysts bearing phosphine and N-heterocyclic carbene (NHC) ligands are traditionally considered homogeneous. However, we demonstrate that under catalytically relevant conditions these systems undergo rapid and reversible metal–ligand bond cleavage, generating complex cocktails of molecular complexes, clusters, and nanoparticulate species. Using a combination of TEM analyses and poisoning experiments, we reveal that the identity of the dominant active species is not intrinsic to the metal/ligand pair but is critically reaction-dependent. For example, ligand-free nanoparticulate Cu species govern the Chan–Evans–Lam coupling, while molecular copper complexes dominate the Cu-AAC click reaction. In Au catalysis, ligandless nanoparticles are prevalent in A³-coupling and alkyne hydration, whereas in hydroamination the IMes ligand plays a striking promoting role within the cocktail, outperforming both phosphine-based and ligand-free systems. Inspired by this insight, we developed a simple, solvent- and silver-free Au/IMes protocol for alkyne hydroamination using bench-stable precursors. This study establishes the \"cocktail of catalysts\" paradigm as a fundamental concept in Au and Cu catalysis and highlights the need to reconsider traditional ligand design strategies when nanoparticulate species dynamically contribute to catalysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"60 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478621","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}
Lingjuan Zhang, Jiayi Zheng, Nan Zhang, Jincong Yuan, Xian-Ming Zhang
Photothermal-driven double hydrogen transfer (DHT) strategies are highly desirable for boosting the hydrogen utilization efficiency of ammonia borane complexes and enabling green hydrogen evolution. In this work, three porphyrin-based CMPs, namely Im-PCMP, NHC(Cu)-PCMP and NHC(Cu)-PCMP(Cu), were synthesized via Suzuki-Miyaura coupling reaction (Nheterocyclic carbene, NHC). NHC(Cu)-PCMP(Cu) showed outstanding catalytic activity in the photothermal reductive hydrogenation of quinoline and its derivatives with high yields and selectivity. The isotopic labeling and control experiments revealed that (1) outstanding photothermal conversion efficiencies (η = 79%) of NHC(Cu)-PCMP(Cu), attributed to the synergistic effects of metal-carbene and porphyrin metallization via bimetallic regulating strategies; (2) enhanced activation performance for the N-H...H-B bond through NHC(Cu)-mediated cooperative catalysis; (3) effective DHT reductive hydrogenation of quinoline and its derivatives with t-BuNH2BH3 as hydrogen donors through heterogeneous photothermal process.
{"title":"N-heterocyclic Carbene(Cu) Synergistic Photothermal Hydrogen Release Involving Double Hydrogen Transfer Catalyzed by Porphyrin(Cu)-Based Conjugated Microporous Polymers for Efficient Quinoline Hydrogenation","authors":"Lingjuan Zhang, Jiayi Zheng, Nan Zhang, Jincong Yuan, Xian-Ming Zhang","doi":"10.1039/d6qi00135a","DOIUrl":"https://doi.org/10.1039/d6qi00135a","url":null,"abstract":"Photothermal-driven double hydrogen transfer (DHT) strategies are highly desirable for boosting the hydrogen utilization efficiency of ammonia borane complexes and enabling green hydrogen evolution. In this work, three porphyrin-based CMPs, namely Im-PCMP, NHC(Cu)-PCMP and NHC(Cu)-PCMP(Cu), were synthesized via Suzuki-Miyaura coupling reaction (Nheterocyclic carbene, NHC). NHC(Cu)-PCMP(Cu) showed outstanding catalytic activity in the photothermal reductive hydrogenation of quinoline and its derivatives with high yields and selectivity. The isotopic labeling and control experiments revealed that (1) outstanding photothermal conversion efficiencies (η = 79%) of NHC(Cu)-PCMP(Cu), attributed to the synergistic effects of metal-carbene and porphyrin metallization via bimetallic regulating strategies; (2) enhanced activation performance for the N-H...H-B bond through NHC(Cu)-mediated cooperative catalysis; (3) effective DHT reductive hydrogenation of quinoline and its derivatives with t-BuNH2BH3 as hydrogen donors through heterogeneous photothermal process.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489358","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}
Room-temperature sodium–sulfur batteries (RT Na–S) hold great potential for energy storage due to the abundance of sodium and sulfur, low costs, and high theoretical energy density. However, their development is limited by the shuttle effect of polysulfides, slow reaction kinetics, and the growth of sodium dendrites. These issues lead to rapid capacity decay and poor cycling stability, which are difficult to mitigate using traditional separators. Inspired by ion channels in biological membranes, we developed a carboxylate-modified MIL-121/Na separator. Its sub-nanometer channels enable highly selective Na+ transport with an ionic conductivity of 2.27 × 10−4 S cm−1, a migration number of 0.74, and a wide electrochemical window of up to 5.1 V. When applied in RT Na–S batteries, it effectively inhibits the polysulfide shuttle and promotes the reaction kinetics, achieving a first-cycle discharge capacity of 1182 mAh g−1 at a 0.5C rate and stable cycling for over 400 cycles, demonstrating excellent rate performance and long cycle life. Even in pouch cells, the performance can be stabilized at a 1C rate for 100 cycles and the cycle-to-cycle stability can be maintained. This study provides a new strategy for separator design to advance high-performance sodium–sulfur batteries.
