Inorganic Chemistry最新文献

Aggregation-Induced Spin-Crossover Switching in a Spin-Labile Iron(II) Complex

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-18 DOI: 10.1021/acs.inorgchem.4c04701

Fangqing Gao, Binbin Wang, Yan Liu, Tengli Wang, Liang Wang, Li-Fei Zou, Shufang Xue, Yunnan Guo

引用次数: 0

Phase Evolution and Thermodynamics of Cubic Li6.25Al0.25La3Zr2O12 Studied by High-Temperature X-ray Diffraction

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-18 DOI: 10.1021/acs.inorgchem.4c03738

Øystein Gullbrekken, Kristoffer Eggestad, Maria Tsoutsouva, Benjamin A. D. Williamson, Daniel Rettenwander, Mari-Ann Einarsrud, Sverre M. Selbach

引用次数: 0

Alternative Metal with an Alternative Mechanism for Metalloporphyrin-Enabled NO Reduction to N2O: A Combined Computational and Experimental Investigation of NO Reduction by Cr Porphyrin with Lewis Acid

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-18 DOI: 10.1021/acs.inorgchem.5c00226

Dariya Baizhigitova, Erwin G. Abucayon, Rahul L. Khade, Tsitsi A. Kapfunde, George B. Richter-Addo, Yong Zhang

{"title":"Alternative Metal with an Alternative Mechanism for Metalloporphyrin-Enabled NO Reduction to N2O: A Combined Computational and Experimental Investigation of NO Reduction by Cr Porphyrin with Lewis Acid","authors":"Dariya Baizhigitova, Erwin G. Abucayon, Rahul L. Khade, Tsitsi A. Kapfunde, George B. Richter-Addo, Yong Zhang","doi":"10.1021/acs.inorgchem.5c00226","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00226","url":null,"abstract":"Nitric oxide (NO) is an important molecule that regulates many physiological processes in humans and plants and contributes to the formation of greenhouse gases. Bacterial NO reductases utilize a di-Fe heme/nonheme active site to couple two NOs to generate nitrous oxide (N2O) via a two-electron mechanism. Here, we report a previously unexplored Cr porphyrin NO complex with a Lewis acid (LA) BF3 for the NO reduction reaction. Density functional theory calculations were first employed to reveal its reaction mechanism with a reasonable barrier for experimental realization. Subsequent experimental synthesis work confirms this reactivity and reports the first nitrosyl Cr porphyrin X-ray crystal structure. Theoretical analysis uncovered a distinctive reaction feature for the Cr system compared to Fe and Co porphyrins: the electron transfer from the metal to the bound NO occurs before LA binding. A comparative study of the NO coupling mechanisms with the three representative metals suggests that the metal reduction potential should be finely tuned, as found in previous studies of NOR enzymatic systems. Overall, this study offers new theoretical and experimental insights to further facilitate the development of alternative NO reduction compounds with biological, environmental, and industrial applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640878","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

Surfactant-Assisted Synthesis of Polycrystalline Binary PdBi Alloy Nanoparticles for Ethanol Electrooxidation

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-18 DOI: 10.1021/acs.inorgchem.4c04951

Yu Zhao, Likang Yang, Junlong Li, Chen Chen, Yidian Wang, Jiasheng Wang, Xuejiang Liao, Dongxiang Li, Peizhi Guo

{"title":"Surfactant-Assisted Synthesis of Polycrystalline Binary PdBi Alloy Nanoparticles for Ethanol Electrooxidation","authors":"Yu Zhao, Likang Yang, Junlong Li, Chen Chen, Yidian Wang, Jiasheng Wang, Xuejiang Liao, Dongxiang Li, Peizhi Guo","doi":"10.1021/acs.inorgchem.4c04951","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04951","url":null,"abstract":"The morphology and compositional modulation of palladium-based nanomaterials are of paramount importance in enhancing the catalytic performance of the ethanol oxidation reaction (EOR). In this study, we employed a simple oil bath method to synthesize PdBi alloy nanoparticles (NPs), maintaining the same elemental ratio. The size of the NPs could be modulated by varying the surfactant dosage. The synthesized PdBi alloys exhibited alterations in the d-band center of Pd, which were attributed to strain and ligand effects. These alterations subsequently affected the adsorption energy of the catalyst surface for the reaction intermediates. The current density of the Pd9Bi/200 NP in the ethanol oxidation reaction was found to be as high as 1042.0 mA mg–1, which is approximately twice that of Pd/C (508.0 mA mg–1). This enhanced activity can be attributed to the modification of the electronic structure and morphology, which enables the material to possess a larger electrochemically active surface area (ESCA), thus providing a substantial number of active sites for the catalytic reaction. Furthermore, the experimental data indicated that increasing the electrocatalytic temperature, pH, and ethanol concentration could accelerate the electrooxidation rate of the EOR. This study presents an effective approach for investigating the role of surfactants in the synthesis of nanomaterials and enhancing the activity and stability of noble metal catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640799","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 and Characterization of Co Complexes Coordinated by a Tetraanionic Bis(amidateanilido) Ligand

