Inorganic Chemistry Frontiers最新文献

Self-assembly of high-nuclear core-shell polyoxovanadates with Lindqvsit templates

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02884h

Shuangxue Wu, Yaomei Fu, Hong-Mei Gan, Liang Zhao, Xinlong Wang, Chao Qin, Zhong-Min Su

引用次数: 0

Regulating π-Type Interactions between O 2p and TM t2g Orbitals via Ti Doping and Surface Dielectric Coatings for Li-Rich Cathode

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02773f

Yituo Wang, Di Zhang, Da Zhang, Chunge Dang, Jianling Li

{"title":"Regulating π-Type Interactions between O 2p and TM t2g Orbitals via Ti Doping and Surface Dielectric Coatings for Li-Rich Cathode","authors":"Yituo Wang, Di Zhang, Da Zhang, Chunge Dang, Jianling Li","doi":"10.1039/d4qi02773f","DOIUrl":"https://doi.org/10.1039/d4qi02773f","url":null,"abstract":"The irreversible anionic redox reaction and oxygen release of Li-rich layered oxide cathodes seriously hinder their commercial application. Here, a synergistic modification strategy of surface dielectric coating (TiNb2O7) and bulk phase Ti doping is proposed in this paper. TiNb2O7, as a dielectric oxide, can generate a reversed electric field during charging to block the migration path of anions inside the material. In addition, the unique three-dimensional Li+ diffusion channels of TiNb2O7 can improve the lithium-ion diffusion kinetics. The bulk-phase Ti doping can increase the energy barrier of the oxygen release reaction, and the stronger Ti-O bond can regulate the electronic structure and π-hybridization of the transition metal and thus stabilize the oxygen skeleton. The results of XPS, CV, and HRTEM show that the synergistic modification strategy fundamentally inhibits oxygen loss and enhances the reversibility of anion redox, while constructing a uniform and stable CEI interface. The co-modification strategy effectively improves the electrochemical performance of the materials. The modified sample can maintain a high capacity of 175.1 mAh g-1 after 500 cycles at 1C. This work provides new insights to improve the oxygen loss problem of Li-rich layered oxide cathodes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880075","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}

引用次数: 0

Cluster-like Mo2N anchoring on reduced graphene oxide as the efficient and deep-degree oxidative desulfurization catalyst

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02670e

Weizhuang Song, Dongxu Wang, Xianyun Yue, Chengxu Jin, Yangchen Wu, Yu Shi, Jiancong Liu, Aiping Wu, Chungui Tian, Honggang Fu

{"title":"Cluster-like Mo2N anchoring on reduced graphene oxide as the efficient and deep-degree oxidative desulfurization catalyst","authors":"Weizhuang Song, Dongxu Wang, Xianyun Yue, Chengxu Jin, Yangchen Wu, Yu Shi, Jiancong Liu, Aiping Wu, Chungui Tian, Honggang Fu","doi":"10.1039/d4qi02670e","DOIUrl":"https://doi.org/10.1039/d4qi02670e","url":null,"abstract":"Oxidative desulfurization (ODS) has been a promising technology for removing sulfur compounds from fuel oil under mild conditions. It is essential to design ODS catalyst exposing plentiful accessible active sites, but it remains a challenge. Here, we have reported the design of cluster-like Mo2N catalyst (1.5 nm) uniformly dispersed on graphene surface by anchoring PMo12 polyoxometalate clusters on polyethyleneimine (PEI)-modified graphite oxide (GO). The obtained Mo2N/rGO-A catalyst has highly exposed active sites and plentiful accessible surface. Importantly, Mo2N catalyst can readily activate oxidant to generate active Mo2N-peroxo intermediates. In the ODS reaction of dibenzothiophene (DBT) with H2O2 as the oxidant, the catalyst can achieve the complete removal of sulfur compounds (1000 ppm) within 15 min, with a reaction rate constant k of 1.94 × 10-1 min-1 at 60 °C, being superior to the corresponding Mo-O-based catalysts, large-sized Mo2N/rGO-D catalyst and the most of the reported transition metal-based catalysts. Furthermore, the catalyst shows good cycling stability with no obvious deactivation after eight cycles. The ODS reaction of DBT over Mo2N/rGO-A catalyst mainly follows a non-radical oxidation mechanism with DBTO2 (dibenzothiophene sulfone) being the only oxidation product based on the free radical scavenger experiment and GC-MS analysis. This work has important implications for the design of efficient and stable small-sized Mo-based catalyst for ODS of fuel oil.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880073","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}

