Inorganic Chemistry最新文献_第2页

Flexible Intervention of Polyoxometalate Support on the Electronegativity of Single Atoms to Enhance Catalytic Activity

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c04978

Yalei Zhang, Xiaofang Su, Tao Zheng, Waqas Ali Shah, Likai Yan, Shujun Li

{"title":"Flexible Intervention of Polyoxometalate Support on the Electronegativity of Single Atoms to Enhance Catalytic Activity","authors":"Yalei Zhang, Xiaofang Su, Tao Zheng, Waqas Ali Shah, Likai Yan, Shujun Li","doi":"10.1021/acs.inorgchem.4c04978","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04978","url":null,"abstract":"The construction of single-atom catalysts (SACs) using polyoxometalates (POMs) as supports has attracted significant attention. Specifically, POMs possess the unique ability to reversibly accept and donate electrons; yet, the potential benefits of this distinctive characteristic on the activity of single atoms have remained unexplored. In this study, we employ density functional theory (DFT) calculations to investigate the synthesis of CH3COOH from CO, CH4, and H2O catalyzed by POM-supported SAC M1/POM (M = Pt, Rh, Ru, Pd, Co), aiming to gain a more comprehensive understanding of the role of POM support in SACs. Our proposed mechanism first involves CH4 activation for producing •CH3 and, at the same time, the catalytic intermediate [M1/POM]−. Then, CO and •CH3 are sequentially adsorbed on the single-atom site of [M1/POM]− and coupled to form COCH3. Finally, as H2O attacks CH3CO, CH3COOH is formed and released. The poorer activity of M1/POM (M = Rh, Ru, Pd, Co) compared with that of Pt1/POM is attributed to the low matching degree in the frontier molecular orbital energy between [M1/POM]− and CO/•CH3, which results in the inaccessibility of CO and •CH3 adsorptions, thus hindering the subsequent CH3COOH formation. Throughout the reaction process, the POM support promotes dynamic switching of single atoms between electron-rich and electron-poor states, leveraging its reversible electron transfer capability. The electron-deficient species •CH3 adsorption and H2O attack are enabled by the regular access of single atoms to electron-saturated state, while timely switching of single atoms to electron-deficient states facilitates CO adsorption and CH3 attack.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"81 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462509","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Predicting Reduction Potentials of Blue Copper Proteins Using Quantum Mechanical Calculations

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05183

Maryam Haji Dehabadi, Mehdi Irani, Ulf Ryde

{"title":"Predicting Reduction Potentials of Blue Copper Proteins Using Quantum Mechanical Calculations","authors":"Maryam Haji Dehabadi, Mehdi Irani, Ulf Ryde","doi":"10.1021/acs.inorgchem.4c05183","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05183","url":null,"abstract":"We have calculated redox potentials of 12 blue copper protein sites comparing 64 computational methods, systematically varying the quantum mechanics (QM) system size, dielectric constants, density functional, and basis sets. All methods were based on structures optimized with combined QM and molecular mechanics (QM/MM) approaches. The redox potentials were evaluated using 10 quality metrics. The best results for relative potentials were achieved using a QM system of intermediate size (∼70 atoms), the TPSS density functional, and a SV(P) basis set, using QM-cluster calculations in a continuum solvent with a dielectric constant of 20, yielding a mean absolute deviation of 0.09 V and a maximum deviation of 0.26 V. For absolute redox potentials, methods using larger QM systems (∼340 atoms), the B3LYP density functional, and larger basis sets perform better, achieving mean signed errors down to −0.27 V. Compared to previous studies on iron–sulfur clusters, redox potentials for blue copper proteins show improved accuracy due to their narrower potential range and simpler coordination environments, but systematic errors are system-dependent. This study underscores the challenges of modeling redox-active sites in proteins and highlights the effectiveness of QM-cluster calculations in a continuum solvent in balancing computational cost with predictive power.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Synthesis, Crystal Structure, and Elementary Electrical Characterization of Quasi-One-Dimensional TiSe3

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05396

Danrui Ni, Teresa Lee, Stephen Zhang, Xianghan Xu, R. J. Cava

引用次数: 0

An Ambiphilic Phosphide with Three Different Coordination Modes to Group 7–10 Metals

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.5c00201

Adrien T. Normand, Hélène Cattey, Marie-José Penouilh, Quentin Bonnin, Paul Fleurat-Lessard, Céline Pichon, Jean-Pascal Sutter

引用次数: 0

pts-Type Aluminoborate with Nonlinear Optical Properties

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05459

Lan Wang, Juan Chen, Guo-Yu Yang

引用次数: 0

Different Stacking Types in a Single Hybrid Cocrystal System: π···π- and π–Hole-Based Organic–Inorganic Planar Assemblies

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05326

Sergey V. Baykov, Eugene A. Katlenok, Artem V. Semenov, Svetlana O. Baykova, Vadim P. Boyarskiy, Nadezhda A. Bokach, Vadim Yu Kukushkin

