Su Zhou, Linshuai Li, Gaoqing Chen, Jingtao Zhao, Lei Lei
Double-perovskite materials with diverse elemental compositions have been developed as high-performance phosphors and scintillators. However, the low doping concentration of activator ions in the host matrix limits the flexible tuning of luminescence properties. In this work, we propose a series of gadolinium, terbium, and europium alloyed double-perovskite lanthanide chlorides (DPLCs) to achieve color-tunable photoluminescence (PL) as well as thermally and radiationally stable X-ray excited optical luminescence (XEOL). The Cs2NaGdCl6 host allows up to 100% and 60% doping concentrations of Tb3+ ions for PL and XEOL, respectively, without concentration quenching. The designed Cs2NaTbCl6 exhibits a high photoluminescence quantum yield of 73.5%. Optical encryption was achieved using Cs2NaTb0.95Eu0.05Cl6, which shows excitation-wavelength-dependent dynamic emission colors. Benefiting from efficient energy transfer from Gd3+ to Tb3+ in the XEOL process, Cs2NaGd0.4Tb0.6Cl6 achieves a high light yield of 27 000 ph MeV−1. With the incorporation of Eu3+, Cs2NaTbGd0.35Tb0.6Eu0.05Cl6 exhibits excellent thermal and radiation stability for scintillation. Moreover, DPLCs embedded in polymethyl methacrylate (PMMA) scintillator films enable high-resolution X-ray imaging with a spatial resolution of 16.6 lp mm−1. This work provides a novel strategy for designing DPLCs with state-of-the-art optical applications.
{"title":"Gd/Tb/Eu alloyed double-perovskite lanthanide halides for color tunable photoluminescence and robust scintillation performance","authors":"Su Zhou, Linshuai Li, Gaoqing Chen, Jingtao Zhao, Lei Lei","doi":"10.1039/d5qi02185e","DOIUrl":"https://doi.org/10.1039/d5qi02185e","url":null,"abstract":"Double-perovskite materials with diverse elemental compositions have been developed as high-performance phosphors and scintillators. However, the low doping concentration of activator ions in the host matrix limits the flexible tuning of luminescence properties. In this work, we propose a series of gadolinium, terbium, and europium alloyed double-perovskite lanthanide chlorides (DPLCs) to achieve color-tunable photoluminescence (PL) as well as thermally and radiationally stable X-ray excited optical luminescence (XEOL). The Cs<small><sub>2</sub></small>NaGdCl<small><sub>6</sub></small> host allows up to 100% and 60% doping concentrations of Tb<small><sup>3+</sup></small> ions for PL and XEOL, respectively, without concentration quenching. The designed Cs<small><sub>2</sub></small>NaTbCl<small><sub>6</sub></small> exhibits a high photoluminescence quantum yield of 73.5%. Optical encryption was achieved using Cs<small><sub>2</sub></small>NaTb<small><sub>0.95</sub></small>Eu<small><sub>0.05</sub></small>Cl<small><sub>6</sub></small>, which shows excitation-wavelength-dependent dynamic emission colors. Benefiting from efficient energy transfer from Gd<small><sup>3+</sup></small> to Tb<small><sup>3+</sup></small> in the XEOL process, Cs<small><sub>2</sub></small>NaGd<small><sub>0.4</sub></small>Tb<small><sub>0.6</sub></small>Cl<small><sub>6</sub></small> achieves a high light yield of 27 000 ph MeV<small><sup>−1</sup></small>. With the incorporation of Eu<small><sup>3+</sup></small>, Cs<small><sub>2</sub></small>NaTbGd<small><sub>0.35</sub></small>Tb<small><sub>0.6</sub></small>Eu<small><sub>0.05</sub></small>Cl<small><sub>6</sub></small> exhibits excellent thermal and radiation stability for scintillation. Moreover, DPLCs embedded in polymethyl methacrylate (PMMA) scintillator films enable high-resolution X-ray imaging with a spatial resolution of 16.6 lp mm<small><sup>−1</sup></small>. This work provides a novel strategy for designing DPLCs with state-of-the-art optical applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903210","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}
Subhankar Sutradhar, Sachidulal Biswas, Sabyasachi Mahapatra, Achintesh Narayan Biswas, Tapan Kanti Paine
