Journal of Catalysis最新文献

{"title":"A perspective of urgently required research into fundamental research into applied catalysis","authors":"Jeroen A. van Bokhoven , Gerhard Mestl","doi":"10.1016/j.jcat.2024.115894","DOIUrl":"10.1016/j.jcat.2024.115894","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115894"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805007","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":"Amino acids as eco-friendly bio-organocatalysts in ROCOP for the preparation of biobased oligomers from fatty acid epoxides and waste sunflower oil","authors":"Valentino Cárdenas-Toledo ,&nbsp;Enrique Francés-Poveda ,&nbsp;Felipe Barrientos-Barichivic ,&nbsp;Jordano Valenzuela ,&nbsp;Oscar A. Douglas-Gallardo ,&nbsp;Mario E. Flores ,&nbsp;Agustín Lara-Sánchez ,&nbsp;Oleksandra S. Trofymchuk ,&nbsp;Francisca Werlinger ,&nbsp;Javier Martínez","doi":"10.1016/j.jcat.2024.115903","DOIUrl":"10.1016/j.jcat.2024.115903","url":null,"abstract":"<div><div>Epoxy fatty acids and waste vegetable oils can be strategically utilized as renewable feedstock for the synthesis of novel bio-based oligomers. Herein, we present an efficient synthetic methodology for producing a wide range of bio-oligomers from the ring-opening copolymerization (ROCOP) reaction of linoleic acid-derived epoxides (MLO, methyl linoleate oxide; ELO, ethyl linoleate oxide; ILO, isopropyl linoleate oxide) or epoxidized sunflower oil (ESO) with cyclic anhydrides (such as phthalic anhydride PA, and maleic anhydride MA). The reaction is catalyzed by a wide variety of commercially available amino acids (AAs) along with tetrabutylammonium iodide (TBAI) serving as a cocatalyst. Among the studied AAs as bio-organocatalysts, L-glutamic acid (L-Glu) exhibited the best performance for the preparation of poly(MLO-<em>co</em>-PA), poly(ELO-<em>co</em>-PA), poly(ILO-<em>co</em>-PA), poly(MLO-<em>co</em>-MA), poly(ELO-<em>co</em>-MA), and poly(ILO-<em>co</em>-MA) achieving a 100 % conversion at 80 °C in only 30 min. In contrast, the synthesis of poly(ESO-<em>co</em>-PA) and poly(ESO-<em>co</em>-MA) required 1 h to reach full conversion under the same conditions. The resulting oligomers were extensively characterized by using NMR, FT-IR, GPC, and TGA. Additionally, a set of computational simulations based on density functional theory (DFT) method was also carried out to support our experimental findings. Climbing-image nudged elastic band (CI-NEB) method was employed to find the minimum energy path (MEP) that describes the reaction mechanism associated with the first step of this chemical transformation. The calculated reaction path provides an energetic and atomistic picture of the studied reaction which aims to understand the role of both catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115903"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832609","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":"Role of coupling and zeolite acidity in the methanol-mediated CO2 conversion to olefins over ZnZrOx-AEI zeolite tandem catalysis","authors":"Ahmed Sajid,&nbsp;Julien Devos,&nbsp;Sven Robijns,&nbsp;Thibaut Donckels,&nbsp;Ibrahim Khalil,&nbsp;Michiel Dusselier","doi":"10.1016/j.jcat.2024.115927","DOIUrl":"10.1016/j.jcat.2024.115927","url":null,"abstract":"<div><div>The tandem conversion of carbon dioxide to olefins (CTO) via methanol over a combination of metal oxide plus zeolite catalysts is a considerable alternative to fossil-based routes to light olefins. Here, AEI type small pore zeolites i.e., SSZ-39 and SAPO-18, in combination with ZnZrOx, are put forward as the excellent tandem catalysts for CTO. We deconvolute the influences of acidity and framework composition on the product selectivity and productivity of light olefins. Post-synthesis steaming was utilized as a strategy to tune the acidity and structure of the zeolites. SSZ-39 steamed at 750 °C showed the highest olefin/paraffin ratio (O/P = 2.1) as compared to the unsteamed SSZ-39 with an O/P ratio of 0.2. In contrast, SAPO-18 steamed at 650 °C showed a maximum O/P ratio of 2.1, whereas steaming at higher temperatures resulted in decreased activities. Propylene was observed as the major olefin for both SSZ-39 