Catalysis Science & Technology最新文献

{"title":"CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex†","authors":"Fereshteh Rezvani ,&nbsp;Xuemei Zhou ,&nbsp;Debora Motta Meira ,&nbsp;George E. Sterbinsky ,&nbsp;Steven L. Tait","doi":"10.1039/d4cy00507d","DOIUrl":"10.1039/d4cy00507d","url":null,"abstract":"<div><div>Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support <em>via</em> a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. <em>In situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO₂) catalyzes CO oxidation <em>via</em> the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO₂. The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5266-5277"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00507d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemically synthesized Ce-doped Cu-mesh catalyst with high activity and stability towards HMF to FDCA conversion†","authors":"Haoran Wu ,&nbsp;Qi Liu ,&nbsp;Didi Li ,&nbsp;Haoyuan Gu ,&nbsp;Hao Liu ,&nbsp;Xiaohui Liu ,&nbsp;Zixu Yang ,&nbsp;Jing Xu ,&nbsp;Minghui Zhu","doi":"10.1039/d4cy00851k","DOIUrl":"10.1039/d4cy00851k","url":null,"abstract":"<div><div>The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to high value-added downstream products is a sustainable and cost-effective strategy. In this study, a series of copper-based HMF oxidation reaction (HMFOR) catalysts were synthesized through a modified chronopotentiometry method using copper mesh as a starting material. The cerium-doped copper mesh catalyst, denoted as Ec CM-Ce demonstrates exceptional performance in the HMFOR, exhibiting remarkable selectivity (99.2%), yield (96.4%), Faraday efficiency (92.6%), and stability (12 cycles without significant activity decay). X-ray diffraction and surface-enhanced <em>in situ</em> Raman spectroscopy demonstrated the transformation of Cu₂O to CuO during the oxidation of HMF to FDCA. Electrochemical impedance spectroscopy and surface-enhanced <em>in situ</em> infrared spectroscopy indicated that cerium enhanced the electron transfer efficiency and adsorption of water as well as organic molecules. This study not only introduces a novel method for synthesizing electro-catalysts but also suggests innovative approaches for the electrochemical HMF oxidation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5199-5205"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205537","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 synthesis of allenes","authors":"Jitender Singh ,&nbsp;Barakha Saxena ,&nbsp;Anuj Sharma","doi":"10.1039/d4cy00361f","DOIUrl":"10.1039/d4cy00361f","url":null,"abstract":"<div><div>Allenes are attractive structural motifs not only prevalent in natural products, functional materials, and bioactive molecules, but also utilized as important synthetic intermediates in organic synthesis. Owing to the importance of allene molecules in organic synthesis and pharmaceuticals, substantial protocols have been developed to access allenes. Amongst them, visible light induced photoredox catalysis has emerged as a powerful tool for accomplishing the synthesis of allenes under mild reaction conditions. The present review article demonstrates the visible light promoted construction of allenes from substrates including 1,3-enynes, propargylic carbonates, homopropargylic alcohols, propargylic oxalates, alkynyl diazo compounds, and terminal alkynyl aziridines.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5143-5160"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141872299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Superacidity in Zr(iv)/Ce(iii) MOF-808: unlocking biodiesel production from microalgae lipids at reduced temperatures†","authors":"Lei Qian ,&nbsp;Jun Cheng ,&nbsp;Kai Xin ,&nbsp;Yuxiang Mao ,&nbsp;Jiacan Tu ,&nbsp;Weijuan Yang","doi":"10.1039/d4cy00545g","DOIUrl":"10.1039/d4cy00545g","url":null,"abstract":"<div><div>To manage production costs and lower the conversion temperature of microalgal lipids, this study engineered superacid sites in MOF-808, facilitating lipid transformation at markedly reduced temperatures. Through simple substitution and activation steps, secondary building units formed by Zr(<span>iv</span>) and Ce(<span>iii</span>) were assembled with benzene-1,3,5-tricarboxylate ligands, resulting in a unique superacid structure. This superacid structure has a Hammett acidity value of less than −14.5 and a deprotonation energy of 1016.25 kJ mol⁻¹, both lower than those of sulfuric acid. Density functional theory and solid-state NMR analyses confirmed the superacidity arises from a weakly constrained superacid proton within a bridging structure, formed by two methanol molecules attracted to adjacent Ce and Zr atoms. Variable temperature infrared spectroscopy demonstrated the low-temperature activation of methanol, with the optimal reaction temperature reduced from 200 °C to 150 °C and pressure reduced by 2952 kPa. Unlike traditional solid superacids, this methanol-based superacid configuration prevents the loss of superacid sites, maintaining over 97% efficiency after five cycles.