Journal of Catalysis最新文献

{"title":"Construction of a copper-bismuth catalyst featuring Bi-N4 sites and synergistic Bi clusters derived from TCPP(Bi)@HKUST-1 for enhanced formaldehyde to butynediol","authors":"Yong Wang ,&nbsp;Yongkang Sun ,&nbsp;Fusheng Huang ,&nbsp;Tingting Wang ,&nbsp;Bin Dai ,&nbsp;Jichang Liu ,&nbsp;Jiangbing Li ,&nbsp;Xuhong Guo","doi":"10.1016/j.jcat.2024.115843","DOIUrl":"10.1016/j.jcat.2024.115843","url":null,"abstract":"<div><div>The construction of functional catalysts that efficiently catalyze in a reducing atmosphere is considered rather challenging. In this study, the catalysts bridged by Bi-N₄ between copper and bismuth species were prepared. Herein, Bi-N₄ and bismuth cluster sites were incorporated into porous carbon–nitrogen networks along with copper nanoparticles (Bi_SAC&amp;Clu-Cu-NC). For the synthesis, metalloporphyrin-modified HKUST-1 (TCPP(Bi)@HKUST-1) was employed as a precursor. Additionally, metalloporphyrin functioned as a capping agent during catalyst preparation, thereby enhancing the dispersion of Bi species after calcination. Notably, the Bi_SAC&amp;Clu-Cu-NC catalyst demonstrated 93.8 % selectivity towards 1,4-butynediol over 20 h at a Bi loading of 0.6 wt% in a reducing atmosphere of acetylene and formaldehyde. Furthermore, a mechanistic model is proposed that elucidates the observed synergistic catalytic behavior based on experimental characterization and DFT calculations. This proposed model is termed “Nanoparticles with Cluster and Single Metal Sites”(NCS mechanism). The retention of the Bi cluster structure within the material matrix plays a pivotal role in enhancing the adsorption and activation of formaldehyde. Interfacial effects between different copper species favour the activation of the reaction substrate acetylene. Additionally, the Bi-N₄ structure can function as a crucial conduit, facilitating electron transfer between Cu and Bi elements and consequently lowering the activation energy barrier for key reaction intermediates.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115843"},"PeriodicalIF":6.5,"publicationDate":"2024-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598066","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":"Dealuminated H–Y zeolites generate, stabilize and catalytically insert carbenes from diazocarbonyl compounds","authors":"Yongkun Zheng,&nbsp;Miguel Espinosa,&nbsp;Marta Mon,&nbsp;Antonio Leyva–Pérez","doi":"10.1016/j.jcat.2024.115835","DOIUrl":"10.1016/j.jcat.2024.115835","url":null,"abstract":"<div><div>Carbenes are among the most powerful reactants in organic synthesis, with capacity to insert into a variety of otherwise stable bonds, and generate two new bonds in a straightforward manner. However, the intrinsic instability of such carbenes makes them to be catalytically generated, in–situ, from precursors such as diazocarbonyl compounds, and the catalyst, in turn, also controls the subsequent insertion reaction. The catalyst is generally a metal complex in solution, mainly Cu, Ag or Rh, but also others, including protons in rare cases. Here we show that carbenes are generated, stabilized and inserted into C–C, C–H, O–H, N–H, Si–H and O–O bonds after reacting diazocarbonyl compounds with catalytic amounts of metal–free, commercially available dealuminated H–Y zeolites. These results open the way to design carbene–mediated organic reactions on readily available and reusable catalytic solids without involving metals.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115835"},"PeriodicalIF":6.5,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598069","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":"Facilitating the electrooxidation of 5-hydroxymethylfurfural on nickel hydroxide through deintercalation","authors":"Yu-Feng Qi ,&nbsp;Kai-Yao Wang ,&nbsp;Hairui Guo ,&nbsp;Yu-Jie Zhang ,&nbsp;Yiwei Zhou ,&nbsp;Cheng Wang","doi":"10.1016/j.jcat.2024.115830","DOIUrl":"10.1016/j.jcat.2024.115830","url":null,"abstract":"<div><div>The electrocatalytic of 5-hydroxymethylfurfural oxidation reaction (HMFOR) is an alternative route for the green production of valuable oxygenated chemicals. Nickel hydroxides, which consist of hydroxide layers and interlayer charge-balancing anions, are a type of promising catalysts for HMFOR. Progresses have been made on elucidating the correlation between the hydroxide layer and HMFOR performance, while the effect of intercalated anions on the activity remains unclear. Herein, two self-supported nickel hydroxide