ACS Catalysis 最新文献

{"title":"Modulating Pt States through Hydroxyl Control for Low-Temperature Aqueous Phase Reforming of Methanol","authors":"Yuyao Yang, Xuan Bie, Xiaoying Qi, Yongqing Xu, Qinghai Li, Yanguo Zhang, Hui Zhou","doi":"10.1021/acscatal.5c00357","DOIUrl":"https://doi.org/10.1021/acscatal.5c00357","url":null,"abstract":"Aqueous phase reforming of methanol (APRM) offers a method for releasing H₂ from the liquid phase, by which H₂ can be stored in methanol safely. It is an efficient way to design high-performance catalysts by controlling the hydroxyl (OH) groups, but its mechanism for affecting the APRM is still unclear. Herein, we loaded Pt on three types of Al₂O₃ (nanopolyhedron, nanosheet, and nanorod Al₂O₃) with different OH contents and types. Among them, Pt/nanorod Al₂O₃ exhibited the highest H₂ production rate of 20.4 μmol g^–1 s^–1 with 96.6% H₂ selectivity at a low temperature of 190 °C. This was attributed to the roles of hydroxyl groups in modulating Pt states. On nanopolyhedron, nanosheet, and nanorod Al₂O₃, the bonding of Pt with O atoms became more favorable as the dehydroxylation happened. In particular, on nanorod Al₂O₃, the dehydroxylation process generated a high density of five-coordinated Al (Al_V) sites, facilitating the dispersion and anchoring of Pt particles. Moreover, the special OH groups (hydrogen bond donor) on nanorod Al₂O₃ promoted Pt particle reduction via the movement of electrons. Ultimately, the results demonstrated the influence of OH groups on the dispersion and reduction of active metals, offering perspectives for designing catalysts for APRM through hydroxyl control.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"21 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dopant-Induced Electron Localization Drives Direct Current Kolbe Coupling of Biomass-Derived Carboxylic Acids","authors":"Wenhua Zhou, Bolong Li, Gaobo Lin, Teng Guo, Chao Chen, Jie Zhu, Haoan Fan, Xuezhi Zhao, Lei Guo, Weiyu Song, Jianghao Wang, Tianfu Wang, Jie Fu","doi":"10.1021/acscatal.5c00403","DOIUrl":"https://doi.org/10.1021/acscatal.5c00403","url":null,"abstract":"The Kolbe coupling of biomass-derived carboxylic acids presents a promising route for sustainable production of value-added chemicals. However, conventional direct current (DC) Kolbe electrolysis typically cleaves functional groups in carboxylic acids, significantly hindering its broader application. Herein, we demonstrate that dopant-induced electron localization in activated carbon (AC) facilitates decarboxylative coupling while preserving functional integrity. Experimental and theoretical results reveal that nitrogen doping in AC (N-AC) modulates the local electronic structure and enhances the adsorption capacity of carboxylic acids. Notably, N-AC exhibits a 10-fold increase in the conversion of 10-undecenoic acid compared to AC, with a selectivity of up to 60 ± 2% for the coupling product. More importantly, N-AC effectively catalyzes carboxylic acids with diverse functional groups. This study provides new insights into the structure–property relationship of N-doped carbon and advances the practical implementation of Kolbe electrolysis for biomass valorization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"71 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703267","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Confinement of Atomically Dispersed Ptδ+ Sites in Zinc-Incorporated Silicalite-1 Zeolite for Enhanced Propane Dehydrogenation","authors":"Jindong Ji, Guoli Fan, Lirong Zheng, Feng Li","doi":"10.1021/acscatal.4c07883","DOIUrl":"https://doi.org/10.1021/acscatal.4c07883","url":null,"abstract":"For industrial use, propylene production requires efficient and cost-effective propane dehydrogenation (PDH) catalysts. Given the scarcity of platinum and toxicity of chromium, enhancing the catalytic activity and high-temperature stability of zinc-based alternative catalysts bearing a limited amount of Pt would be ideal. Here, we successfully created a low-loaded platinum-confined and zinc-incorporated MFI-type silicalite-1 zeolite catalyst via a facile one-pot synthesis route aided by a micro-liquid film reactor. It was demonstrated that highly dispersed Zn ions were fully incorporated into the S-1 framework, while atomically dispersed Pt^δ+ binding to the framework oxygen atoms could be firmly confined in the S-1 micropores. The as-constructed catalyst with only 0.041 wt % Pt loading displayed an impressively ultralow deactivation rate constant of approximately 0.0007 h^–1 in the PDH at the WHSV of 2.4 h^–1 and 600 °C. More significantly, the catalyst achieved a remarkably high propylene production