Catalysis Science & Technology最新文献

{"title":"Tuning catalytic performance of platinum single atoms by choosing the shape of cerium dioxide supports†","authors":"Petrus C. M. Laan ,&nbsp;Martijn J. Mekkering ,&nbsp;Felix J. de Zwart ,&nbsp;Alessandro Troglia ,&nbsp;Roland Bliem ,&nbsp;Kai Zhao ,&nbsp;Norbert J. Geels ,&nbsp;Bas de Bruin ,&nbsp;Gadi Rothenberg ,&nbsp;Joost N. H. Reek ,&nbsp;Ning Yan","doi":"10.1039/d4cy00484a","DOIUrl":"10.1039/d4cy00484a","url":null,"abstract":"<div><div>The local coordination environment of single atom catalysts (SACs) often determines their catalytic performance. To understand these metal–support interactions, we prepared Pt SACs on cerium dioxide (CeO₂) cubes, octahedra and rods, with well-structured exposed crystal facets. The CeO₂ crystals were characterized by SEM, TEM, pXRD, and N₂ sorption, confirming the shape-selective synthesis, identical bulk structure, and variations in specific surface area, respectively. EPR, XPS, TEM and XANES measurements showed differences in the oxygen vacancy density following the trend rods &gt; octahedra &gt; cubes. AC-HAADF-STEM, XPS and CO-DRIFTS measurements confirmed the presence of only single Pt²⁺ sites, with different surface platinum surface concentrations. We then compared the performance of the three catalysts in ammonia borane hydrolysis. Precise monitoring of reaction kinetics between 30–80 °C gave Arrhenius plots with hundreds of data points. All plots showed a clear inflection point, the temperature of which (rods &gt; octahedra &gt; cubes) correlates to the energy barrier of ammonia borane diffusion to the Pt sites. These activity differences reflect variations in the – facet dependent – degree of stabilization of intermediates by surface oxygen lone pairs and surface–metal binding strength. Our results show how choosing the right macroscopic support shape can give control over single atom catalysed reactions on the microscopic scale.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5662-5670"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11322700/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141998941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient glycolysis of used PET bottles into a high-quality valuable monomer using a shape-engineered MnOx nanocatalyst†","authors":"Bhattu Swapna ,&nbsp;Nittan Singh ,&nbsp;Suranjana Patowary ,&nbsp;Pankaj Bharali ,&nbsp;Giridhar Madras ,&nbsp;Putla Sudarsanam","doi":"10.1039/d4cy00823e","DOIUrl":"10.1039/d4cy00823e","url":null,"abstract":"<div><div>The chemical recycling of used polyethylene terephthalate (PET) bottles, a widely used plastic in the modern world, to obtain valuable monomers offers a promising solution to address post-consumer plastic-related environmental concerns. In this study, we have developed an efficient heterogeneous catalytic approach using a shape-engineered manganese oxide (MnO_x) nanocatalyst with a well-defined rod morphology to facilitate the glycolysis of PET with biomass-derived ethylene glycol to produce a high-quality bis(2-hydroxyethyl) terephthalate (BHET) valuable monomer under mild conditions. The nanorod morphology of the MnO_x material, specifically the MnO_x calcined at 500 °C (MnO_x-500), exhibited remarkable catalytic efficiency in converting used PET bottles into BHET. At a temperature of 180 °C for 3 h, the MnO_x-500 nanocatalyst achieved a complete conversion of PET with a 86% isolated yield of BHET, surpassing the performance of various metal oxides, such as CeO₂, TiO₂, and Nb₂O₅. Qualitative analysis of the isolated BHET monomer crystals was conducted using NMR, FT-IR, HR-MS, and powder XRD, along with assessments of thermal stability through TGA and DSC studies. Furthermore, the study demonstrated the catalyst's stability and reusability, suggesting the practical application potential of this methodology. The structure–activity correlation, revealed through comprehensive characterization of the nanostructured MnO_x materials, highlighted the crucial role of the oxygen vacancy defects and the acidic properties in the MnO_x-500 nanocatalyst for efficient PET glycolysis to obtain the desired BHET monomer.