This work reports the in-situ synthesis of monolayer hybrid chiral perovskite films R/S-MBAPbBr₃@MBA₂PbBr₄ via temperature modulation, which combining the chiral one-dimensional (1D) R/S-MBAPbBr3 perovskite with two-dimensional (2D) non-luminescent (R/S-MBA)2PbBr4 perovskite. The as-synthesized chiral hybrid films exhibit stronger circularly polarized luminescence (CPL) response than that of the corresponding 1D chiral perovskite films. The circularly polarization-resolved transient absorption (TA) spectra reveal that the enhancement of CPL response stems from the energy transfer between chiral 2D perovskite structure and the defect states of chiral 1D perovskite structure, which can increase the imbalanced spin population in the defect levels. In addition, the CPL response can be further improved by combining the chiral perovskite hybrid films with achiral silver nanowires. TA spectra demonstrate that the localized plasma field enhances the carrier recombination rate without altering their spin polarization lifetime. This work provides guidance for the synthesis of chiral perovskite films with strong CPL response and further provides insight into the relevant mechanism of CPL enhancement.
{"title":"Synergistic Amplification of Circularly Polarized Luminescence in Chiral Perovskite Films via Energy Transfer and Localized Surface Plasmon Resonance","authors":"ting li,Yuan Wang,Laipeng Sun,Yu Wang,Jiaqi Zhao","doi":"10.1039/d6qi02193j","DOIUrl":"https://doi.org/10.1039/d6qi02193j","url":null,"abstract":"This work reports the in-situ synthesis of monolayer hybrid chiral perovskite films R/S-MBAPbBr₃@MBA₂PbBr₄ via temperature modulation, which combining the chiral one-dimensional (1D) R/S-MBAPbBr3 perovskite with two-dimensional (2D) non-luminescent (R/S-MBA)2PbBr4 perovskite. The as-synthesized chiral hybrid films exhibit stronger circularly polarized luminescence (CPL) response than that of the corresponding 1D chiral perovskite films. The circularly polarization-resolved transient absorption (TA) spectra reveal that the enhancement of CPL response stems from the energy transfer between chiral 2D perovskite structure and the defect states of chiral 1D perovskite structure, which can increase the imbalanced spin population in the defect levels. In addition, the CPL response can be further improved by combining the chiral perovskite hybrid films with achiral silver nanowires. TA spectra demonstrate that the localized plasma field enhances the carrier recombination rate without altering their spin polarization lifetime. This work provides guidance for the synthesis of chiral perovskite films with strong CPL response and further provides insight into the relevant mechanism of CPL enhancement.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010174","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}
Vasiliki I. Karagianni,Vasiliki Aggeli,Christos Dimitriou,Ioannis Vamvasakis,Yiannis Deligiannakis,Gerasimos S Armatas,Manolis J. Manos
Efficiently remediating divergent classes of water pollutants, specifically soft Lewis acid cations (Pb2+) and highly toxic oxyanions (Cr6+), remains a paramount challenge in environmental chemistry and engineering due to the completely opposing surface chemistries required for their respective immobilization. Herein, we present a new metal sulfide, namely T-AMS-1, (NH4+)1.6(TU)2.3Mn0.8Sn2.2S6•0.3(H2O) (TU=thiourea), an analog of the well-known KMS-1, synthesized via a solventfree, molten thiourea flux route. Unlike KMS-type materials that host alkali metal ions, T-AMS-1 forms a hybrid organicinorganic intercalated structure in which ammonium (NH4+) cations and neutral thiourea (TU) molecules fill the interlayer space. Under optimal batch conditions, T-AMS-1 exhibits rapid kinetics (≤5 min), a high maximum removal capacity (194 mg g -1 ), and selectivity for Pb2+ ions vs. common competitive ionic species. Similarly, for Cr6+ at pH=3, the material displays rapid kinetics (≤4 min), a high removal capacity (157 mg Cr6+ g -1 ), and exceptional selectivity for Cr6+, maintaining outstanding performance even in highly complex real water and seawater matrices. Notably, T-AMS-1, as calcium alginate beads employed as the stationary phase within a column containing sea sand, demonstrates a notable ability to capture both species from real samples under continuous flow and is reusable. This work establishes a solvent-free synthetic strategy for multi-functional, layered metal sulfides that act as versatile platforms for targeted environmental decontamination.
