Catalysis Science & Technology最新文献

{"title":"C(sp²)-C(sp²) and C(sp²)-C(sp³) Nickel-Catalyzed Kumada-Corriu and Buchwald-Hartwig Cross-Coupling of Aryl Sulfamates Enabled by Sterically-Demanding, Electron-Rich IPr*^OMe N-Heterocyclic Carbenes.","authors":"Marlena Kardela, Michal Szostak, Elwira Bisz","doi":"10.1039/D5CY00685F","DOIUrl":"10.1039/D5CY00685F","url":null,"abstract":"<p><p>Nickel-catalyzed cross-coupling reactions are among the most powerful tools in organic synthesis owing to the low cost, natural abundance and high activity of versatile nickel catalysts. However, there is a scarcity of efficient Ni-catalyzed systems for the cross-coupling of bench-stable, readily accessible and orthogonal C-O electrophiles. Herein, we report the cross-coupling of aryl sulfamates enabled by sterically-demanding and electron-rich N-heterocyclic carbenes. The study identified sulfamates as the most reactive C-O electrophiles enabled by a combination of IPr*^OMe bearing sterically-demanding <i>ortho</i>-diphenyl wingtip substitution and NiF₂ exploiting the fluoride effect. The system enables efficient C(sp²)-C(sp²) and C(sp²)-C(sp³) cross-coupling avoiding hydrolysis, homocoupling and unselective C-O and S-N cleavages, providing a powerful platform for the orthogonal use of C-O electrophiles. The system is also applicable to Buchwald-Hartwig amination. The broad access to electron-rich, sterically-demanding N-heterocyclic carbenes combined with the high reactivity of aryl sulfamates furnishes a commanding avenue for the development of Ni-catalyzed processes in academic and industrial research.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" ","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12463454/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184297","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":"A kinetic model for Pd-based hydrogenation of acetylene-rich streams typical of post-plasma applications.","authors":"Victor Rosa, Fabio Cameli, Yves Schuurman, Kevin M Van Geem, Georgios D Stefanidis","doi":"10.1039/d5cy00529a","DOIUrl":"10.1039/d5cy00529a","url":null,"abstract":"<p><p>The advancement of electrified chemical processes prompts interest in novel technologies such as plasma-based methane (CH₄) conversion into high-demand chemicals. Specifically, nanosecond-pulsed discharges (NPDs) coupled with downstream Pd-based catalysts have demonstrated the best performance in a two-step, integrated process for converting CH₄ into ethylene (C₂H₄). Given the untested composition range involved in this application, the focus of this work is the isolated performance of Pd-based catalysts in typical post-plasma conditions. Extensive campaigns of experiments are run in both traditional and novel stream compositions. The differences with traditional tail-end olefin-rich hydrogenation are highlighted, and a hybrid steady-state kinetic model is proposed, combining the traditional Langmuir-Hinshelwood-Hougen-Watson (LHHW) approach with an improved reversible adsorption methodology. The ability to accurately predict C₂H₂ hydrogenation kinetics with C₂H₂-rich and C₂H₄-poor streams is achieved by the new model, contrary to existing conventional models. Preliminary insights into catalyst optimization for scalable plasma-to-olefin routes are presented.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" ","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12442368/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084519","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":"Heterometallic Li/Zn, Li/Al and Li/In catalysts for <i>rac</i>-lactide ring-opening polymerisation: \"ate\" or \"non-ate\" pathways?","authors":"Thitirat Piyawongsiri, Anand J Gaston, Maisarah Abdul Rahman, Jack W J Hughes, George E Rudman, Phoebe A Lowy, Gary S Nichol, Carole A Morrison, Khamphee Phomphrai, Jennifer A Garden","doi":"10.1039/d5cy00872g","DOIUrl":"10.1039/d5cy00872g","url":null,"abstract":"<p><p>The ring-opening polymerisation (ROP) of lactide (LA) is an attractive route to produce aliphatic polyesters, with bimetallic catalysts displaying some of the highest catalyst activities to date. While a range of heterometallic catalysts have been reported to outperform their homometallic analogues, the origins of cooperativity are not always well understood. Previous studies indicate that the reaction pathways may differ for different metal heterocombinations, especially when an alkali metal is combined with zinc or aluminium. Here, a series of homo- and hetero-metallic complexes combining Li with Al, Zn or In, supported by an asymmetric methyl-ester substituted salen ligand (<b>H</b> _<b>2</b> <b>L</b>), have been synthesised and characterised by single-crystal X-ray diffraction, to probe potential differences. The heterobimetallic <b>LLiZnCl</b>, <b>LLiAlCl</b> _<b>2</b> , and <b>LLiInCl</b> _<b>2</b> complexes were all active for <i>rac</i>-LA ROP in the presence of an epoxide initiator, with <b>LLiInCl</b> _<b>2</b> offering the most efficient polymerisation while homobimetallic <b>LLi</b> _<b>2</b> was inactive. Investigations into the roles of the different metals through X-ray diffraction and DFT structural studies suggest that oxophilicity, Lewis acidity, and electronegativity difference between the two metals all play a role, with the high oxophilicity and Lewis acidity of Al overriding the \"ate\" pathway.