室温钠硫电池（RT Na-S）由于其丰富的钠和硫、低成本和高理论能量密度而具有巨大的储能潜力。然而，多硫化物的穿梭效应、反应动力学缓慢以及钠枝晶的生长限制了它们的发展。这些问题导致产能快速衰减和循环稳定性差，使用传统分离器很难缓解这些问题。受生物膜中离子通道的启发，我们开发了一种羧酸修饰的MIL-121/Na分离器。其亚纳米通道具有高选择性的Na+传输，离子电导率为2.27 × 10−4 S cm−1，迁移数为0.74，电化学窗口宽达5.1 V。应用于RT Na-S电池时，有效抑制多硫化物穿梭，促进反应动力学，在0.5C倍率下实现1182 mAh g−1的第一次循环放电容量，稳定循环超过400次，表现出优异的倍率性能和较长的循环寿命。即使在袋状电池中，性能也可以在1C速率下稳定100次，并且可以保持循环到循环的稳定性。该研究为推进高性能钠硫电池的隔膜设计提供了新的思路。
{"title":"Constructing dynamic Na+ transport channels in RT Na–S battery separators to suppress polysulfide shuttling and accelerate reaction kinetics","authors":"Xiaoxue Mao, Zhiyong Xiong, Yuhao Xiang, Shihang Guo, Xin Chen, Hongyang Zeng, Jian Jiang, Sirui Wan, Yi Li, Maowen Xu","doi":"10.1039/d6qi00121a","DOIUrl":"https://doi.org/10.1039/d6qi00121a","url":null,"abstract":"Room-temperature sodium–sulfur batteries (RT Na–S) hold great potential for energy storage due to the abundance of sodium and sulfur, low costs, and high theoretical energy density. However, their development is limited by the shuttle effect of polysulfides, slow reaction kinetics, and the growth of sodium dendrites. These issues lead to rapid capacity decay and poor cycling stability, which are difficult to mitigate using traditional separators. Inspired by ion channels in biological membranes, we developed a carboxylate-modified MIL-121/Na separator. Its sub-nanometer channels enable highly selective Na<small><sup>+</sup></small> transport with an ionic conductivity of 2.27 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small>, a migration number of 0.74, and a wide electrochemical window of up to 5.1 V. When applied in RT Na–S batteries, it effectively inhibits the polysulfide shuttle and promotes the reaction kinetics, achieving a first-cycle discharge capacity of 1182 mAh g<small><sup>−1</sup></small> at a 0.5C rate and stable cycling for over 400 cycles, demonstrating excellent rate performance and long cycle life. Even in pouch cells, the performance can be stabilized at a 1C rate for 100 cycles and the cycle-to-cycle stability can be maintained. This study provides a new strategy for separator design to advance high-performance sodium–sulfur batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"197 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478622","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}
Marharyta Vynoslavska, Thomas Louis-Goff, Huu Vinh Trinh, Eileen Chen, Bao Nguyen, Arnold L. Rheingold, Glenn P. A. Yap, Christian Ehm, Jakub Hyvl
Organobismuth-catalyzed olefin difluorocarbenation is a reagent-efficient approach to 1,1-difluorocyclopropanes, requiring only near-stoichiometric amounts of TMS-CF3 due to the ability to release CF2 in a controlled manner, while allowing even the challenging transformation of electron-poor alkenes. However, slow reaction times, high reaction temperature, and high catalytic loadings represent some drawbacks of this approach. Herein, we investigate how ligand design affects the two key steps of the catalytic cycle: the CF2 α-elimination reaction and transmetallation. We show that a strong donor atom trans to the CF3 group efficiently lowers the barrier of the rate-determining step, CF2 α-elimination, and can also accelerate the transmetallation step. Transmetallation is far more sensitive to ligand effects. Notably, we found that complexes bearing tetradentate ligands exhibited improved reactivity in both catalytic steps, leading to a 3-fold improvement in performance over the original catalyst used in the reference reaction with stilbene.