有效修复不同类型的水污染物，特别是软路易斯酸阳离子（Pb2+）和高毒性氧离子（Cr6+），仍然是环境化学和工程中的一个重大挑战，因为它们各自的固定所需的完全相反的表面化学。本文提出了一种新的金属硫化物，即T-AMS-1， （NH4+）1.6(TU)2.3Mn0.8Sn2.2S6•0.3(H2O) （TU=硫脲），它是众所周知的KMS-1的类似物，通过无溶剂的熔融硫脲助熔剂路线合成。与含有碱金属离子的kms型材料不同，T-AMS-1形成了一种杂化的有机无机插层结构，其中铵（NH4+）阳离子和中性硫脲（TU）分子填充了层间空间。在最佳批处理条件下，T-AMS-1表现出快速的动力学（≤5 min），高的最大去除率（194 mg g -1），以及对Pb2+离子的选择性。同样，对于pH=3的Cr6+，该材料表现出快速的动力学（≤4分钟），高去除能力（157 mg Cr6+ g -1），以及对Cr6+的卓越选择性，即使在高度复杂的真实水和海水基质中也保持出色的性能。值得注意的是，T-AMS-1作为海藻酸钙珠珠，在含有海砂的柱中作为固定相，在连续流动下从实际样品中捕获两种物质的能力显著，并且可重复使用。这项工作建立了一种无溶剂合成策略，用于多功能，层状金属硫化物，作为目标环境净化的多功能平台。
{"title":"An ammonium-thiourea-intercalated layered metal sulfide for efficient removal of Pb2+ and Cr6+ from aqueous solutions","authors":"Vasiliki I. Karagianni,Vasiliki Aggeli,Christos Dimitriou,Ioannis Vamvasakis,Yiannis Deligiannakis,Gerasimos S Armatas,Manolis J. Manos","doi":"10.1039/d6qi01326k","DOIUrl":"https://doi.org/10.1039/d6qi01326k","url":null,"abstract":"Efficiently remediating divergent classes of water pollutants, specifically soft Lewis acid cations (Pb2+) and highly toxic oxyanions (Cr6+), remains a paramount challenge in environmental chemistry and engineering due to the completely opposing surface chemistries required for their respective immobilization. Herein, we present a new metal sulfide, namely T-AMS-1, (NH4+)1.6(TU)2.3Mn0.8Sn2.2S6•0.3(H2O) (TU=thiourea), an analog of the well-known KMS-1, synthesized via a solventfree, molten thiourea flux route. Unlike KMS-type materials that host alkali metal ions, T-AMS-1 forms a hybrid organicinorganic intercalated structure in which ammonium (NH4+) cations and neutral thiourea (TU) molecules fill the interlayer space. Under optimal batch conditions, T-AMS-1 exhibits rapid kinetics (≤5 min), a high maximum removal capacity (194 mg g -1 ), and selectivity for Pb2+ ions vs. common competitive ionic species. Similarly, for Cr6+ at pH=3, the material displays rapid kinetics (≤4 min), a high removal capacity (157 mg Cr6+ g -1 ), and exceptional selectivity for Cr6+, maintaining outstanding performance even in highly complex real water and seawater matrices. Notably, T-AMS-1, as calcium alginate beads employed as the stationary phase within a column containing sea sand, demonstrates a notable ability to capture both species from real samples under continuous flow and is reusable. This work establishes a solvent-free synthetic strategy for multi-functional, layered metal sulfides that act as versatile platforms for targeted environmental decontamination.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"192 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149013598","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 multivariate approach allows to achieve a controlled degree of structural heterogeneity within metal-organic frameworks (MOFs), offering a powerful means to finely tune the properties of the framework at the molecular level. In this work, we apply this concept to the MIL-140A(Ce) framework to systematically introduce multiple fluorinated terephthalate linkers (Fx-BDC2-), enabling precise modulation of the cooperative CO2 adsorption behaviour through the control of the framework's degree of fluorination. By simultaneously incorporating and varying the nature and content of Fx-BDC2- co-linkers (x = 1, 2, 3) while maintaining F4-BDC2- as a fixed component, we synthesised a large library of mixed-linker F4:Fx_MIL-140A(Ce) materials, whose nature of solid solutions was demonstrated. Across the series, we found that cooperative CO2 adsorption occurs above a threshold degree of fluorination of the framework of 75%, independently of fluorine positional isomerism, as demonstrated by the series of o-, m-, and pF2-BDC2- co-linkers, and is not determined by the content of the perfluorinated linker. The implication of the fluorination threshold on CO2/CH4 selectivity was also assessed, revealing that the onset of CO2-induced cooperative adsorption above this threshold is associated with a dramatic increase in selectivity towards CO2. Since the degree of fluorination of single-linker MOFs is intrinsically fixed, the mixed-linker strategy represents an effective route to continuously tune the framework's composition, thereby enabling the establishment of a structural design principle to control the emergence of cooperative CO₂ adsorption.
