Journal of Catalysis最新文献

{"title":"Turning substrates from electron-poor to electron-rich for nonsacrificial aerobic hydroxylation under visible light","authors":"Zelin Du, Gen Li, Yawei Liu, Yan Xu, En-Qing Gao, Dawei Zhang","doi":"10.1016/j.jcat.2024.115907","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115907","url":null,"abstract":"Aerobic oxidation of arylboronic acids under visible light has been intensively explored for synthesis of phenols, for which the need for sacrificial electron-donor agents detracts from the benignancy and sustainability. Here we present the first demonstration of nonsacrificial photocatalytic hydroxylation of arylboronic acids. By turning the electron-poor substrates to electron-rich, the photocatalytic aerobic oxidation proceeds through a mechanism completely different from previous ones, involving the direct oxidation of the aryl-B substrates to aryl radicals through visible-light-induced single-electron transfer to photocatalysts. The protocol not only obviates the need for sacrificial electron donors but also allows efficient reactions in water. It is applicable to various photocatalysts, either homogeneous or heterogeneous. The work provides a green alternative to the traditional methods for synthesis of phenols, and the insight gained from it may open new perspectives for organic photosynthesis that involve aryl radicals.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"49 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832607","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, Enrique Francés-Poveda, Felipe Barrientos-Barichivic, Jordano Valenzuela, Oscar A. Douglas-Gallardo, Mario E. Flores, Agustín Lara-Sánchez, Oleksandra S. Trofymchuk, Francisca Werlinger, Javier Martínez","doi":"10.1016/j.jcat.2024.115903","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115903","url":null,"abstract":"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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"24 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-16","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":"Leveraging Machine learning and active motifs-based catalyst design for discovery of oxygen reduction electrocatalysts for hydrogen peroxide production","authors":"Gwonho Yu, Dong Hyeon Mok, Ho Yeon Jang, Hyun Dong Jung, Samira Siahrostami, Seoin Back","doi":"10.1016/j.jcat.2024.115906","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115906","url":null,"abstract":"As the demand for hydrogen peroxide (H₂O₂) increases across various industries, there is a growing need for eco-friendly production process to replace the energy-intensive and environmentally polluting anthraquinone process. In particular, the electrochemical production of H₂O₂ via the two-electron oxygen reduction reaction (2e-ORR) is being highlighted as a promising alternative. However, achieving high selectivity for 2e-ORR over the four-electron reduction reaction (4e-ORR), remains challenging. We introduce an integrative strategy that combines active motifs-based design with a machine learning to discover promising catalysts for electrochemical H₂O₂ production. Inspired by single-site alloys that destabilize the binding strength of O* adsorbate, thereby improving the 2e-ORR selectivity, we expanded the chemical space through elemental substitution and efficiently explored this expanded chemical space using machine learning methods. By employing these approaches, we discovered active, selective and stable 2e-ORR catalysts that are not present in the existing database and demonstrated better stability compared to the materials within the database. This work highlights the potential of integrating active motifs-based catalyst design with machine learning to efficiently explore the vast chemical space, accelerating the discovery of novel catalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142823225","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":"Mechanistic insights into RuⅣ/RuⅢ and ·OH-co-participated selective oxidation of thioethers into sulfoxides and sulfones over a Ru-Co3O4 electrocatalyst","authors":"Ming Xiang, Tianmin Zhang, Weijie Li, Yingjie Ding, Jiaqi Chen, Cheng Fu, Zhaoxiong Yan, Zhihua Xu","doi":"10.1016/j.jcat.2024.115905","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115905","url":null,"abstract":"Heterogeneous electrocatalysis is an advanced tactics to oxidize organic sulfides into value-added products, concurrently being accompanied with hydrogen production in the aqueous electrolyte. However, the insufficient oxidizing ability of redox mediators and competitive oxygen evolution reaction (OER) inhibited the late-stage oxygenation of thioethers to produce sulfones. Herein, a RuO₂-loaded Co₃O₄ electrocatalyst (Ru-Co₃O₄) was constructed to oxidize thioethers at the potential range of 0.7–0.8 V (vs. Ag/AgCl) at which the OER did not sharply occur, and various sulfoxides and sulfones were