Inorganic Chemistry最新文献

{"title":"Uranyl-Polyoxometalate as a Heterogeneous Catalyst for Visible-Light-Driven Oxidation Coupling of Amines","authors":"Xiaoyue Wang, Mengyuan Cheng, Yanan Liu, Dongdi Zhang, Jingyang Niu","doi":"10.1021/acs.inorgchem.5c00919","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00919","url":null,"abstract":"Developing efficient heterogeneous visible-light-responsive photocatalysts to achieve organic oxidation reactions is essential. We synthesized the uranyl-polyoxometalate (POM) compound Na₃[H₁₉(UO₂)₂(μ₂-O)(Se₂W₁₄O₅₂)₂]·41H₂O (denoted as <b>U2</b>) by incorporating uranyl (VI) ions (UO₂²⁺) into the POM framework and conducted the photocatalytic oxidation reaction of the uranyl-POM compounds. Results revealed that the introduction of uranyl groups not only extended the light absorption range of <b>U2</b> to 500 nm but also promoted its carrier separation efficiency and charge transfer rate remarkably. Meanwhile, the synergistic effect among the components enhanced the catalytic activity notably. The U2-catalyzed oxidative coupling of the benzylamine reaction was completed within 6 h under a green solvent-free system with a high yield of 98.7%. The turnover number and turnover frequency reached 1974 and 329 h^–1, respectively, far exceeding the activity of uranyl or POM used alone. Furthermore, <b>U2</b> was demonstrated to exhibit excellent recyclability, maintaining its activity over five consecutive cycles without significant degradation. Incorporating uranyl into POMs to form <b>U2</b> achieves excellent catalytic performance in the heterogeneous photocatalytic oxidation coupling of benzylamine to N-benzylidenebenzylamine under solvent-free conditions (yield = 98.7%; turnover number = 1974; turnover frequency = 329 h^–1).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202423","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}

{"title":"Isolation, Architecture of Ag8-Cluster Modified Polyoxometalate for Water Reduction into Hydrogen Driven by Visible Light","authors":"Ling-Tong Xu, Yan Zhao, Pin-Fang Yan, Hua Mei, Yan Xu","doi":"10.1021/acs.inorgchem.5c01055","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01055","url":null,"abstract":"To alleviate the shortage of oil resources, photocatalytic water decomposition into hydrogen (H₂) is an efficient method to produce clean and green energy with the potential to replace oil in many fields. Under hydrothermal conditions, two Strandberg-type phosphomolybdates were synthesized, formulated as [Ag₄(C₈H₆N₂)₆H₂O][H₂P₂Mo₅O₂₃]·1H₂O (<b>1</b>) and [Ag(C₄H₄N₂)]₈[H₂P₂Mo₅O₂₃]₂·11H₂O (<b>2</b>), based on MoO₃, Ag(NO₃)₃, H₃PO₄ and two N-containing organic ligands (quinoxaline and pyridazine). The single-crystal structure analysis indicates that compound <b>1</b> showed one-dimensional chain constructed from [Ag₃(C₈H₆N₂)₄]³⁺, [Ag(C₈H₆N₂)₂]⁺ cations and [H₂P₂Mo₅O₂₃]^4– anions, while compound <b>2</b> features a two-dimensional-layered structure formed by interesting [Ag(C₄H₄N₂)O]₈ clusters connecting [H₂P₂Mo₅O₂₃]^4– anions. Under visible light irradiation, both compounds showed excellent performance in hydrogen production. After 8 h of visible light irradiation, the H₂ yields were 243.6 (<b>1</b>) and 401.1 (<b>2</b>) μmol, which have wide application prospects in the photocatalysis field. Meanwhile, comparative experiments showed that the Ag⁺ ions significantly promoted hydrogen production under visible light, serving as a crucial active center in the photocatalytic water decomposition into the hydrogen process.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202428","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}