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-18 DOI: 10.1021/acs.inorgchem.4c05005

Avery LeComte, Rachel Sailer, Samyadeb Mahato, Warren VandeVen, Wen Zhou, Alisa R. Paterson, Morgane Desmau, Amani M. Ebrahim, Fabrice Thomas, Linus Chiang

{"title":"Synthesis and Characterization of Co Complexes Coordinated by a Tetraanionic Bis(amidateanilido) Ligand","authors":"Avery LeComte, Rachel Sailer, Samyadeb Mahato, Warren VandeVen, Wen Zhou, Alisa R. Paterson, Morgane Desmau, Amani M. Ebrahim, Fabrice Thomas, Linus Chiang","doi":"10.1021/acs.inorgchem.4c05005","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05005","url":null,"abstract":"The synthesis and characterization of a square planar CoII complex coordinated by the tetraanionic bis(amidateanilido) L4– ligand, 12–, and its corresponding one-electron oxidized forms 2–, 3, and 4+ are discussed herein. 12– undergoes aerobic oxidation to form 2–, a square planar S = 1 CoIII complex. This aerobic reactivity is attributed to a remarkably negative CoII/CoIII potential, as observed in its cyclic voltammogram, which is among the most negative CoII/CoIII couples reported. This supports the conclusion that the L4– ligation is strongly stabilizing to the oxidized CoIII center. The cyclic voltammogram of 2– also reveals that further oxidations are possible at mild potentials. Indeed, the stoichiometric addition of a suitable chemical oxidant yields a ligand-oxidized S = 1/2 CoIII complex, 3, while the addition of a further equivalent of the oxidant putatively yields 4+. The formation of the ligand oxidized species 3 suggests that bis(amidateanilido) ligation can further behave as a redox-active ligand upon additional oxidation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640800","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

Incorporation of Cu(I) Sites into Zeolite via a Controllable Reduction Strategy for Ethylene/Ethane Separation

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-18 DOI: 10.1021/acs.inorgchem.5c00029

Wen-Jun He, Jia-Xin Shen, Kai-Bo Zhang, Yu-Xia Li, Jing Zhao, Lin-Bing Sun

{"title":"Incorporation of Cu(I) Sites into Zeolite via a Controllable Reduction Strategy for Ethylene/Ethane Separation","authors":"Wen-Jun He, Jia-Xin Shen, Kai-Bo Zhang, Yu-Xia Li, Jing Zhao, Lin-Bing Sun","doi":"10.1021/acs.inorgchem.5c00029","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00029","url":null,"abstract":"The development of effective adsorbents for efficient separation of ethylene (C2H4) and ethane (C2H6) is crucial for the petrochemical sector, yet this is still difficult because of their comparable molecule sizes and physical characteristics. Cu(I) could generate π-complexes with molecules containing unsaturated bonds, enabling Cu(I)-based adsorbents to selectively and efficiently separate C2H4 from C2H6. However, the traditional autoreduction method typically requires extreme temperatures (≥700 °C) to convert Cu(II) to Cu(I), leading to high energy consumption. In this study, we present a controllable reduction strategy that employs methanol as the reductant to efficiently and controllably convert Cu(II) in Y zeolite to Cu(I). With this approach, Cu(I) sites could be formed under a modest temperature of 200 °C. Due to the generated Cu(I) sites, the C2H4 uptake for Cu(I)-Y reaches 3.85 mmol/g and the C2H4/C2H6 selectivity is 19.21. This performance surpasses those of benchmark adsorbents, including CuX (2.31 mmol/g, 1.06), Cu(I)-doped mesoporous carbon MC-Cu-2 (1.94 mmol/g, 4.00), and Cu+@MIL-101 (2.46 mmol/g, 14.00).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640877","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

Dual Active Sites along with Hydrophobic Structure Modulation of Vanadium Hexacyanoferrate for Aqueous Zn-Ion Batteries

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-17 DOI: 10.1021/acs.inorgchem.4c05245

Bingbing Hu, Dongshan Li, Meixin Li, Jiayu Jiang, Yingyang Zhao, Tianlun Du, Zideng Zhou, Hong Pu, Guangqiang Ma, Zhi Li