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5574-5587"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient reductive amination of 5-hydroxymethylfurfural by iridium-catalysed transfer hydrogenation†","authors":"Haoying Liu ,&nbsp;Weijun Tang ,&nbsp;Dong Xue ,&nbsp;Jianliang Xiao ,&nbsp;Chao Wang","doi":"10.1039/d4cy00812j","DOIUrl":"10.1039/d4cy00812j","url":null,"abstract":"<div><div>Transfer hydrogenative reductive amination of 5-(hydroxymethy)furfural (HMF) has been accomplished, catalysed by a cyclometalated iridium catalyst with formic acid as a hydrogen source. The catalytic system afforded a TON of 9600 and TOF of 14 400 h⁻¹, and the reaction can be successfully scaled up to a 10 gram scale at a substrate-to-catalyst ratio of 10 000. A wide range of amines could be coupled with HMF to afford furan derived products, including modified drug molecules, key intermediates for drug synthesis and potential monomers for polymer synthesis.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5764-5769"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A review of fuel cell cathode catalysts based on hollow porous materials for improving oxygen reduction performance†","authors":"Zexu Jia ,&nbsp;Xiaoqiu Lin ,&nbsp;Congju Li","doi":"10.1039/d4cy00830h","DOIUrl":"10.1039/d4cy00830h","url":null,"abstract":"<div><div>Fuel cells are highly efficient green power generation devices that convert chemical energy into electricity. They have great potential for use in transportation, households, and power stations. The oxygen reduction reaction (ORR) represents a key electrochemical process in fuel cells, significantly impacting energy conversion efficiency. The limitations to further commercialization of fuel cells stem from several fundamental and technical issues, including the slow oxygen reduction reaction (ORR) at the cathode and the use of a large number of precious metal catalysts. This paper critically evaluates recent reports on material selection and structural optimization of catalysts, highlighting the successful strategies employed in these studies. Hollow porous catalysts are a highly cost-effective alternative to precious metal catalysts, owing to their significantly lower manufacturing costs and potential structural benefits. The potential for hollow porous materials to replace precious metal catalysts is indicated by their low cost, high specific surface area, potential structural advantages, and abundant surface defects. This text provides a comprehensive understanding of efficient catalyst design and fabrication by reviewing research results on hollow porous materials and structures applied to ORR electrocatalysis. The potential for the continued development of hollow porous catalysts in fuel cells is envisaged.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5505-5524"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile synthesis of hierarchical nanocrystalline H[Fe,Al]ZSM-5 with boosted lifetime for DTG reactions","authors":"Jianqing Li ,&nbsp;Hui Wang ,&nbsp;Guangbo Liu ,&nbsp;Tao He ,&nbsp;Zhiqi Wang ,&nbsp;Jingli Wu ,&nbsp;Jinhu Wu","doi":"10.1039/d4cy00838c","DOIUrl":"10.1039/d4cy00838c","url":null,"abstract":"<div><div>Dimethyl ether to gasoline (DTG) process is an important way to obtain transportation fuels from non-petroleum routes due to the ever-decreasing fossil energy under “dual-carbon” background, and the development of catalyst with long lifetime remains an important challenge. Herein, the hierarchical nanocrystalline H[Fe,Al]ZSM-5 zeolites composed of loosely aggregated nanocrystals were prepared by adding a mesoporous template and prolonging the aging time, and their physicochemical properties and reactivity over the DTG reaction were investigated and compared with that of conventional H[Fe,Al]ZSM-5. The size of individual nanocrystals became smaller and more uniform, and the nanocrystals were loosely aggregated with abundant intercrystal mesopores, resulting in the significant enhancement of catalyst lifetime. Furthermore, the acid intensity of hierarchical nanocrystalline zeolites weakened, and the strong acid amount was reduced. DTG reaction results illustrated that the hierarchical nanocrystalline zeolite of Mes-ZSM-5 using a mesoporous template exhibited the longest lifetime (182 h) with 100% DME conversion, and gasoline yield remained more than 70%. Moreover, the C₅⁺ selectivity was up to 76.6%; meanwhile, the contents of aromatics, benzene and durene were as low as 40%, 0.6% and 1.7%, respectively. The obtained gasoline product had a higher RON (research octane numbers).