Catalysis Today最新文献

{"title":"The effect of mechanochemical mixing conditions on V2O5/WO3-TiO2 and zeolite Y hybrid catalyst for selective catalytic reduction of NOx with NH3","authors":"Hyun Sub Kim ,&nbsp;Se Won Jeon ,&nbsp;Hongbeom Park ,&nbsp;Inhak Song ,&nbsp;Do Heui Kim","doi":"10.1016/j.cattod.2025.115568","DOIUrl":"10.1016/j.cattod.2025.115568","url":null,"abstract":"<div><div>V₂O₅/WO₃-TiO₂ (VWTi) catalysts are widely utilized in selective catalytic reduction with NH₃ (NH₃-SCR) for stationary sources. However, their susceptibility to ammonium bisulfate (ABS) formation due to the presence of SO₂ and H₂O in flue gases poses a significant challenge. Improving the removal of ABS formed on VWTi catalysts can enhance their SO₂ resistance, and zeolites with strong acid sites are promising materials for trapping ABS. To optimize the interaction between VWTi catalysts and zeolites, two sample preparation methods were evaluated in this work: hand-mixing and ball milling. This study investigates the catalytic activity and SO₂ resistance of these samples to evaluate the effectiveness of the mixing techniques. The sample mixed using a mixer mill (20 Hz, 10 min) exhibited superior NO_x conversion and SO₂ resistance compared to the hand-mixed VWTi and zeolite Y sample. This improvement in catalytic performance was attributed to the preservation of the TiO₂ particle during the ball milling process, coupled with partial fragmentation of the zeolite that facilitated intimate contact between mixed particles. In contrast, extending this approach to a MnO_x + zeolite Y hybrid system revealed no synergistic effect, as the MnO_x active material suffered structural damage during the ball milling process. These findings underscore the importance of ensuring that the active material maintains its structural integrity while allowing the ABS-trapping material to undergo controlled fragmentation. Such balance is crucial for maximizing the intimate contact between components and achieving optimal catalytic performance.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115568"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106190","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":"Synthesis of hydroxyapatite – containing catalysts from bone waste – conventional route versus microwaves","authors":"Gabriela Petcu ,&nbsp;Mariana Patrascu ,&nbsp;Virginia-Cora Gheorghe ,&nbsp;Gabriela Ionescu ,&nbsp;Marilena Radoiu ,&nbsp;Aneta Magdziarz ,&nbsp;Cosmin Mărculescu","doi":"10.1016/j.cattod.2025.115538","DOIUrl":"10.1016/j.cattod.2025.115538","url":null,"abstract":"<div><div>The use of the hydroxyapatite (HA) contained in animal bone residues for the synthesis of active catalysts is an innovative solution to manage large quantities of bone waste (BW). In this study, two methods of preparing HA - containing catalysts were explored: i) conventional route using bone char (BC) from BW calcined at 500–900 °C, and ii) microwaves route using aqueous phase extraction from BW by a microwave (MW) -assisted process at 95 °C. BC mainly consisted of B-type HA, in which carbonate groups replace phosphate in the structure; however, its low surface area limited its catalytic performance. Modification with silica, MW treatment and surfactant charge had a critical effect on the formation of the porous structure, and consequently, on increasing the surface area of the composite catalysts. Cationic surfactants promoted silica network formation and resulted in improved porous structures due to their weaker interaction with the positively charged BC. The obtained HA-containing catalysts were demonstrated to be effective platforms for immobilising metallic species. Incorporating Ti and Zn by direct synthesis generated highly dispersed active sites, as confirmed by physicochemical characterization. Notably, an increase in sea buckthorn pyrolysis temperature (from 250 °C to 600 °C) was observed after just 5 min of MW irradiation using catalysts produced via the MW-assisted method, indicating enhanced heat transfer within the reactor. Meanwhile, catalysts produced via the conventional method significantly impacted the composition of the pyrolysis gas phase by promoting the formation of CO₂ and hydrocarbons ≥C₂, such as C₂H₂, C₂H₆, C₃H₈, C₄H₁₀, C₅H₁₂, and C₆H₁₄.