Inorganic Chemistry最新文献_第4页

Structures and Properties of the C6v Symmetric Mn2Ge12 Cluster and Its One-Dimensional Nanostructure. C6v对称Mn2Ge12簇及其一维纳米结构的结构与性质

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c00382

Li-Juan Zhao,Xi-Ling Xu,Wei-Jun Zheng,Hong-Guang Xu

引用次数: 0

Axial Nitrogen Coordination Engineering of Fe Single-Atom Catalyst for Enhanced Peroxidase-like Activity. 增强过氧化物酶类活性的铁单原子催化剂轴向氮配位工程。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02515

Xu Liu,Jianping Guan,Nianhui Zhou,Jinhua Hu,Tianyu Tao,Yi Zhang,Tao Gan,Shibin Wang,Yu Xiong

{"title":"Axial Nitrogen Coordination Engineering of Fe Single-Atom Catalyst for Enhanced Peroxidase-like Activity.","authors":"Xu Liu,Jianping Guan,Nianhui Zhou,Jinhua Hu,Tianyu Tao,Yi Zhang,Tao Gan,Shibin Wang,Yu Xiong","doi":"10.1021/acs.inorgchem.5c02515","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02515","url":null,"abstract":"Mimicking the hierarchical structure as well as the asymmetric Fe-N5 sites in natural horseradish peroxidase (HRP) is of great importance in developing Fe1/CN with high peroxidase-like (POD-like) activity. In this work, Fe1/CN with an asymmetric FeN5 moiety and ordered porous structure (FeN5/CN) is fabricated by an ammonia-assisted redispersion strategy, which shows high structural similarity with HRP. Therefore, FeN5/CN shows an excellent catalytic efficiency (specific activity = 117.9 U/mg, kcat/Km = 2185 mM-1 s-1) and selectivity (Km = 0.059 mM) in a POD-like reaction. Based on the high catalytic properties of FeN5/CN, a sensor for the detection of carbosulfan with a low limit of detection of 3.1 nM is assembled. Interestingly, FeN5/CN activates H2O2 via a superoxide pathway, while ·OH, 1O2, and ·O2- can all be detected in the FeN4/CN involved catalytic system. Mechanistic study by density functional theory calculations combined with experimental results illustrates that Fe-N5 sites provide moderate adsorption of *OH, enlarging and decreasing the reaction energy to form ·OH and ·O2-, respectively, while Fe-N4 sites exhibited higher affinity toward the OH* intermediate, resulting in the facile O-O bond cleavage from H2O2 molecule and prohibited the process of *OH desorption to ·OH.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533383","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

Structure and Bond Dissociation Variations in Dialumenes: A Comparative DFT Study on N,P- versus N,N-Bidentate Ligand Effects. 二铝烯的结构和键解离变化：N，P-与N，N-双齿配体效应的比较DFT研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02012

Weiyi Li,Cai-Qin Li,Ying-Kun Yan,Lei Sun,Wang Guan

{"title":"Structure and Bond Dissociation Variations in Dialumenes: A Comparative DFT Study on N,P- versus N,N-Bidentate Ligand Effects.","authors":"Weiyi Li,Cai-Qin Li,Ying-Kun Yan,Lei Sun,Wang Guan","doi":"10.1021/acs.inorgchem.5c02012","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02012","url":null,"abstract":"Herein, we report a comprehensive density functional theory (DFT) calculation to investigate the distinct dissociation behaviors of dialumenes supported by amidophosphine, amidinate, and β-diketiminate (BDI) ligands. Calculations reveal that amidophosphine and amidinate ligands stabilize the Al═Al double bond via a dynamic equilibrium with their aluminyl monomers. Conversely, the BDI ligand preferentially stabilizes mononuclear Al(I) species over dimerization. According to energy decomposition analysis (EDA) and charge decomposition analysis (CDA), this distinct behavior is attributed to the enhanced Pauli's repulsion and diminished orbital interaction between the BDI-stabilized aluminyl fragments. Notably, despite the constrained N-Al-N bite angle imposed by the amidinate ligand, the enhanced stability of the Al═Al bond emerges through limited aluminyl monomer deformation and effective ligand-metal conjugation. A systematic comparison with the hydrogenated amidophosphine ligand systems further demonstrates that the ligand-metal conjugation critically modulates Al═Al bond dissociation, primarily through steric repulsion between the amino lone pairs and Al-Al cores. These key ligand parameters derived from specific ligand systems in this study provide a theoretical foundation for future dialumene design.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533478","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

Quantitative Mapping of Oxygen Affinity to Local Chemical Environments in Ti-Zr-Nb-Ta Alloys via Machine Learning. 通过机器学习定量绘制Ti-Zr-Nb-Ta合金中氧对局部化学环境的亲和力。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c01713

Tingting Zhou,Dan Jian,Meiqi Wei,Guoqing Zhang,Yuhan Zhou,Yuqing Huang,Qi Wang,Maobing Shuai

{"title":"Quantitative Mapping of Oxygen Affinity to Local Chemical Environments in Ti-Zr-Nb-Ta Alloys via Machine Learning.","authors":"Tingting Zhou,Dan Jian,Meiqi Wei,Guoqing Zhang,Yuhan Zhou,Yuqing Huang,Qi Wang,Maobing Shuai","doi":"10.1021/acs.inorgchem.5c01713","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01713","url":null,"abstract":"Simultaneously enhancing strength and ductility is a longstanding challenge in materials science. Recent studies show that incorporating oxygen into Ti-Zr-family refractory high-entropy alloys (HEAs) can overcome this trade-off, with improved properties stemming from interstitial oxygen occupancy. However, oxygen occupancy is inherently site-specific and strongly influenced by local chemical environments, complicating quantitative predictions of oxygen solution energies at individual sites. Here, we address this challenge in the Ti-Zr-Nb-Ta system by combining high-throughput first-principles calculations with machine learning (ML). Representing local environments with Smooth Overlap of Atomic Positions features, our ML model accurately predicts oxygen solution energies from initial, unrelaxed atomic configurations (R2 = 0.93, mean absolute error = 0.11 eV), enabling analysis of oxygen occupancy trends and spatial correlations over extensive compositional ranges. Two critical descriptors─the average oxygen solution energy and its standard deviation─are proposed to quantify overall oxygen affinity and distribution heterogeneity within each composition. Notably, these descriptors correlate closely with experimentally reported strength and ductility enhancements, highlighting that controlled oxygen interstitial occupancy is crucial for optimizing mechanical properties. Our findings provide fundamental insights into oxygen solution behaviors in HEAs and facilitate the design of oxygen-containing HEAs with controlled oxygen incorporation and distribution.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533485","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

IF 4.3 2区化学