{"title":"Electrochemically Formed Defect-Rich Bismuthene–Bismuth Oxycarbonate Nanosheets Promote Selective Reduction of CO2 to Formic Acid","authors":"Deepak Kumar, Lin Gu, Abhishek Dutta Chowdhury, Arindam Indra","doi":"10.1021/acs.inorgchem.5c01015","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01015","url":null,"abstract":"Formic acid has a high hydrogen storage capacity and is a valuable chemical for industrially important reactions. The industrial production of formic acid proceeds through the carbonylation of methanol to form methyl formate and its subsequent hydrolysis. This process requires high temperature and pressure, and it relies on the use of fossil fuels. In this context, the electrochemical reduction of CO₂ to HCOOH as the selective C₁ product has emerged as an efficient technique for carbon fixation. Herein, we report the electrochemical transformation of bismuth phytate to active catalyst bismuthene–bismuth oxycarbonate nanosheets under cathodic CO₂ reduction conditions. The electrochemically derived catalyst showed an atomic-level thickness (6.5 nm) with a highly disordered structure. The catalyst reduced CO₂ to HCOOH as the major product with a faradaic efficiency of &gt;94%, and the selectivity of formic acid formation was found to be &gt;97% under optimized conditions. Further, the catalyst demonstrates durability, maintaining a constant current density over 6 h. The two-dimensional nanosheet morphology, atomic-level thickness, and highly disordered structure of the active catalyst provide high selectivity for the formic acid formation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"112 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202426","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}

{"title":"Modulating the Electroactivity of CuCo₂O₄ for Hydrogen Evolution Assisted by Benzyl Alcohol Oxidation via the Morphological Structure.","authors":"Huiqin Yu, Fang Li, Pengfei Du, Jing Cao, Haili Lin","doi":"10.1021/acs.inorgchem.5c01879","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01879","url":null,"abstract":"<p><p>The catalytic activity and morphological structure are closely related. Herein, the spinel structure CuCo₂O₄ with different morphologies was constructed as the research model for the electrocatalytic benzyl alcohol (BA) oxidation and hydrogen evolution reaction (HER). By modulating the morphological structure, oxygen vacancy, and the high valence active centers, the octahedral CuCo₂O₄ exhibited superior electrocatalytic activity and stability compared to other CuCo₂O₄ samples with nanoplate/nanowire morphologies. Meanwhile, density functional theory calculations elucidated that octahedral CuCo₂O₄ could significantly lower the reaction energy barriers of BA oxidation. Furthermore, the crystal orbital Hamilton population analysis was exploited to probe the intermediate adsorption/desorption on the vacancies. The morphology structure and vacancy effect contributed to the improved electrocatalytic performance. The present work demonstrated the important influence of the morphology structure and the accompanying electronic/vacancy effect on the catalytic activity experimentally and theoretically.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144207149","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}

{"title":"Two Chiral EuIII Enantiomeric Pairs with Significantly Enhanced Photophysical and Third-Harmonic Generation Performances through the Coordination Roles of Enantiopure Bi- and Tridentate N-Donors","authors":"Xiaodi Du, Chunyang Li, Congli Gao, Xiaoyu Cai, Jinying Huang, Qianrong Li, Tao Wu, Xi-Li Li","doi":"10.1021/acs.inorgchem.5c01372","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01372","url":null,"abstract":"For inserting enantiopure bi- and tridentate N-donors (¹L_<i>R</i>/¹L_<i>S</i> and ²L_<i>R</i>/²L_<i>S</i>) into the precursor Eu(hfac)₃(H₂O)₂ to replace two H₂O molecules, respectively, two pairs of chiral eight- and nine-coordinate Eu^III enantiomers Eu(hfac)₃(¹L_<i>R</i>)/Eu(hfac)₃(¹L_<i>S</i>) (<b>D-1</b>/<b>L-1</b>) and Eu(hfac)₃(²L_<i>R</i>)/Eu(hfac)₃(²L_<i>S</i>) (<b>D-2</b>/<b>L-2</b>) were isolated, in which hfac^– = hexafluoroacetylacetonate, ¹L<i>_R</i>/¹L_<i>S</i> = (−)/(+)-4,5-pinene-2,2′-bipyridine, and ²L_<i>R</i>/²L_<i>S</i> = (−)/(+)-2,6-bis(4′,5′-pinene-2′-pyridyl)pyridine. Compared with Eu(hfac)₃(H₂O)₂, two chiral Eu^III enantiomeric pairs not only show significant improvements in their photophysical performances but also display highly boosted third-harmonic generation (THG) effects, and the THG strengths of <b>D-1</b>/<b>L-1</b> and <b>D-2</b>/<b>L-2</b> are more than 14 and 27 times that of Eu(hfac)₃(H₂O)₂, respectively. Especially, <b>D-2</b> and <b>L-2</b> with symmetric tridentate N-donors only have strong THG effects, while <b>D-1</b> and <b>L-1</b> with asymmetric bidentate N-donors simultaneously hold THG and SHG (second-harmonic generation) responses. More notably, from Eu(hfac)₃(H₂O)₂ to eight-coordinate <b>D-1</b> and <b>L-1</b>, and further to nine-coordinate <b>D-2</b> and <b>L-2</b>, their THG strengths present successive considerable enhancements as degrees of π-electron conjugation of their ligands continue to rise. Furthermore, the circularly polarized luminescence (CPL) properties of two chiral Eu^III enantiomeric pairs were also examined.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202308","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}