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115538"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020275","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":"Amine-incorporated bridged polysilsesquioxane as a catalyst support for aqueous phase phenol hydrogenation","authors":"Snehal S. Patil ,&nbsp;James Nana Gyamfi ,&nbsp;Luke Gillespie ,&nbsp;Yehia Khalifa ,&nbsp;Seval Gunduz ,&nbsp;Paul L. Edmiston ,&nbsp;Umit S. Ozkan","doi":"10.1016/j.cattod.2025.115567","DOIUrl":"10.1016/j.cattod.2025.115567","url":null,"abstract":"<div><div>Cyclohexanone is an important chemical used predominantly as an intermediate in nylon manufacturing. Phenol hydrogenation, a key route for producing cyclohexanone, results in a mixture of cyclohexanone and cyclohexanol. In this work, we have attempted to enhance the selectivity of phenol hydrogenation to cyclohexanone by doping amine functionalities in aryl-bridged polysilsesquioxane (ABPS), an organosilica support for palladium catalyst. Amine sites were successfully incorporated without compromising the textural properties and the structure of the organosilica via co-condensation of bis(trimethoxysilylethyl)benzene and bis(trimethoxysilylpropyl)amine, bridged organosilane precursors. Phenol hydrogenation activity experiments were conducted in an autoclave batch reactor at 200 °C and 50 bar. Amine-doping led to a significant increase in the cyclohexanone selectivity. CO₂ TPD, phenol TPD, and aqueous phase adsorption experiments revealed that the enhanced strength of phenol adsorption in non-planar mode and preferential adsorption of phenol over cyclohexanone on basic amine-doped catalysts were responsible for the increase in cyclohexanone selectivity.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115567"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145119217","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":"Effect of membrane properties on CO2 methanation reaction by using distributor type membrane reactor","authors":"Yuka Shimizu ,&nbsp;Hiroto Tsuyuki ,&nbsp;Marcin Moździerz ,&nbsp;Grzegorz Brus ,&nbsp;Shinichi Ookawara ,&nbsp;Keita Yabe ,&nbsp;Aleksandra Roszko ,&nbsp;Elzbieta Fornalik-Wajs ,&nbsp;Mikihiro Nomura","doi":"10.1016/j.cattod.2025.115569","DOIUrl":"10.1016/j.cattod.2025.115569","url":null,"abstract":"<div><div>CO₂ methanation by using distributor type membrane reactor was investigated to control the reaction rate by distributed reactant feeding through membrane. Accurate evaluation of the thermal conductivity of the porous Al₂O₃ membrane, considering its fine physical and chemical structures, was achieved by measurements using Laser Flash Analysis. In the solid part of the 1TC sample, the thermal conductivity was found to be 36.4 % lower than that of non-porous alumina. A catalytic membrane with a silica separation layer, having an H₂ permeance of 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and an H₂/CO₂ selectivity of 35.9, was used in the distributor type membrane reactor test, and a CO₂ conversion of 92.3 % was obtained at 350 ℃. Based on these results, simulation was performed using Ansys Fluent to investigate the influence of membrane thermal conductivity and permselectivity. The CO₂ permeance of the membrane was set equal to 3.91 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ for all conditions. It was shown that the CO₂ permselective membrane (H₂/CO₂ selectivity = 35.9) produced about 1.4 times CH₄ than the H₂ permselective membrane (H₂/CO₂ selectivity = 0.10), and that higher thermal conductivity of the membrane suppressed the temperature rise in the reactor.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115569"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227247","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":"Operando IR of catalytic reactions under microwaves at 5.8 GHz","authors":"Frédéric Thibault-Starzyk ,&nbsp;Ana Neto ,&nbsp;Sébastien Thomas ,&nbsp;Carlos Henriques ,&nbsp;Gary Bond","doi":"10.1016/j.cattod.2025.115571","DOIUrl":"10.1016/j.cattod.2025.115571","url":null,"abstract":"<div><div>A new spectroscopic cell was designed for operando IR observation of heterogeneous catalysis under microwave irradiation. Oxidation of CO on Pt-H-BEA zeolite was performed under conventional and microwave heating at the same space velocity to assess the efficiency of microwave heating, which was confirmed by an infrared in-situ temperature scale. A temperature of 230–240°C was obtained after 2 min microwave irradiation. Infrared monitoring evidences a moderate sintering of the platinum particles after microwave irradiation, probably due to hotspots on the metal. Infrared observation indicates a strong perturbation of electron density in the Pt particles by microwave during catalysis.