catalysts (i.e., pristine Ni(OH)₂/CP-F and deintercalated Ni(OH)₂/CP-A) are employed for revealing the relationship between anion-deintercalation and HMFOR activity. Physical characterizations demonstrate that the deintercalation phenomenon can alter the d-band center and increase the electron density of the Ni site. This endows the deintercalated Ni(OH)₂/CP-A with improved electrochemical properties (conversion = 99.99 %; FDCA yield &gt; 99 %; FE &gt; 99 %), enhanced adsorption strength for HMF, and increased intrinsic activity, compared to the pristine Ni(OH)₂/CP-F. This work not only reports an excellent HMFOR electrocatalyst, but also manifests the crucial effect of deintercalation on the electrochemical oxidation performance of Ni(OH)₂.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115830"},"PeriodicalIF":6.5,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597915","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":"Facilitating catalytic research via better data reporting and curation: A case study of propane dehydrogenation on Ga/H-ZSM-5","authors":"Zhaoqi Zhao,&nbsp;Bingjun Xu","doi":"10.1016/j.jcat.2024.115838","DOIUrl":"10.1016/j.jcat.2024.115838","url":null,"abstract":"<div><div>In the field of experimental heterogeneous catalysis, the generation, analysis, and curation of large-scale, high-quality datasets are crucial yet challenging. This work highlights the significance of proper data reporting and curation through a case study on propane dehydrogenation over Ga/H-ZSM-5 catalysts. We demonstrate the challenges and benefits of analyzing larger datasets across multiple publications in the identification of active structures and elucidation of reaction mechanisms. The findings highlight the need for reporting reliable datasets in accessible format to facilitate integration and comparison of catalytic data across different studies, potentially leading to novel scientific insights.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115838"},"PeriodicalIF":6.5,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598076","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 alumina on the performance of Ag/ZnO based catalysts for carbon dioxide hydrogenation","authors":"Paul Maurice Leidinger ,&nbsp;Vitaly L. Sushkevich ,&nbsp;Chiara Pischetola ,&nbsp;Frank Krumeich ,&nbsp;Jeroen A. van Bokhoven ,&nbsp;Luca Artiglia","doi":"10.1016/j.jcat.2024.115837","DOIUrl":"10.1016/j.jcat.2024.115837","url":null,"abstract":"<div><div>We study silver-zinc oxide type catalysts with and without the addition of alumina and perform structural analysis and activity tests for the hydrogenation of carbon dioxide. Adding alumina has a dispersing effect on the zinc oxide without structurally altering the silver phase. An alumina-surface enriched ZnO/Al₂O₃ phase is observed with an increased surface reducibility. Ag/ZnO has a high selectivity towards carbon monoxide (63 ± 12 %) and methane (24 ± 3 %) and low selectivity towards methanol (13 ± 0.5 %). Operando infrared (SSITKA-FTIR) and mass spectrometric product detection indicate methane formation via an adsorbed carbon monoxide (CO_ads) intermediate. The selectivity changes gradually with increasing alumina content, up to 80 ± 3 % toward methanol, and 20 ± 4 % carbon monoxide without methane detection, combined with a tripling of the space time yield to 0.65 ± 0.02<!--> <!-->mmol_MeOH*<span><math><msubsup><mi>g</mi><mrow><mi>c</mi><mi>a</mi><mi>t</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msubsup></math></span>*h⁻¹ at 250 °C and 30<!--> <!-->bar. Kinetic analysis suggests that the selectivity change originates from hindering the CO-pathway, while the formate pathway leading to methanol remains active.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115837"},"PeriodicalIF":6.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594353","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":"Theoretical investigation on propane dehydrogenation over extraframework Ga hydride species trapped at Al-pairs in MFI zeolite","authors":"Zhe Feng,&nbsp;Xin Liu,&nbsp;Changgong Meng","doi":"10.1016/j.jcat.2024.115834","DOIUrl":"10.1016/j.jcat.2024.115834","url":null,"abstract":"<div><div>Ga/ZSM-5 is widely used to catalyze propane dehydrogenation (PDH). For the harsh operation conditions, the detailed active species, and the plausible reaction pathways that are responsible for the observed superior PDH performance remain unresolved for Ga/ZSM-5. Reduced extraframework Ga hydride species