Three iron(II)-triflate complexes supported by trinucleating (L1), dinucleating (L2) and mononucleating tris(2-pyridylmethyl)amine (TPA) nitrogen donor ligand framework, [(L1)Fe3(OTf)6] (1), [(L2)Fe2(OTf)4] (2), and [(TPA)Fe(OTf)2] (3) were synthesized and evaluated as catalysts for water oxidation. All complexes efficiently catalyse the water-oxidation reaction at near-neutral pH in borate buffer, using Oxone (KHSO₅) as the sacrificial oxidant. Among them, complex 1 exhibits the highest catalytic activity, with a turnover frequency (TOF) of 2.1 × 10-4 h-1, underscoring the role of nuclearity in dictating the kinetics of the water-oxidation reaction. Complex 1 represents one of the active homogeneous iron-based catalysts for chemical water oxidation reported to date. An iron(V)-oxo oxidant is implicated in the O-O bond formation step, with borate buffer facilitating cooperative interactions between the iron centres. Oxone mediates the iron-oxo generation, and the subsequent nucleophilic attack of water at the iron-oxo unit leads to dioxygen formation. The isolation of a borate-bridged diiron(III) complex from 2 offers insights into the nature of the active species responsible for initiating the catalytic cycle. It also highlights how multiple metal centres, engaged in cooperative interactions, enhance catalytic efficiency and improve the structural robustness of flexible molecular systems in iron-based water-oxidation catalysis.
{"title":"Chemical Water Oxidation by Nonheme Iron Catalysts Supported by Di-and Trinucleating N4 Donor Ligands: Unveiling the Role of Coordinating Buffer in Directing Cooperative Catalysis","authors":"Subhankar Sutradhar, Sachidulal Biswas, Sabyasachi Mahapatra, Achintesh Narayan Biswas, Tapan Kanti Paine","doi":"10.1039/d5qi01852h","DOIUrl":"https://doi.org/10.1039/d5qi01852h","url":null,"abstract":"Three iron(II)-triflate complexes supported by trinucleating (L1), dinucleating (L2) and mononucleating tris(2-pyridylmethyl)amine (TPA) nitrogen donor ligand framework, [(L1)Fe3(OTf)6] (1), [(L2)Fe2(OTf)4] (2), and [(TPA)Fe(OTf)2] (3) were synthesized and evaluated as catalysts for water oxidation. All complexes efficiently catalyse the water-oxidation reaction at near-neutral pH in borate buffer, using Oxone (KHSO₅) as the sacrificial oxidant. Among them, complex 1 exhibits the highest catalytic activity, with a turnover frequency (TOF) of 2.1 × 10-4 h-1, underscoring the role of nuclearity in dictating the kinetics of the water-oxidation reaction. Complex 1 represents one of the active homogeneous iron-based catalysts for chemical water oxidation reported to date. An iron(V)-oxo oxidant is implicated in the O-O bond formation step, with borate buffer facilitating cooperative interactions between the iron centres. Oxone mediates the iron-oxo generation, and the subsequent nucleophilic attack of water at the iron-oxo unit leads to dioxygen formation. The isolation of a borate-bridged diiron(III) complex from 2 offers insights into the nature of the active species responsible for initiating the catalytic cycle. It also highlights how multiple metal centres, engaged in cooperative interactions, enhance catalytic efficiency and improve the structural robustness of flexible molecular systems in iron-based water-oxidation catalysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895236","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}
Ahram Yoo, Sujeong Lee, Sojin Oh, Songhee Kim, Moonhyun Oh
Developing cost-effective and durable alternatives to platinum (Pt)-based oxygen reduction reaction (ORR) catalysts is essential for advancing energy conversion and storage technologies. Carbon-based materials are promising candidates, and their ORR activity can be further enhanced through heteroatom doping (e.g., nitrogen, phosphorus) and increased porosity to improve mass transport. Here, we present an efficient method for synthesizing highly active carbon-based ORR catalysts via salt-protected carbonization of a metal–organic framework (MOF). In this approach, a MOF/urea composite encapsulated in NaCl (MOF-5/urea@NaCl) undergoes one-step pyrolysis. The salt shell serves two critical functions: (1) preventing premature loss of nitrogen sources, enabling effective nitrogen incorporation, and (2) trapping gas molecules generated during the pyrolysis, which act as templates to enhance the porosity of the final product. The resulting porous carbon exhibits substantial nitrogen doping, a large surface area, and high pore volume—features that collectively yield excellent ORR performance. The catalyst shows markedly enhanced activity compared to its counterpart prepared without salt protection and even surpasses commercial Pt/C in electrochemical activity, stability, and methanol tolerance.