rate of 188.1 mol_C3H6·g_Pt^–1·h^–1 at the higher WHSV of 12 h^–1, far surpassing those of the state-of-the-art PtZn- and PtSn-based catalysts for PDH operated at the medium WHSV values. By combining the multiple characterizations and density functional theory calculations, it was unveiled that the high catalytic efficiency and high-temperature stability of the catalyst was ascribed to the formation of unique atomically dispersed Pt^δ+–O–Zn structures in the catalyst. This work proposes an effective strategy for tuning the nature of active metal sites in zeolites to create high-performance catalysts across diverse heterogeneous catalytic processes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spatially Patterned Architectures to Modulate CO2 Reduction Cascade Catalysis Kinetics","authors":"Marisé García-Batlle, Pablo Fernandez, Colton J. Sheehan, Shi He, Thomas E. Mallouk, Gregory N. Parsons, James F. Cahoon, Rene Lopez","doi":"10.1021/acscatal.5c01176","DOIUrl":"https://doi.org/10.1021/acscatal.5c01176","url":null,"abstract":"Electrochemical CO₂ reduction using renewable sources of electrical energy holds promise for converting CO₂ into fuels and chemicals. The complex interactions among chemical/electrochemical reactions and mass transport make it difficult to analyze the effect of an individual process on electrode performance based only on experimental methods. Here, we developed a generalized steady-state simulation to describe an electrode surface in which sequential cascade catalysts are patterned in a periodic trench design. If appropriately constructed, this trench geometry is hypothesized to be able to yield a higher net current density for a CO₂ reduction (CO₂R) cascade reaction. We have used realistic experimental reaction kinetics to investigate the role of trench geometry in mass transport, local microenvironments, and selectivity for a model CO₂R cascade reaction. The model considers local concentration gradients of bicarbonate species at quasi-equilibrium and catalytic surface reactions based on concentration-dependent Butler–Volmer kinetics. Our results suggest that varying the spatial distribution of active sites plays a significant role in facilitating effective mass transport between active sites, modulating selectivity for the cascade reaction, and enhancing the yield of desirable cascade products. Moreover, we observe that this trench geometry significantly alters the cascade reaction rate by affecting the local pH, which can cause inadvertent depletion of available aqueous CO₂ to limit the CO₂R cascade kinetics and modest suppression of the hydrogen evolution reaction (HER). The results highlight the trade-offs between mass transport, pH, and reaction kinetics that become apparent only when considering the coupled physics of all processes at the electrode surface. This model can thus serve as a primary tool to build more selective and efficient patterned architectures for the CO₂R cascade catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxidative Dehydrogenation of Ethane Combined with CO2 Splitting via Chemical Looping on In2O3 Modified with Ni–Cu Alloy","authors":"Kosuke Watanabe, Takuma Higo, Koki Saegusa, Sakura Matsumoto, Hiroshi Sampei, Yuki Isono, Akira Shimojuku, Hideki Furusawa, Yasushi Sekine","doi":"10.1021/acscatal.4c07737","DOIUrl":"https://doi.org/10.1021/acscatal.4c07737","url":null,"abstract":"Modified In₂O₃ has the potential to be a better oxygen storage material due to its readily reducible surface and abundant bulk lattice oxygen released with a marked valence change from In³⁺ to In⁰. This work describes that In₂O₃ modified with a Ni–Cu alloy supports a chemical looping system consisting of oxidative dehydrogenation of ethane and CO₂ splitting at the low temperature of 873 K with a large oxygen capacity (>4 wt %). This reaction system is achieved through dynamic changes between Ni–Cu binary alloy and Ni–Cu–In ternary alloy associated with the redox of indium species. Meticulous material screening, characterization, and theoretical calculations have revealed that the Ni–Cu alloy promotes the redox of In₂O₃ by activating ethane and by incorporating reduced indium species.