{"title":"Balancing transmetallation and CF2 α-elimination barriers in organobismuth-catalyzed olefin difluorocarbenation","authors":"Marharyta Vynoslavska, Thomas Louis-Goff, Huu Vinh Trinh, Eileen Chen, Bao Nguyen, Arnold L. Rheingold, Glenn P. A. Yap, Christian Ehm, Jakub Hyvl","doi":"10.1039/d5qi02576a","DOIUrl":"https://doi.org/10.1039/d5qi02576a","url":null,"abstract":"Organobismuth-catalyzed olefin difluorocarbenation is a reagent-efficient approach to 1,1-difluorocyclopropanes, requiring only near-stoichiometric amounts of TMS-CF<small><sub>3</sub></small> due to the ability to release CF<small><sub>2</sub></small> in a controlled manner, while allowing even the challenging transformation of electron-poor alkenes. However, slow reaction times, high reaction temperature, and high catalytic loadings represent some drawbacks of this approach. Herein, we investigate how ligand design affects the two key steps of the catalytic cycle: the CF<small><sub>2</sub></small> α-elimination reaction and transmetallation. We show that a strong donor atom <em>trans</em> to the CF<small><sub>3</sub></small> group efficiently lowers the barrier of the rate-determining step, CF<small><sub>2</sub></small> α-elimination, and can also accelerate the transmetallation step. Transmetallation is far more sensitive to ligand effects. Notably, we found that complexes bearing tetradentate ligands exhibited improved reactivity in both catalytic steps, leading to a 3-fold improvement in performance over the original catalyst used in the reference reaction with stilbene.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478620","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}
Mian He, Yaqi Zhang, Jiali Lou, Jiamin Wei, Xuhui Sun, Meng An, Shenghua Zhou, Xiaoqian Wei, Xiaokai Song
Construction of favorable transfer pathways that ensure rapid mass transfer capability is critical for the design of Fe-N-C electrocatalysts. Typically, two-dimensional (2D) Fe-N-C catalysts exhibit fast mass transfer in the in-plane direction; however, their microporous nature limits mass transfer efficiency in the vertical direction. Herein, we report the fabrication of 2D monolayered Fe-N-C carbon honeycomb catalysts (2D Fe-CH) with aligned vertical mass transfer channels between each porous carbon polyhedron. The 2D monolayered architecture ensures efficient in-plane mass transfer, while the meticulously designed vertically aligned channels enhancing mass transfer in the perpendicular direction. These aligned channels enable maximum exposure of Fe single atoms and improve the accessibility of these active sites. Compared to the 2D monolayered Fe-N-C carbon particle array catalyst (2D Fe-CPA) without vertical channels, the 2D Fe-CH catalyst demonstrates significantly enhanced performance toward the oxygen reduction reaction. The half wave potential reaches up to 0.891 V vs. RHE in 0.1 M KOH. Molecular dynamics simulations combined with DRT analysis reveal that the enhanced performance is attributed to the presence of vertically aligned mass transfer channels.