{"title":"Salt-protected carbonization of a metal–organic framework for enhanced nitrogen doping and high porosity leading to efficient performance in oxygen reduction reaction","authors":"Ahram Yoo, Sujeong Lee, Sojin Oh, Songhee Kim, Moonhyun Oh","doi":"10.1039/d5qi02283e","DOIUrl":"https://doi.org/10.1039/d5qi02283e","url":null,"abstract":"Developing cost-effective and durable alternatives to platinum (Pt)-based oxygen reduction reaction (ORR) catalysts is essential for advancing energy conversion and storage technologies. Carbon-based materials are promising candidates, and their ORR activity can be further enhanced through heteroatom doping (e.g., nitrogen, phosphorus) and increased porosity to improve mass transport. Here, we present an efficient method for synthesizing highly active carbon-based ORR catalysts via salt-protected carbonization of a metal–organic framework (MOF). In this approach, a MOF/urea composite encapsulated in NaCl (MOF-5/urea@NaCl) undergoes one-step pyrolysis. The salt shell serves two critical functions: (1) preventing premature loss of nitrogen sources, enabling effective nitrogen incorporation, and (2) trapping gas molecules generated during the pyrolysis, which act as templates to enhance the porosity of the final product. The resulting porous carbon exhibits substantial nitrogen doping, a large surface area, and high pore volume—features that collectively yield excellent ORR performance. The catalyst shows markedly enhanced activity compared to its counterpart prepared without salt protection and even surpasses commercial Pt/C in electrochemical activity, stability, and methanol tolerance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"259 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895731","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}
Reactive transition metal fragments can incorporate elemental chalcogens to form polynuclear chalcogen-rich clusters, which may contain either mono-, di- or polychalcogenide ligands or several such ligands in combined form. In an effort to explore the coordination chemistry of chalcogenide ligands with titanium, we have carried out the reaction of [Cp*TiCl3] with various chalcogen sources, such as selenium, sulfur, and CS2. The in-situ reaction of [Cp*TiCl3] with [LiBH4], followed by treatment with selenium powder at elevated temperature yielded unique pentametallic [{(Cp*Ti)4Ti}(μ3-η1:η2-Se2)4(μ3-η2:η2-Se2)2(μ-O)2] (1), tetrametallic [(Cp*Ti)4(μ-Se)(μ3-Se)2(μ3-η2:η2-Se2)2(μ4-O)] (2), and trimetallic [(Cp*Ti)2(Cp*TiCl)(µ-O)3(µ-1,3-Se3)] (3) titanium-chalcogenide clusters. Cluster 1 is a rare example of a dodecahedron core {TiSe8} featuring two different coordination modes of diselenide ligands; μ3-η1:η2-Se2 and μ3-η1:η2-Se2. While cluster 2 has a Ti4-tetrahedral core with a μ4-oxo group located inside the core. Interestingly, cluster 3 displays a µ-1,3-Se3 ligand in the Ti3-trimetallic framework. In contrast, when a similar reaction was performed with sulfur powder instead of selenium powder, it led to the formation of a bimetallic octasulfide complex, [(Cp*Ti)2(μ-η2:η2-S2)(µ-1,3-S3)(μ-η1:η2:η1-S3)] (4). Complex 4 shows various sulfide coordination modes: μ-η2:η2-S2, µ-1,3-S3, and μ-η1:η2:η1-S3. Additionally, a similar reaction with CS2 ligand resulted in a homocubane-like trimetallic polysulfide cluster, [(Cp*Ti)3(μ-S)3(μ3-κ2:κ2:κ2-CHS4)] (5), where three µ-S ligands coordinate to one face of the Ti3 triangle, and one μ3-κ2:κ2:κ2-CHS4 ligand bridges the other side. All the complexes have been characterized using multinuclear NMR, UV-vis, and IR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were also carried out to understand their bonding and electronic structures.