{"title":"Switchable cooperative CO adsorption in multivariate fluorinated MIL-140A(Ce) metal-organic frameworks","authors":"Francesca Nerli,Dario Rocchi,Virginia Guiotto,Marco Lessi,Valentina Crocellà,Marco Taddei","doi":"10.1039/d6qi01836j","DOIUrl":"https://doi.org/10.1039/d6qi01836j","url":null,"abstract":"The multivariate approach allows to achieve a controlled degree of structural heterogeneity within metal-organic frameworks (MOFs), offering a powerful means to finely tune the properties of the framework at the molecular level. In this work, we apply this concept to the MIL-140A(Ce) framework to systematically introduce multiple fluorinated terephthalate linkers (Fx-BDC2-), enabling precise modulation of the cooperative CO2 adsorption behaviour through the control of the framework's degree of fluorination. By simultaneously incorporating and varying the nature and content of Fx-BDC2- co-linkers (x = 1, 2, 3) while maintaining F4-BDC2- as a fixed component, we synthesised a large library of mixed-linker F4:Fx_MIL-140A(Ce) materials, whose nature of solid solutions was demonstrated. Across the series, we found that cooperative CO2 adsorption occurs above a threshold degree of fluorination of the framework of 75%, independently of fluorine positional isomerism, as demonstrated by the series of o-, m-, and pF2-BDC2- co-linkers, and is not determined by the content of the perfluorinated linker. The implication of the fluorination threshold on CO2/CH4 selectivity was also assessed, revealing that the onset of CO2-induced cooperative adsorption above this threshold is associated with a dramatic increase in selectivity towards CO2. Since the degree of fluorination of single-linker MOFs is intrinsically fixed, the mixed-linker strategy represents an effective route to continuously tune the framework's composition, thereby enabling the establishment of a structural design principle to control the emergence of cooperative CO₂ adsorption.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"293 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149013602","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}
Ying Chen,Qingyi Feng,Yeqing Yang,Xiaocong Shen,Pingkang Li,Mingyue Yang,Xue Li,Xiang-Long Huang,Yun-Xiao Wang
Despite high theoretical energy density, low cost, and abundant natural resources, the development of emerging room-temperature sodium–sulfur (Na–S) batteries is still confronting many challenges. These key issues include the insulating nature of solid sulfur, the shuttle effect of polysulfides, sluggish reaction kinetics, and sodium dendrite growth. Doped carbon materials hold multiple advantages including tunable electronic structures, abundant polar sites, high specific surface areas, and outstanding electrocatalytic activity, which make them promising for dendrite-free sodium anodes and electrochemically stable sulfur cathodes. This review systematically deciphers the research development of doped carbon materials for Na–S batteries. The electrochemical principles and core challenges of Na–S batteries are discussed first. The key roles of doping sites in Na–S electrochemistry and various typical doping configurations are then elaborated. Next, we place emphasis on the practical applications of doped carbons in Na–S batteries, including cathode hosts, separators/interlayers, and sodium anode skeletons. Finally, the challenges and future directions are summarized, aiming to guide advanced material designs for Na–S batteries.
{"title":"Doped carbons for room-temperature Na–S batteries: a comprehensive review","authors":"Ying Chen,Qingyi Feng,Yeqing Yang,Xiaocong Shen,Pingkang Li,Mingyue Yang,Xue Li,Xiang-Long Huang,Yun-Xiao Wang","doi":"10.1039/d6qi01714b","DOIUrl":"https://doi.org/10.1039/d6qi01714b","url":null,"abstract":"Despite high theoretical energy density, low cost, and abundant natural resources, the development of emerging room-temperature sodium–sulfur (Na–S) batteries is still confronting many challenges. These key issues include the insulating nature of solid sulfur, the shuttle effect of polysulfides, sluggish reaction kinetics, and sodium dendrite growth. Doped carbon materials hold multiple advantages including tunable electronic structures, abundant polar sites, high specific surface areas, and outstanding electrocatalytic activity, which make them promising for dendrite-free sodium anodes and electrochemically stable sulfur cathodes. This review systematically deciphers the research development of doped carbon materials for Na–S batteries. The electrochemical principles and core challenges of Na–S batteries are discussed first. The key roles of doping sites in Na–S electrochemistry and various typical doping configurations are then elaborated. Next, we place emphasis on the practical applications of doped carbons in Na–S batteries, including cathode hosts, separators/interlayers, and sodium anode skeletons. Finally, the challenges and future directions are summarized, aiming to guide advanced material designs for Na–S batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010175","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}
Ferroelastic crystals possess the intrinsic ability to undergo reversible switching of spontaneous strain under external mechanical stimuli, holding tremendous potential for sensing, data storage, and flexible wearable electronics. Owing to their exceptional flexibility and biocompatibility, pure organic ferroelastics have become attractive candidate materials for ferroelastic applications. However, the fabrication of organic ferroelastics via the strategy of pH-regulated protonation remains unreported to date. Herein, we tune the protonation degree of DABCO through pH adjustment, successfully synthesizing monoprotonated DABCO-TFMS·H2O (DABCO = triethylenediamine, TFMS = trifluoromethanesulfonate) and diprotonated DABCO-(TFMS)2. The former undergoes low-temperature phase transitions without ferroelastic behaviour, while the latter exhibits a pronounced 4/mmmFmmm-type ferroelastic phase transition at 403 K, with reversible rearrangement of ferroelastic domains upon application of external mechanical stress. This work expands the ferroelastic material library, demonstrates that pH-regulated protonation is a robust strategy for achieving controllable phase transitions, and opens a new research paradigm for the development of next-generation flexible electronics and switchable devices.