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5588-5598"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329360","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"2D/2D Mo2CTx/g-C3N4 with a strong coupling interface via one-step NH4Cl-assisted calcination for enhanced photocatalytic hydrogen production†","authors":"Haiting Zou ,&nbsp;Miaomiao Pan ,&nbsp;Ping Wang ,&nbsp;Feng Chen ,&nbsp;Xuefei Wang ,&nbsp;Huogen Yu","doi":"10.1039/d4cy00882k","DOIUrl":"10.1039/d4cy00882k","url":null,"abstract":"<div><div>Mo₂CT_x is regarded as a potential cocatalyst to substitute noble metals in photocatalytic hydrogen production owing to its good electrical conductivity and a large number of active sites. However, Mo₂CT_x-based photocatalysts by the conventional physical mixing method always display a weak coupling interface between Mo₂CT_x and photocatalysts due to the large block-layered structure of Mo₂CT_x, which results in slow photogenerated-electron transfer of photocatalysts, thereby leading to unsatisfactory hydrogen production efficiency. Considering that <em>in situ</em> construction and the 2D/2D structure can increase the contact area and enhance the coupling interface interaction, in this study, a strategy of constructing a 2D/2D Mo₂CT_x/g-C₃N₄ photocatalyst from pre-etched Mo₂CT_x and guanidine hydrochloride (CH₆ClN₃) through a one-step NH₄Cl-assisted calcination method is realized by the gas-expansion exfoliation of Mo₂CT_x and <em>in situ</em> generation of thin g-C₃N₄ nanosheets. Experimental results unveiled that the 2D/2D Mo₂CT_x/g-C₃N₄ composite photocatalyst exhibits an exceptional H₂-evolution activity (125 μmol h⁻¹ g⁻¹, AQE = 3.88%), which is almost 25 and 18 times greater than that of pure g-C₃N₄ and physically mixed Mo₂CT_x–g-C₃N₄, respectively. The enhanced photocatalytic H₂-production efficiency is attributed to the robust coupling interface between Mo₂CT_x and g-C₃N₄ in 2D/2D Mo₂CT_x/g-C₃N₄, which promotes the fast photogenerated electron transfer from g-C₃N₄ to Mo₂CT_x and achieves an optimized Gibbs free energy. This study offers a novel perspective on preparing high-efficiency 2D/2D MXene-based photocatalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5731-5738"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergism between B–N atomic pair for promoting the catalytic cracking of 1,2-dichloroethane†","authors":"Yaqi Yao ,&nbsp;Hongying Zhuo ,&nbsp;Fanan Wang ,&nbsp;Guiyue Bi ,&nbsp;Jinming Xu ,&nbsp;Xiaofeng Yang ,&nbsp;Yanqiang Huang","doi":"10.1039/d4cy00774c","DOIUrl":"10.1039/d4cy00774c","url":null,"abstract":"<div><div>The catalytic cracking of 1,2-dichloroethane (EDC) to obtain vinyl chloride (VCM) monomer is a crucial step in the production of polyvinyl chloride (PVC). The heteroatom-doped carbon catalysts have exhibited desired performance; however, the underlying mechanism is still not fully understood. Herein, a series of B–N co-doped carbon (BNC), N-doped carbon (NC), B-doped carbon (BC) and pure carbon (C) catalysts were prepared for EDC catalytic cracking, and the synergistic mechanism between B and N was carefully investigated. The BNC catalyst exhibits prominently higher activities with an EDC conversion of 53.9% at 250 °C. Through a combination of experimental and theoretical analyses, it is rationalized that the formation of the B–N atomic pair contributes to the enhanced performance and the electronic interaction between the B–N atomic pair imparts greater basicity to the N sites, which reduces the activation energy barrier for C–H bond cleavage by 0.34 eV. The present results provide a theoretical foundation for the precise design of highly efficient non-metallic carbon-based catalysts for EDC cracking.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5599-5607"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00774c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of polyunsaturation – insights into the hydroformylation of oleochemicals†","authors":"Thomas Friedrich Hubertus Roth ,&nbsp;Maximilian Lukas Spiekermann ,&nbsp;David Lütkenhaus ,&nbsp;Fabian Niefer ,&nbsp;Dieter Vogt ,&nbsp;Thomas Seidensticker","doi":"10.1039/d4cy00839a","DOIUrl":"10.1039/d4cy00839a","url":null,"abstract":"<div><div>Although the hydroformylation of vegetable oil-derived oleochemicals, such as methyl oleate, is a highly demanded reaction and has been intensively studied, little is known about the influence of naturally occurring polyunsaturated (PU) components and their effect on the homogeneous rhodium catalyst. This is now examined in detail in the presented work by conducting systematic perturbation experiments. For the first time, it can be verified that the isomerisation of double bonds in polyunsaturated oleochemicals generates conjugated double bond systems that form stable η³-Rh allyl species and thus temporarily inhibit the catalyst. However, based on these findings, hydroformylation activity can be significantly increased by selective hydrogenation of PU to monounsaturated components. In the case of sunflower methyl ester, the turnover frequency multiplied by a factor of 8 and reached 3201 h⁻¹, the highest rate reported in the context of methyl oleate hydroformylation. These effects were shown for both phosphine and phosphite ligands under both mono- and biphasic conditions and for methyl esters with different PU content, stressing the magnitude of this effect. This work makes it possible to support long-observed phenomena with the underlying mechanism scientifically. This lays the scientific basis for efficiently converting oleochemicals into valuable intermediates through hydroformylation for an increased share of renewable carbon in the chemical value chain.