and SAPO-18 in line with the cage-defining ring size of AEI. It was found through FT-IR and NH₃-TPD that the increase in the steaming temperature decreases the Brønsted acidity of SSZ-39 which inhibits both the secondary hydrogenation of olefins to paraffins and the methanol-assisted hydrogen transfer reaction. Coupling of CO₂ to methanol (CTM) with methanol to olefins (MTO) reaction increased the CO₂ conversion and selectivity towards methanol equivalents by suppressing CO production in tandem systems as compared to the sole CTM reaction. The effect of catalyst bed configuration on product selectivity over the best performing catalyst was also studied, and the highest O/P ratio (3.7) was observed for a powder mixed system opposed to dual bed or mixed bed systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115927"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879900","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":"Z-Selective hydrosulfoxidation of alkynes with thiols and hydrogen peroxide Enabled by a Multifunctional octamolybdate","authors":"Xianghua Zeng ,&nbsp;Hao Xu ,&nbsp;Yongge Wei","doi":"10.1016/j.jcat.2024.115892","DOIUrl":"10.1016/j.jcat.2024.115892","url":null,"abstract":"<div><div>Although sulfoxide is an important structural motif found in biological molecules and prevalent feedstocks in synthetic chemistry, a general and sustainable access route to (<em>Z</em>)-<em>α,β</em>-unsaturated sulfoxides remains highly<!--> <!-->challenging due to the thermodynamic instability of <em>Z</em>-type geometric and the notorious sulfur nucleophiles poisoning of metal catalyst. Here we report a new protocol based on homogeneous octamolybdate-catalyzed <em>anti</em>-hydrothiolation and after <em>Z</em>-retentive sulfoxidation methodology, allowing access to (<em>Z</em>)-<em>α,β</em>-unsaturated sulfoxides from commercially available alkynes, thiols and H₂O₂. Control experiment investigations indicate that the molecular molybdenum is a thiyl radical initiator, <em>Z</em>-type geometric mediator and sulfoxidation catalyst. Notably, this one-pot reaction features broad substrate scopes with high stereoselectivity (Z/E up to &gt; 99:1) and mild reaction conditions, thus providing a promising approach for the preparation of <em>Z</em>-vinyl sulfoxide compounds.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115892"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777047","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":"Au@Snβ zeolite as stable and active catalyst for the conversion of glycerol to methyl lactate","authors":"Shengqiang Zhou ,&nbsp;Tianliang Lu ,&nbsp;Lipeng Zhou ,&nbsp;Xiaomei Yang","doi":"10.1016/j.jcat.2024.115913","DOIUrl":"10.1016/j.jcat.2024.115913","url":null,"abstract":"<div><div>Au/Sn-zeolite catalysts showed high activity for selective conversion of glycerol to methyl lactate, but suffered from poor stability under the reaction conditions in our previous report (ACS Catal. 2017, 7, 7274). Encapsulation of Au nanoparticles within zeolite is a promising strategy to enhance their stability in catalytic reaction. Herein, one-pot synthesis of Au@Snβ was achieved by a mercaptosilane-assisted hydrothermal synthesis method. The protocol involves crystallization of Snβ synthesis gels around coordinated Au precursors, resulting in Snβ framework constraining Au coordination complexes. The confinement of small (∼2.89 nm) and uniform Au particles within Snβ was achieved. The bifunctional catalyst composed of oxidative sites (Au) and Lewis acid sites (Sn) gave 77.3 % methyl lactate (MLA) yield from the base-free selective conversion of glycerol (GLY). The TOF value of Au@Snβ was higher than that of Au/Sn-zeolite in our previous report. Moreover, the special structure protects Au nanoparticles from sintering or agglomeration and improves the stability and recyclability in selective oxidation of GLY to MLA.