{"title":"Understanding the Photocatalytic Water Reduction Capability of NaM(WO4)2 (M = Ga, Sc) by the Electronic Structure and Bond Characteristic Analysis","authors":"Congying Huang, Guangxiang Lu, Zien Cheng, Pengfei Jiang, Rihong Cong, Tao Yang","doi":"10.1021/acs.inorgchem.5c00556","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00556","url":null,"abstract":"<i>m</i>-WO₃ has a narrow band gap, making it a promising photocatalyst. However, its antibonding W–O orbitals limit water reduction capability due to insufficient reduction potential. Incorporating a weakly bonded <i>M</i>–O in Na<i>M</i>(WO₄)₂ (M = Ga, Sc) enhances W–O covalency compared to that in <i>m</i>-WO₃, resulting in a more negative conduction band minimum (CBM) potential, sufficient for photocatalytic water reduction. Here, Na<i>M</i>(WO₄)₂ (M = Ga, Sc) were synthesized via high-temperature solid-state reactions, and their precise structures were determined through Rietveld refinement of high-resolution XRD data. Density functional theory (DFT) calculations were performed to analyze the electronic structures, and bond characters were further examined using the crystal orbital Hamilton population (COHP), crystal orbital bond index (COBI), and electron localization function (ELF). Experimentally, NaGa(WO₄)₂ loaded with 0.63 wt % Pd and NaSc(WO₄)₂ loaded with 0.94 wt % Pd exhibited photocatalytic H₂ generation rates of 2.45 and 6.30 μmol/h, respectively, under UV irradiation in a methanol aqueous solution. Apparent quantum yields at 295 nm are estimated to be 0.66 and 2.21%, respectively. Notably, NaSc(WO₄)₂ displayed a superior photocatalytic activity, which can be attributed to its more negative CBM potential, as discussed through a comparison of their electronic structures.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"135 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202286","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}

{"title":"Rearrangement of Sb···Br Secondary Bonds Resulting in Reversible Transformation between Dimeric and Chain-Like Antimony Bromide Hybrid Materials: Tunability of Electron Self-Trapped Luminescence and Proton Conductivity","authors":"Jiantao Yuan, Nan Zhang, Jian Zhang, Xian-Ming Zhang","doi":"10.1021/acs.inorgchem.5c01356","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01356","url":null,"abstract":"Single-crystal-to-single-crystal (SCSC) transformation materials are of great research interest because of their promising applications, among which multifunctional switching as next-generation intelligent materials in photoelectric devices is rare, and the corresponding mechanism remains unclear. Herein, we present two organic–inorganic hybrid antimony halides, namely (H₂dach)₂Sb₂Br₁₀·4H₂O (<b>1</b>) and (H₂dach)SbBr₅ (<b>2</b>) (dach = 1,2-diaminocyclohexane) and their reversible mutual SCSC transformation. <b>1</b> and <b>2</b> adopt zero-dimensional discrete butterfly-like [Sb₂Br₁₀]^4– dimers and one-dimensional infinite [SbBr₅]_<i>n</i>^2<i>n</i>– chains, respectively, possessing abundant Sb···Br secondary bonds due to the strong stereochemical activity of 5s² lone-pair electrons in Sb(III). Detailed structural analyses reveal that the reversible SCSC transformation is triggered by the rearrangement of Sb···Br secondary bonds, which enables the 25-time modulation of electron self-trapped photoluminescence with broadband orange emission. Humidity-dependent photoluminescence behavior of dehydrated <b>2</b> was also observed, which can be used to sense trace amounts of water. Furthermore, SCSC transformation via dehydration–rehydration could tailor hydrogen-bonding networks, resulting in switchable proton conductivity. The simulated kinetic mechanism of SCSC transformation by DFT is in agreement with the experimentally observed rearrangement of Sb···Br secondary bonds. This work demonstrates that the rearrangement of Sb···Br in hybrid halide systems is beneficial for elucidating dynamic transformation processes and promoting the development of multifunctional materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202314","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}