{"title":"Different Stacking Types in a Single Hybrid Cocrystal System: π···π- and π–Hole-Based Organic–Inorganic Planar Assemblies","authors":"Sergey V. Baykov, Eugene A. Katlenok, Artem V. Semenov, Svetlana O. Baykova, Vadim P. Boyarskiy, Nadezhda A. Bokach, Vadim Yu Kukushkin","doi":"10.1021/acs.inorgchem.4c05326","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05326","url":null,"abstract":"The planar bis-chelated complex [Pd(N∩O)2] (1; N∩O = 4-MeC5H3NNC(O)NMe2) exhibits two distinct stacking modes with electron-deficient aromatics: π···π stacking with hexafluorobenzene (C6F6) versus charge-transfer π–hole interactions with 1,2,4,5-tetracyanobenzene (TCB). Cocrystallization of the complex with C6F6 or TCB yields cocrystals 1·3(C6F6) and 1·2TCB, respectively, which display different colors and stacking patterns despite similar structural motifs. Comprehensive analysis using X-ray diffraction, combined with quantum theory of atoms-in-molecules (QTAIM), an independent gradient model based on Hirshfeld partition (IGMH), extended transition state natural orbital for chemical valence theory with charge displacement function (ETS-NOCV/CDF), many-body interaction analysis, and symmetry-adapted perturbation theory (SAPT), reveals fundamentally different interaction mechanisms. In 1·3(C6F6), the stacking is primarily governed by intermolecular polarization without significant charge transfer, with dispersion forces contributing approximately 70% of the attractive energy. In contrast, 1·2TCB exhibits pronounced charge transfer (35 me) and significant inductive components alongside dispersion forces, characteristic of π–hole interactions. This dichotomy in stacking behavior provides new insights into the nature of organic–inorganic planar assemblies and demonstrates that seemingly similar structural patterns can arise from distinctly different combinations of noncovalent forces, which is essential for rational crystal engineering of hybrid materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Bimetallic Metal–Organic Framework Catalyst to Accelerate Sulfur Conversion Kinetics for High-Performance Lithium–Sulfur Batteries

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05376

Han Lu, Zichun Luo, Xingbo Wang, Jiaxiang Guo, Xiang Yan, Lin Yang, Jiayi Wang, Wen Liu, Zhongwei Chen

{"title":"Bimetallic Metal–Organic Framework Catalyst to Accelerate Sulfur Conversion Kinetics for High-Performance Lithium–Sulfur Batteries","authors":"Han Lu, Zichun Luo, Xingbo Wang, Jiaxiang Guo, Xiang Yan, Lin Yang, Jiayi Wang, Wen Liu, Zhongwei Chen","doi":"10.1021/acs.inorgchem.4c05376","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05376","url":null,"abstract":"Lithium–sulfur (Li–S) batteries are highly attractive due to their exceptional theoretical energy density (2600 Wh kg–1) and low cost. However, their practical deployment is limited by critical issues, including pronounced polysulfide shuttling and slow reaction kinetics. In this study, we report the development of a novel Mo–Zn bimetallic ZIF-8 catalyst designed to address these issues. Compared with pristine ZIF-8, the Mo-ZIF-8 catalyst exhibited an effectively tuned surface area and pore structure, significantly enhancing its ability to trap polysulfides. Moreover, the optimized pore architecture increased the exposure of active sites, strengthening the chemical interactions between Mo-ZIF-8 and sulfur species and thereby accelerating sulfur reaction kinetics. The incorporation of Mo also induced a redistribution of the electronic structure around the Zn active sites, boosting the intrinsic conductivity of the catalyst and reducing the electrochemical diffusion resistance during the redox processes. The synergistic design of Mo–Zn active sites further enhanced the chemical adsorption of lithium polysulfides and catalytic conversion of sulfur species. As a result, Li–S batteries with Mo-ZIF-8-modified separators exhibit minimal capacity decay (0.04% per cycle) over 1000 cycles at 1C. Under a high sulfur loading of 5.8 mg cm–2, they achieve an areal capacity of 5.8 mAh cm–2, retaining 5.0 mAh cm–2 after 100 cycles. These findings highlight the potential of bimetallic metal–organic framework (MOF) catalysts in advancing the Li–S battery performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Unexpected Role of Fluorine in the Band Gap Narrowing of Silver Niobium and Tantalum Pyrochlore Oxyfluorides

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05119

Celine Moussa, Frédérique Pourpoint, Sébastien Saitzek, Theodosios Famprikis, Pascal Roussel, Houria Kabbour, Edouard Boivin

