Inorganic Chemistry最新文献_第3页

Cu Nanoclusters and Rh Single-Atom-Modified N-Doped Carbon for Electroreduction of Nitrate to Ammonia. 铜纳米簇和Rh单原子修饰n掺杂碳电还原硝酸盐制氨。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03508

Wenhan Dai,Yahan Fang,Junfeng Huang,Zhongwei Wang,Jian Li,Mudong Tu,Huijiao Wang,Jun Yang,Cailing Xu,Hua Li

{"title":"Cu Nanoclusters and Rh Single-Atom-Modified N-Doped Carbon for Electroreduction of Nitrate to Ammonia.","authors":"Wenhan Dai,Yahan Fang,Junfeng Huang,Zhongwei Wang,Jian Li,Mudong Tu,Huijiao Wang,Jun Yang,Cailing Xu,Hua Li","doi":"10.1021/acs.inorgchem.5c03508","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03508","url":null,"abstract":"To tackle the pressing issue of nitrate (NO3-) pollution in wastewater and simultaneously convert it into ammonia (NH3), Cu nanocluster-modified Rhodium (Rh) single atoms anchored on N-doped carbon were synthesized via pyrolysis of a zeolitic imidazolate framework-8 (ZIF-8) precursor and applied to the electrochemical reduction of nitrate at a low concentration. Structural characterizations (X-ray powder diffractometer (XRD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and X-ray photoelectron spectroscopy (XPS)) confirmed the coexistence of Rh single atoms and Cu nanoclusters as well as their strong electronic interactions. Mechanistic investigations revealed that Rh sites enhanced *H generation via water dissociation and promoted NO3- adsorption, thereby facilitating *H transfer and subsequent hydrogenation steps. As a result, the optimized Cu97.5Rh2.5/NC catalyst exhibited outstanding NO3-RR performance, with a Faradaic efficiency (FE) of 84.53%, an NH3 yield rate of 1252.22 μg·h-1 mgcat-1 at -1.0 V vs reversible hydrogen electrode (RHE), an NH3 selectivity of 89.13% at -1.0 V vs RHE, and a NO3- conversion rate of 93.34% at -1.1 V vs RHE. This work presents a rational design for atom-economical catalysts, enabling sustainable NH3 electrosynthesis from nitrate-laden wastewater and reducing effluent NO3--N to meet World Health Organization (WHO) drinking water standards.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"93 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194547","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

One-Pot Microemulsion Strategy for Fabricating Ni@MgAl2O4 Catalysts with Enhanced Sintering and Coking Resistances for Dry Reforming of Methane. 一锅微乳液法制备甲烷干法重整中抗烧结、抗焦化Ni@MgAl2O4催化剂。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03399

Jinjin Liu,Qijie Yi,Chi Zhang,Wenxiang Tang

{"title":"One-Pot Microemulsion Strategy for Fabricating Ni@MgAl2O4 Catalysts with Enhanced Sintering and Coking Resistances for Dry Reforming of Methane.","authors":"Jinjin Liu,Qijie Yi,Chi Zhang,Wenxiang Tang","doi":"10.1021/acs.inorgchem.5c03399","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03399","url":null,"abstract":"In the context of increasing global energy demand and greenhouse gas (GHG) emissions, the dry reforming of methane (DRM) to syngas can simultaneously convert CH4 and CO2 into syngas (H2 and CO), which is both environmentally friendly and energy valuable. Carbon deposits and the sintering of active metals often lead to catalyst deactivation. In this work, one-pot microemulsion and impregnation methods have been employed to synthesize Ni@MgAl2O4 and Ni/MgAl2O4 catalysts, respectively, and the effects of different calcination temperatures on the physicochemical properties of the loaded catalysts were investigated. It was shown that Ni@MgAl2O4 exhibited good structural stability and strong metal-support interaction. In addition, the surfaces of Ni@MgAl2O4-800 are rich in adsorbed oxygen species and basic sites, which are favorable for CO2 adsorption and activation and inhibit carbon deposition. In the DRM reaction, the Ni@MgAl2O4-800 catalyst exhibited the highest CH4 and CO2 conversions in the tested temperature range. Its initial conversion of CH4 and CO2 was 92.5 and 93.1%, respectively (800 °C, WHSV = 30,000 mL·gcat-1·h-1). After 20 h of continuous running, the decreases of CH4 and CO2 conversion were <5 and 9%, respectively, and no obvious carbon deposition was observed, which showed good reactivity and anticarbon deposition performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194548","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