trapped at zeolite framework Al-pairs, including ^b[GaH]²⁺, [Ga]⁺-BAS, [GaH₂]⁺-BAS, etc. are an important kind of Ga species known as active species for PDH. In this work, the PDH pathways these over these Ga species were investigated theoretically at temperatures and pressures relevant to experiments. We showed that dynamically generated undercoordinated ^b[GaH]²⁺ would exhibit significantly higher catalytic activity at PDH conditions as compared with other Ga hydride species. The most plausible PDH pathway over ^b[GaH]²⁺ is the carbenium pathway. The Ga species and BAS act in concert in promoting the H₂ elimination and β-H transfer, and in turning PDH efficient. Ga hydride species may also form as intermediates along the PDH pathways as active sites for subsequent activation and conversion of propane, suggesting the evolution of Ga hydride species trapped by Al-pairs in Ga/ZSM-5 at operation conditions. The findings are expected to pave the way for better understanding of the experimentally observed operation condition dependent PDH performance of Ga/ZSM-5.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115834"},"PeriodicalIF":6.5,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579843","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":"In-situ generated hydrogen for selective hydrogenolysis of lignin catalyzed by Mg-Al mixed oxides with nested Ni nanoparticles","authors":"Yun Tian ,&nbsp;Mengqiao Gao ,&nbsp;Zhiyang Tang ,&nbsp;Fukun Li ,&nbsp;Qiang Zeng ,&nbsp;Jinxing Long ,&nbsp;Xuehui Li","doi":"10.1016/j.jcat.2024.115833","DOIUrl":"10.1016/j.jcat.2024.115833","url":null,"abstract":"<div><div>Conversion of lignin to valuable chemicals without external hydrogen presents a significative but challengeable endeavor. Herein, an efficient approach has been proposed for the lignin hydrogenolysis with <em>in-situ</em> hydrogen in the presence of Ni nanoparticles nested in layered double oxides (LDOs). 84.4 % conversion of lignin was achieved over 30Ni-Mg₃Al-LDOs, affording a 21.3 % yield of monomers, and 38.0 % of which was identified as 4-ethylphenol. Catalyst characterizations revealed that this excellent performance of lignin conversion should be ascribed to the highly dispersed Ni nanoparticles, strong interfacial interactions between Ni and LDOs, and suitable basicity of catalysts. Furthermore, the roles of the solvent (1,4-dioxane aqueous solution) and the lignin methoxyl groups as hydrogen resources were distinguished, and the former acted as an initial hydrogen to promote lignin depolymerization, and the latter was responsible for the high yield of 4-ethylphenol. In addition, a plausible reaction pathway for lignin hydrogenolysis has been proposed.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115833"},"PeriodicalIF":6.5,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566095","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":"Lithium iodide promoted CO2 hydrogenation towards ethanol via biphasic lewis-acid-base pairs synergistic catalysis","authors":"Ke Zheng ,&nbsp;Yufeng Li ,&nbsp;Huanhuan He,&nbsp;Bing Liu,&nbsp;Yuebing Xu,&nbsp;Xiaohao Liu","doi":"10.1016/j.jcat.2024.115832","DOIUrl":"10.1016/j.jcat.2024.115832","url":null,"abstract":"<div><div>Ethanol synthesis via CO₂ hydrogenation is of great importance in view of its high-value utilization. Herein, combining with heterogeneous and homogenous catalysis, we have developed an efficient biphasic Lewis-acid-base pairs synergistic catalysis strategy from CO₂ hydrogenation. Apart from conventional heterogeneous ethanol synthesis route, it was surprisingly found that LiI homogenous promoter significantly enhanced CO₂ conversion, ethanol selectivity, and productivity. LiI promoted CO₂ dissolution in pure water and accelerated reaction intermediates consumption, favoring CO₂ conversion. In detail, it can weaken C-O bond of CH₃OH intermediate through Li⁺-I^- Lewis-acid-base catalysis. The formed CH₃I* with lower bond energy for C-I was more facile to dissociate into CH₃*, favoring its subsequent coupling with CO* to form ethanol. In combination of Rh₁/CeTiO_x catalyst, LiI promoter, and methanol as solvent, a record-breaking ethanol yield was achieved (223.1 mmol·g⁻¹·h⁻¹). The obtained ethanol yield was about 18.7 times of that reported the best result in literatures. Especially, the established catalyst system could also be applied for synthesis of higher-carbon-number alcohols by the CO₂ hydrogenation with other alcohols solvent (C_nH_2n+1OH, n = 2,3…).