{"title":"Flexible organic ferroelastic crystals solution pH engineering","authors":"Zeng-Jie Xiao,Ya-Ting Zou,Peng-Cheng Zhuge,Cha-Hui Du,Ji Liu,Lei Pan,Hao-Fei Ni,Lou-Kai Ye,Ya-Yuan Luo,Yi Zhang,Zhi-Xu Zhang,Da-Wei Fu","doi":"10.1039/d6qi01533f","DOIUrl":"https://doi.org/10.1039/d6qi01533f","url":null,"abstract":"Ferroelastic crystals possess the intrinsic ability to undergo reversible switching of spontaneous strain under external mechanical stimuli, holding tremendous potential for sensing, data storage, and flexible wearable electronics. Owing to their exceptional flexibility and biocompatibility, pure organic ferroelastics have become attractive candidate materials for ferroelastic applications. However, the fabrication of organic ferroelastics via the strategy of pH-regulated protonation remains unreported to date. Herein, we tune the protonation degree of DABCO through pH adjustment, successfully synthesizing monoprotonated DABCO-TFMS·H2O (DABCO = triethylenediamine, TFMS = trifluoromethanesulfonate) and diprotonated DABCO-(TFMS)2. The former undergoes low-temperature phase transitions without ferroelastic behaviour, while the latter exhibits a pronounced 4/mmmFmmm-type ferroelastic phase transition at 403 K, with reversible rearrangement of ferroelastic domains upon application of external mechanical stress. This work expands the ferroelastic material library, demonstrates that pH-regulated protonation is a robust strategy for achieving controllable phase transitions, and opens a new research paradigm for the development of next-generation flexible electronics and switchable devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010176","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}
Crystallization control is of fundamental importance for the preparation of nanomaterials with multi-scale morphologies and tailored functionalities. This work presents an interface-confined non-classical crystallization pathway for calcite, enabled by insoluble g-C3N4 that concurrently serves as a C/N donor, a surface-directing functional matrix, and a physical nanoscale confining scaffold. The resulting nitrogen-incorporated hybrid products exhibit a particle-attachment assembly superstructure with abundant interfacial porosity. A comparative control with soluble urea, which follows a classical ion-mediated crystallization pathway under identical hydrothermal conditions, confirms the critical role of g-C3N4 in directing particle-mediated growth. X-ray absorption near-edge spectroscopy (XANES) analyses reveal that g-C3N4-directed oriented attachment is effective in promoting heteroatom incorporation and exposing active sites, owing to the intrinsic coordination structure that enables in situ nitrogen incorporation within primary particles. Moreover, the resulting olive-shaped hybrid superstructure facilitates dopant diffusion and pore formation during subsequent decarbonation. The derived CaO exhibits a non-monotonic CO2 uptake behavior, peaking at 0.701 g-CO2/g-CaO during the second cycle while sustaining a capacity retention of 70.2% over 30 cycles. Density functional theory (DFT) analysis verified that nitrogen-induced oxygen defects can induce pronounced charge redistribution at the CO2/CaO interface and strengthen the adsorbate-surface interaction. These findings demonstrate a non-classical crystallization pathway for constructing heteroatom-modified Ca-based materials, with potential for application in calcium looping for CO2 capture.
