Journal of Catalysis最新文献

{"title":"Electronic and geometric features controlling the reactivity of Mg-vanadate and V2O5 surfaces toward the initial C–H activation of C1–C3 alkanes – A DFT+U study","authors":"Hansel Montalvo-Castro, Álvaro Loaiza-Orduz, Randall J. Meyer, Craig Plaisance, David Hibbitts","doi":"10.1016/j.jcat.2024.115800","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115800","url":null,"abstract":"This work employs density functional theory (DFT+U) calculations to explore initial C–H activations in C₁–C₃ alkanes on V₂O₅, MgV₂O₆ (meta-vanadate), Mg₂V₂O₇ (pyro-vanadate), and Mg₃V₂O₈ (ortho-vanadate) surfaces. These materials are selective catalysts for the oxidative dehydrogenation (ODH) of alkanes into alkenes, which offers practical and thermodynamic advantages over non-oxidative alkane dehydrogenation. The geometric and electronic properties that govern the reactivity of these materials, however, have not been explored by theory despite their importance in controlling rate determining alkane initial C–H activation during ODH catalysis. In this work, we explore fourteen low-energy surfaces of Mg<em>_x</em>V₂O<em>_x</em>₊₅ (<em>x</em> = 0–3) exposing 64 distinct O atoms (reaction sites). C–H activation barriers are largest on Mg₃V₂O₈, lower and similar for Mg₂V₂O₇ and MgV₂O₆, and lowest for V₂O₅ surfaces; these predicted trends are consistent with measured ODH reactivity in earlier studies. Barriers are lowest (on average) when alkanes react with O atoms bound to a single V atom, with bridging O atoms having slightly higher barriers, and three-fold O atoms having the largest activation barriers. However, there is scattering within each subset indicating that factors beyond O-atom coordination have a significant role in the barriers. Vacancy formation energies (VFE) and the O 2p band energies were found to be weak descriptors of surface O reactivity for alkane activation barriers. Hydrogen addition energy (HAE) and methyl addition energy (MAE) values, in contrast, were found to correlate well with alkane activation barriers. MAE, however, outperforms HAE correlations because of the tendency of H* to form H-bonds with nearby surface O atoms, and those H-bonds are absent in C–H activation transition states causing scatter in the correlation of barriers with HAE. Constrained-orbital DFT methods were used to establish a theoretical thermochemical cycle that decouples surface reduction by CH₃* into three components: surface distortion, orbital localization, and bond formation. These results give insights into how Mg:V ratios, surface structure (O-atom coordination), and reducibility (HAE, MAE) impact the reactivity of vanadium-based metal oxides toward alkane activation.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"40 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450011","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":"Synergistic regulation of g-C3N4 band structure by phosphorus and sodium doping to enhance photocatalytic hydrogen peroxide production efficiency","authors":"Yuting Wang ,&nbsp;Mengxiang Wang ,&nbsp;Xuya Zhang ,&nbsp;Xinru Pan ,&nbsp;Yongpeng Cui ,&nbsp;Daoqing Liu ,&nbsp;Yajun Wang ,&nbsp;Wenqing Yao","doi":"10.1016/j.jcat.2024.115807","DOIUrl":"10.1016/j.jcat.2024.115807","url":null,"abstract":"<div><div>In addressing the industrial need for a simple, equipment-minimal, and non-toxic method of in-situ hydrogen peroxide (H₂O₂) production, this paper presents a cost-effective, environmentally friendly photocatalyst. Our design strategy focuses on the dual-element doping of phosphorus and sodium into graphitic carbon nitride (g-C₃N₄), chosen to synergistically enhance photocatalytic performance. This approach yields a notable H₂O₂ production concentration of 3001.64 μmol·g⁻¹·L^-1 within 100 min, using isopropanol as a sacrificial agent, which was 61-fold increase compared to bulk g-C₃N₄. Density Functional Theory (DFT) calculations were performed to elucidate the alterations in the band structure of the catalyst induced by dual-element doping, which consequentially engendered an asymmetric intrinsic electric field. Additionally, oxygen’s transition state affinity due to phosphorus doping was also investigated to reveal the mechanisms of synergistic catalysis. This development contributes to meeting industrial demands for pollutant degradation via Fenton processes and presents a sustainable alternative to traditional H₂O₂ production methods.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115807"},"PeriodicalIF":6.