{"title":"Dual Active Sites along with Hydrophobic Structure Modulation of Vanadium Hexacyanoferrate for Aqueous Zn-Ion Batteries","authors":"Bingbing Hu, Dongshan Li, Meixin Li, Jiayu Jiang, Yingyang Zhao, Tianlun Du, Zideng Zhou, Hong Pu, Guangqiang Ma, Zhi Li","doi":"10.1021/acs.inorgchem.4c05245","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05245","url":null,"abstract":"Prussian blue analogs (PBAs) have attracted significant attention for use in aqueous zinc-ion batteries (AZIBs) because of their open framework, tunability, and ease of preparation. However, PBAs are still faced with low specific capacity or poor cycling performance as cathode materials for AZIBs, which is attributed to the insufficient number of active sites and structural instability due to water molecules. In this study, vanadium with multivalent properties has been introduced to form a dual active site with Fe, providing multiple electron transfers and possessing a higher specific capacity. Meanwhile, a coprecipitation method is used to form a β-cyclodextrin (β-CD) surface layer with an excluded-volume effect and rich hydroxyl side groups on the surface of vanadium hexacyanoferrate (VOHCF). The surface layer effectively prevents the direct interaction of VOHCF with active water molecules in the electrolyte while also regulating the desolvation structure of Zn2+, enhancing the long-cycle stability of electrode materials. The prepared β-cyclodextrin-vanadium hexacyanoferrate (β-CD-VOHCF) achieves a high reversible capacity (204.1 mAh·g–1 at 0.2 A·g–1), and the capacity retention ratio improves by 65% compared with VOHCF after 3200 cycles at 5 A·g–1. This study offers new ideas to inhibit vanadium dissolution and establish a foundation for the development of VOHCF.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640883","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

Exploring the Synergistic Interplay of Optical, Morphological, and Catalytic Features in Ga-Doped ZnO Nanoparticles: Harnessing Their Potential for Photocatalytic Dye Degradation under UV-Green Light Irradiation

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-17 DOI: 10.1021/acs.inorgchem.4c04790

Alessandra Piras, Chiara Olla, Luca Fusaro, Nikolay Tumanov, An-Sofie Kelchtermans, Dries De Sloovere, Ken Elen, Carlo Maria Carbonaro, An Hardy, Peter Adriaensens, Carmela Aprile, Marlies Van Bael

{"title":"Exploring the Synergistic Interplay of Optical, Morphological, and Catalytic Features in Ga-Doped ZnO Nanoparticles: Harnessing Their Potential for Photocatalytic Dye Degradation under UV-Green Light Irradiation","authors":"Alessandra Piras, Chiara Olla, Luca Fusaro, Nikolay Tumanov, An-Sofie Kelchtermans, Dries De Sloovere, Ken Elen, Carlo Maria Carbonaro, An Hardy, Peter Adriaensens, Carmela Aprile, Marlies Van Bael","doi":"10.1021/acs.inorgchem.4c04790","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04790","url":null,"abstract":"This work explores the synthesis and characterization of undoped ZnO, Ga-doped ZnO (Ga:ZnO), and γ-Ga2O3 quasi-spherical nanoparticles and their catalytic activity in Rhodamine B photodegradation under UV–visible light exposure. Gallium dopant incorporation into Ga:ZnO was confirmed by inductively coupled plasma optical emission spectroscopy (ICP-OES), Fourier transform infrared (FT-IR), and powder X-ray diffraction (XRD), maintaining the hexagonal wurtzite structure with an additional zinc gallium carbonate Layered Double Hydroxide (LDH) phase at higher dopant concentrations. TEM images revealed no significant alteration in the morphology or size of the nanoparticles. 71Ga-NMR indicated the location of the gallium atoms within the ZnO lattice, showing coordination changes with an increasing dopant concentration. Ga-doped ZnO nanoparticles demonstrated reduced efficiency under UV light compared to commercial references. γ-Ga2O3 exhibited superior performance in UV-C for Rhodamine B degradation, diminishing under UV-A, attributed to nanoparticle agglomeration. ZnO and Ga:ZnO catalysts showed optimal performance under green light irradiation, highlighting their performances over the commercial zinc oxide material. Photoluminescence measurements suggested favorable gallium dopant incorporation, with no substantial variation of oxygen vacancies, consequently retaining the photocatalytic properties of ZnO, which are crucial for Rhodamine B degradation under green light irradiation. This study elucidates the intricate relationship among gallium doping, material properties, and photocatalytic performance, providing valuable insights for developing advanced photocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640879","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