{"title":"Interfacial confinement-driven non-classical crystallization: activated mesocrystals for calcium-based CO 2 capture","authors":"Mingchun Li,Cunliang Shen,Xin Yu,Xinxin Tian,Laishi Li,Yusheng Wu","doi":"10.1039/d6qi01535b","DOIUrl":"https://doi.org/10.1039/d6qi01535b","url":null,"abstract":"Crystallization control is of fundamental importance for the preparation of nanomaterials with multi-scale morphologies and tailored functionalities. This work presents an interface-confined non-classical crystallization pathway for calcite, enabled by insoluble g-C3N4 that concurrently serves as a C/N donor, a surface-directing functional matrix, and a physical nanoscale confining scaffold. The resulting nitrogen-incorporated hybrid products exhibit a particle-attachment assembly superstructure with abundant interfacial porosity. A comparative control with soluble urea, which follows a classical ion-mediated crystallization pathway under identical hydrothermal conditions, confirms the critical role of g-C3N4 in directing particle-mediated growth. X-ray absorption near-edge spectroscopy (XANES) analyses reveal that g-C3N4-directed oriented attachment is effective in promoting heteroatom incorporation and exposing active sites, owing to the intrinsic coordination structure that enables in situ nitrogen incorporation within primary particles. Moreover, the resulting olive-shaped hybrid superstructure facilitates dopant diffusion and pore formation during subsequent decarbonation. The derived CaO exhibits a non-monotonic CO2 uptake behavior, peaking at 0.701 g-CO2/g-CaO during the second cycle while sustaining a capacity retention of 70.2% over 30 cycles. Density functional theory (DFT) analysis verified that nitrogen-induced oxygen defects can induce pronounced charge redistribution at the CO2/CaO interface and strengthen the adsorbate-surface interaction. These findings demonstrate a non-classical crystallization pathway for constructing heteroatom-modified Ca-based materials, with potential for application in calcium looping for CO2 capture.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"82 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010177","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}
Rational regulation of interfacial electronic interactions and built-in electric fields in heterojunction photocatalysts is crucial for promoting charge separation while preserving strong redox capability in solar driven catalytic processes. A bifunctional S-scheme van der Waals heterojunction composed of CuInS2 and hollow porous tubular carbon nitride (CIS-TCNx) was constructed, achieving optimized band alignment and enhanced visible-light absorption. Density functional theory calculations showed that constructed S-scheme van der Waals heterojunction exhibits intense electronic interaction across the CIS-TCN boundary. In addition, the strengthened interfacial electric field (IEF) delivers sufficient driving force to guide ordered electron movement, thereby further promoting charge separation. The optimized CIS-TCN20 sample achieves a H2 production activity of 700.15 μmol g -1 h -1 in the absence of Pt cocatalyst, nearly 14-fold greater than bare CIS. With the addition of a Pt cocatalyst, H2 production rate of CIS-TCN20 could be reached 6214.14 μmol g -1 h -1 . Meanwhile, the CIS-TCN20/PMS/Vis system removes 93.3% of tetracycline (TC) and displays outstanding oxidative capability. Quenching tests reveal that singlet oxygen ( 1 O2) and sulfate radicals (SO4 •-) serve as the main reactive species. LC-MS analysis was conducted to elucidate the transformation pathways and intermediate species, while complementary toxicity evaluation verified the attenuation of ecological hazards. In addition, economic analysis indicates the practical feasibility of the CIS-TCN20 system.This study presents a viable approach for designing high-performance S-scheme heterostructures for simultaneous H2 generation and antibiotic removal under visible-light irradiation.
在太阳能驱动的催化过程中，合理调节异质结光催化剂的界面电子相互作用和内置电场对于促进电荷分离同时保持强氧化还原能力至关重要。构建了由CuInS2和中空多孔氮化碳（CIS-TCNx）组成的双功能S-scheme van der Waals异质结，实现了优化的波段排列和增强的可见光吸收。密度泛函理论计算表明，构建的s型范德华异质结在CIS-TCN边界上表现出强烈的电子相互作用。此外，增强的界面电场（IEF）提供了足够的驱动力来引导有序的电子运动，从而进一步促进电荷分离。优化后的CIS- tcn20样品在不含Pt助催化剂的情况下，产氢活性为700.15 μmol g -1 h -1，比裸CIS高近14倍。添加Pt助催化剂后，CIS-TCN20的H2产率可达6214.14 μmol g -1 h -1。CIS-TCN20/PMS/Vis体系对四环素（TC）的去除率为93.3%，具有良好的氧化性能。淬火试验表明，单线态氧（1o2）和硫酸盐自由基（SO4•-）是主要的活性物质。LC-MS分析阐明了转化途径和中间物种，互补毒性评价验证了生态危害的衰减。此外，经济分析表明了CIS-TCN20系统的实际可行性。本研究提出了一种在可见光照射下同时生成H2和去除抗生素的高性能s方案异质结构设计的可行方法。