引用次数: 0

Fluoride Binding in Unlikely Partners: The Formation of Anion-Anion Complexes with [M(EGTA)]⁻ and [M(OBETA)]⁻ (M = Gd3+, Y3+)

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02908a

Lorenzo Risolo, Marco Ricci, Daniela Lalli, Carlos Platas-Iglesias, Mauro Botta

{"title":"Fluoride Binding in Unlikely Partners: The Formation of Anion-Anion Complexes with [M(EGTA)]⁻ and [M(OBETA)]⁻ (M = Gd3+, Y3+)","authors":"Lorenzo Risolo, Marco Ricci, Daniela Lalli, Carlos Platas-Iglesias, Mauro Botta","doi":"10.1039/d4qi02908a","DOIUrl":"https://doi.org/10.1039/d4qi02908a","url":null,"abstract":"Anionic metal complexes (M = Gd3+, Y3+) with two homologous acyclic aminopolycarboxylate ligands, heptadentate (OBETA) and octadentate (EGTA), were prepared and characterized using both relaxometric NMR (for Gd3+) and high-resolution NMR (for Y3+). The addition of fluoride to aqueous solutions of these complexes led to the formation of ternary complexes where F⁻ displaces a coordinated water molecule from the metal ion's inner coordination sphere. In the Gd3+ complexes, this exchange process was tracked by monitoring changes in the nuclear magnetic relaxation rate of water protons, allowing calculation of the binding affinity. For the diamagnetic Y3+ complexes, the exchange was followed through variable-temperature high-resolution 19F NMR experiments. Calculated enthalpic and entropic contributions to the activation free energy suggest a dissociative exchange mechanism for the monohydrated [M(EGTA)(H2O)]⁻ and an associative mechanism for the dihydrated [M(OBETA)(H2O)2]⁻. Additionally, an unusual dimeric structure was observed for the dihydrated complexes, where two anionic complexes are bridged by fluoride. Detailed DFT calculations confirmed the presence of the dimer, showing a Y–F bond length of 2.33 Å and a 1JY–F NMR coupling constant of 38.0 Hz, in excellent agreement with the experimental value.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880071","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}

引用次数: 0

Near-infrared luminescence AgPd alloy superatomic clusters

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02655a

Xiao-Hong Ma, Jian-Hua Qin, Fei-Fan Wang, Peng Luo, Xi-Yan Dong

{"title":"Near-infrared luminescence AgPd alloy superatomic clusters","authors":"Xiao-Hong Ma, Jian-Hua Qin, Fei-Fan Wang, Peng Luo, Xi-Yan Dong","doi":"10.1039/d4qi02655a","DOIUrl":"https://doi.org/10.1039/d4qi02655a","url":null,"abstract":"Atomically precise superatomic nanoclusters have attracted considerable interest due to their remarkable structures and intriguing photoluminescence properties. Nevertheless, achieving a high photoluminescence quantum yield (PLQY) in the near-infrared (NIR) region of superatomic nanoclusters continues to pose a considerable challenge. Here, we report a novel bimetallic nanocluster prepared utilizing an alloying strategy, formulated as [Ag14Pd(PFBT)6(TPP)8](TPP) (abbreviated as Ag14Pd). Notably, this cluster demonstrates a remarkable NIR emission, achieving a PLQY of 15% in the solid state, which is rare for metal nanoclusters. Both experimental and theoretical analyses indicate that Ag14Pd exhibits a characteristic 8-electron superatomic structure with a 1S21P6 electronic shell closure. Furthermore, due to their bright luminescence and exceptional photostability, Ag14Pd clusters hold promising potential for applications as NIR inks for three-dimensional (3D) printing of various objects and models.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880069","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}

引用次数: 0

Probing the Influence of Imidazolylidene- and Triazolylidene-Based Carbenes on the Catalytic Potential of Dioxomolybdenum and Dioxotungsten Complexes in Dexoxygenation Catalysis

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02392g

Florian Rochus Neururer, Florian Heim, Marc Baltrun, Philipp Boos, Julia Beerhues, Michael Seidl, Stephan Hohloch