构建保证快速传质能力的良好传递途径是设计Fe-N-C电催化剂的关键。通常，二维（2D） Fe-N-C催化剂在平面方向上表现出快速的传质；然而，它们的微孔性质限制了它们在垂直方向上的传质效率。在此，我们报道了二维单层Fe-N-C碳蜂窝催化剂（2D Fe-CH）的制备，每个多孔碳多面体之间具有对齐的垂直传质通道。二维单层结构确保了有效的面内传质，而精心设计的垂直排列通道增强了垂直方向的传质。这些排列的通道可以最大限度地暴露铁单原子，并提高这些活性位点的可及性。与无垂直通道的二维单层Fe-N-C碳颗粒阵列催化剂（2D Fe-CPA）相比，二维Fe-CH催化剂的氧还原性能显著提高。与RHE相比，在0.1 M KOH条件下半波电位高达0.891 V。分子动力学模拟结合DRT分析表明，性能的增强归因于垂直排列的传质通道的存在。
{"title":"Aligned Vertical Mass Transfer Channels in 2D Monolayered Fe-N-C Carbon Honeycomb for Efficient Oxygen Reduction","authors":"Mian He, Yaqi Zhang, Jiali Lou, Jiamin Wei, Xuhui Sun, Meng An, Shenghua Zhou, Xiaoqian Wei, Xiaokai Song","doi":"10.1039/d6qi00133e","DOIUrl":"https://doi.org/10.1039/d6qi00133e","url":null,"abstract":"Construction of favorable transfer pathways that ensure rapid mass transfer capability is critical for the design of Fe-N-C electrocatalysts. Typically, two-dimensional (2D) Fe-N-C catalysts exhibit fast mass transfer in the in-plane direction; however, their microporous nature limits mass transfer efficiency in the vertical direction. Herein, we report the fabrication of 2D monolayered Fe-N-C carbon honeycomb catalysts (2D Fe-CH) with aligned vertical mass transfer channels between each porous carbon polyhedron. The 2D monolayered architecture ensures efficient in-plane mass transfer, while the meticulously designed vertically aligned channels enhancing mass transfer in the perpendicular direction. These aligned channels enable maximum exposure of Fe single atoms and improve the accessibility of these active sites. Compared to the 2D monolayered Fe-N-C carbon particle array catalyst (2D Fe-CPA) without vertical channels, the 2D Fe-CH catalyst demonstrates significantly enhanced performance toward the oxygen reduction reaction. The half wave potential reaches up to 0.891 V vs. RHE in 0.1 M KOH. Molecular dynamics simulations combined with DRT analysis reveal that the enhanced performance is attributed to the presence of vertically aligned mass transfer channels.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478625","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}
Electrocatalytic water splitting, as a key clean energy technology, enables sustainable hydrogen production and plays a critical role in the global energy transition and the path to carbon neutrality. In this context, dual-metal catalysts (DMCs) have emerged as a major research focus in electrocatalytic water splitting. Their distinct structural and electronic properties allow them to surpass the limitations of single-metal catalysts, providing a more abundant supply of active sites, improved electronic modulation, and faster reaction kinetics. This review systematically summarizes recent advances in DMCs, which capitalize on unique synergistic effects to advance electrocatalytic water splitting. It begins by classifying synthesis strategies for two primary DMCs architectures: dual-atom catalysts and dual-metal nanocatalysts. The discussion then details their superior performance in hydrogen evolution reaction, oxygen evolution reaction, and overall water splitting, highlighting enhanced activity and stability. Furthermore, this review highlights that the superior performance of DMCs stems from dual-metal synergy. This synergy enables precise electronic structure modulation and/or creates unique tandem catalysis mechanisms, which collectively contribute to significantly lowered reaction energy barriers and optimized pathways in water splitting. This work presents a comprehensive overview of DMCs in electrocatalytic water splitting, offering a systematic presentation of both synthesis methods and the mechanisms underlying their superior performance. The insights presented herein aim to direct future research toward the development of high-performance, cost-effective catalysts for electrocatalytic water splitting.