{"title":"Bifunctional S-Scheme CuInS 2 /Hollow Porous Tubular Carbon Nitride van der Waals Heterojunction with Reinforced Interfacial Electric Field for Photocatalytic Hydrogen Evolution and Antibiotic Degradation","authors":"Yihan Tang,Weiyan Su,Mengjiao Yu,Guangyu Wu,Weinan Xing,Yudong Huang","doi":"10.1039/d6qi01706a","DOIUrl":"https://doi.org/10.1039/d6qi01706a","url":null,"abstract":"Rational regulation of interfacial electronic interactions and built-in electric fields in heterojunction photocatalysts is crucial for promoting charge separation while preserving strong redox capability in solar driven catalytic processes. A bifunctional S-scheme van der Waals heterojunction composed of CuInS2 and hollow porous tubular carbon nitride (CIS-TCNx) was constructed, achieving optimized band alignment and enhanced visible-light absorption. Density functional theory calculations showed that constructed S-scheme van der Waals heterojunction exhibits intense electronic interaction across the CIS-TCN boundary. In addition, the strengthened interfacial electric field (IEF) delivers sufficient driving force to guide ordered electron movement, thereby further promoting charge separation. The optimized CIS-TCN20 sample achieves a H2 production activity of 700.15 μmol g -1 h -1 in the absence of Pt cocatalyst, nearly 14-fold greater than bare CIS. With the addition of a Pt cocatalyst, H2 production rate of CIS-TCN20 could be reached 6214.14 μmol g -1 h -1 . Meanwhile, the CIS-TCN20/PMS/Vis system removes 93.3% of tetracycline (TC) and displays outstanding oxidative capability. Quenching tests reveal that singlet oxygen ( 1 O2) and sulfate radicals (SO4 •-) serve as the main reactive species. LC-MS analysis was conducted to elucidate the transformation pathways and intermediate species, while complementary toxicity evaluation verified the attenuation of ecological hazards. In addition, economic analysis indicates the practical feasibility of the CIS-TCN20 system.This study presents a viable approach for designing high-performance S-scheme heterostructures for simultaneous H2 generation and antibiotic removal under visible-light irradiation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149003571","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 high toxicity of mustard gas and its severe threat to public safety have spurred efforts to develop catalysts for rapid degradation. Layered vanadium oxides are promising potential catalysts owing to their abundant and tunable active sites. Herein, via intercalation of [Ni(Hppz)3]2+ complexes (Hppz = 2-(1H-pyrazol-3-yl)pyridine), we synthesised a layered mixed-valence vanadium oxide, Na[Ni(C8N3H7)]3(V3IVV5VO20) (V8O20-Ni), featuring an interlayer spacing of 11.5 Å. The large interlayer spacing and wavy layer structures maximise active sites exposure, while mixed-valence V5+/V4+ centres facilitate efficient charge transfer during oxidation. To verify structure-activity relationships, [Ni(C8N3H7)](V2O6) (V2O6-Ni) and [Ni(C8N3H7)](V6O16) (V6O16-Ni) were synthesized as comparisons referenec. In the catalytic oxidation of the chemical warfare agent simulant 2‑chloroethyl ethyl sulfide (CEES), V8O20-Ni exhibited exceptional degradation performance with a short half‑life (t1/2 = 0.52 min), delivering a record turnover frequency (TOF) of 207 min-1. The catalyst also displays broad substrate compatibility and robust stability, maintaining superior activity after six cycles. This work establishes an interlayer-embedding strategy for constructing high-performance layered vanadium oxide catalysts applicable to selective oxidation reactions.
{"title":"Layered Vanadium Oxides with Expanded Interlayer Spacing for Rapid Degradation of Mustard Gas Simulants","authors":"Jianbo Yang,Yinhua Zhu,Jiayu Chen,Jinyun Wu,Jun Xing Wang,Hua Mei,Yan Xu","doi":"10.1039/d6qi01475e","DOIUrl":"https://doi.org/10.1039/d6qi01475e","url":null,"abstract":"The high toxicity of mustard gas and its severe threat to public safety have spurred efforts to develop catalysts for rapid degradation. Layered vanadium oxides are promising potential catalysts owing to their abundant and tunable active sites. Herein, via intercalation of [Ni(Hppz)3]2+ complexes (Hppz = 2-(1H-pyrazol-3-yl)pyridine), we synthesised a layered mixed-valence vanadium oxide, Na[Ni(C8N3H7)]3(V3IVV5VO20) (V8O20-Ni), featuring an interlayer spacing of 11.5 Å. The large interlayer spacing and wavy layer structures maximise active sites exposure, while mixed-valence V5+/V4+ centres facilitate efficient charge transfer during oxidation. To verify structure-activity relationships, [Ni(C8N3H7)](V2O6) (V2O6-Ni) and [Ni(C8N3H7)](V6O16) (V6O16-Ni) were synthesized as comparisons referenec. In the catalytic oxidation of the chemical warfare agent simulant 2‑chloroethyl ethyl sulfide (CEES), V8O20-Ni exhibited exceptional degradation performance with a short half‑life (t1/2 = 0.52 min), delivering a record turnover frequency (TOF) of 207 min-1. The catalyst also displays broad substrate compatibility and robust stability, maintaining superior activity after six cycles. This work establishes an interlayer-embedding strategy for constructing high-performance layered vanadium oxide catalysts applicable to selective oxidation reactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"38 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993840","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}