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449730","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":"Production of docosahexaenoic acid through enzymatic hydrolysis of Omega-3 rich oil","authors":"Ernestina García-Quinto ,&nbsp;Raquel Aranda-Cañada ,&nbsp;Jose M. Guisan ,&nbsp;Gloria Fernandez-Lorente","doi":"10.1016/j.jcat.2024.115797","DOIUrl":"10.1016/j.jcat.2024.115797","url":null,"abstract":"<div><div>Docosahexaenoic acid (DHA), an essential omega-3 fatty acid, is crucial for the normal development and function of the brain. Its production can be achieved through the partial hydrolysis of DHA-rich triglycerides catalyzed by lipases, particularly from fish oils. In this work, the characterization of anchovy oil capsules revealed that they offer a pure and concentrated source of DHA, with more than 90 % of the oil in the form of triglycerides. Therefore, the hydrolysis reaction was studied with the aim of releasing 100 % of the DHA present in this oil, using different immobilized lipases with maximum enzyme loading on the hydrophobic support Immobeads-C18. The study’s results revealed that our immobilization strategy through hydrophobic adsorption improved the catalytic properties of activity and selectivity of the TLL lipase compared to other biocatalysts described in the literature. Additionally, complete hydrolysis of the oil was achieved in just 24 h with the NS40-C18 derivative, which could be reused up to 6 cycles without loss of activity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115797"},"PeriodicalIF":6.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450008","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective dealumination of large pore Zeolite Beta for effective Brønsted acid site utilization","authors":"Pranit Samanta,&nbsp;Mohd. Ussama,&nbsp;Gourav Shrivastav,&nbsp;M. Ali Haider,&nbsp;K.K. Pant,&nbsp;Manjesh Kumar","doi":"10.1016/j.jcat.2024.115796","DOIUrl":"10.1016/j.jcat.2024.115796","url":null,"abstract":"<div><div>Tuning of Al sites through spatial and geometric distribution is a novel pursuit for deterministic catalytic performance. To design an efficient Zeolite Beta for phenol alkylation with optimal physicochemical attributes, we conducted a systematic study with a series of dicarboxylic acids to selectively extract the framework and/or non-framework Aluminium. Herein, the post-synthetic treatment resulted in dealuminated catalysts of silicon-to-aluminum ratio ∼15–53. Extensive Al and Si NMR studies glean the selective extraction of aluminum from the zeolitic framework along with recomposition in T sites. The potency study alludes to the convoluted role of pH, chelating ability, and/or site accessibility for complexation. The differentiated Al extraction results in the emergence of unique super-strong acid sites. The novelty of our approach was established using phenol alkylation with cyclohexanol wherein we observed the highest conversion and desired C<img>C alkylated product formation for the malonic acid-treated Zeolite Beta.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115796"},"PeriodicalIF":6.5,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444436","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":"Electrochemically driven nonheme iron complex-catalyzed oxidation reactions using water as an oxygen source","authors":"Songgang Huang ,&nbsp;Yan Wang ,&nbsp;Si Si ,&nbsp;Mei Yan ,&nbsp;Weimin Zhang ,&nbsp;Wenhua Ji ,&nbsp;Jie Chen ,&nbsp;Wonwoo Nam ,&nbsp;Bin Wang","doi":"10.1016/j.jcat.2024.115792","DOIUrl":"10.1016/j.jcat.2024.115792","url":null,"abstract":"<div><div>High-valent metal-oxo species have been invoked as key intermediates in enzymatic and biomimetic oxidation reactions. The generation of high-valent metal-oxo species using water (H₂O) as an oxygen source represents one of the most environmentally friendly approaches in developing biologically inspired oxidation catalysis. Herein, we report the electrochemical oxidation of benzylic C−H bonds and alcohols utilizing a mononuclear nonheme iron(III)-monoamidate complex [Fe^III(dpaq)(H₂O)]²⁺ (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-<em>N</em>-quinolin-8-yl-acetamidate) as a catalyst and H₂O as an oxygen source. Selective benzylic C−H bond oxidation of alkanes to ketones was achieved in 43–85 % yields, and primary and secondary alcohols were converted to the corresponding aldehydes and ketones, respectively, in 46–95 % yields. The generation of an iron(V)-oxo species [Fe^V(O)(dpaq)]²⁺ from proton-coupled electron-transfer (PCET) oxidation of the iron(III) aqua complex [Fe^III(dpaq)(H₂O)]²⁺ was evidenced by cyclic voltammetry analysis; the iron(V)-oxo species [Fe^V(O)(dpaq)]²⁺ was recently detected using transient absorption spectroscopy in water oxidation reactions. Mechanistic studies revealed that electrochemical oxidation of alcohols catalyzed by Fe^III(dpaq) is a two-electron oxidation process, hydrogen-atom transfer (HAT) from the α-C−H bond of alcohols by iron(V)-oxo species is the rate-determining step, and there is a remarkable charge transfer from the highly electrophilic iron(V)-oxo species to the alcohols in the HAT step. This research paves a significant groundwork aimed at developing electrochemically driven biomimetic asymmetric oxidation reactions catalyzed by nonheme metal complexes supported by chiral ligands.