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5278-5290"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comprehensive understanding of ethylene epoxidation on copper catalysts: a microkinetic study with coverage effects†","authors":"Zhuozheng Wang ,&nbsp;Wenbo Xie ,&nbsp;Yarong Xu ,&nbsp;Yulan Han ,&nbsp;Jiayan Xu ,&nbsp;P. Hu","doi":"10.1039/d4cy00617h","DOIUrl":"10.1039/d4cy00617h","url":null,"abstract":"<div><div>Ethylene epoxidation is one of the fundamental industrial reactions, garnering extensive theoretical and experimental studies. While silver has traditionally been the catalyst of choice for this reaction, copper has received comparatively little attention. In this study, we apply a coverage-dependent microkinetic modeling to quantitatively investigate ethylene epoxidation on Cu(111), serving as a model system to study the intrinsic activity and selectivity of Cu catalysts. The coverage-dependent simulation takes into account both self and cross-interactions of adsorbates, as well as the coverage effects on the transition states of each elementary step. In contrast, the coverage-independent modeling is conducted without considering coverage effects. We observe that the coverage-dependent modelling reveals the Cu(111) surface with coverage exceeding 30% oxygen atoms with a high turnover frequency (log(TOF) = 2.65) at 500 K. In contrast, the coverage-independent results indicate the Cu(111) surface being completely covered by oxygen atoms, leading to detrimental poisoning effects (log(TOF) = −2.47). We show that the EO selectivity on Cu(111) can be at a high level of 80% under all studied conditions in contrast to only ∼40% EO selectivity on Ag(111). Detailed structural analyses unveil the fundamental reasons why Cu catalysts are more selective for ethylene epoxidation. Furthermore, we suggest that reducing temperature and increasing oxygen pressure can effectively improve EO selectivity for industrial ethylene epoxidation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5291-5303"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00617h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure sensitivity of the low-temperature dehydrogenation of perhydro dibenzyltoluene on supported platinum nanoparticles†","authors":"Yazan Mahayni ,&nbsp;Lukas Maurer ,&nbsp;Franziska Auer ,&nbsp;Andreas Hutzler ,&nbsp;Peter Wasserscheid ,&nbsp;Moritz Wolf","doi":"10.1039/d4cy00032c","DOIUrl":"10.1039/d4cy00032c","url":null,"abstract":"<div><div>In this study, the structure sensitivity of the dehydrogenation reactions of the commonly used liquid organic hydrogen carrier (LOHC) molecules perhydro dibenzyltoluene (H18-DBT) and perhydro benzyltoluene (H12-BT) is investigated. We focus on the hydrogen release at moderate reaction temperatures, which is particularly relevant to enable heat integration of the LOHC dehydrogenation process with, for example, high-temperature fuel cells for an enhanced overall efficiency. To determine the most suitable platinum nanoparticle size with the highest surface specific productivity, a colloidal approach was used for the synthesis of Pt/Al₂O₃ catalysts with well-defined nanoparticle sizes. These catalysts were used in the dehydrogenation reactions of H18-DBT and H12-BT in the temperature ranges of 250–280 °C and 220–240 °C, respectively. A structure sensitivity was identified in both cases, which becomes particularly prominent at lower reaction temperatures. This is attributed to the overall slower reaction kinetics and the amplified differences of the adsorption strength on different surface sites. A maximum in surface specific productivity was found for catalysts with a Pt nanoparticle size of 2.6 nm for H18-DBT and 2.3 nm for H12-BT dehydrogenation. It is assumed that the observed structure sensitivity is mainly due to an optimal surface composition of the nanoparticles with an ideal balance between strongly adsorbing corner and edge sites and less active terrace sites. At low temperatures, desorption from low coordinated sites is limiting for nanoparticles below 2.3 nm, while the increasing share of terrace sites in nanoparticles larger than 2.7 nm reduces the overall productivity of the catalyst due to their lower specific activity. This behavior becomes less pronounced at higher temperatures. The dehydrogenation of H12-BT was even shown to be rather structure insensitive at 240 °C.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5464-5473"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00032c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorescence-based pH-shift assay with wide application scope for high-throughput determination of enzymatic activity in enzyme mining and engineering†‡","authors":"Avinash Vellore Sunder ,&nbsp;Marie-Luise Reif ,&nbsp;Wolf-Dieter Fessner","doi":"10.1039/d4cy00566j","DOIUrl":"10.1039/d4cy00566j","url":null,"abstract":"<div><div>A number of enzymes important for biocatalyst development or as drug targets are associated with a pH shift during their catalytic reaction, owing to the concommitant release or uptake of protons. Here, we show that an enzyme assay developed using the fluorescent pH indicator HPTS can be adapted for reliable and continuous activity determination of representative enzymes from multiple EC classes that operate in the viable pH range 5.5–8.5, using ratiometric measurement (<em>F</em>₄₈₅/<em>F</em>₄₀₅). Kinetic measurements obtained with this method closely match literature values determined using other assay types. Further, the assay was employed to screen variants of transketolase from <em>Geobacillus stearothermophilus</em> (TK_gst) aimed at engineering substrate promiscuity and remote enantioselectivity for 3-hydroxyaldehydes. The fluorescence-based assay displayed 70-fold improved sensitivity in comparison to an absorption-based assay for transketolase screening, with a limit of detection of 0.044 mM and <em>Z</em>-factor of 0.52. Double-site mutagenesis at the G264 and S385 positions yielded variants with 5–15-fold increased activity on the tested 3-hydroxyaldehydes compared to the TK_gst (L382F) base variant. Although the directed evolution engineering strategy did not achieve significant remote enantioselectivity in this first round of mutagenesis, the simple fluorescence-based pH-shift assay was shown to be useful as a versatile primary high-throughput screen for <em>in vitro</em> enzyme engineering.