Inorganic Chemistry最新文献_第10页

MOF-Derived Ni5P4 Nanoparticles Based on the Microemulsion Strategy for Supercapacitors and Water Splitting

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-03-20 DOI: 10.1021/acs.inorgchem.4c0549610.1021/acs.inorgchem.4c05496

Sencheng Cai, Guancheng Xu*, Jiahui Jiang, Adil Emin, Qihao Wu, Shuai Liu, Yuying Feng and Li Zhang*,

{"title":"MOF-Derived Ni5P4 Nanoparticles Based on the Microemulsion Strategy for Supercapacitors and Water Splitting","authors":"Sencheng Cai, Guancheng Xu*, Jiahui Jiang, Adil Emin, Qihao Wu, Shuai Liu, Yuying Feng and Li Zhang*, ","doi":"10.1021/acs.inorgchem.4c0549610.1021/acs.inorgchem.4c05496","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05496https://doi.org/10.1021/acs.inorgchem.4c05496","url":null,"abstract":"With the rapid advancement of energy storage and conversion systems (ESCSs), renewable energy can achieve a smooth and continuous output capacity. Nevertheless, commercial precious metal-based multifunctional ESCSs materials are plagued by issues like scarcity and high production costs. This study adopted microemulsion and chemical vapor deposition (CVD) strategies to fabricate single crystal Ni5P4 nanoparticles successfully. Due to its excellent crystal integrity and high electrical conductivity, single crystal Ni5P4 offers abundant active sites for redox reactions. Additionally, it allows electrons and ions to move more efficiently and freely, making it a highly promising multifunctional material for ESCSs. For supercapacitors (SCs), the prepared Ni5P4-10 electrode possesses a battery-like behavior with a high specific capacity of 1643.13 F g–1@0.5 A g–1. The corresponding assembled Ni5P4-10//AC hybrid SCs (HSCs) exhibit a maximum energy density of 37.78 Wh kg–1 at a power density of 400 W kg–1. Furthermore, Ni5P4-10 displays low overpotentials of 150 mV@HER and 250 mV@OER at 10 mA cm–2 when it serves as an electrocatalyst. This study offers a novel perspective for the design of MOF-derived multifunctional ESCSs materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 12","pages":"6125–6136 6125–6136"},"PeriodicalIF":4.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737541","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

Examining Order–Disorder Structural Transition of Gd2Zr2–xCexO7 Using Synchrotron Techniques

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.4c04795

Khushveer Kaur, Graham King, Andrew P. Grosvenor

{"title":"Examining Order–Disorder Structural Transition of Gd2Zr2–xCexO7 Using Synchrotron Techniques","authors":"Khushveer Kaur, Graham King, Andrew P. Grosvenor","doi":"10.1021/acs.inorgchem.4c04795","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04795","url":null,"abstract":"Depending on the radius ratio of A and B site cations, A2B2O7-type oxides can adopt different crystal structures, including the pyrochlore-, defect fluorite-, or bixbyite-type structures. Gd2Zr2O7 with a rGd3+/rZr4+ ratio of 1.46 is an example that exhibits a polymorphic transition between the pyrochlore- and defect fluorite-type structures. To delve deeper into these polymorphic transitions, Ce was introduced as a substitute in the B-site of Gd2Zr2O7. Gd2Zr2–xCexO7 (0 ≤ x ≤ 2) was synthesized using a coprecipitation method and annealed at 1400 °C. Previous investigations yielded disparate results regarding the structures adopted due to the challenge of detecting the low-intensity superstructural peaks associated with the pyrochlore and bixbyite structures using conventional lab-based X-ray diffraction (XRD) instruments. Utilizing synchrotron XRD with a high signal/noise ratio resolves these contradictions and aids in the structure analysis for Gd2Zr2–xCexO7. Based on synchrotron XRD data, a combination of defect fluorite and pyrochlore phases was observed for x = 0–0.25, the defect fluorite structure was adopted when x = 0.5–1.75, and the bixbyite structure was observed when x = 2. Ce L3 and Zr K-edge X-ray absorption near edge spectroscopy (XANES) spectra revealed that both cations were present in 4+ oxidation states.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660726","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

X-ray Spectroscopy Characterization of Electronic Structure and Metal–Metal Bonding in Dicobalt Complexes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.5c00508