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115792"},"PeriodicalIF":6.5,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444390","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":"Mn-doped Bi2O3 grown on PTFE-treated carbon paper for electrochemical CO2-to-formate production","authors":"Junjie Shi ,&nbsp;Paulina Pršlja ,&nbsp;Milla Suominen ,&nbsp;Benjin Jin ,&nbsp;Jouko Lahtinen ,&nbsp;Lilian Moumaneix ,&nbsp;Xiangze Kong ,&nbsp;Tanja Kallio","doi":"10.1016/j.jcat.2024.115798","DOIUrl":"10.1016/j.jcat.2024.115798","url":null,"abstract":"<div><div>BiO_x shows promising selectivity in catalyzing the electrochemical reduction of CO₂ to formate, but the process suffers from high overpotential and a low rate. Moreover, the active sites are still ambiguous under electrochemical conditions. Herein, we introduce Mn-doping to enhance the activity of binder-free Bi₂O₃ and elaborate on active sites through <em>in situ</em> Raman and density functional theory (DFT) analyses. The Mn-doped Bi₂O₃ transforms to Mn-doped Bi₂(CO₃)O₂ in KHCO₃ and subsequently reduces to Mn-modified metallic Bi under cathodic potentials. The undoped Bi₂O₃ is found to follow the same phase transitions but at a different rate. The DFT analyzes the impact of doping the Bi(012) with Mn and indicates significantly improved selectivity for formate generation. Further, the importance of the substrate’s hydrophobicity for long-term stability is demonstrated. This study offers in-depth insights into the design and understanding of doped BiO_x-based electrodes for CO₂ reduction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115798"},"PeriodicalIF":6.5,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boosting the catalytic performance of core-shell structured Ru@Pd/SBA-15 in 2-ethyl-anthraquinone hydrogenation by tuning d-band center","authors":"Yue Zhang ,&nbsp;Rongrong Zhang ,&nbsp;Guozhu Liu ,&nbsp;Li Wang ,&nbsp;Zhiyong Pan","doi":"10.1016/j.jcat.2024.115793","DOIUrl":"10.1016/j.jcat.2024.115793","url":null,"abstract":"<div><div>Core-shell Ru@Pd/SBA-15 catalysts with various atomic layer numbers of Pd were prepared by changing the Pd/Ru ratio and Pd coating temperature. The results of characterizations show that the compressive strain of Pd atoms and electron transfer from Ru to Pd result in a downward shift in the <em>d</em>-band center of core–shell catalysts. Density functional theory calculations further reveal that the reduced <em>d</em>-band center of Pd <em>via</em> strain and electronic effects weakens the adsorption ability of Pd. A roughly volcano-shaped correlation between the <em>d</em>-band center and 2-ethyl-anthraquinone (EAQ) hydrogenation activity is experimentally observed. The catalyst with Pd shell of 2 atomic layers provides medium adsorption strength for EAQ and hydrogenated product, thereby exhibiting the highest activity of 0.37 molH₂·gMet⁻¹·min⁻¹, with a selectivity of 97.3%. This work provides a facile strategy for optimizing hydrogenation performance by modulating the strain and electron effects between the Ru core and Pd shell through regulating the number of shell layers.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115793"},"PeriodicalIF":6.5,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439604","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":"Enhanced CO2 hydrogenation reaction by Tuning interfacial Cu/ZnOx through synergistic interactions in the precursors","authors":"Wei Zheng ,&nbsp;Chao Sun ,&nbsp;Zejian Dong ,&nbsp;Lifeng Zhang ,&nbsp;Xi Wang ,&nbsp;Langli Luo","doi":"10.1016/j.jcat.2024.115794","DOIUrl":"10.1016/j.jcat.2024.115794","url":null,"abstract":"<div><div>The Cu/ZnO/Al₂O₃ is a typical industrial catalyst for water–gas-shift reaction and methanol synthesis, and is also gaining momentum in CO₂ hydrogenation reaction. The dynamic evolution of the phases and microstructures of the precursor of this catalyst leads to a notable synergistic effect that defines its overall catalytic function and performance. To gain insights into the role and interaction between the relevant precursors, we compared Cu/ZnO/Al₂O₃ catalysts using a conventional co-precipitation and a fractional precipitation method, where the latter one shows an enhanced Cu/ZnO_x interface due to a thorough and strong interaction between two components in the precursor. The ZnO_x decoration on Cu with unsaturated Zn^δ+ species boosted the methanol formation to a rate of 508 g_CH3OH‧kg_cat⁻¹‧h⁻¹ with 58 % selectivity at 513 K and 3 MPa. This work provides mechanistic insights into the synergistic interplay between the involved phases in the Cu/ZnO/Al₂O₃ catalyst.