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115913"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849487","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":"Tuning the sterics: Rh-catalyzed hydroformylation reactions with ferrocene based diphosphorus ligands","authors":"Subhayan Dey ,&nbsp;Lea Dettling ,&nbsp;Dalma Gál ,&nbsp;Clemens Bruhn ,&nbsp;Zsolt Kelemen ,&nbsp;Christian Müller ,&nbsp;Rudolf Pietschnig","doi":"10.1016/j.jcat.2024.115871","DOIUrl":"10.1016/j.jcat.2024.115871","url":null,"abstract":"<div><div>The mono- and bidentate ligands FcPPh₂ (<strong>1</strong>), FcP<em>^t</em>Bu₂ (<strong>2</strong>), FcPMes₂ (<strong>3</strong>), Fc’(PPh₂)₂ (<strong>dppf</strong>), Fc’(PMes₂)₂ (<strong>4</strong>), Fc’(PMes₂)(PPh₂) (<strong>5</strong>), and Fc’(PMes₂)(P<em>^t</em>Bu₂) (<strong>6</strong>) (Fc and Fc’ stand for 1- and 1,1′-substituted ferrocene, respectively) were reacted with Rh(I)-precursors. Maintaining P:Rh stoichiometric ratios of 2:1, dimeric Vaska-type complexes featuring P-Rh-P bridges (<strong>7</strong>–<strong>15</strong>), and monomeric complexes with [Rh(CO)₂(acac)] moieties (<strong>16</strong>–<strong>22</strong>) were obtained. Complexes <strong>16</strong>–<strong>22</strong> were further applied in the Rh-catalyzed hydroformylation of 1-octene, while the linear-to-branched ratio (l/b) of the formed aldehydes decreases with the increase of steric bulk at the P atoms, which was further verified by theoretical calculations. For ligands <strong>3</strong>–<strong>5</strong>, activation of the C–H bonds of the <em>o</em>-CH₃ units of the mesityl substituent occurred with Rh(I), forming complexes with rare five-membered [C₃PRh^(III)] rings (<strong>10</strong>, <strong>18a</strong>, <strong>20</strong> and <strong>21a</strong>). Complexes <strong>8</strong>, <strong>10</strong>, <strong>11</strong>, <strong>13</strong>, <strong>15</strong> and <strong>17</strong> were unambiguously characterized by means of single crystal X-ray diffraction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115871"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760243","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":"Temperature-dependent switchable synthesis of imines and amines via coupling of alcohols and amines using pyrrolyl-imine ruthenium catalysts","authors":"Ran Liu,&nbsp;Yujia Hou,&nbsp;Mengxuan Bai,&nbsp;Zhangang Han,&nbsp;Zhiqiang Hao,&nbsp;Jin Lin","doi":"10.1016/j.jcat.2024.115895","DOIUrl":"10.1016/j.jcat.2024.115895","url":null,"abstract":"<div><div>A series of pyrrolyl-imine supported Ru(II) complexes <strong>2a-2d</strong> were prepared and used as efficient catalysts for chemodivergent coupling of alcohols and amines to give imines <strong>5</strong> and amines <strong>6</strong> in 48–99 % yields. Notably, the selectivity in this reaction is simply governed by the reaction temperature. The current catalytic system was carried out in an open atmosphere in air with low catalyst loading (0.1 mol%) and displayed good functional-group compatibility.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115895"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804819","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":"CatTestHub: A benchmarking database of experimental heterogeneous catalysis for evaluating advanced materials","authors":"Atharva S. Burte ,&nbsp;Advaith Nair ,&nbsp;Lars C. Grabow ,&nbsp;Paul J. Dauenhauer ,&nbsp;Susannah L. Scott ,&nbsp;Omar A. Abdelrahman","doi":"10.1016/j.jcat.2024.115902","DOIUrl":"10.1016/j.jcat.2024.115902","url":null,"abstract":"<div><div>The ability to quantitatively compare newly evolving catalytic materials and technologies is hindered by the widespread availability of catalytic data collected in a consistent manner. While certain catalytic chemistries have been widely studied across decades of scientific research, quantitative comparisons based on literature information is hindered by variability in reaction conditions, types of reported data, and reporting procedures. Here, we present CatTestHub, an open-access database dedicated to benchmarking experimental heterogeneous catalysis data. Combining systematically reported catalytic activity data for selected probe chemistries, with relevant material characterization and reactor configuration information, the database provides a collection of catalytic benchmarks for distinct classes of active site functionality. Through key choices in data access, availability, and traceability, CatTestHub seeks to