{"title":"Dual-Metal Catalysts for Promoting Electrocatalytic Water Splitting","authors":"Cui Gao, Xiu-Li Lu, Tongbu Lu","doi":"10.1039/d5qi02561c","DOIUrl":"https://doi.org/10.1039/d5qi02561c","url":null,"abstract":"Electrocatalytic water splitting, as a key clean energy technology, enables sustainable hydrogen production and plays a critical role in the global energy transition and the path to carbon neutrality. In this context, dual-metal catalysts (DMCs) have emerged as a major research focus in electrocatalytic water splitting. Their distinct structural and electronic properties allow them to surpass the limitations of single-metal catalysts, providing a more abundant supply of active sites, improved electronic modulation, and faster reaction kinetics. This review systematically summarizes recent advances in DMCs, which capitalize on unique synergistic effects to advance electrocatalytic water splitting. It begins by classifying synthesis strategies for two primary DMCs architectures: dual-atom catalysts and dual-metal nanocatalysts. The discussion then details their superior performance in hydrogen evolution reaction, oxygen evolution reaction, and overall water splitting, highlighting enhanced activity and stability. Furthermore, this review highlights that the superior performance of DMCs stems from dual-metal synergy. This synergy enables precise electronic structure modulation and/or creates unique tandem catalysis mechanisms, which collectively contribute to significantly lowered reaction energy barriers and optimized pathways in water splitting. This work presents a comprehensive overview of DMCs in electrocatalytic water splitting, offering a systematic presentation of both synthesis methods and the mechanisms underlying their superior performance. The insights presented herein aim to direct future research toward the development of high-performance, cost-effective catalysts for electrocatalytic water splitting.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471108","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}
Shenglong Wu, Yang Zhang, Yue Zhu, Wenzhen Du, Jie Wu, Weijie Zhang, Qiongguang Li
Vanadium (V)-based oxides are considered as promising cathodes for aqueous zinc ion batteries (AZIBs) due to their various oxidation states and crystal structures, whilst sluggish kinetics and severe V-dissolution lead to rapid capacity fading and unsatisfied cycle life. Herein, a niobium (Nb) pillaring coupling with polyethylene glycol assistance strategy (PNVO) that overcomes the limitation of inability of Nb-doped V-oxide separation, achieving Nb-pillaring effect and thus good structural stability, and enables abundant oxygen vacancy and enhanced kinetics, resulting in good rate performance, is described for the first time. This approach has resulted in high reversible capacity of 403 mAh g-1 and 244 mAh g-1 at 1 A g-1 and 10 A g-1, respectively, and remarkable cyclability with 68% capacity retention after 3000 cycles at 5 A g-1. Quantitative comparison of V-dissolution suggested PNVO-2 exhibited a low dissolution rate of 8.93%, while that for PVO and VO was 11.25% and 16.07%, respectively. These findings not only confirm the positive effect of Nb-pillaring on inhibition of V-dissolution, but also highlight the promising practical application of V-based cathodes for AZIBs.
钒(V)基氧化物由于其不同的氧化态和晶体结构而被认为是很有前途的水性锌离子电池阴极，但动力学缓慢和严重的V溶解导致容量快速衰减和循环寿命不理想。本文首次描述了一种铌（Nb）柱化偶联与聚乙二醇辅助策略（PNVO），克服了铌掺杂v -氧化物无法分离的限制，实现了铌柱化效应，从而获得了良好的结构稳定性，并实现了丰富的氧空位和增强的动力学，从而获得了良好的速率性能。这种方法产生了高可逆容量，在1 A g-1和10 A g-1下分别为403 mAh g-1和244 mAh g-1，并且在5 A g-1下循环3000次后具有68%的容量保留率。v -溶出度定量比较表明，PNVO-2的溶出率较低，为8.93%，而PVO和VO的溶出率分别为11.25%和16.07%。这些研究结果不仅证实了铌柱对抑制v -溶解的积极作用，而且突出了v基azib阴极的实际应用前景。
{"title":"Inhibition of Vanadium Cathode Dissolution in Zinc Ion batteries Via Niobium Pillaring","authors":"Shenglong Wu, Yang Zhang, Yue Zhu, Wenzhen Du, Jie Wu, Weijie Zhang, Qiongguang Li","doi":"10.1039/d6qi00190d","DOIUrl":"https://doi.org/10.1039/d6qi00190d","url":null,"abstract":"Vanadium (V)-based oxides are considered as promising cathodes for aqueous zinc ion batteries (AZIBs) due to their various oxidation states and crystal structures, whilst sluggish kinetics and severe V-dissolution lead to rapid capacity fading and unsatisfied cycle life. Herein, a niobium (Nb) pillaring coupling with polyethylene glycol assistance strategy (PNVO) that overcomes the limitation of inability of Nb-doped V-oxide separation, achieving Nb-pillaring