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115571"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155985","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":"Revisiting rate-determining stage and prime activator for selective water-gas shift acceleration via redox mechanism","authors":"So Hyeon Park ,&nbsp;Tao Zhou ,&nbsp;Seonggeun Park ,&nbsp;Taekyung Yu ,&nbsp;Jongsik Kim","doi":"10.1016/j.cattod.2025.115541","DOIUrl":"10.1016/j.cattod.2025.115541","url":null,"abstract":"<div><div>Halloysite can be deprotonated and dehydrated to transform into polymorphic Kaolinite, whose non-reducible Al³⁺/Al⁴⁺ (M_II^3+/4+) are positioned adjacent to reducible Pd^δ+/Ag^δ+ (M_I^δ+; δ≤2) to facilitate •H confinement in Pd_XAg_4-X alloys (X=1–3) functioning as M_I^δ+ reservoirs for expediting H₂ release. This is conducive to provoke water-gas shift (WGS) preferentially via redox mechanism that has been controversial in terms of rate-determining step (RDS) and major activator. To this end, Kaolinite-supported Pd_XAg_4-X alloys were synthesized to impart M_II^3+/4+-O^2--M_I^δ+-O^2--M_II^3+/4+ interfaces, where the redox mechanism can be accelerated using M_I^δ+ or proximal oxygen vacancy (O_V) as the main activator. The amounts and electron (e^-) affinity of M_I^δ+/O_V species varied with dissimilar X values or their exposure to hydro-thermal aging (HT) environments, thereby linking with WGS kinetic parameters of the catalysts. The hierarchies of the energy barriers for the HT-unsubjected/subjected catalysts were con-current to their trends on e^- affinity with O_V species rather than those with M_I^δ+ counterparts. This demonstrated that the RDS is either CO₂ desorption from M_I^δ+/O_V or H₂O homolysis on O_V. Moreover, the ranks of the collision frequencies for the HT-unsubjected/subjected catalysts exactly matched their trends on O_V quantities rather than those on M_I^δ+ quantities. This indicated that O_V sites outweigh M_I^δ+ species to accelerate the redox mechanism as the prime activators. This study uncovers how to design or regulate the catalytic surfaces for prompting the WGS exclusively via the redox mechanism.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115541"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020272","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":"Zeolite-supported palladium nanoparticles as universal heterogeneous Tsuji–Trost allylic alkylation catalysts","authors":"Adéla Olšovská ,&nbsp;Martin Kamlar ,&nbsp;Subhajyoti Samanta ,&nbsp;Jan Veselý ,&nbsp;Jiří Čejka ,&nbsp;Michal Mazur","doi":"10.1016/j.cattod.2025.115537","DOIUrl":"10.1016/j.cattod.2025.115537","url":null,"abstract":"<div><div>The Tsuji–Trost allylic alkylation is mainly performed in homogeneous systems; however, developing efficient alternative, heterogeneous catalysts remains crucial for sustainable synthesis. This study introduces zeolite-supported palladium catalysts as viable heterogeneous catalysts in this reaction. The active catalysts, Pd@USY and Pd@deAl-USY, were synthesized <em>via</em> controlled impregnation and reduction to achieve ultrasmall Pd nanoparticles (2.2 nm and 2.5 nm in diameter, respectively). Pd@lay-MFI, serving as a reference material containing large nanoparticles (&gt;20 nm), proved inactive in the reaction. Among the prepared materials, Pd@USY exhibited optimal performance in the model Tsuji–Trost reaction between diethyl malonate and allyl acetate, achieving complete conversion within 2 h under mild conditions (room temperature, dichloromethane, K₂CO₃), with activity directly correlated to nanoparticle size: inactive Pd@lay-MFI featured substantially bigger particles, while sub-3 nm particles in active catalysts enabled efficient substrate activation. The reaction scope demonstrated broad substrate compatibility, though nucleophilicity and α-substitution heavily influenced reactivity, and bulky substituents reduced conversion due to zeolite pore diffusion constraints and steric hindrance during nucleophilic attack. Catalyst reuse was feasible for at least two cycles before the catalyst became deactivated. The analysis of the deactivation mechanism is ongoing. Notably, the loss of activity was reversible, as regeneration successfully restored catalytic performance. The catalyst was stable against sintering, leaching, or poisoning. In conclusion, Pd@USY represents a promising heterogeneous alternative for Tsuji–Trost allylic alkylation, combining high activity, selectivity, and operational simplicity.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115537"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144989397","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":"Hydrogen production from aqueous formic acid solution using Pt/Cs with different preparation methods","authors":"Shuka Murakami,&nbsp;Hiroyasu Fujitsuka,&nbsp;Motoaki Kawase","doi":"10.1016/j.cattod.2025.115575","DOIUrl":"10.1016/j.cattod.2025.115575","url":null,"abstract":"<div><div>Formic acid is a promising hydrogen carrier because of its high hydrogen content and small enthalpy of dehydrogenation. Hydrogen is generally produced from formic acid via liquid-phase decomposition over catalysts. Catalysts consisting of noble metals that are stable in acidic solutions and carbon supports without acidic sites causing side reactions have several advantages, such as the high activity and ease of separation. To enhance catalytic activity, the