</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115832"},"PeriodicalIF":6.5,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566094","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":"Construction of magnetically separable S-scheme BiFeO3/Cl-g-C3N4 heterostructure photocatalyst for simultaneous removal of Cr(Ⅵ) and tetracycline in aqueous solution: Performance and mechanism insight","authors":"Tianrui Xu ,&nbsp;Guanghui Wang ,&nbsp;Zehua Liu ,&nbsp;Nansheng Deng ,&nbsp;Xuewen Zhang","doi":"10.1016/j.jcat.2024.115821","DOIUrl":"10.1016/j.jcat.2024.115821","url":null,"abstract":"<div><div>A green, efficient and recyclable magnetic BiFeO₃/Cl-g-C₃N₄ photocatalyst was prepared for the simultaneous removal of Cr(Ⅵ) and tetracycline (TC) from water by wet chemical and thermal synthesis methods. Experimental results revealed that BiFeO₃/Cl-g-C₃N₄ achieved a removal efficiency of 96.1 % for Cr(Ⅵ) and 98.2 % for TC under visible light irradiation for 50 min at pH 6. The results of the work function, charge density difference, UV–vis DRS, PL, PC and EIS tests indicate the formation of S-scheme heterojunctions between BiFeO₃ and Cl-g-C₃N₄, which exhibits superior carrier separation and migration efficiency. The evidence for interfacial charge transfer from BiFeO₃ to Cl-g-C₃N₄ within BiFeO₃/Cl-g-C₃N₄ was further corroborated by means of ISIXPS, EPR and KPFM. Moreover, calculations of the density of states demonstrate that the introduction of Cl enhances the reduction capability of BiFeO₃/Cl-g-C₃N₄. Results from ESR tests and trapping experiments has demonstrated that the singlet oxygen (¹O₂) and electrons are the primary active species. Furthermore, the high removal rates of TC and Cr(VI) from industrial wastewater and groundwater, coupled with the lower ecotoxicity of TC degradation intermediates, indicate that BiFeO₃/Cl-g-C₃N₄ has the potential for practical applications. After five cycles, the BiFeO₃/Cl-g-C₃N₄ still removed 90.5 % of TC and 96 % of Cr(Ⅵ).</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115821"},"PeriodicalIF":6.5,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519376","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":"On the catalytic behaviors of Cu/SiO2 and Cu/γ-Al2O3 for dimethyl oxalate hydrogenation from microkinetic analysis including a plug flow reactor model","authors":"Han-Jie Xiao ,&nbsp;Hui-Han Zheng ,&nbsp;Ming Lei ,&nbsp;Jing-Hong Zhou ,&nbsp;De Chen ,&nbsp;Xing-Gui Zhou ,&nbsp;Yi-An Zhu","doi":"10.1016/j.jcat.2024.115822","DOIUrl":"10.1016/j.jcat.2024.115822","url":null,"abstract":"<div><div>Cu-based catalysts have been widely used in dimethyl oxalate (DMO) hydrogenation due to their ability to activate C-O/C=O bonds without breaking C–C bonds. In this work, the electronic structures of Cu/SiO₂ and Cu/γ-Al₂O₃ as well as their catalytic performance have been studied by the machine-learning-based stochastic surface walking-global neural network potential (SSW-NN) method, density functional theory calculation, and microkinetic analysis including a plug flow reactor (PFR) model. Among SiO₂- and γ-Al₂O₃-supported Cu_n (n = 1–9), the Cu₅ and Cu₇ clusters are held most tightly on SiO₂(111) and γ-Al₂O₃(110), respectively. The electron transfer from Cu₅ to SiO₂(111) leads to the formation of Cu^δ+ and Cu⁰, which are responsible for the stabilization of unsaturated C and O atoms in the intermediates, respectively, while on γ-Al₂O₃(110) an electron-rich Cu⁰-Al_3c site is most active. Both the Cu^δ+-Cu⁰ and the Cu⁰-Al_3c sites synergistically catalyze the dissociation of gas-phase species and hydrogenation of intermediates. Under the typical operating conditions, although the selectivity towards methyl glycolate (MG) is invariably highest at the reactor inlet, Cu₅/SiO₂(111) and Cu₇/γ-Al₂O₃(110) are actually selective for the production of ethylene glycol (EG) and ethanol (EtOH), respectively, if the overall selectivity is taken into consideration, signifying the importance of including a reactor model to probe the kinetics of series of consecutive reactions. The dissociation of DMO is found to be the rate-determining step, and the high energy barrier for EG dissociation on Cu₅/SiO₂(111) hinders its deep hydrogenation while the relatively low barrier on Cu₇/γ-Al₂O₃(110) is beneficial to the formation of EtOH.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115822"},"PeriodicalIF":6.5,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519958","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}