{"title":"Polymetallic Titanium Chalcogenide Clusters Comprising {En}2- Ligands (E = S, Se; n = 1−3)","authors":"Subhash Bairagi, Soumen Giri, Debipada Chatterjee, Soham Chowdhury, Sundargopal Ghosh","doi":"10.1039/d5qi01882j","DOIUrl":"https://doi.org/10.1039/d5qi01882j","url":null,"abstract":"Reactive transition metal fragments can incorporate elemental chalcogens to form polynuclear chalcogen-rich clusters, which may contain either mono-, di- or polychalcogenide ligands or several such ligands in combined form. In an effort to explore the coordination chemistry of chalcogenide ligands with titanium, we have carried out the reaction of [Cp*TiCl3] with various chalcogen sources, such as selenium, sulfur, and CS2. The in-situ reaction of [Cp*TiCl3] with [LiBH4], followed by treatment with selenium powder at elevated temperature yielded unique pentametallic [{(Cp*Ti)4Ti}(μ3-η1:η2-Se2)4(μ3-η2:η2-Se2)2(μ-O)2] (1), tetrametallic [(Cp*Ti)4(μ-Se)(μ3-Se)2(μ3-η2:η2-Se2)2(μ4-O)] (2), and trimetallic [(Cp*Ti)2(Cp*TiCl)(µ-O)3(µ-1,3-Se3)] (3) titanium-chalcogenide clusters. Cluster 1 is a rare example of a dodecahedron core {TiSe8} featuring two different coordination modes of diselenide ligands; μ3-η1:η2-Se2 and μ3-η1:η2-Se2. While cluster 2 has a Ti4-tetrahedral core with a μ4-oxo group located inside the core. Interestingly, cluster 3 displays a µ-1,3-Se3 ligand in the Ti3-trimetallic framework. In contrast, when a similar reaction was performed with sulfur powder instead of selenium powder, it led to the formation of a bimetallic octasulfide complex, [(Cp*Ti)2(μ-η2:η2-S2)(µ-1,3-S3)(μ-η1:η2:η1-S3)] (4). Complex 4 shows various sulfide coordination modes: μ-η2:η2-S2, µ-1,3-S3, and μ-η1:η2:η1-S3. Additionally, a similar reaction with CS2 ligand resulted in a homocubane-like trimetallic polysulfide cluster, [(Cp*Ti)3(μ-S)3(μ3-κ2:κ2:κ2-CHS4)] (5), where three µ-S ligands coordinate to one face of the Ti3 triangle, and one μ3-κ2:κ2:κ2-CHS4 ligand bridges the other side. All the complexes have been characterized using multinuclear NMR, UV-vis, and IR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were also carried out to understand their bonding and electronic structures.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895235","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}
Hao Zhou, Yikai Wang, Hua Wang, Heye Fu, Ranran Li, Yuekai Zhang, Hong Zhao, Cuishuang Jiang, Tingting Yu, Xia Sun, Maoshuai He, Wenxian Wei, Tao Yang
Hydrogen has garnered attention as a promising carbon-free energy carrier capable of addressing escalating energy demands and environmental concerns. However, hydrogen production via alkaline water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER). Although Ni₃Se₂ has attracted interest as a non-precious metal-based OER catalyst, its performance remains suboptimal. In this work, we present a trimetallic-doped electrocatalyst, CoWCe-Ni₃Se₂, which exhibits outstanding OER performance in alkaline media. The catalyst demonstrates only 204 mV to achieve a current density of 100 mA cm⁻², along with a notably small Tafel slope of 33.59 mV dec⁻¹. Furthermore, it shows exceptional operational durability, maintaining 95% of its initial activity over 90 hours of continuous electrolysis. Mechanistic insights derived from density functional theory (DFT) calculations reveal that the co-doping of W and Ce facilitates the adsorption of critical *OOH intermediates and significantly lowers the energy barrier of the rate-determining step (RDS). The enhanced catalytic performance is attributed to the improved electrical conductivity, increased active surface area, and optimized adsorption/desorption behavior of reaction intermediates. Beyond introducing a highly active and stable OER electrocatalyst, this study provides a fundamental understanding of the synergistic effects of multi-element doping for the rational design of high-performance catalysts.