Arun S. Asundi, Roel L. M. Bienenmann, Daniël L. J. Broere, Ritimukta Sarangi

{"title":"X-ray Spectroscopy Characterization of Electronic Structure and Metal–Metal Bonding in Dicobalt Complexes","authors":"Arun S. Asundi, Roel L. M. Bienenmann, Daniël L. J. Broere, Ritimukta Sarangi","doi":"10.1021/acs.inorgchem.5c00508","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00508","url":null,"abstract":"Developing multimetallic complexes with tunable metal–metal interactions has long been a target of synthetic inorganic chemistry efforts due to the unique properties that such compounds can exhibit. However, understanding relationships between metal–metal bonding and chemical properties is challenging due to system-dependent factors that influence metal–metal and metal–ligand interactions, including ligand identity, coordination geometry, and metal–metal distance. In this work, we apply X-ray absorption and emission spectroscopy and quantum chemical calculations to describe electronic structure and bonding in a series of dicobalt complexes. The compounds with silane ligands and pseudo-octahedral coordination geometry exhibit Co–Co σ and multicentered bonding character, which we characterize from both the occupied and vacant perspectives via their contributions to the Co X-ray emission and absorption spectra, respectively. In contrast, the dicobalt complexes with a pseudotetrahedral coordination environment do not exhibit Co–Co bonding due to symmetry constraints on orbital overlap. We extend these insights to the theoretical evaluation of related dicobalt complexes to explain how ligand coordination and symmetry dictate the presence or absence of a Co–Co bond. This work highlights how fundamental insights into electronic structure and bonding through X-ray spectroscopy uncover important factors governing metal–metal interactions and guide the rational design of multimetallic complexes with tunable metal–metal bonds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661115","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

Modulating Copper(II) Coordination and Antimicrobial Activity: Effects of d-Amino Acid Substitution and Retro-Inverso Modification in Human Saliva MUC7 Peptide

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.5c00438

Joanna Wątły, Klaudia Szarszoń, Monika Sabieraj, Arian Kola, Robert Wieczorek, Tomasz Janek, Daniela Valensin

{"title":"Modulating Copper(II) Coordination and Antimicrobial Activity: Effects of d-Amino Acid Substitution and Retro-Inverso Modification in Human Saliva MUC7 Peptide","authors":"Joanna Wątły, Klaudia Szarszoń, Monika Sabieraj, Arian Kola, Robert Wieczorek, Tomasz Janek, Daniela Valensin","doi":"10.1021/acs.inorgchem.5c00438","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00438","url":null,"abstract":"Fragments of MUC7, a salivary protein involved in nonimmune defense, arise from proteolytic cleavage in saliva and exhibit antimicrobial properties. However, their therapeutic use is limited by low stability due to further degradation. To address this, a native MUC7 fragment was modified using d-amino acids and the retro-inverso strategy. Given the role of metal ions in enhancing antimicrobial peptides, we analyzed the bioinorganic chemistry of these systems with Cu(II) and assessed their antimicrobial activity against fungal and bacterial strains. This study is the first to explore the correlation between metal binding mode, structure, stability, and antimicrobial activity of retro-inverso peptides as well as Cu(II) coordination in such systems. A combination of experimental techniques (potentiometry, mass spectrometry, UV–vis, circular dichroism, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopy) and density functional theory calculations characterized their coordination chemistry. Our results demonstrate that the “standard” enantiomeric exchange and retro-inverso modifications of the MUC7 fragment have a minimal effect on the secondary structure and biological activity of the studied peptides and their Cu(II) complexes. However, these modifications significantly influence on the thermodynamic stability of studied systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654197","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

Surface-Confined Anchoring of Highly Dispersed Nanocobalt Promotes Advanced Oxidation for Eliminating Health-Threatening Organics

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.5c0061110.1021/acs.inorgchem.5c00611

Haijian Wang, Yicheng Zhang, Xinyue Cui, Xiqian Cao, Yang Su, Mengshan Chen, Jinghu Wang, Xue Zhao* and Yingtang Zhou*,