Experimental and Theoretical Study of the Formation of Noble Gas Monoxide Cations in the Gas Phase. 气态惰性气体一氧化碳阳离子形成的实验与理论研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-10-01 DOI: 10.1021/acs.inorgchem.5c03228

Sandrina Oliveira,Nuno A G Bandeira,Leonor Maria,João P Leal,José M Carretas,Bernardo Monteiro,Joaquim Marçalo

{"title":"Experimental and Theoretical Study of the Formation of Noble Gas Monoxide Cations in the Gas Phase.","authors":"Sandrina Oliveira,Nuno A G Bandeira,Leonor Maria,João P Leal,José M Carretas,Bernardo Monteiro,Joaquim Marçalo","doi":"10.1021/acs.inorgchem.5c03228","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03228","url":null,"abstract":"Reactions of Ng+ ions (Ng = Kr, Xe) with strong oxidants O3 and N2O were examined by FTICR/MS, employing electron ionization in the ICR cell under very low pressure. For Kr+, only electron transfer was observed, showing that, due to the high ionization energy of Kr, this highly exoenergetic reaction channel dominated. The lower ionization energy of Xe compared to those of O3 and N2O allowed for the formation of XeO+ in the reaction of Xe+ with O3; however, Xe+ was nonreactive with N2O. The experimental O atom dissociation energies of O3 and N2O at 298.15 K, 25.5 and 39.9 kcal mol-1, respectively, indicate that, if a previous experimental and theoretical estimate of the dissociation energy D(Xe+-O) = 51 kcal mol-1 is right, formation of XeO+ in the reaction of Xe+ with N2O should be observed under our experimental conditions. Therefore, we assessed the reaction profiles of Xe+ with O3 and N2O using state-specific CASPT2 and MP2, respectively, to try to comprehend the different outcomes of these oxygen-bond cleavage reactions. Calculations showed that, although exoenergetic, the N2O reaction has a higher activation energy than that of O3, which agrees with the experiments where N2O was ineffective in the formation of XeO+.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203896","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

Realizing the Magnetostructural Correlation of a Highly Anisotropic Fe(III) Porphyrin Complex through Ab Initio Approaches. 用从头算方法实现高各向异性铁（III）卟啉配合物的磁结构相关。

IF 4.7 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c02754

Mayurika Das, Sujit Kamilya, Debopam Sarkar, Subhankar Mandal, Sher Singh Meena, Jiri Pechousek, Radovan Herchel, Abhishake Mondal

引用次数: 0

Dual-Mechanism Insights into the Peroxidase-like Activity of Co3O4 Nanoparticles: Nonradical and Superoxide Radical Catalysis. Co3O4纳米颗粒过氧化物酶样活性的双重机制：非自由基和超氧化物自由基催化。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c02729

Shufeng Liang,Yun Zhao,Yunhui Zhang,Xing Zhao,Miaomiao Li,Yunpeng Wang,Hui Han,Yanling Yu,Yan Dai,Yujing Guo