{"title":"Enhancing Oxygen Evolution Catalysis of Ni₃Se₂ via Trimetallic Modulation","authors":"Hao Zhou, Yikai Wang, Hua Wang, Heye Fu, Ranran Li, Yuekai Zhang, Hong Zhao, Cuishuang Jiang, Tingting Yu, Xia Sun, Maoshuai He, Wenxian Wei, Tao Yang","doi":"10.1039/d5qi01922b","DOIUrl":"https://doi.org/10.1039/d5qi01922b","url":null,"abstract":"Hydrogen has garnered attention as a promising carbon-free energy carrier capable of addressing escalating energy demands and environmental concerns. However, hydrogen production via alkaline water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER). Although Ni₃Se₂ has attracted interest as a non-precious metal-based OER catalyst, its performance remains suboptimal. In this work, we present a trimetallic-doped electrocatalyst, CoWCe-Ni₃Se₂, which exhibits outstanding OER performance in alkaline media. The catalyst demonstrates only 204 mV to achieve a current density of 100 mA cm⁻², along with a notably small Tafel slope of 33.59 mV dec⁻¹. Furthermore, it shows exceptional operational durability, maintaining 95% of its initial activity over 90 hours of continuous electrolysis. Mechanistic insights derived from density functional theory (DFT) calculations reveal that the co-doping of W and Ce facilitates the adsorption of critical *OOH intermediates and significantly lowers the energy barrier of the rate-determining step (RDS). The enhanced catalytic performance is attributed to the improved electrical conductivity, increased active surface area, and optimized adsorption/desorption behavior of reaction intermediates. Beyond introducing a highly active and stable OER electrocatalyst, this study provides a fundamental understanding of the synergistic effects of multi-element doping for the rational design of high-performance catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895234","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}
Chloé Blais, Aurélien Chang, Christine Hénaff, Carole Daiguebonne, Aimin Yao, Régis Gautier, Guillaume Calvez, Yan Suffren, Kevin Bernot, Olivier Guillou
A series of lanthanide coordination polymers with general chemical formula [Ln 2 (dcpa) 3 (H 2 O)] ∞ (Ln = La-Er except Pm plus Y; H 2 dcpa = 4,5-dichloro-phthalic acid), has been obtained by micro-waves assisted synthesis. Isostructural hetero-lanthanides molecular alloys in which the emissive ions are highly diluted by non-emitting ions have also been prepared. These compounds exhibit unexpectedly high luminescence intensities. Based on photo-physics measurements and theoretical calculations this strong luminescence was attributed to unusually low non-radiative vibrational de-excitation. Intermetallic Tb 3+ → Eu 3+ energy transfers have also been estimated in the frame of Forster's mechanism. This study opens the way to the design of series of compounds, with strong and highly tunable luminescence in the visible domain, which is of interest for materials traceability.