{"title":"Surface-Confined Anchoring of Highly Dispersed Nanocobalt Promotes Advanced Oxidation for Eliminating Health-Threatening Organics","authors":"Haijian Wang, Yicheng Zhang, Xinyue Cui, Xiqian Cao, Yang Su, Mengshan Chen, Jinghu Wang, Xue Zhao* and Yingtang Zhou*, ","doi":"10.1021/acs.inorgchem.5c0061110.1021/acs.inorgchem.5c00611","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00611https://doi.org/10.1021/acs.inorgchem.5c00611","url":null,"abstract":"Peroxymonosulfate (PMS)-based advanced oxidation processes are effective in eliminating health-threatening persistent organic pollutants (POPs), but they require the participation of high-performance catalysts. In this study, a highly dispersed nanocobalt species (Co-NHCSs) was constructed on nitrogen-doped hollow carbon spheres by using the double confinement mechanism of complexation confinement combined with spatial confinement. The Co-NHCSs/PMS system has a high degradation efficiency of 95.2% for tetracycline within 30 min, and the degradation performance was almost not attenuated after repeated use 10 times. The Co-NHCSs/PMS system can also resist the interference of a complex water environment to achieve efficient degradation of POPs in multiple scenarios. Reactive oxygen quenching experiments and electron paramagnetic resonance confirmed that Co-NHCSs promoted the activation of PMS into ·OH, SO4·–, and 1O2 with high oxidation potential, which promoted the degradation of POPs. Density functional theory calculations show that nano-Co anchored on NHCSs can spontaneously capture and activate PMS on either a planar carbon matrix or a curved carbon matrix, which is the key to the efficient degradation of POPs by the Co-NHCSs/PMS system. This study not only provides an innovative way to construct nanometal catalysts but also reveals the transformation behavior of PMS on cobalt-based materials, which is of great significance for promoting PMS-based wastewater treatment technology.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 12","pages":"6389–6401 6389–6401"},"PeriodicalIF":4.3,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737407","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

Examining Order–Disorder Structural Transition of Gd2Zr2–xCexO7 Using Synchrotron Techniques

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.4c0479510.1021/acs.inorgchem.4c04795

Khushveer Kaur, Graham King and Andrew P. Grosvenor*,

{"title":"Examining Order–Disorder Structural Transition of Gd2Zr2–xCexO7 Using Synchrotron Techniques","authors":"Khushveer Kaur, Graham King and Andrew P. Grosvenor*, ","doi":"10.1021/acs.inorgchem.4c0479510.1021/acs.inorgchem.4c04795","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04795https://doi.org/10.1021/acs.inorgchem.4c04795","url":null,"abstract":"Depending on the radius ratio of A and B site cations, A2B2O7-type oxides can adopt different crystal structures, including the pyrochlore-, defect fluorite-, or bixbyite-type structures. Gd2Zr2O7 with a rGd3+/rZr4+ ratio of 1.46 is an example that exhibits a polymorphic transition between the pyrochlore- and defect fluorite-type structures. To delve deeper into these polymorphic transitions, Ce was introduced as a substitute in the B-site of Gd2Zr2O7. Gd2Zr2–xCexO7 (0 ≤ x ≤ 2) was synthesized using a coprecipitation method and annealed at 1400 °C. Previous investigations yielded disparate results regarding the structures adopted due to the challenge of detecting the low-intensity superstructural peaks associated with the pyrochlore and bixbyite structures using conventional lab-based X-ray diffraction (XRD) instruments. Utilizing synchrotron XRD with a high signal/noise ratio resolves these contradictions and aids in the structure analysis for Gd2Zr2–xCexO7. Based on synchrotron XRD data, a combination of defect fluorite and pyrochlore phases was observed for x = 0–0.25, the defect fluorite structure was adopted when x = 0.5–1.75, and the bixbyite structure was observed when x = 2. Ce L3 and Zr K-edge X-ray absorption near edge spectroscopy (XANES) spectra revealed that both cations were present in 4+ oxidation states.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 12","pages":"5913–5922 5913–5922"},"PeriodicalIF":4.3,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737482","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

BaLa4(SiS4)2(BS3)2: Structurally Ordered Thioborate-Thiosilicate Obtained by Adjusting the Cationic Size

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.5c0008310.1021/acs.inorgchem.5c00083