{"title":"Dual-Mechanism Insights into the Peroxidase-like Activity of Co3O4 Nanoparticles: Nonradical and Superoxide Radical Catalysis.","authors":"Shufeng Liang,Yun Zhao,Yunhui Zhang,Xing Zhao,Miaomiao Li,Yunpeng Wang,Hui Han,Yanling Yu,Yan Dai,Yujing Guo","doi":"10.1021/acs.inorgchem.5c02729","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02729","url":null,"abstract":"Although the Co3O4 nanozyme has been reported to exhibit peroxidase (POD) mimicking activity, its explicit catalytic mechanism remains indefinable. This study systematically investigates the POD-like catalytic mechanism of Co3O4 nanoparticles (NPs) through integrated experimental and theoretical approaches. The results reveal that their catalytic activity originates from dual synergistic pathways: the nonradical and the radical pathways. In the nonradical pathways, Co3O4 NPs mediate electron transfer from the substrate (e.g., 3,3',5,5'-tetramethylbenzidine, TMB) to H2O2 through the Co(III)/Co(II) redox couple, as its redox potential lies between that of TMB and H2O2. During the radical pathways, electron paramagnetic resonance (EPR) and fluorescent or UV-vis probe experiments demonstrate that H2O2 preferentially decomposes into superoxide radicals (O2•-) over hydroxyl radicals (•OH). Furthermore, density functional theory calculations reveal that H2O2 exhibits a relatively lower activation barrier (0.78 eV) to generate O2•- on the Co3O4 (110) facet, compared to the higher barrier (1.72 eV) for •OH formation. Additionally, the distinct degradation behaviors of organic dyes provide further validation of the proposed mechanism. This research will encourage further exploration into the catalytic mechanisms of nanozymes, thereby facilitating their rational design and application.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"93 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194556","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

H©Cu4I4-: A Planar Tetracoordinate Hydrogen Superhalogen Anion Stabilized by Covalent Multicenter Bonding. H©Cu4I4-：一种共价多中心键稳定的平面四配位超卤素氢阴离子。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c03367

Li-Xia Bai,Ya-Xuan Cheng,Mesías Orozco-Ic,Jin-Chang Guo

引用次数: 0

(C7H10N)3Bi2I9·I2: Synergistic Cooperation of π-Conjugated Cations and Distorted [BiI6] Octahedra Enabling a Large Infrared Birefringence. （C7H10N）3Bi2I9·I2: π共轭阳离子与畸变[BiI6]八面体的协同作用，实现大红外双折射。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c03848

Dingxuan Zhao,Shihui Ma,Jiajia Wang,Fei Liang,Dazhi Lu,Kui Wu,Ning Ye,Zhanggui Hu

{"title":"(C7H10N)3Bi2I9·I2: Synergistic Cooperation of π-Conjugated Cations and Distorted [BiI6] Octahedra Enabling a Large Infrared Birefringence.","authors":"Dingxuan Zhao,Shihui Ma,Jiajia Wang,Fei Liang,Dazhi Lu,Kui Wu,Ning Ye,Zhanggui Hu","doi":"10.1021/acs.inorgchem.5c03848","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03848","url":null,"abstract":"Birefringent crystals can modulate the polarization of light and have important applications in optoelectronic and photonic fields in the infrared optical communication band. However, existing birefringent crystals exhibit a significant decrease in birefringence (Δn ≤ 0.26) in the infrared waveband due to the dispersion effect. Herein, we designed a new organic-inorganic hybrid halide (C7H10N)3Bi2I9·I2, which possesses a layered structure with π-conjugation cations. Though the structure has a stereochemical inert lone pair Bi3+, the compound exhibits a large birefringence of 0.39@589 nm (sodium D-line), which is consistent with the theoretical calculations of 0.386@589 nm. Remarkably, first-principles calculations reveal that it still maintains a large birefringence of 0.42@1064 nm and 0.32@1550 nm. This can be attributed to the highly distorted nature of the π-conjugated 1-ethylpyridinium cation and the significant distortion of the BiI6 octahedra. This work highlights the persistently neglected potential of organic-inorganic hybrid halide materials as birefringent crystals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"75 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189163","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

Asymmetric Coordination in a Thermoluminescent Pb-Based MOF Enables High-Dose X-ray Detection. 热释光pb基MOF中的不对称配位实现了高剂量x射线检测。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c03789

Qian Yang,Tianping Wang,Shuya Zhang,Sen Mei,Jia Li,Feifan Zhong,Yanlong Wang,Hanzhou Liu,Zhifang Chai,Shuao Wang