produced selectively with moderate to good yields. Mechanism studies revealed that the Ru-Co₃O₄ electrocatalyst afforded Ru⁴⁺ active species and hydroxyl radicals (·OH) at a low potential. The generated Ru^Ⅳ/Ru^Ⅲ redox couple was responsible for the oxidation of sulfides into sulfur-related cation radicals which then reacted with ·OH and deprotonated to form oxygenation products. This work provided a reasonable proposal for the design of heterogeneous electrocatalysts, which could effectively drive the organic oxygenation reactions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"28 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142823287","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":"Prolonging triplet-state lifetimes to boost the energy and electron transfer in conjugated organic polymers for photocatalytic amide formation","authors":"Weijie Zhang, Bingxin Wang, Luting Liu, Xinye Luo, Quan Wan, Bing Yi, Weijie Chi, Hai Yang","doi":"10.1016/j.jcat.2024.115898","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115898","url":null,"abstract":"Long-lived triplet excited states have been regarded as active species in the implementation of photochemical strategies owing to their associated high energy and electron transfer abilities, yet it was still challenging to fulfill this in polymeric photocatalysis. Herein, we formulated a built-in donor–acceptor interaction control strategy to prolong the excited-state lifetime in conjugated organic polymers (COPs) by minimizing the exciton binding energy in the first excited state. The resultant COPs decorated with tris([1,2,4]triazolo)[4,3-a:4′,3′-c:4′’,3′’-e][1,3,5]triazine exhibited excellent activities in photocatalytic amide formation (95 % yield), which was much higher than that of triazine rings as an analogous moiety(66 % yield) owing to its prolonged triplet-state lifetimes (τ = 30.5 µs) and the improved photo-induced charge separation efficiency. These results not only demonstrate the feasibility of realizing triplet excited states for heterogeneous photocatalysis through molecular engineering but also offers insights into energy and electron transfer at the molecular level.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"20 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820648","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, Advaith Nair, Lars C. Grabow, Paul J. Dauenhauer, Susannah L. Scott, Omar A. Abdelrahman","doi":"10.1016/j.jcat.2024.115902","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115902","url":null,"abstract":"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 information, and reactor configuration, 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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-13","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":"A review on uranyl-based photocatalysts in photocatalytic organic transformation","authors":"Peng Gao, Zewen Shen, Yana Chen, Tao Jiang, Zhuoyu Ji, Guixia Zhao, Junrong Yue, Yezi Hu, Xiangke Wang, Xiubing Huang, Martin Muhler, Lisha Yin","doi":"10.1016/j.jcat.2024.115900","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115900","url":null,"abstract":"Depleted uranium as a mildly radioactive waste product from the ²³⁵U enrichment process is stocked worldwide, which can be considered as ideal photocatalyst for light-driven photo-redox reactions. Under light irradiation, the generated excited-state *UO₂²⁺ possesses strong oxidative ability and long-lived fluorescence lifetime via ligand to metal charge transfer (LMCT), which can be effectively quenched by organic substrates via hydrogen atom transfer (HAT) and single electron transfer (SET) processes. The applications of both homogeneous and heterogeneous uranyl-based photocatalysts (including uranyl salts, uranyl-loading composite catalysts, uranyl-based complexes, and uranyl-based metal–organic frameworks) exhibit their advances in unique electronic structure, excellent photochemical properties, and outstanding photocatalytic performance in organic photo-transformation reactions. This review is to highlight the light-driven transformation of organic substances over various types of homogeneous and heterogeneous uranyl-based photocatalysts. The current research survey verifies that spent nuclear waste possesses great potential to construct efficient photocatalysts for light-driven organics transformation.