Álvaro Vílchez,Rosario M. Pérez Colodrero,David Marrero-López,Inés R. Salcedo,Aurelia Visa,Pascual Olivera Pastor,Aurelio Cabeza Díaz
A series of biphasic cobalt phosphide-based HER electrocatalysts were obtained by pyrolyzing cobalt 2-carboxyethyl(phenyl)phosphinate precursors in 5% H2–Ar. Among them, CoL2@750, composed of o-CoP (78 wt.%) and o-Co2P (22 wt.%), with an average particle size of ~19 nm, exhibited remarkable hydrogen evolution reaction (HER) activity under acidic, neutral, and alkaline conditions. Supported on carbon fibre paper (CFP), at a loading of 4 mg·cm-2, this catalyst (CoL2@750/CFP-4) achieved overpotentials of 78, 98, and 260 mV at 10 mA·cm-2, respectively, with enhanced kinetics and stability relative to other catalyst preparations. When coupled with a RuO2 anode in an alkaline water-splitting device, a cell voltage of ~1.54 V at 10 mA·cm-2 was obtained and operated stably from ~50 up to at least 100 h. Additional insights into key properties of the assembled CoL2@750/CFP-4 electrode, including particle size distribution and catalyst leaching, were obtained through computed X-ray microtomography (µ-CT) analysis.
{"title":"Tailoring Cobalt Phosphide HER Electrocatalysts from Cobalt 2-Carboxyethyl(phenyl)phosphinate Precursors","authors":"Álvaro Vílchez,Rosario M. Pérez Colodrero,David Marrero-López,Inés R. Salcedo,Aurelia Visa,Pascual Olivera Pastor,Aurelio Cabeza Díaz","doi":"10.1039/d6qi01333c","DOIUrl":"https://doi.org/10.1039/d6qi01333c","url":null,"abstract":"A series of biphasic cobalt phosphide-based HER electrocatalysts were obtained by pyrolyzing cobalt 2-carboxyethyl(phenyl)phosphinate precursors in 5% H2–Ar. Among them, CoL2@750, composed of o-CoP (78 wt.%) and o-Co2P (22 wt.%), with an average particle size of ~19 nm, exhibited remarkable hydrogen evolution reaction (HER) activity under acidic, neutral, and alkaline conditions. Supported on carbon fibre paper (CFP), at a loading of 4 mg·cm-2, this catalyst (CoL2@750/CFP-4) achieved overpotentials of 78, 98, and 260 mV at 10 mA·cm-2, respectively, with enhanced kinetics and stability relative to other catalyst preparations. When coupled with a RuO2 anode in an alkaline water-splitting device, a cell voltage of ~1.54 V at 10 mA·cm-2 was obtained and operated stably from ~50 up to at least 100 h. Additional insights into key properties of the assembled CoL2@750/CFP-4 electrode, including particle size distribution and catalyst leaching, were obtained through computed X-ray microtomography (µ-CT) analysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"59 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980720","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}
Zhi-Wei Chen,Xiao Chen,Xin-Rui Sun,Fang-Li Chen,Xin-Yue Wang,Hao Wu,Cheng-Yang Yue,Xiao-Wu Lei
Low-dimensional organic-inorganic cuprous halides have gained significant interest with wide potential applications in solidstate lighting, anti-counterfeiting, luminescence sensing, scintillation, etc., due to diverse coordination geometries and excellent optoelectronic properties. Nevertheless, controllable structural regulation and integrated multifunction in a structural platform remains a great challenge. Herein, two pairs of Cu(I) halide family of (MOPPZ)2Cu2X6 and (MOPPZ)2Cu4X8 (MOPPZ = 1-(2-Methoxyphenyl)piperazine, X = Br, I) were successfully synthesized in the same halide system through elaborate crystal engineering strategy. The different anionic skeletons enable these cuprous halides to display multicolor broadband light emissions arising from self-trapped excitons (STEs). Systematic studies reveal that (MOPPZ)2Cu4X8 show lower emission energies and higher luminescence efficiency than (MOPPZ)2Cu2X6, owing to stronger Cu•••Cu interactions and electron-phonon coupling, respectively. Interestingly, these halides show intriguing reversible stimulus-response phase transitions with dynamic photoluminescence (PL) switching, endowing them with significant potential for high-level anticounterfeiting and information encryption-decryption. In addition, (MOPPZ)2Cu4I8 exhibits excellent radioluminescence performance with a high light yield of 34400 photons MeV -1 , low detection limit of 470 nGy s -1 , which is attributed to the synergistic effect of high photoluminescence quantum yield (PLQY = 95.5%) and heavy atom effect. A high spatial resolution of 18 lp mm -1 in X-ray imaging was achieved on flexible (MOPPZ)2Cu4I8 screen, demonstrating significant potential in practical X-ray imaging application. This work realizes the integrated reversible stimuli-responsive PL switching and high-efficiency Xray scintillation in 0D Cu(I)-based metal halide, offering new insights for development of multifunctional optoelectronic devices.