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CO2 Reduction Over Iron–Nickel Alloy Catalysts─Tandem Effect of Support and Alloy Composition","authors":"Kin de Kock, Shaine Raseale, Wijnand Marquart, Thierry Verfaille, Michael Claeys, Nico Fischer","doi":"10.1021/acscatal.4c07514","DOIUrl":"https://doi.org/10.1021/acscatal.4c07514","url":null,"abstract":"The effect of the Fe:Ni ratio in metallic nanoalloys and the nature of metal oxide overlayer supports (MO_<i>x</i>@Al₂O₃) on catalytic activity, selectivity, and stability in the reverse water–gas shift reaction (RWGS) was investigated. To obtain the Fe_<i>y</i>Ni alloy phase, oxidic (Ni_<i>y</i>Fe_1–<i>y</i>)Fe₂O₄ precursor nanoparticles of varying composition were synthesized (Fe:Ni = 3, 4, and 6, as well as pure iron oxide) with a narrow size distribution and without the use of surfactants. The effect of the varying physical properties of the respective bulk oxides on catalyst performance was circumvented via the preparation of bespoke support materials by impregnating a γ-Al₂O₃ carrier with MO_<i>x</i> overlayers (<i>M</i> = Cr or Ga). The surface of the prepared materials is related to the chemical and electronic properties of the respective MO_<i>x</i>, but the pore geometry of γ-Al₂O₃ is maintained. An inert high-surface-area SiO₂ support material was also tested to isolate the performance of the Fe_<i>y</i>Ni phases. The reduced catalysts contain a mixture of the bcc and fcc alloy phases irrespective of the support material. The relative concentrations of each phase are a function of iron content, with an increase in iron content increasing the concentration of the bcc alloy phase. The bcc phase has a high affinity toward reoxidation via CO₂ activation, while the fcc phase was only found to be partially reoxidized at elevated temperatures (above 600 °C). When exposed to RWGS conditions, all samples tested show &gt;99.5% CO selectivity. The SiO₂-supported samples deactivate rapidly, while the alloys supported on the MO_<i>x</i>@Al₂O₃ overlayers, specifically when supported on CrO_<i>x</i>@Al₂O₃, form a tandem system, supporting high activity and stability. The catalytic performance is dependent on both the alloy composition and the MO_<i>x</i> support, with the surprising observation of a reversal of the trend in activity with iron content between CrO_<i>x</i>@Al₂O₃ and GaO_<i>x</i>@Al₂O₃. Spent catalyst characterization showed that the rapid deactivation seen on SiO₂ cannot be explained by sintering, oxidation, or carbon deposition. The deactivation is instead attributed to the consumption of the bcc phase under reaction conditions. The results show that there is a beneficial interaction between the fcc phase, an exsoluted amorphous Fe-oxide formed from the bcc phase, and the active support, which enhances the catalytic performance in the RWGS.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of Local Chemical Environment on the Catalytic Properties of Ir1/CeO2 Single-Atom Catalysts in CO Oxidation","authors":"Carlo Federico Pauletti, Matteo Farnesi Camellone, Simone Piccinin","doi":"10.1021/acscatal.5c01147","DOIUrl":"https://doi.org/10.1021/acscatal.5c01147","url":null,"abstract":"Supported single-atom catalysts (SACs) are of great interest in catalysis due to their highly efficient use of costly noble metals and unique reactivities, which are deeply influenced by the local coordination environment of the active site. Herein, the catalytic properties of single Ir adatoms on CeO₂ have been simulated at finite temperature with ab initio thermodynamics and microkinetic modeling, deriving analytical expressions for the turnover frequency of the catalyst at different operative regimes, compatible with experimental conditions. According to our findings, the adsorption geometry of single Ir adatoms on CeO₂ is governed by the surface termination, resulting in remarkably different catalytic activities: on the (110) surface, the high stability of square-planar IrO_<i>x</i>(CO)_<i>y</i> units results in a high propensity toward CO poisoning. On the (111) surface, the local environment of the Ir adatom allows for a greater number of ligands, resulting in greater catalytic activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"57 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Late-Stage N-Atom Deletion of Multisubstituted 2-Azabicyclo[2.1.1]Hexanes","authors":"Ken Lin, Qi Sun, Pengcheng Tang, Saizhou Wang, Mengjie Jiao, Tao Zhang, Hongjian Lu","doi":"10.1021/acscatal.5c01734","DOIUrl":"https://doi.org/10.1021/acscatal.5c01734","url":null,"abstract":"Rigid three-dimensional scaffolds such as 2-azabicyclo[2.1.1]hexanes (aza-BCHs) and bicyclo[1.1.1]pentanes (BCPs) serve as unique saturated isosteres of arenes, offering distinct substitution patterns due to their differing molecular exit vectors. This study introduces a skeletal editing strategy that efficiently transforms multisubstituted aza-BCHs into BCPs via an O-diphenylphosphinylhydroxylamine-promoted N-atom deletion process. This method effectively addresses the challenge of creating sterically hindered (2°)C–C(3°) bonds by removing a nitrogen atom