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816352","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":"Diatomic cobalt–catalyzed cyclization of o-aminobenzyl alcohol with amidine for the synthesis of quinazolines","authors":"Guozhang Fu, Yunong Li, Zhuoqun Hou, Shasha Wang, Shaohua Jiang, Tianxiang Chen, Tsz Woon Benedict Lo, Xiuwen Chen","doi":"10.1016/j.jcat.2024.115889","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115889","url":null,"abstract":"This article describes the development of a stable and reusable diatomic cobalt catalyst for the synthesis of various quinazoline derivatives via the dehydrogenation cyclization reaction of anthranilic alcohol with amidine in a simple and environmental friendly manner. Crystallographic studies reveal that the superior catalytic reactivity can be attributed to the synergistic cooperation between the adjacent cobalt active centers within a confined domain for the co-adsorption and co-activation of substrates. This work provides new insights into the application of heterogeneous catalysts in organic synthesis.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"10 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804821","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-driven aldehyde ammoxidation to nitrile via •O2– and •NHx radicals generation over Ni(OH)2/TiO2 p-n heterojunctions","authors":"Yiwei Zhou, Jian Zhao, Hairui Guo, Cheng Wang","doi":"10.1016/j.jcat.2024.115897","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115897","url":null,"abstract":"Aldehydes ammoxidation is a green and promising route for selective synthesis of nitrile, but developing low-cost and efficient catalytic system under mild condition remains a challenge. Herein, we explore a novel catalytic system where the designed Ni(OH)₂/TiO₂ p-n heterojunction catalyst could efficiently drive aldehydes ammoxidation with NH₃·H₂O and O₂ at ambient temperature and pressure by using visible-light as the only energy input. The superoxide (^•O₂^–) generated by reducing O₂ with photogenerated electrons and amino radicals (^•NH_x) produced by oxidizing NH₃·H₂O with photogenerated holes, are successfully identified as key species for the formation of nitriles. Meanwhile, ^•NH_x and ^•O₂^– radicals individually work on the formation of the intermediate aldimine intermediate and its oxidation to nitrile. The performance of the engineered Ni(OH)₂/TiO₂ p-n heterojunctions in the reaction process is much more superior to other catalyst systems. This study develops nitrile synthesis route under mild conditions and present new opportunities for constructing low-cost photocatalyst for chemical synthesis. It also provides a better understanding of the radical species and how they work in aldehydes ammoxidation reactions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"48 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809767","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":"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":"https://doi.org/10.1016/j.jcat.2024.115894","url":null,"abstract":"<h2>Section snippets</h2><section><section><h2>Catalyst production</h2>In the future circular economy, industry will be forced to use raw materials of even lower qualities. Hence, understanding of the role of impurities on catalysis will become more important. Moreover, legislation on the registration of chemical substances, like REACH in Europe, will continue to become harsher in the future, and already now renders expensive and time-consuming toxicity tests necessary. This too will lead to an increasing pressure to more and more substitute currently-used</section></section><section><section><h2>Catalyst performance and stability in the catalytic process</h2>Industrially applied catalysts exist in a very broad variety of different shapes optimized for their processes from powders for fluidized bed applications, granules of different size, particularly shaped extrudates or tablets, to extended structures, like honeycombs. The vast majority of academic research on the other hand is done on materials that generally do not resemble actual catalysts. The much-diminished attention on single-crystal surfaces studied in ultra-high vacuum is indicative of</section></section><section><section><h2>The future of fundamental applied catalysis research</h2>The above-mentioned indicates that there are many fundamental questions that need to be addressed before the catalytic process can be fully appreciated. The desire to achieve sustainability necessitates significant advances in our tool box and efforts to characterize the catalytic process. A concerted effort between academic and industrial research and development will greatly help such endeavor. To appreciate the applied catalytic process, not only do the fundamentals of catalysis need to be</section></section><section><section><h2>CRediT authorship contribution statement</h2><strong>Jeroen A. van Bokhoven:</strong> Writing – review &amp; editing, Writing – original draft, Conceptualization. <strong>Gerhard Mestl:</strong> Writing – review &amp; editing, Writing – original draft, Conceptualization.</section></section><section><section><h2>Declaration of competing interest</h2>The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.</section></section>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"9 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-10","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}