低维有机-无机卤化亚铜由于其多样的配位几何结构和优异的光电性能，在固态照明、防伪、发光传感、闪烁等方面具有广泛的应用前景。然而，结构平台的可控结构调节和综合多功能仍然是一个巨大的挑战。本文通过精细的晶体工程策略，在同一卤化物体系中成功合成了（MOPPZ）2Cu2X6和（MOPPZ）2Cu4X8 （MOPPZ = 1-（2-甲氧基苯基）哌嗪，X = Br， I）两对Cu(I)卤化物族。不同的阴离子骨架使这些卤化亚铜能够显示由自捕获激子（STEs）产生的多色宽带光发射。系统研究表明，与（MOPPZ）2Cu2X6相比，（MOPPZ）2Cu4X8具有更低的发射能量和更高的发光效率，这是由于Cu••••Cu相互作用和电子-声子耦合更强。有趣的是，这些卤化物具有动态光致发光（PL）开关，显示出有趣的可逆刺激-响应相变，使它们具有高水平防伪和信息加密-解密的巨大潜力。此外，（MOPPZ）2Cu4I8表现出优异的辐射发光性能，其光产率高达34400个光子MeV -1，检测限低至470 nGy s -1，这是由于高光致量子产率（PLQY = 95.5%）和重原子效应的协同作用。在柔性（MOPPZ）2Cu4I8屏幕上实现了18 lp mm -1的高空间分辨率x射线成像，显示出在实际x射线成像应用中的巨大潜力。本工作在0D Cu(I)基金属卤化物中实现了可逆刺激响应PL开关和高效x射线闪烁的集成，为多功能光电器件的发展提供了新的见解。
{"title":"Reversible Stimulus-Responsive Photoluminescence Switching in Organic Cuprous Halide Scintillators for Multifunctional Applications","authors":"Zhi-Wei Chen,Xiao Chen,Xin-Rui Sun,Fang-Li Chen,Xin-Yue Wang,Hao Wu,Cheng-Yang Yue,Xiao-Wu Lei","doi":"10.1039/d6qi01685e","DOIUrl":"https://doi.org/10.1039/d6qi01685e","url":null,"abstract":"Low-dimensional organic-inorganic cuprous halides have gained significant interest with wide potential applications in solidstate lighting, anti-counterfeiting, luminescence sensing, scintillation, etc., due to diverse coordination geometries and excellent optoelectronic properties. Nevertheless, controllable structural regulation and integrated multifunction in a structural platform remains a great challenge. Herein, two pairs of Cu(I) halide family of (MOPPZ)2Cu2X6 and (MOPPZ)2Cu4X8 (MOPPZ = 1-(2-Methoxyphenyl)piperazine, X = Br, I) were successfully synthesized in the same halide system through elaborate crystal engineering strategy. The different anionic skeletons enable these cuprous halides to display multicolor broadband light emissions arising from self-trapped excitons (STEs). Systematic studies reveal that (MOPPZ)2Cu4X8 show lower emission energies and higher luminescence efficiency than (MOPPZ)2Cu2X6, owing to stronger Cu•••Cu interactions and electron-phonon coupling, respectively. Interestingly, these halides show intriguing reversible stimulus-response phase transitions with dynamic photoluminescence (PL) switching, endowing them with significant potential for high-level anticounterfeiting and information encryption-decryption. In addition, (MOPPZ)2Cu4I8 exhibits excellent radioluminescence performance with a high light yield of 34400 photons MeV -1 , low detection limit of 470 nGy s -1 , which is attributed to the synergistic effect of high photoluminescence quantum yield (PLQY = 95.5%) and heavy atom effect. A high spatial resolution of 18 lp mm -1 in X-ray imaging was achieved on flexible (MOPPZ)2Cu4I8 screen, demonstrating significant potential in practical X-ray imaging application. This work realizes the integrated reversible stimuli-responsive PL switching and high-efficiency Xray scintillation in 0D Cu(I)-based metal halide, offering new insights for development of multifunctional optoelectronic devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"87 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980717","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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