{"title":"Probing the Influence of Imidazolylidene- and Triazolylidene-Based Carbenes on the Catalytic Potential of Dioxomolybdenum and Dioxotungsten Complexes in Dexoxygenation Catalysis","authors":"Florian Rochus Neururer, Florian Heim, Marc Baltrun, Philipp Boos, Julia Beerhues, Michael Seidl, Stephan Hohloch","doi":"10.1039/d4qi02392g","DOIUrl":"https://doi.org/10.1039/d4qi02392g","url":null,"abstract":"We report the synthesis of dianionic OCO supported NHC and MIC complexes of heavy group VI metals with the general formula (OCO)MO2 (OCO = bis-phenolate benzimidazolylidene M = Mo (1-Mo), bis-phenolate triazolylidene M = Mo (2-Mo), M = W (2-W) and bis-phenolate imidazolylidene, M = Mo (3-Mo), W (3-W)). These complexes are tested in the catalytic deoxygenation of nitroarenes using pinacol as a sacrificial oxygen atom acceptor/reducing agent to examine the influence of the carbene and the metal center in this transformation. This reveals that molybdenum based triazolylidene complex 2-Mo is by far the most active catalyst and TOFs of up to 263 h-1 are observed, while the tungsten analogues are basically inactive. Mechanistic studies suggest, that the superiority of the triazolylidene-based complex 2-Mo is a result of a more stable metal carbene bond compared to the other NHC complexes 1-Mo and 3-Mo. This is proven by the structural isolation of a triazolylidene pinacolate complex 5-Mo, that can be thermally converted to a µ-oxodimolybdneum(V) complex 7-Mo. The latter complex is very oxophilic and stoichiometrically deoxygenates nitro- and nitrosoarenes at room temperature. In contrast, azoarenes are not reductively cleaved by 7-Mo, suggesting direct deoxygenation reaction of the nitroarenes to the corresponding anilines with nitrosoarenes as the only intermediates. In summary, this work showcases the major influence of the NHC/MIC donor on the catalytic properties of early transition metal complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880070","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}

引用次数: 0

Building an In-rich interphase to stabilize lithium metal anodes with a solid-like electrolyte

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-24 DOI: 10.1039/d4qi02970d

Jiashuai Li, Dongze Li, Qiufen Li, Mengxi Bai, Xiang Wang, Xiaoyan Lin, Siyuan Shao, Ziqi Wang

{"title":"Building an In-rich interphase to stabilize lithium metal anodes with a solid-like electrolyte","authors":"Jiashuai Li, Dongze Li, Qiufen Li, Mengxi Bai, Xiang Wang, Xiaoyan Lin, Siyuan Shao, Ziqi Wang","doi":"10.1039/d4qi02970d","DOIUrl":"https://doi.org/10.1039/d4qi02970d","url":null,"abstract":"Lithium metal is an ideal candidate for the anode material of high-energy-density batteries due to its high theoretical specific capacity and low electrochemical potential. However, dendritic growth and poor reversibility prevent its practical applications. To address these issues of Li metal anode in conventional liquid electrolytes, we developed a solid-like electrolyte (SLE) leveraging a metal-organic framework (MOF) with chelated indium ions on its ligands. The SLE exhibits excellent ionic conductivity of 1.39 S cm-1 at 30 °C and a Li ion transference number of 0.46, enabling efficient Li ion transport. The ordered microtunnels within the SLE promote uniform Li deposition, effectively suppressing dendrite formation. Notably, the SLE induces the formation of an indium-rich interphase on Li metal anodes during cycling, which reduces the energy barrier for interfacial Li ion diffusion and enhances anode reversibility. As a result, Li symmetric cells with the SLE achieve stable plating and stripping for over 1200 hours and support a high critical current density of 2.0 mA cm-2. Benefiting from these advantages, the solid-like LiFePO4 cells demonstrate exceptional room-temperature performance, delivering a reversible capacity of 78 mAh g-1 at an ultra-high rate of 10 C and maintaining stable cycling for over one year at 0.1 C without short-circuit.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"70 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880076","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}

引用次数: 0

‘Kick-in the head’: High-performance and air-stable mononuclear DyIII single-molecule magnets with pseudo-D6h symmetry from an [1+1] Schiff-base macrocycle approach†

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-23 DOI: 10.1039/d4qi02756f

Alexandros Armenis, Arpan Mondal, Sean R Giblin, Dimitris Alexandropoulos, Jinkui Tang, Richard Layfield, Theocharis C Stamatatos