surface area of the active metal should be increased. However, conventional impregnation methods are not completely suitable for this purpose because of the weak metal–carbon interactions. To solve this problem, a preparation method using an ion-exchange resin as a precursor for the carbon support was employed. In this study, we investigated the effect of the preparation method of carbon-supported Pt catalysts on their catalytic activity for the liquid-phase decomposition of formic acid. The catalysts prepared from ion-exchange resins exhibited Pt loadings of approximately 26–28 wt% and Pt particle sizes of 2–3 nm; therefore, this method can realize a higher dispersion degree of Pt nanoparticles than an impregnation method. Moreover, the produced catalysts demonstrated a higher activity for the dehydrogenation of formic acid than those of the catalysts prepared by the impregnation method. Additionally, the carbonization temperature strongly affected the catalyst properties, such as the pore size and metal accessibility. Consequently, the catalyst activity for the decomposition of formic acid varied depending on the carbonization temperature. We also formulated a new reaction model considering hydrogen adsorption.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115575"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155984","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 editorial: Trends in catalyst design and novel catalytic materials","authors":"József S. Pap,&nbsp;Andrzej Kotarba,&nbsp;Małgorzata Witko,&nbsp;David Kubička","doi":"10.1016/j.cattod.2025.115539","DOIUrl":"10.1016/j.cattod.2025.115539","url":null,"abstract":"<div><div>While target reactions in catalysis remain consistent, the approach to designing and developing new catalysts continually evolves. This evolution is driven by advancements in materials science and investigative methods, leading to a deeper understanding of structure-reactivity relationships. This interdisciplinary synergy is fundamental to catalyst design and the creation of novel catalytic materials.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115539"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263110","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":"Electrochemical hydrogen evolution and its reaction mechanism of hydroxypyridinate-bridged dirhodium(II) phenanthroline complex","authors":"Natsumi Yano,&nbsp;Kozo Sato,&nbsp;Makoto Handa,&nbsp;Yusuke Kataoka","doi":"10.1016/j.cattod.2025.115542","DOIUrl":"10.1016/j.cattod.2025.115542","url":null,"abstract":"<div><div>A new 6-fluoro-2-hydroxypyridinate (fhp)-bridged dirhodium(II) complex containing a 1,10-phenanthroline (phen) ligand, [Rh₂(μ-fhp)₃(η¹-fhp)(phen)] (<strong>1</strong>), was prepared and characterized using nuclear magnetic resonance spectroscopy, electrospray ionization mass spectroscopy, elemental analysis, and synchrotron single crystal X-ray diffraction (SCXRD) analyses. In DMF, <strong>1</strong> was found to catalyze electrochemical proton reduction to evolve hydrogen in the presence of trifluoroacetic acid (Htfa) as a proton source. The turnover frequency and overpotential for hydrogen evolution catalyzed by <strong>1</strong> were 13263 s⁻¹ and 457 mV, respectively. Interestingly, the intermediate species for the hydrogen evolution reaction, [Rh₂(μ-fhp)₃(phen)(η¹-tfa)] (<strong>1-IM</strong>), could be crystallized from DMF solution of <strong>1</strong> in the presence of Htfa and was also characterized by synchrotron SCXRD. The reaction mechanism for the hydrogen evolution was thoroughly investigated based on the theoretically predicted redox potentials, p<em>K</em>a values, free energies, and binding energies. The findings are as follows: (i) the formation of the one-electron reduced species <strong>[1-IM]</strong>^{<strong>−</strong>} serves as an initial trigger for hydrogen evolution; (ii) <strong>1-IM</strong> transforms into a protonated species, which immediately undergoes one-electron reduction; (iii) initial protonation occurs at the axial position of the Rh₂ core, followed by a second one-electron reduction, possibly through a concerted proton-electron transfer (CPET); and (iv) the final reaction intermediate was identified as [2H_ax-Rh₂(μ-fhp)₃(phen)(η¹-tfa)] (<strong>[2H</strong>_{<strong>ax</strong>}<strong>-1-IM]</strong>), in which two protons are bound in a side-on fashion at the axial position of the Rh₂ core, their coordination being assisted by the tfa ligand. These results indicated that <strong>1-IM</strong> promotes the electrochemical hydrogen evolution via an ECEC mechanism (E: electron transfer, C: chemical reaction).</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115542"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009889","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}