{"title":"Highly optically-diluted lanthanide coordination polymers with unexpected strong luminescence","authors":"Chloé Blais, Aurélien Chang, Christine Hénaff, Carole Daiguebonne, Aimin Yao, Régis Gautier, Guillaume Calvez, Yan Suffren, Kevin Bernot, Olivier Guillou","doi":"10.1039/d5qi02306h","DOIUrl":"https://doi.org/10.1039/d5qi02306h","url":null,"abstract":"A series of lanthanide coordination polymers with general chemical formula [Ln 2 (dcpa) 3 (H 2 O)] ∞ (Ln = La-Er except Pm plus Y; H 2 dcpa = 4,5-dichloro-phthalic acid), has been obtained by micro-waves assisted synthesis. Isostructural hetero-lanthanides molecular alloys in which the emissive ions are highly diluted by non-emitting ions have also been prepared. These compounds exhibit unexpectedly high luminescence intensities. Based on photo-physics measurements and theoretical calculations this strong luminescence was attributed to unusually low non-radiative vibrational de-excitation. Intermetallic Tb 3+ → Eu 3+ energy transfers have also been estimated in the frame of Forster's mechanism. This study opens the way to the design of series of compounds, with strong and highly tunable luminescence in the visible domain, which is of interest for materials traceability.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895730","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}
Hangkai Shi, Liang Zhao, Weizhou Wang, Shuyi Pang, Hongdong Li, Jing-Qi Chi, Jianping Lai, Lei Wang
Electrocatalytic urea synthesis, as an emerging carbon-neutral technology, aims to directly synthesize urea from waste gases such as CO2 and NO3 -under mild conditions, which is of great significance for achieving sustainable energy development and environmental governance. However, its large-scale application is restricted by competitive side reactions, low C-N coupling efficiency and an unclear reaction mechanism. Currently, various metal catalysts have been developed and extensively studied to address these challenges. Cu-based catalysts have demonstrated great potential in this field due to their unique electronic structure, adjustable valence states, and excellent coupling ability for key reaction intermediates. This review systematically summarizes the research progress of Cu-based catalysts in electrocatalytic urea synthesis in recent years, and elaborates on the basic reaction mechanism of urea electro-synthesis. Furthermore, the modification strategies of different Cu-based catalysts were discussed in detail. Through in situ characterization and theoretical calculation, the influence rules of the intermediates produced during the reaction on the C-N coupling efficiency and selectivity were deeply analyzed. Finally, in view of the current challenges in this field, such as the need to improve Faraday efficiency and yield. This review offer a guidance for the design of the next generation of high performance urea electrosynthesis catalysts.
{"title":"Cu-based Catalysts for Electrocatalytic Urea Synthesis from CO2 and NO3-: Mechanism, Design and Perspectives","authors":"Hangkai Shi, Liang Zhao, Weizhou Wang, Shuyi Pang, Hongdong Li, Jing-Qi Chi, Jianping Lai, Lei Wang","doi":"10.1039/d5qi02240a","DOIUrl":"https://doi.org/10.1039/d5qi02240a","url":null,"abstract":"Electrocatalytic urea synthesis, as an emerging carbon-neutral technology, aims to directly synthesize urea from waste gases such as CO2 and NO3 -under mild conditions, which is of great significance for achieving sustainable energy development and environmental governance. However, its large-scale application is restricted by competitive side reactions, low C-N coupling efficiency and an unclear reaction mechanism. Currently, various metal catalysts have been developed and extensively studied to address these challenges. Cu-based catalysts have demonstrated great potential in this field due to their unique electronic structure, adjustable valence states, and excellent coupling ability for key reaction intermediates. This review systematically summarizes the research progress of Cu-based catalysts in electrocatalytic urea synthesis in recent years, and elaborates on the basic reaction mechanism of urea electro-synthesis. Furthermore, the modification strategies of different Cu-based catalysts were discussed in detail. Through in situ characterization and theoretical calculation, the influence rules of the intermediates produced during the reaction on the C-N coupling efficiency and selectivity were deeply analyzed. Finally, in view of the current challenges in this field, such as the need to improve Faraday efficiency and yield. This review offer a guidance for the design of the next generation of high performance urea electrosynthesis catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"38 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895756","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}
Sohee Lee, Seoyeon Kim, Byung Hak Jhun, Hyokyung Kim, Jaeheung Cho, Eun Jin Cho, Youngmin You
Solvent effects in chemical reactions are typically associated with energetic control. In photocatalysis, however, the ability of solvents to influence excited-state lifetimes offers a promising avenue for improving reaction efficiency. Herein, we report a solvatochronic effect whereby the excited-state lifetime of a photocatalyst can be extended by use of an appropriate solvent. Specifically, a linear, heteroleptic Au(I) complex bearing carbazolide and N-heterocyclocarbene ligands exhibits an excited-state lifetime of 12 μs in the Lewis basic solvent DMSO, but only 0.30 μs in the non-Lewis basic solvent CH2Cl2. This lifetime prolongation arises from a combined effect of accelerated intersystem crossing to the ligand-localized triplet state and suppressed nonradiative decay, driven by solvent basicity and viscosity, respectively. The long-lived Au excited state facilitates Dexter-type energy transfer to unactivated styrenes, initiating intermolecular [2+2] cycloaddition reactions. These findings reveal a new mode of solvent control-temporal modulation-and present a general, catalyst-structureindependent strategy for enhancing photocatalytic reactivity.