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5551-5558"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00839a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scalable and green juglone synthesis via heterogeneous photocatalysis in a photomicroreactor†","authors":"Mohsin Pasha ,&nbsp;Yuhan Wang ,&nbsp;You Ma ,&nbsp;Guozhi Qian ,&nbsp;Xiao Xue ,&nbsp;Hong Zhang ,&nbsp;Yong Yang ,&nbsp;Minjing Shang ,&nbsp;Pengfei Zhang ,&nbsp;Yuanhai Su","doi":"10.1039/d4cy00778f","DOIUrl":"10.1039/d4cy00778f","url":null,"abstract":"<div><div>The selection of green and scalable heterogeneous photocatalysis is always a great dilemma for the chemistry and chemical engineering communities. In this report, we resolved this vital conundrum by synergistically examining the scalability and green potential of heterogeneous photocatalysis for juglone synthesis. We scaled up juglone productivity and the space–time yield to 15 g per day and 43.87 g L⁻¹ h⁻¹, respectively, <em>via</em> heterogeneous photocatalysis with a high-power LED as a light source and Amb–<em>m</em>-TcPP as a photocatalyst, which was fabricated by incorporating <em>meso</em>-tetracarboxyphenylporphyrine (<em>m</em>-TcPP) over the polystyrene ion-exchange resin Amberlyst-15. Amb–<em>m</em>-TcPP showed excellent recyclability in multiple cycles and exhibited high photostability for 12 h continuous operation without <em>m</em>-TcPP leaching with a turnover frequency of 409.7 h⁻¹. The apparent rate constants were higher than those in previously employed heterogeneous photocatalysis, and intrinsic rate constants of intermediate steps were evaluated using transition state theory with quantum mechanical models using DFT simulations, which was useful for gaining mechanistic insights into this photooxidation process. Finally, heterogeneous DHN photooxidation was confirmed to be well aligned with green chemistry principles, and <em>E</em> factors were found to be under an acceptable range. Thus, this heterogeneous DHN photooxidation can be regarded as a green and sustainable synthesis route for multigram juglone production.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5755-5763"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CeO2-modified monolithic ceramic foams for efficient catalytic ozonation of refractory organic pollutants in a continuous-flow reactor†","authors":"Yang Zhao ,&nbsp;Wenfei Ding ,&nbsp;Xiaochi Chen ,&nbsp;Shuo Chen","doi":"10.1039/d4cy00710g","DOIUrl":"10.1039/d4cy00710g","url":null,"abstract":"<div><div>Heterogeneous catalytic ozonation is valid for the advanced oxidation of organic pollutants in wastewater, but it is usually used in the packing bed with granular supports/catalysts with considerable fluid resistance and unsatisfactory ozone utilization efficiency in practical wastewater treatment. Herein, CeO₂-modified monolithic ceramic foams (CeO₂/AlCF) were developed for the efficient catalytic ozonation of refractory organic pollutants in a continuous-flow mode. The TOC removal efficiency of phenol by CeO₂/AlCF was about 80% with a hydraulic retention time (HRT) of 12 min. The system also showed high TOC removal efficiencies (68%–81%) for other organic pollutants including oxalic acid, 2,4-dimethylphenol, and <em>p</em>-nitrophenol. The chemical oxygen demand (COD) of the biological treatment effluent of petrochemical wastewater decreased from 136 mg L⁻¹ to 45.2 mg L⁻¹ with a COD removal efficiency of nearly 67%. The ozone utilization efficiencies of CeO₂/AlCF ranged from 53% to 73%, which were much higher than those of granular catalysts (42–68%). The quenching experiments and EPR analysis revealed that the process followed a hydroxyl radical mechanism. H₂ temperature-programmed reduction (H₂-TPR) analysis showed that the transition of Ce⁴⁺ to Ce³⁺ in CeO₂/AlCF was much easier than that in CeO₂ and hence had a better catalytic capability.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5653-5661"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}