Ya-Xiang Han, Ming-Zhi Zhang, Chun-Li Hu and Jiang-Gao Mao*,

{"title":"BaLa4(SiS4)2(BS3)2: Structurally Ordered Thioborate-Thiosilicate Obtained by Adjusting the Cationic Size","authors":"Ya-Xiang Han, Ming-Zhi Zhang, Chun-Li Hu and Jiang-Gao Mao*, ","doi":"10.1021/acs.inorgchem.5c0008310.1021/acs.inorgchem.5c00083","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00083https://doi.org/10.1021/acs.inorgchem.5c00083","url":null,"abstract":"Thioborates are of interest as nonlinear optical materials, birefringent materials, and solid-state electrolytes. Under the dilemma that all known thioborate–thiosilates are disordered structures with co-occupied atomic sites, the first structurally ordered thioborate-thiosilicate, BaLa4(SiS4)2(BS3)2, has been successfully obtained by adjusting the cationic size. It features a novel 3D tunnel network assembled by La–B–S chains and La–Si–S bilayers. In addition, BaLa4(SiS4)2(BS3)2 exhibits good chemical and thermal stability (up to 880 °C), wide light transmission range (0.4–11 μm), wide band gap (3.25 eV), moderate birefringence (0.076 @ 546 nm), and high laser-induced damage threshold (6 × AgGaS2). Theoretical calculations showed that the [BS3]3– functional group is the main contributor to birefringence. This work enriches the structure types of thioborate-thiosilicate and expands insights into mixed anionic thioborates.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 12","pages":"6259–6264 6259–6264"},"PeriodicalIF":4.3,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737520","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

V-doped Co2P Anchored on the N–P-Doped Three-Dimensional Covalently Cross-Linked Graphene As a Hydrogen Evolution Reaction Catalyst for Alkaline Water/Seawater Splitting

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.4c0553710.1021/acs.inorgchem.4c05537

Shaopei Jia*, Yanfeng Gao, Xiaofei Ma, Yunfei Cao, Quan Huang, Qian Zhang, Zhixin Wang, Yanjie Wang, Yuanyuan Li, Dan Li, Renkai Chang and Yunchao Mu*,

{"title":"V-doped Co2P Anchored on the N–P-Doped Three-Dimensional Covalently Cross-Linked Graphene As a Hydrogen Evolution Reaction Catalyst for Alkaline Water/Seawater Splitting","authors":"Shaopei Jia*, Yanfeng Gao, Xiaofei Ma, Yunfei Cao, Quan Huang, Qian Zhang, Zhixin Wang, Yanjie Wang, Yuanyuan Li, Dan Li, Renkai Chang and Yunchao Mu*, ","doi":"10.1021/acs.inorgchem.4c0553710.1021/acs.inorgchem.4c05537","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05537https://doi.org/10.1021/acs.inorgchem.4c05537","url":null,"abstract":"Designing and synthesizing highly efficient and stable electrocatalysts of seawater electrolysis for the hydrogen evolution reaction is important for realizing green hydrogen production. Herein, a heterostructured V-doped Co2P anchored on N–P-doped three-dimensional covalently cross-linked graphene (V–Co2P@NPPC/3DG) electrocatalysts was synthesized with the help of V-doped ZIF-67 as an intermediate and a controlled phosphidation process. The as-prepared V–Co2P@NPPC/3DG-1:5 had low overpotentials of 98.3 and 88.3 mV (at 10 mA cm–2) in alkaline water and artificial seawater, respectively, and the corresponding Tafel slopes were 56.4 and 51.0 mV dec–1. The electrolyzer with a flowing alkaline artificial seawater assembled from V–Co2P@NPPC/3DG-1:5 with a commercial RuO2 catalyst exhibited a cell voltage of 1.54 V at 10 mA cm–2, which is close to that of Pt/C||RuO2 (1.52 V). Notably, the cell voltage of V–Co2P@NPPC/3DG-1:5||RuO2 was lower than that of Pt/C||RuO2 at a high current density (>58 mA cm–2), which exhibited superior stability. V doping effectively enhanced the intrinsic activity of Co2P, and the complexation with NPPC/3DG achieved full exposure of the active sites while enhancing the charge transfer rate during HER. This work will attract attention to the role of metal compound-carbon support interactions in enhancing the intrinsic activity, conductivity, and stability of electrocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 12","pages":"6147–6158 6147–6158"},"PeriodicalIF":4.3,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737591","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