{"title":"Role of Disorder on the Unusual Composition Dependence of the Structures in V-Doped LaNbO4","authors":"Ahmadi Jaya Permana, Bryce G. Mullens, Maxim Avdeev, Bruce Cowie, Jeremy Wykes, Brendan J. Kennedy","doi":"10.1021/acs.inorgchem.5c00514","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00514","url":null,"abstract":"A series of vanadium-doped orthoniobates of the type La(Nb_1–<i>x</i>V_<i>x</i>)O₄ (<i>x</i> = 0.00–0.40) were synthesized using a solid-state method, and their long-range average and short-range local structures comprehensively investigated using a combination of high-resolution neutron powder diffraction (NPD) and synchrotron X-ray powder diffraction (S-XRD) that produced accurate and precise structures of several members of the series. The structures evolve from a monoclinic fergusonite-type to a tetragonal scheelite-type structure as the V content increases. Substituting Nb⁵⁺ by the smaller V⁵⁺ cations induces an atypical expansion in lattice parameters, most notably an increase in unit cell volume within the monoclinic fergusonite phase, attributed to pronounced elongation of the longer crystallographic <i>c</i>-axis. A progressive shift from distorted six-coordinate octahedra to four-coordinate tetrahedra of the mixed Nb/V site upon V doping was established through X-ray absorption and Raman spectroscopy. Variable-temperature S-XRD measurements were employed to assess the influence of V incorporation on the thermally induced ferroelastic monoclinic fergusonite-to-tetragonal scheelite phase transition, including quantification of the coefficients of thermal expansion. The anomalous compositional and thermal dependence of the unit cell parameters is correlated with cation displacements.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202312","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}

{"title":"Guest Exchange as a Synthetic Strategy for Hydrogen-Bonded Organic Frameworks.","authors":"Shun Ohta, Momo Ishii, Tatsunari Murakami, Masaaki Okazaki","doi":"10.1021/acs.inorgchem.5c01697","DOIUrl":"10.1021/acs.inorgchem.5c01697","url":null,"abstract":"<p><p>Hydrogen-bonded organic frameworks (HOFs) are mainly synthesized via recrystallization from solutions that contain molecular building blocks; however, this is not an infallible strategy. For example, the formation of hydrogen bonds between the building blocks and molecules of the crystallization solvent may prevent the construction of the frameworks. Herein, we propose a guest-exchange-based strategy for converting non-HOF crystals to HOFs. Specifically, non-HOF crystals of bis(benzimidazole)ZnCl₂ complex <b>1</b> (bis(benzimidazole) = phenylbis(benzimidazol-2-yl)methane) obtained from its <i>N</i>,<i>N</i>-dimethylformamide (DMF) solution (<b>1</b>₂·(DMF)₅) were converted to HOF crystals via the exchange of DMF to acetone or tetrahydrofuran by exposing <b>1</b>₂·(DMF)₅ to the corresponding vapor. Interestingly, the complete guest exchange is not always required, which further emphasizes the convenience of the guest-exchange strategy in HOF synthesis. We also demonstrate that HOF crystals synthesized via guest exchange can serve as an adsorber for acetone and diethyl-ether vapors.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"10353-10358"},"PeriodicalIF":4.3,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144100970","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}

{"title":"Pyrazine-Functionalized Bio-MOFs for Selective Luminescence Sensing of Colchicine and Nitrofurazone in Aqueous Solutions","authors":"Fei-Long Luo, Hao-Bo Wang, Kun Wu, Dong Luo, Yifang Zhao, Yong-Liang Huang, Weigang Lu","doi":"10.1021/acs.inorgchem.5c01125","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01125","url":null,"abstract":"By employing a mix-linker strategy, we have successfully synthesized two isostructural anionic microporous biological metal–organic frameworks (Bio-MOFs), showing excellent chemical stability across a pH range of 3–14 in the aqueous phase. Luminescence titration studies reveal that replacing the benzene core of the carboxylate linker with pyrazine leads to markedly enhanced energy transfer from the linker to the metal cluster, significantly increasing the emission intensity. This linker engineering strategy endows the MOF with superior performance in antibiotic sensing with limits of detection of 1.5 μM for colchicine (COL) and 0.8 μM for nitrofurazone (NFZ). Additionally, the title MOF exhibited selective detection of COL and NFZ in the presence of potential interfering species, including other antibiotics or serum species. Moreover, a mixed matrix film was fabricated by dispersing the MOF crystalline powders on a polycaprolactone sheet, demonstrating real-time on-site monitoring of COL and NFZ in aqueous solutions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202313","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}