{"title":"Solvatochrony: Solvatochronic Photocatalysts and Their Applications in Intermolecular [2+2] Cycloaddition Reaction of Unactivated Styrenes","authors":"Sohee Lee, Seoyeon Kim, Byung Hak Jhun, Hyokyung Kim, Jaeheung Cho, Eun Jin Cho, Youngmin You","doi":"10.1039/d5qi02352a","DOIUrl":"https://doi.org/10.1039/d5qi02352a","url":null,"abstract":"Solvent effects in chemical reactions are typically associated with energetic control. In photocatalysis, however, the ability of solvents to influence excited-state lifetimes offers a promising avenue for improving reaction efficiency. Herein, we report a solvatochronic effect whereby the excited-state lifetime of a photocatalyst can be extended by use of an appropriate solvent. Specifically, a linear, heteroleptic Au(I) complex bearing carbazolide and N-heterocyclocarbene ligands exhibits an excited-state lifetime of 12 μs in the Lewis basic solvent DMSO, but only 0.30 μs in the non-Lewis basic solvent CH2Cl2. This lifetime prolongation arises from a combined effect of accelerated intersystem crossing to the ligand-localized triplet state and suppressed nonradiative decay, driven by solvent basicity and viscosity, respectively. The long-lived Au excited state facilitates Dexter-type energy transfer to unactivated styrenes, initiating intermolecular [2+2] cycloaddition reactions. These findings reveal a new mode of solvent control-temporal modulation-and present a general, catalyst-structureindependent strategy for enhancing photocatalytic reactivity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895732","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}
This Review focuses on functionalization of the [closo-B10H10]2- anion in the apical positions in the context of the development of functional molecular materials. The most salient feature of the anion is its high lying HOMO (-4.14 eV, DFT), which due to its symmetry and distribution readily interacts with apical -substituents, and participates in intra- and inter-molecular photo-induced charge transfer processes. Such molecules are characterized by photonic and electronic properties, which can be controlled by judicious choice of substituents. Until recently, derivatives of the [closo-B10H10]2- with apical substituents (B(1) and B(10) substitution) were limited since most electrophilic substitution reactions give the equatorial products (B(2) substitution). The recent discovery of a fully selective phenyliodination reaction of the [closo-B10H10]2- anion has opened up access to a much greater variety of apical derivatives. This Review describes methods for apical substitution in [closo-B10H10]2- using mainly [closo-B10H8-10-X-1-N2]- and [closo-B10H8-10-X-1-IPh]- intermediates. It shows the scope of apical substituents connected with C, N, P, O, S, Se, and B atoms and halogens currently available through direct substitution and functional group transformations, and demonstrates their use as building blocks for emerging classes of functional materials.