balance the fundamental information needs of chemical catalysis and the FAIR data design principles. Details of the database architecture and the means through which to navigate it are presented, highlighting examples of catalytic insights readily drawn from the available benchmarking data. In its current iteration, CatTestHub spans over 250 unique experimental data points, collected over 24 solid catalysts, that facilitated the turnover of 3 distinct catalytic chemistries. A roadmap is presented through which to expand the open-access platform that serves as a community wide benchmark, primarily through continuous addition of kinetic information on select catalytic systems by members of the heterogeneous catalysis community at large.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115902"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820654","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":"Visible-light-promoted phosphorylation carbonylation of unactivated alkenes","authors":"Ren-Guan Miao ,&nbsp;Yuanrui Wang ,&nbsp;Xiao-Feng Wu","doi":"10.1016/j.jcat.2024.115933","DOIUrl":"10.1016/j.jcat.2024.115933","url":null,"abstract":"<div><div>Phosphorus-containing compounds represent a class of chemicals of great significance. Therefore, it is of high value to develop efficient C-P bond formation methods. However, the activity of phosphoryl radicals results in the facile formation of hydrophosphination products when difunctionalized carbonylation was performed with the addition of alkenes. In this study, we presented a visible light-promoted phosphorylation carbonylation reaction of unactivated alkenes. Both visible light catalyst and oxidant-promoted generating phosphoryl radical from diarylphosphine oxide, which subsequently adding to unactivated alkenes and followed by intramolecular migration in the presence of carbon monoxide to yield the targeted phosphorus-containing carbonyl compounds.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115933"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888893","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 synthesis of a heterogeneous NHC–CO2 catalyst for continuous DMC production","authors":"Zhentao Zhao ,&nbsp;Yuxin Wang ,&nbsp;Guangwen Xu ,&nbsp;Lei Shi","doi":"10.1016/j.jcat.2024.115910","DOIUrl":"10.1016/j.jcat.2024.115910","url":null,"abstract":"<div><div>N-heterocyclic carbene CO₂ adducts (NHC–CO₂) are typical zwitterionic ionic liquid compounds, known for their strong nucleophilicity and significant catalytic ability. However, NHC–CO₂ is sensitive to water, and its complex and polluting preparation process limits its widespread application. Furthermore, most reported NHC–CO₂ compounds function as homogeneous catalysts, posing considerable challenges for separation. In this study, an in-situ green synthesis method was employed to develop a heterogeneous NHC–CO₂ catalyst, PS–IMIL. This approach not only prevents direct contact between the catalyst and water but also simplifies the preparation process and mitigates environmental pollution. The synthesis conditions of PS–IMIL were optimized, and its structure and properties were analyzed. Furthermore, the synthesis mechanism of PS–IMIL was investigated, and its kinetics were also studied. The results indicate that the interaction between the material ethylene carbonate (EC) and the precursor is crucial for the in-situ synthesis of PS–IMIL. The prepared PS–IMIL not only preserves the catalytic ability of NHC–CO₂ but also exhibits characteristics of being metal- and halogen-free. Remarkably, the catalytic activity and structure of PS–IMIL remain unchanged after 300 h of continuous use in dimethyl carbonate (DMC) production. Compared to similar catalysts, PS–IMIL exhibits excellent catalytic activity and stability. This study provides a solid theoretical and practical reference for the development of heterogeneous NHC–CO₂ catalysts. The synthesized PS–IMIL demonstrates significant potential for the industrial production of DMC and other carbonate esters.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115910"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849518","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}