{"title":"The Unexpected Role of Fluorine in the Band Gap Narrowing of Silver Niobium and Tantalum Pyrochlore Oxyfluorides","authors":"Celine Moussa, Frédérique Pourpoint, Sébastien Saitzek, Theodosios Famprikis, Pascal Roussel, Houria Kabbour, Edouard Boivin","doi":"10.1021/acs.inorgchem.4c05119","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05119","url":null,"abstract":"Mixed anion compounds have attracted growing interest in solid-state chemistry as a way to tailor physical properties. In this work, we synthesized new silver niobium and tantalum pyrochlore oxyfluorides by an ion-exchange reaction from Na2M2O5F2 (M = Nb or Ta). Instead of a classical Na+/Ag+ cation exchange, a less conventional dual cation and anion exchange reaction (2 Na+ + F–)/(Ag+ + H2O) takes place. Indeed, chemical and thermal analyses, as well as Rietveld refinement and 19F NMR, reveal the formation of AgTa2O5F·H2O and Na0.4Ag0.8Nb2O5F1.2·0.8H2O leading to a significant band gap narrowing of approximately 0.4 eV, as determined by diffuse reflectance spectroscopy. DFT calculations show that Ag 4d–O 2p states are located at the edge of the valence band and that the presence of fluorine in the coordination sphere of Ag promotes the hybridization and hence contributes to the band gap narrowing.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Discovery of a p-Type Thermoelectric Material in the [Bi2]m[Bi2Q3]n Family through the Regulation of Carrier Concentration

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c04724

Lei Li, Yu-Meng Wang, Yu-Qian Wu, Ya-Nan Wei, Yu-Lu Xiang, Ling Chen, Fei Jia, Li-Ming Wu

{"title":"Discovery of a p-Type Thermoelectric Material in the [Bi2]m[Bi2Q3]n Family through the Regulation of Carrier Concentration","authors":"Lei Li, Yu-Meng Wang, Yu-Qian Wu, Ya-Nan Wei, Yu-Lu Xiang, Ling Chen, Fei Jia, Li-Ming Wu","doi":"10.1021/acs.inorgchem.4c04724","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04724","url":null,"abstract":"In recent years, many potential n-type near-room-temperature thermoelectric materials belonging to the [Bi2]m[Bi2Q3]n family have been discovered, whereas new p-type thermoelectric materials are relatively rare. In this study, Sb is doped based on n-type Bi0.6Sb0.4Te by adjusting the carrier concentration and then transforms the materials into p-type thermoelectric materials. A novel p-type near-room-temperature thermoelectric material, Bi0.45Sb0.55Te, is discovered in this family. With an increase in doping concentration of Sb, leads to a significant decrease in the bipolar diffusion thermal conductivity. Moreover, when the doping concentration is >50%, the lattice thermal conductivity increases with Sb doping, which is mainly due to the transformation of the host and guest atoms. Furthermore, based on the excessive Bi and Se atoms doping of Bi0.45Sb0.55Te, the ZT value at room temperature can reach approximately 0.44, making Bi0.47Sb0.55TeSe0.05 become a potential room-temperature p-type thermoelectric material.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"50 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Evaluation of the Potential of a Ratiometric Fluorescence Sensor for Sensitively Recognizing 1-Hydroxypyrene in Real Urine Samples Based on a Stable Zn-MOF

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-20 DOI: 10.1021/acs.inorgchem.4c05281

Shuting Xu, Junxi Liu, Bo Zhang, Jiandong Pang, Yan Yang, Jun Li

{"title":"Evaluation of the Potential of a Ratiometric Fluorescence Sensor for Sensitively Recognizing 1-Hydroxypyrene in Real Urine Samples Based on a Stable Zn-MOF","authors":"Shuting Xu, Junxi Liu, Bo Zhang, Jiandong Pang, Yan Yang, Jun Li","doi":"10.1021/acs.inorgchem.4c05281","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05281","url":null,"abstract":"In the work, a 3D Zn-based MOF, [CH3(NH2)2][Zn2(obdb)(OH)]·DMF (compound 1) has been formed successfully through the self-assembly of Zn(II) ion and organic linker H4obdb (4′,4‴-oxybis[1,1′-biphenyl]-3,5-dicarboxylic acid, a high-symmetrical tetra-carboxylate ligand) under solvothermal conditions. In the structure of compound 1, Zn and the symmetry-generated ones constitute a tetra-nuclear cluster [Zn4(μ2-COO)8(μ3–OH)2], and then by the coordination of tetra-nuclear clusters and the organic linkers, a 3D stair-like framework containing a 1D rectangular channel with the porosity of 47.3% is generated. Interestingly, compound 1 is confirmed to possess striking air and pH stability. Noteworthily, the results of detecting studies certify that compound 1 can serve as a prospective ratiometric fluorescence sensor for selectively recognizing 1-hydroxypyrene (1-HP) among diverse urine components and a promising fluorescence probe for Asp from other 11 kinds of amino acids depended on “turn-off” effects decorated with high quenching efficiencies (97.5% for 1-HP and 94.3% for Asp) and outstanding sensitivity with Ksv values of 1.84 × 105 M–1 for 1-HP and 1.41 × 104 M–1 for Asp in a DMF-H2O binary system. Amazingly, the sensing capacities of compound 1 maintain similar levels in fresh human urine compared with those in the DMF-H2O binary system, giving the Ksv values of 5.79 × 104 M–1 for 1-HP and 1.72 × 104 M–1 for Asp.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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