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5375-5384"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00566j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141880530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The evolution of Pt with different initial sizes during propane oxidation over Pt–CeO2 catalysts†","authors":"Jinshi Dong ,&nbsp;Shijun Huang ,&nbsp;Shengtong Li ,&nbsp;Panpan Chang ,&nbsp;Jiaqiang Yang","doi":"10.1039/d4cy00900b","DOIUrl":"10.1039/d4cy00900b","url":null,"abstract":"<div><div>Pt-based catalysts are widely used in catalytic combustion of hydrocarbons and play an important role in emission control. However, developing a Pt catalyst for efficient conversion of hydrocarbons at low temperatures remains challenging. Herein, the structure–performance relationship between Pt size and C₃H₈ oxidation activity was studied over Pt–CeO₂ catalysts. The samples with different Pt initial states of single atoms and nanoparticles were obtained by different reduction treatments. No obvious differences were found between the two catalysts in the performances of C₃H₈ oxidation. The Pt states were found to be dynamically changing during C₃H₈ oxidation, and the evolution behaviors were closely related to the Pt initial states; Pt single atoms continuously sintered into clusters and then transformed into Pt nanoparticles with elevated reaction temperatures, while initial Pt nanoparticles firstly dispersed into small clusters and then re-sintered into nanoparticles. It is concluded that the different adsorption properties of C₃H₈ and O₂ on Pt species with different sizes are responsible for their different evolution behaviors during C₃H₈ oxidation based on DFT analyses.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5211-5217"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research development of anti-CO poisoning in electrocatalytic methanol oxidation processes: a review","authors":"Zhixun Wei ,&nbsp;Shuyan Yu ,&nbsp;Congju Li","doi":"10.1039/d4cy00726c","DOIUrl":"10.1039/d4cy00726c","url":null,"abstract":"<div><div>This review examines research advancements in anti-CO poisoning during the electrocatalytic methanol oxidation reaction (MOR). The article details catalyst design and optimization strategies, experimental studies, and control measures. An in-depth analysis of intermediate product generation mechanisms, factors affecting anti-CO poisoning, and experimental studies supports MOR development. Anti-CO poisoning strategies encompass catalyst selection, reaction condition optimization, intermediate control, surface modification, carrier effects, atmosphere modulation, and catalyst regeneration and recycling. Experimental studies focus on electrode preparation, electrolyte selection, and electrocatalytic reactions. Results indicate that optimizing experimental methods and conditions enhances MOR stability and effectiveness by improving catalysts' anti-CO poisoning ability. Methanol electrocatalysis represents a clean and effective energy conversion technology. Kinetic and thermodynamic analyses of anti-CO poisoning in methanol electrocatalysis provide a theoretical basis for catalyst design and optimization. Comprehensive research on MOR intermediate products, CO generation mechanisms, factors influencing CO poisoning, characterization methods, experimental studies, and optimization measures provides a foundation for MOR development and its application in green chemistry and renewable energy.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5128-5142"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141872295","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study of promoted Cu/ZnO and Cu/ZrO2 catalysts for dimethyl adipate hydrogenolysis†","authors":"Jaroslav Aubrecht ,&nbsp;Violetta Pospelova ,&nbsp;Sharmistha Saha ,&nbsp;Miloslav Lhotka ,&nbsp;Iva Paterová ,&nbsp;David Kubička","doi":"10.1039/d4cy00686k","DOIUrl":"10.1039/d4cy00686k","url":null,"abstract":"<div><div>Two supports (ZnO, ZrO₂) and four promoters (Al₂O₃, ZnO, CoO_x, NiO) were investigated to design environmentally-friendly Cu-based hydrogenolysis catalysts. Both catalyst characterization and activity in dimethyl adipate hydrogenolysis were described. While ZrO₂ improved the reducibility of CuO nanoparticles, these particles were less stable under reaction conditions. ZnO provided better stabilization and reduced coke formation. CoO_x, used as a promoter, increased the surface availability of dissociated H₂ and stabilized Cu nanoparticles with a high surface area. Conversely, Al₂O₃ or NiO promoters improved neither catalyst performance nor selectivity due to the higher number of acid–base sites. The essential role of ZnO, whether used as support or a single promoter, was attributed to Cu–ZnO synergy that enhanced the activity in dimethyl adipate hydrogenolysis and improved desired selectivity to hexane-1,6-diol. Overall, the hydrogenolysis activity (TOF_H) was 5 times higher for ZnO-supported catalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5364-5374"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00686k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141880533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}