{"title":"Apical functionalization of the [closo-B10H10]2- anion: Building blocks for modern materials","authors":"Piotr Kaszynski, Litwin Jacob","doi":"10.1039/d5qi02162f","DOIUrl":"https://doi.org/10.1039/d5qi02162f","url":null,"abstract":"This Review focuses on functionalization of the [closo-B10H10]2- anion in the apical positions in the context of the development of functional molecular materials. The most salient feature of the anion is its high lying HOMO (-4.14 eV, DFT), which due to its symmetry and distribution readily interacts with apical -substituents, and participates in intra- and inter-molecular photo-induced charge transfer processes. Such molecules are characterized by photonic and electronic properties, which can be controlled by judicious choice of substituents. Until recently, derivatives of the [closo-B10H10]2- with apical substituents (B(1) and B(10) substitution) were limited since most electrophilic substitution reactions give the equatorial products (B(2) substitution). The recent discovery of a fully selective phenyliodination reaction of the [closo-B10H10]2- anion has opened up access to a much greater variety of apical derivatives. This Review describes methods for apical substitution in [closo-B10H10]2- using mainly [closo-B10H8-10-X-1-N2]- and [closo-B10H8-10-X-1-IPh]- intermediates. It shows the scope of apical substituents connected with C, N, P, O, S, Se, and B atoms and halogens currently available through direct substitution and functional group transformations, and demonstrates their use as building blocks for emerging classes of functional materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"94 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895758","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 oriented synthesis of metal-organic frameworks (MOFs) is always the goal that scientists strive for. Exhaustive method and orthogonal experiment are generally the most labor-intensive but also the most effective synthetic strategies. An artificial intelligence synthetic method that powered by generative large language model DeepSeek is adopted. Based on N, N’-bis(carboxymethyl)-1, 4, 5, 8-naphthalenediimide (H2CMNDI) and transition metals ions Zn(II) and Cd(II), we synthesized a series of novel MOFs. Conventional microanalysis methods were employed to analyze the structure and properties of the MOFs. The synthesized MOFs meet our expected performance and exhibit stimulus-responsive activity. They possess recoverable photochromic properties, rapidly darkening significantly under ultraviolet light and then regaining their original color upon heating and being kept away from light in a static state, which can be used for encryption applications. Additionally, the Zn-MOF can detect ammonia water sensitively, with a limit of detection as low as 3.28 μM. The synthesis and application of this series of MOFs are an excellent exploration and a good example of the oriented synthesis of MOFs.
金属有机骨架的定向合成一直是科学家们追求的目标。穷举法和正交试验通常是最费力但也是最有效的综合策略。采用了一种基于生成式大型语言模型DeepSeek的人工智能综合方法。以N， N ' -二（羧甲基）- 1,4,5,8 -萘二酰亚胺（H2CMNDI）和过渡金属离子Zn（II）和Cd（II）为原料，合成了一系列新型mof。采用常规的微量分析方法对mof的结构和性能进行了分析。合成的MOFs符合我们的预期性能，并表现出刺激反应活性。它们具有可恢复的光致变色特性，在紫外线照射下迅速变暗，然后加热后恢复原来的颜色，并且在静态状态下远离光线，可用于加密应用。此外，Zn-MOF对氨水的检测灵敏度高，检测限低至3.28 μM。该系列MOFs的合成和应用是MOFs定向合成的一个很好的探索和实例。
{"title":"AI-Powered Oriented Synthesis of Naphthalenediimide-based MOFs for Photochromic Encryption and Ammonia Sensing","authors":"Jing Wang, Chao Zhang, Ming-Rui Zhang, Yun-Huan Xue, Zi-Xin You, Ming-Dong Zhou","doi":"10.1039/d5qi02459e","DOIUrl":"https://doi.org/10.1039/d5qi02459e","url":null,"abstract":"The oriented synthesis of metal-organic frameworks (MOFs) is always the goal that scientists strive for. Exhaustive method and orthogonal experiment are generally the most labor-intensive but also the most effective synthetic strategies. An artificial intelligence synthetic method that powered by generative large language model DeepSeek is adopted. Based on N, N’-bis(carboxymethyl)-1, 4, 5, 8-naphthalenediimide (H<small><sub>2</sub></small>CMNDI) and transition metals ions Zn(II) and Cd(II), we synthesized a series of novel MOFs. Conventional microanalysis methods were employed to analyze the structure and properties of the MOFs. The synthesized MOFs meet our expected performance and exhibit stimulus-responsive activity. They possess recoverable photochromic properties, rapidly darkening significantly under ultraviolet light and then regaining their original color upon heating and being kept away from light in a static state, which can be used for encryption applications. Additionally, the Zn-MOF can detect ammonia water sensitively, with a limit of detection as low as 3.28 μM. The synthesis and application of this series of MOFs are an excellent exploration and a good example of the oriented synthesis of MOFs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"121 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145847193","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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