encased within bulky alkyl groups, and reconstructing the strained aza-BCH structure into a more strained BCP without generating undesired ring-opening diene byproducts. The aza-BCHs used can be prepared from a modified intermolecular [3 + 2] cycloaddition between bicyclo[1.1.0]butanes and imines, making this method practical. This approach achieves remarkable efficiency, with yields up to 99% and scalability to decagram quantities. The resulting BCP carboxylates can be further functionalized through decarboxylation, highlighting the potential for programmed and divergent synthesis of multisubstituted BCPs. The broad substrate scope and high functional group tolerance of this protocol emphasize its versatility, making it particularly valuable for late-stage skeletal editing of aza-BCHs contained peptides, natural products, and pharmaceuticals.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition","authors":"Lingyun Yao, Xinlan Zou, Jian Zhang, Yang-Zi Liu, Quannan Wang, Hanliang Zheng, Xusheng Shao, Wei-Ping Deng","doi":"10.1021/acscatal.5c01239","DOIUrl":"https://doi.org/10.1021/acscatal.5c01239","url":null,"abstract":"The transition metal-catalyzed asymmetric [<i>n</i> + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable ketene precursors. Herein, we report a visible-light-driven, palladium-catalyzed asymmetric [4 + 2] cycloaddition of vinyl benzoxazinanones with siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives with satisfactory diastereo- and enantioselectivities. The transient generation of siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for the success of the present cycloaddition. The ¹³C-labeling experiments reveal a Brook rearrangement pathway involving a [1,3]-silyl migration process. The side arm effects of BOX ligand and silyl steric hindrance of α-ketoacylsilanes play crucial roles in the stereoselectivity control, and theoretical calculations provide crucial insights into the stereochemical outcome in the reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Steering the Selectivity of Electrochemical CO2 Reduction on the Cu Catalyst via the Interplay between the Electrode Morphology and Electrolyte Anion Identity","authors":"Cornelius A. Obasanjo, Gelson T. S. T. da Silva, Fatima Gonzalez Marin, Lucia H. Mascaro, Cao-Thang Dinh","doi":"10.1021/acscatal.4c08113","DOIUrl":"https://doi.org/10.1021/acscatal.4c08113","url":null,"abstract":"Electrochemical carbon dioxide (CO₂) reduction (ECR) holds promise as a viable pathway for the generation of fuels and chemicals. Several strategies have been explored to enhance the product selectivity of ECR on copper (Cu) catalysts. A systematic approach to optimize the local reaction microenvironment, however, remains elusive. Engineering the electrode structure and reaction microenvironment is a facile but effective strategy for steering the product selectivity of ECR reactions and can enable the rational design of highly selective Cu electrodes. Herein, we demonstrate that the synergy between an optimized Cu gas diffusion electrode (GDE) morphology and electrolyte anion identity can steer ECR product selectivity toward ethylene (C₂₊) or methane via the local CO₂ availability, pH, and electrode morphology regulation. We show that using a relatively thin 100 nm Cu catalyst layer (CL) sputtered on an optimized macropore-sized hydrophobic poly(tetrafluoroethylene) substrate promotes methane selectivity at high reaction rates. We achieved a methane partial current density of 126 mA cm^–2 and a Faradaic efficiency (FE) of 42%. In contrast, a relatively thick 500 nm Cu CL favors ethylene production, reaching a high FE of 52% at 250 mA cm^–2 (with a total C₂₊ value of 77%) in a near-neutral KHCO₃ electrolyte. Utilizing KI electrolyte significantly enhances methane selectivity, achieving ca. 56% at a partial current density of 168 mA cm^–2 while effectively suppressing the hydrogen evolution reaction (HER) on the thin CL. Furthermore, on the relatively thick CL, a higher C₂₊ FE of 84% was achieved at 250 mA cm^–2, demonstrating the impact of electrolyte anion identity and CL thickness on product selectivity in ECR. In addition, we find that a further increase in the Cu CL thickness does not result in a superior C₂₊ performance in KI compared to the KHCO₃ electrolyte. Our result highlights the critical role of the interplay between Cu electrode morphology and the electrolyte anion identity, which can facilitate efficient CO₂ mass transport, enable selective Cu sites, and tune local pH – thereby steering ECR product selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"97 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}