Osmium(IV) Tetraaryl Complexes Formed from Prefunctionalized Ligands

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-17 DOI: 10.1021/acs.inorgchem.4c05589

Clarissa Olivar, Joseph M. Parr, Cynthia Avedian, Thomas Saal, Luana Zagami, Ralf Haiges, Mukund Sharma, Michael S. Inkpen

{"title":"Osmium(IV) Tetraaryl Complexes Formed from Prefunctionalized Ligands","authors":"Clarissa Olivar, Joseph M. Parr, Cynthia Avedian, Thomas Saal, Luana Zagami, Ralf Haiges, Mukund Sharma, Michael S. Inkpen","doi":"10.1021/acs.inorgchem.4c05589","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05589","url":null,"abstract":"Transition metal(IV) tetraaryl, M(aryl)4, complexes hold great promise as functional building blocks for complex organometallic materials, yet their widespread utility depends on the development of improved synthetic protocols and a deeper understanding of their chemical structure–property relationship(s). Here we show that Os(aryl)4 complexes with preinstalled functional groups (–F, –Cl, –Br, –I, and –SMe) can be prepared from reactions between (Oct4N)2[OsBr6] and Grignard reagents formed by halogen/magnesium insertion or exchange. This approach provides access to compounds that may otherwise prove challenging to prepare through postfunctionalization strategies, such as those comprising halogens in the 2- or 5-positions. We characterize these, as well as previously reported, materials using single-crystal X-ray diffraction, solution voltammetry, and UV–vis spectroscopy. Through a comparison of 13 differently substituted complexes, we identify correlations between their electrochemical and optical gaps, and between the E1/2 of their 0/1+ redox event and an adjusted Hammett parameter that accounts for all aryl ligand substituents. The electronic property trends observed are further rationalized through a series of first-principles calculations based on density functional theory. Together, this work lays a foundation for advancing new preparative methods to further derivatize such species, and a robust experimental data set to help benchmark future experimental and computational compound characterization.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640884","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

Peripheral-Carbazole-Group-Functionalized Tetradentate Carbene Platinum(II)/Palladium(II) Phosphorescent Complexes: Synthesis, Structures, and Optical Tuning

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-17 DOI: 10.1021/acs.inorgchem.5c00213

Qiuxia Li, Zhigang Zhao, Meng Wu, Peng Liu, Meng Zhao, Jing Zhang, Feiyang Li, Jiayu Cui, Aihua Yuan, Chao Shi

{"title":"Peripheral-Carbazole-Group-Functionalized Tetradentate Carbene Platinum(II)/Palladium(II) Phosphorescent Complexes: Synthesis, Structures, and Optical Tuning","authors":"Qiuxia Li, Zhigang Zhao, Meng Wu, Peng Liu, Meng Zhao, Jing Zhang, Feiyang Li, Jiayu Cui, Aihua Yuan, Chao Shi","doi":"10.1021/acs.inorgchem.5c00213","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00213","url":null,"abstract":"We designed and synthesized two novel tetradentate carbene ligands, IM-carme and IM-cardtb, both containing a peripheral carbazole group, with methyl and 3,5-ditert-butyl-phenyl groups on their carbene moieties, respectively. Thus, four new tetradentate carbene platinum(II) and palladium(II) complexes (Pt-carme, Pt-cardtb, Pd-carme, and Pd-cardtb) were synthesized. The X-ray structures reveal that the 3,5-ditert-butyl-phenyl group promotes a head-to-tail stacking arrangement and intermolecular metal–metal interactions (Pt–Pt or Pd–Pd), whereas the methyl group leads to a head-to-head stacking pattern and intermolecular π–π interactions. Notably, all complexes emit narrow-band (43–55 nm) phosphorescence ranging from sky blue to deep blue within the wavelength range of 439–502 nm, and the 3, 5-ditert-butyl-phenyl-substituted complexes (Pt-cardtb or Pd-cardtb) have longer emission wavelength, higher emission efficiency, and longer emission lifetime than the corresponding methyl-substituted complexes (Pt-carme or Pd-carme). Theoretical calculations demonstrate that the T1 state of these complexes exhibits prominent ILCT from the peripheral carbazole group, skeletal carbazole-phenoxy moieties to the benzimidazole and pyridine moieties, as well as MLCT characteristics. Furthermore, the platinum complexes exhibit more pronounced MLCT effects than the corresponding palladium complexes, leading to shorter lifetime and higher efficiency. This research offers novel insights for designing tetradentate carbene platinum(II)/palladium(II) phosphorescent materials featuring peripheral functional groups.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640885","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