{"title":"Asymmetric Coordination in a Thermoluminescent Pb-Based MOF Enables High-Dose X-ray Detection.","authors":"Qian Yang,Tianping Wang,Shuya Zhang,Sen Mei,Jia Li,Feifan Zhong,Yanlong Wang,Hanzhou Liu,Zhifang Chai,Shuao Wang","doi":"10.1021/acs.inorgchem.5c03789","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03789","url":null,"abstract":"Metal-organic frameworks (MOFs) are emerging as promising thermoluminescent (TL) materials due to their structural tunability, mild synthesis conditions, and well-defined structure-property relationships. However, their application in high-dose X-ray detection remains largely unexplored. Herein, we report SCU-600, a Pb-based MOF featuring asymmetric coordination of the organic ligand 2,6-dimethylterephthalic acid, in which the two inequivalent carboxylate groups adopt different binding modes with Pb2+ ions. This coordination asymmetry induces significant steric effects, giving rise to an ant-type topology and a wide bandgap of 3.48 eV. Owing to this wide bandgap, SCU-600 exhibits a broad linear TL response over 1-280 Gy (R2 = 0.994). SCU-600 also demonstrates high sensitivity with a low detection threshold of 2.89 × 10-2 Gy, excellent thermal stability up to 657.8 K, strong radiation resistance under 10 kGy γ-ray exposure, and robust reusability over 12 cycles. Mechanistic studies reveal that the TL emission originates from radiation-induced oxygen-centered radicals generated through intramolecular charge transfer. Furthermore, electron paramagnetic resonance confirms the formation of two distinct radical species in SCU-600, attributed to the asymmetric coordination environment. This work not only demonstrates the potential of SCU-600 for high-dose radiation detection in applications such as clinical radiotherapy and agricultural irradiation but also establishes coordination symmetry as a key design parameter for tailoring TL performance in MOF-based materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194553","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

Regulating Electron Transfer in a POM-Based MOF Photocatalyst with Dual Active Sites for Enhanced N2 Oxidation. 调控双活性位pom基MOF光催化剂的电子转移以促进N2氧化。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c03997

Xiaohong Li,Yuteng Zhang,Haihui Yu,Meng Sun,Haifeng Zhang

{"title":"Regulating Electron Transfer in a POM-Based MOF Photocatalyst with Dual Active Sites for Enhanced N2 Oxidation.","authors":"Xiaohong Li,Yuteng Zhang,Haihui Yu,Meng Sun,Haifeng Zhang","doi":"10.1021/acs.inorgchem.5c03997","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03997","url":null,"abstract":"Nitric acid (HNO3) serves as a vital industrial raw material and ranks among the most widely manufactured chemicals. Recently, photocatalytic systems have been explored as an environmentally friendly pathway for direct N2 utilization in oxidation reactions. However, progress has been hindered by the high activation barrier of the N≡N bond and severe electron-hole recombination in catalysts. Here, we highlight that polyoxometalates (POMs)-based metal-organic frameworks (MOFs) (Mo72Cr30/UiO-66) enable highly efficient HNO3 synthesis, owing to a dual-site mechanism. The results reveal that oxygen vacancies on UiO-66 capture electrons from Mo72Cr30, inducing adjacent metals to form Zr3+ with unpaired electrons, which transfer to N2 antibonding orbitals, thereby lowering the activation barrier. Furthermore, the holes enrich on the Mo72Cr30 surface to oxidize water for generating strong oxidative reactive oxygen species hydroxyl radical (•OH), thus facilitating HNO3 production. The distinct site synergy of Mo72Cr30 and UiO-66 for N2 activation results in an exceptional activity of 646.3 μg g-1 h-1, which far surpasses the performance of Mo72Cr30 and UiO-66 alone by approximately 18-fold and 6-fold, respectively. Our study offers a novel design vision for photocatalytic materials and presents a promising approach for advancing sustainable artificial N2 fixation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"93 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194875","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

Reactions of Borafluorene with Iminophosphines: PN Insertion and Skeletal Editing to Phosphafluorene. 硼氟烯与亚膦的反应：PN插入和对氟磷的骨架编辑。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-09-30 DOI: 10.1021/acs.inorgchem.5c03700

Yijie Li,Leonardo I Lugo-Fuentes,J Oscar C Jimenez-Halla,Caleb D Martin

引用次数: 0