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115794"},"PeriodicalIF":6.5,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431489","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":"Self-assembly of decavanadate and Ni(HCO3)2 into nanoparticles anchored on carbon nitride for efficient photocatalytic Minisci-type alkylation","authors":"Peihe Li ,&nbsp;Qingguang Li ,&nbsp;Gelan Wang ,&nbsp;Ye Lu ,&nbsp;Limei Duan ,&nbsp;Jie Bai ,&nbsp;Sarina Sarina ,&nbsp;Jinghai Liu","doi":"10.1016/j.jcat.2024.115789","DOIUrl":"10.1016/j.jcat.2024.115789","url":null,"abstract":"<div><div>Photocatalysis Minisci-type reactions involving carbon-centered radicals (CCRs) have emerged as a hot and significant topic in the field of organic synthesis chemistry. Herein, we present a nickel-vanadium nanoparticle anchored on carbon nitride catalyst (NiV-CN) and persulfate as a hydrogen atom transfer (HAT) precursor. This catalyst enables the photocatalytic Minisci-type CCR alkylation. The nickel-vanadium nanoparticles are synthesized via electrostatic attraction between [V₁₀O₂₈]⁶⁻ anions and Ni(HCO₃)₂, with in situ self-assembly occurring during the hydrothermal process. In the model reaction of 4-methylquinoline with cyclohexane, the NiV-CN catalyst showed high stability, without significant loss its catalytic activity after three cycles. The CCRs was extended to cycloalkanes, adamantanes, and cyclic ethers, which react with quinoline, isoquinoline, and benzothiazole to provide the corresponding products in moderate to excellent yields. Mechanism studies indicate that nickel-vanadium nanoparticles play a crucial role in the formation process of carbon-centered radicals by activating the persulfate precursor into sulfate radicals under visible-light irradiation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"439 ","pages":"Article 115789"},"PeriodicalIF":6.5,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142415764","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":"Unlocking dynamic intermetallic synergy: Ir/Ni alloy nanoparticles catalyze CO2 hydrogenation to formic acid in ionic liquid environments","authors":"Rodrigo Webber ,&nbsp;Muhammad I. Qadir ,&nbsp;Marcus V. Castegnaro ,&nbsp;Renato B. Pontes ,&nbsp;Kácris I.M. da Silva ,&nbsp;Jairton Dupont","doi":"10.1016/j.jcat.2024.115791","DOIUrl":"10.1016/j.jcat.2024.115791","url":null,"abstract":"<div><div>The Bimetallic Ir/Ni alloy nanoparticles (∼2.0 nm) are prepared in 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIm.NTf₂) ionic liquid, which have a unique architecture, featuring an Ir-rich alloy core surrounded by a Ni-rich alloy. The prepared bimetallic NPs exhibited efficient activity for the hydrogenation of CO₂ to formic acid (1.02 M) with TOFs of 151.7 h⁻¹ as compared to their counterparts; Ir NPs (TOF 38.5 h⁻¹) and Ni NPs (TOF 0) in 1-n-butyl-3-methylimidazolium acetate (BMIm.OAc) IL solutions. This synergistic metal dilution effect arises from the inter-particle heterogeneities present in our Ir/Ni alloy NPs, causing alterations in surface structure and composition with an increase in the number of d-band holes. It offers a diverse population of active sites and tunes the adsorbate migration between reactive intermediates. The BMIm.OAc IL representes multifunctional roles, acting as a buffer and creating an IL-solvent cage around the NPs, reactants, and reactive intermediates. This alters the entropy by increasing the number of microstates, overcoming thermodynamic limitations. The synchrotron X-ray photoelectron spectroscopy and soft-XANES analyses reveal that the Ir/Ni NPs have variable electron density, the NPs surface have lower electron density than those at inner regions, which enhance the number of valence vacancies. The dilution of iridium with nickel in our Ir/Ni NPs attributes the abundance of d-band holes and O-p holes to the high oxidation state at the surface, and increases the presence of lattice vacancies. These distinct characteristics of NPs significantly boost the FA formation as compared to their counterparts. DFT calculations confirmed that the formation of FA follows the hydrogenation of HCO₃* reactive intermediates.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"439 ","pages":"Article 115791"},"PeriodicalIF":6.5,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142415617","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}