{"title":"‘Kick-in the head’: High-performance and air-stable mononuclear DyIII single-molecule magnets with pseudo-D6h symmetry from an [1+1] Schiff-base macrocycle approach†","authors":"Alexandros Armenis, Arpan Mondal, Sean R Giblin, Dimitris Alexandropoulos, Jinkui Tang, Richard Layfield, Theocharis C Stamatatos","doi":"10.1039/d4qi02756f","DOIUrl":"https://doi.org/10.1039/d4qi02756f","url":null,"abstract":"Using the [1+1] condensation approach for the preparation of new macrocyclic scaffolds (\"L\" _\"phen\" ^\"N6\" and \"L\" _\"phen\" ^\"N4O2\" ) with the rigid phenanthroline-based ‘head’ unit produces the air-stable mononuclear compounds [Dy(\"L\" _\"phen\" ^\"N6\" )(Ph3SiO)2](PF6) (1-\"L\" _\"phen\" ^\"N6\" ) and [Dy(\"L\" _\"phen\" ^\"N4O2\" )(Ph3SiO)2](PF6) (1-\"L\" _\"phen\" ^\"N4O2\" ) through a stepwise metal-ion templated synthesis. Both compounds exhibit pseudo-D6h symmetry with different degrees of distortion from the ideal hexagonal bipyramidal geometry, depending on the planarity of the equatorial macrocycles and the intramolecular π-π stacking interactions between the phenyl groups of the apical siloxide ligand and the equatorial macrocycle. Both compounds are single-molecule magnets (SMMs) with large energy barriers for the magnetization reversal, exhibiting out-of-phase AC susceptibility signals up to 75 K or 90 K. The closer-to-ideal D6h complex 1-\"L\" _\"phen\" ^\"N4O2\" possesses a Ueff of 1360 K, which is the highest reported barrier among all mononuclear DyIII SMMs synthesized using the [1+1] Schiff-base macrocycle approach. The experimental results are supported by ab initio calculations, which indicate relaxation of the magnetization via the first- or second-excited state for 1-\"L\" _\"phen\" ^\"N6\" and 1-\"L\" _\"phen\" ^\"N4O2\" , respectively. The combined results demonstrate the ability of Schiff-base macrocycles to facilitate the synthesis of high-performance and air-stable SMMs through a chemical modulation of the individual carbonyl ‘head’ and amine subunits, deciphering the factors which affect the magnetic dynamics of SMMs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874667","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}

引用次数: 0

The rise and fall of copper hydride clusters. A snapshot of hexanuclear-to-dodecanuclear expansion

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-23 DOI: 10.1039/d4qi02845g

Dewmi A Ekanayake, Jeanette A Krause, Hairong Guan

引用次数: 0

Cu-based electrode material for controlled selective electrooxidation of tetrahydroisoquinoline

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2024-12-23 DOI: 10.1039/d4qi02707h

Yizhou Zhang, Rongxian Zhang, Qi Zhang, Yilin Deng, Jiexin Guan, Yizhou Ling, Guo Xing Zhu

{"title":"Cu-based electrode material for controlled selective electrooxidation of tetrahydroisoquinoline","authors":"Yizhou Zhang, Rongxian Zhang, Qi Zhang, Yilin Deng, Jiexin Guan, Yizhou Ling, Guo Xing Zhu","doi":"10.1039/d4qi02707h","DOIUrl":"https://doi.org/10.1039/d4qi02707h","url":null,"abstract":"The oxygen evolution reaction with a high energy barrier on the anode during water electrolysis is the main factor limiting its large-scale application. A viable strategy is to explore anode substitution reactions to replace the oxygen evolution reaction in water electrolysis. In this study, the selective electrooxidation of tetrahydroisoquinoline (THIQ) was demonstrated on a specially designed and prepared Cu2S electrode, which was coupled with the hydrogen evolution reaction. The process exhibits high selectivity of over 90% for the micro-electrooxidation of THIQ to dihydroisoquinoline (DHIQ). The high selectivity is caused by the fact that oxygen evolution reaction (OER) blocks the transformation from DHIQs to isoquinolines (IQs) and by the excellent performance of the designed catalytic electrode from ds-region material. The in situ Raman and XPS investigation confirmed that the main active substance is Cu(III) species that was in situ derived on the surface of Cu2S. Based on the results of DFT calculations, a possible catalytic reaction mechanism of Cu-based catalysts for the selective micro-electrooxidation of THIQs was proposed.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874666","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}

引用次数: 0