effect and thus good structural stability, and enables abundant oxygen vacancy and enhanced kinetics, resulting in good rate performance, is described for the first time. This approach has resulted in high reversible capacity of 403 mAh g-1 and 244 mAh g-1 at 1 A g-1 and 10 A g-1, respectively, and remarkable cyclability with 68% capacity retention after 3000 cycles at 5 A g-1. Quantitative comparison of V-dissolution suggested PNVO-2 exhibited a low dissolution rate of 8.93%, while that for PVO and VO was 11.25% and 16.07%, respectively. These findings not only confirm the positive effect of Nb-pillaring on inhibition of V-dissolution, but also highlight the promising practical application of V-based cathodes for AZIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"83 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471109","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}
Qi Chen, Chenyang Zhang, Hu Wang, Yuexiao Pan, Hongzhou Lian, Jun Lin, Liyi Li
Single-component materials capable of exhibiting both excitation-dependent fluorescence and time-resolved afterglow are highly desirable for advanced photonic applications, yet remain scarce. Herein, we report a novel zero-dimensional (0D) organic–inorganic hybrid perovskite (OIHP), (BPY)2ZrCl6:Sb3+([BPY]+ = N-butyl-pyridinium cation), which exhibits excitation-dependent fluorescence and green afterglow properties. This dual emission originates from distinct luminescent centers: self-trapped excitons (STEs) and d–d transitions within the [ZrCl6]2− octahedra, and the organic [BPY]+ cations. The incorporation of Sb3+ enables efficient energy transfer from the host to the [SbCl6]3− dopant, leading to broadly tunable white-light emission from green to orange-red and a notable reduction in afterglow lifetime. Density functional theory calculations revealed the origin of the afterglow, and the band narrowing and exciton localization effects caused by Sb3+ doping. Leveraging this tunable emission and time-resolved afterglow, we demonstrate high-quality white light-emitting diodes (WLEDs) and a dynamic anti-counterfeiting system using ASCII-based time-gated decoding. This work provides insights into energy-transfer engineering in 0D OIHP and establishes a material platform that integrates efficient lighting with advanced information encryption.
{"title":"Single-component zero-dimensional (BPY)2ZrCl6:Sb3+ hybrid perovskite exhibiting excitation-dependent multi-color fluorescence and afterglow for advanced hierarchical anti-counterfeiting","authors":"Qi Chen, Chenyang Zhang, Hu Wang, Yuexiao Pan, Hongzhou Lian, Jun Lin, Liyi Li","doi":"10.1039/d5qi02511g","DOIUrl":"https://doi.org/10.1039/d5qi02511g","url":null,"abstract":"Single-component materials capable of exhibiting both excitation-dependent fluorescence and time-resolved afterglow are highly desirable for advanced photonic applications, yet remain scarce. Herein, we report a novel zero-dimensional (0D) organic–inorganic hybrid perovskite (OIHP), (BPY)<small><sub>2</sub></small>ZrCl<small><sub>6</sub></small>:Sb<small><sup>3+</sup></small>([BPY]<small><sup>+</sup></small> = <em>N</em>-butyl-pyridinium cation), which exhibits excitation-dependent fluorescence and green afterglow properties. This dual emission originates from distinct luminescent centers: self-trapped excitons (STEs) and d–d transitions within the [ZrCl<small><sub>6</sub></small>]<small><sup>2−</sup></small> octahedra, and the organic [BPY]<small><sup>+</sup></small> cations. The incorporation of Sb<small><sup>3+</sup></small> enables efficient energy transfer from the host to the [SbCl<small><sub>6</sub></small>]<small><sup>3−</sup></small> dopant, leading to broadly tunable white-light emission from green to orange-red and a notable reduction in afterglow lifetime. Density functional theory calculations revealed the origin of the afterglow, and the band narrowing and exciton localization effects caused by Sb<small><sup>3+</sup></small> doping. Leveraging this tunable emission and time-resolved afterglow, we demonstrate high-quality white light-emitting diodes (WLEDs) and a dynamic anti-counterfeiting system using ASCII-based time-gated decoding. This work provides insights into energy-transfer engineering in 0D OIHP and establishes a material platform that integrates efficient lighting with advanced information encryption.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478626","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：