X-ray Spectroscopy Characterization of Electronic Structure and Metal–Metal Bonding in Dicobalt Complexes

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.5c0050810.1021/acs.inorgchem.5c00508

Arun S. Asundi, Roel L. M. Bienenmann, Daniël L. J. Broere and Ritimukta Sarangi*,

{"title":"X-ray Spectroscopy Characterization of Electronic Structure and Metal–Metal Bonding in Dicobalt Complexes","authors":"Arun S. Asundi, Roel L. M. Bienenmann, Daniël L. J. Broere and Ritimukta Sarangi*, ","doi":"10.1021/acs.inorgchem.5c0050810.1021/acs.inorgchem.5c00508","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00508https://doi.org/10.1021/acs.inorgchem.5c00508","url":null,"abstract":"Developing multimetallic complexes with tunable metal–metal interactions has long been a target of synthetic inorganic chemistry efforts due to the unique properties that such compounds can exhibit. However, understanding relationships between metal–metal bonding and chemical properties is challenging due to system-dependent factors that influence metal–metal and metal–ligand interactions, including ligand identity, coordination geometry, and metal–metal distance. In this work, we apply X-ray absorption and emission spectroscopy and quantum chemical calculations to describe electronic structure and bonding in a series of dicobalt complexes. The compounds with silane ligands and pseudo-octahedral coordination geometry exhibit Co–Co σ and multicentered bonding character, which we characterize from both the occupied and vacant perspectives via their contributions to the Co X-ray emission and absorption spectra, respectively. In contrast, the dicobalt complexes with a pseudotetrahedral coordination environment do not exhibit Co–Co bonding due to symmetry constraints on orbital overlap. We extend these insights to the theoretical evaluation of related dicobalt complexes to explain how ligand coordination and symmetry dictate the presence or absence of a Co–Co bond. This work highlights how fundamental insights into electronic structure and bonding through X-ray spectroscopy uncover important factors governing metal–metal interactions and guide the rational design of multimetallic complexes with tunable metal–metal bonds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 12","pages":"6378–6388 6378–6388"},"PeriodicalIF":4.3,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737698","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

Surface-Confined Anchoring of Highly Dispersed Nanocobalt Promotes Advanced Oxidation for Eliminating Health-Threatening Organics

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-19 DOI: 10.1021/acs.inorgchem.5c00611

Haijian Wang, Yicheng Zhang, Xinyue Cui, Xiqian Cao, Yang Su, Mengshan Chen, Jinghu Wang, Xue Zhao, Yingtang Zhou

{"title":"Surface-Confined Anchoring of Highly Dispersed Nanocobalt Promotes Advanced Oxidation for Eliminating Health-Threatening Organics","authors":"Haijian Wang, Yicheng Zhang, Xinyue Cui, Xiqian Cao, Yang Su, Mengshan Chen, Jinghu Wang, Xue Zhao, Yingtang Zhou","doi":"10.1021/acs.inorgchem.5c00611","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00611","url":null,"abstract":"Peroxymonosulfate (PMS)-based advanced oxidation processes are effective in eliminating health-threatening persistent organic pollutants (POPs), but they require the participation of high-performance catalysts. In this study, a highly dispersed nanocobalt species (Co-NHCSs) was constructed on nitrogen-doped hollow carbon spheres by using the double confinement mechanism of complexation confinement combined with spatial confinement. The Co-NHCSs/PMS system has a high degradation efficiency of 95.2% for tetracycline within 30 min, and the degradation performance was almost not attenuated after repeated use 10 times. The Co-NHCSs/PMS system can also resist the interference of a complex water environment to achieve efficient degradation of POPs in multiple scenarios. Reactive oxygen quenching experiments and electron paramagnetic resonance confirmed that Co-NHCSs promoted the activation of PMS into ·OH, SO4·–, and 1O2 with high oxidation potential, which promoted the degradation of POPs. Density functional theory calculations show that nano-Co anchored on NHCSs can spontaneously capture and activate PMS on either a planar carbon matrix or a curved carbon matrix, which is the key to the efficient degradation of POPs by the Co-NHCSs/PMS system. This study not only provides an innovative way to construct nanometal catalysts but also reveals the transformation behavior of PMS on cobalt-based materials, which is of great significance for promoting PMS-based wastewater treatment technology.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"56 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654196","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