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" ","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12407087/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144999210","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":"Photocatalyzed ring-opening polymerization of ε-caprolactone","authors":"Yicheng Fan, Xiuyuan Ni and Wenbin Fu","doi":"10.1039/D5CY00845J","DOIUrl":"https://doi.org/10.1039/D5CY00845J","url":null,"abstract":"<p >Photocatalyzed polymerization by semiconductors has recently contributed to the methods of polymer synthesis. In this work, we developed a new type of photocatalyzed polymerization with ring-opening polymerization of lactone. A complex catalyst was designed consisting of nitrogen-doped TiO<small>₂</small> (N–TiO<small>₂</small>), iodonium salt (Ph<small>₂</small>I<small>⁺</small>PF<small>₆</small><small>⁻</small>) and H<small>₂</small>O. Poly(ε-caprolactone) (PCL) with a narrow molecular weight distribution was synthesized under visible light irradiation. By using electron spin resonance (ESR), <em>in situ</em><small>¹</small>H-nuclear magnetic resonance (<small>¹</small>H-NMR) and MALDI-TOF mass spectrometry, the mechanism studies clearly presented the reactions of the three components in the ternary catalyst. This polymerization was ruled by the route in which ε-caprolactone (ε-CL) was activated by H<small>⁺</small>. H<small>⁺</small> was photogenerated from the oxidation reaction of H<small>₂</small>O. Meanwhile, H<small>⁺</small> was stabilized by the photogenerated PF<small>₆</small><small>⁻</small>, forming Brønsted acid H<small>⁺</small>PF<small>₆</small><small>⁻</small>. The relationship between the monomer conversions and PCL molecular weights was studied.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5807-5815"},"PeriodicalIF":4.2,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184000","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":"Plasma-assisted surface modification of heterogeneous catalysts: principles, characterization, and applications","authors":"Si Jiang, Yong Yin, Yang Zhang, Zimeng Li, Shuai Guo, Yaogeng Lu, Zhaoxi Zhang, Tianle Zhu, Yifei Sun and Xiang Li","doi":"10.1039/D5CY00844A","DOIUrl":"https://doi.org/10.1039/D5CY00844A","url":null,"abstract":"<p >Owing to its abundance of highly reactive species (<em>e.g.</em>, radicals, ions, and excited species), plasma technology has been extensively employed for surface modification of heterogeneous materials, playing a pivotal role in industrial chemical production, energy conversion, and environmental remediation. Therefore, a systematic understanding of plasma modification mechanisms, combined with comprehensive characterization and analysis, is of paramount importance. Plasma precisely manipulates the physical structure, chemical properties, and electronic structure of catalysts through two key pathways, including physical processes such as sputtering, etching, and morphology engineering, as well as chemical pathways like radical reactions, functionalization, and doping. In this paper, we discuss the underlying mechanisms responsible for enhanced catalytic performance on plasma-treated catalysts, focusing on plasma's ability to tailor morphology, porosity, surface area, active sites, vacancy concentration, heteroatom doping, band structures and Fermi levels. Then, we introduce the primary characterization techniques typically employed to analyze plasma-assisted modification processes. Notably, plasma-assisted surface modification technology has shown high effectiveness in representative catalytic applications, including oxidation reactions, reduction reactions, catalytic reforming, photocatalysis, and electrocatalysis. Finally, the current challenges and promising future research directions in this field are addressed.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5635-5668"},"PeriodicalIF":4.2,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183936","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":"Zn and O/OH synergy in H2 activation and CO2 hydrogenation over Cu nanoparticles catalysts","authors":"Caixia Song, Xiaojiao Zhang, Xuan Zhao, Yiwei Jia, Dong Duan and Hui Li","doi":"10.1039/D5CY00814J","DOIUrl":"https://doi.org/10.1039/D5CY00814J","url":null,"abstract":"<p >The CO<small>₂</small> hydrogenation reaction to produce methanol holds great significance as it contributes to achieving a CO<small>₂</small>-neutral economy. In this work, we present a molecular-level understanding of how Zn atom doping and oxygen or hydroxyl groups play a crucial role in facilitating CO<small>₂</small> hydrogenation on the surface of Cu nanoparticles by density functional theory calculations. Computational evidence proves a higher selectivity of CO<small>₂</small> hydrogenation to HCOO* species as a crucial intermediate in methanol synthesis <em>via</em> the “formate” pathway than that to COOH* <em>via</em> the “RWGS + CO hydro” pathway, by comparing the catalytic performance of pure Cu nanoparticles. Our work highlights the synergistic effect among the doped Zn atom, oxygen or hydroxyl groups and Cu atoms, all of which serve as key parameters in the H<small>₂</small> dissociation and CO<small>₂</small> conversion, which significantly reduces the barriers not only in the CO<small>₂</small> hydrogenation to HCOO, but also in the whole process of CO<small>₂</small> hydrogenation to methanol. The electronic characteristics of the catalysts altered by Zn atom doping and oxygen or hydroxyl groups when H<small>₂</small> or CO<small>₂</small> is adsorbed further confirm their synergistic effect in favor of CO<small>₂</small> hydrogenation. By elucidating the specific roles of these components, we contribute to advancing our understanding of the underlying mechanisms and provide valuable insights for optimizing methanol synthesis processes.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5724-5736"},"PeriodicalIF":4.2,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183976","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":"Biomass or bio-mess: tackling reproducibility in biomass-derived carbon electrocatalysts†","authors":"Shir Tabac-Agam, Shelly Burda, Syeda M. Zahan, Dario R. Dekel and David Eisenberg","doi":"10.1039/D4CY00991F","DOIUrl":"https://doi.org/10.1039/D4CY00991F","url":null,"abstract":"<p >The pyrolysis of biomass is a promising route toward carbon electrodes, but its adoption in electrocatalysis is mostly limited to the oxygen reduction reaction. To prepare precise active sites for other electrocatalytic reactions in the oxygen, nitrogen, and carbon cycles, the complexity of both the biomass precursor and the pyrolysis process must be reigned in. We now report a two-stage strategy for stabilizing the synthesis of a reproducible electrocatalyst for a reaction requiring a precise active site, namely the hydrazine oxidation reaction. The strategy starts with a common yet variable biomass (ground coffee waste) and proceeds through (1) optimized activation by a range of methods, and (2) scalable introduction of Fe–N<small>₄</small> centers. The result is a sustainable, highly active, and most importantly, reproducible, Fe–N–C electrocatalyst. This work should help the scientific and technological communities to realize the full potential of biomass as a source for carbon electrodes.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5678-5689"},"PeriodicalIF":4.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183938","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":"Development of non-noble Ni metal-based (Yb1−xCox)2O3−δ catalysts for green H2 production via ammonia decomposition","authors":"Yeon-Bin Choi, Tae Wook Kang, Seo Ra Woo, Do yun Kim, Sun Woog Kim and Byungseo Bae","doi":"10.1039/D5CY00603A","DOIUrl":"https://doi.org/10.1039/D5CY00603A","url":null,"abstract":"<p >We herein report the preparation of non-noble metal supported Yb<small>₂</small>O<small>₃</small>–Co<small>₃</small>O<small>₄</small> inorganic catalysts for application in H<small>₂</small> production <em>via</em> ammonia (NH<small>₃</small>) decomposition. The NH<small>₃</small> decomposition reaction for H<small>₂</small> production was studied using <em>α</em>wt%Ni/(Yb<small>_{1−<em>x</em>}</small>Co<small>_<em>x</em></small>)<small>₂</small>O<small>_{3−<em>δ</em>}</small> catalysts according to various Co dopant ratios and Ni loadings to evaluate the dependence of oxygen vacancies as active sites. The introduction of Co<small>₃</small>O<small>₄</small> into Yb<small>₂</small>O<small>₃</small> with a Ni metal support improved the oxygen vacancy density of the catalyst to enhance NH<small>₃</small> decomposition activity for H<small>₂</small> production. The electron-deficient nature of oxygen vacancies enabled the catalysts to act as electron acceptors, facilitating the associative N desorption from NH<small>₃</small> to produce N<small>₂</small> in the NH<small>₃</small> cracking process. The structure–property relationship established in these studies suggests that the oxygen vacancies on the <em>α</em>wt%Ni/(Yb<small>_{1−<em>x</em>}</small>Co<small>_<em>x</em></small>)<small>₂</small>O<small>_{3−<em>δ</em>}</small> catalysts serve as active sites for NH<small>₃</small> decomposition. The 16wt%Ni/(Yb<small>_0.92</small>Co<small>_0.08</small>)<small>₂</small>O<small>_{3−<em>δ</em>}</small> catalyst showed the highest catalytic activity, which exhibited an NH<small>₃</small> conversion of 100% at temperatures as low as 550 °C and the constant H<small>₂</small> production rate of 6.23 kg per day.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5690-5699"},"PeriodicalIF":4.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183939","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":"Conversion of dimethyl ether and methanol to hydrocarbons over zeolites with BEA, MRE, and MWW structures","authors":"Maria V. Magomedova, Vera A. Ostroumova, Ilya A. Davidov, Ekaterina G. Galanova, Anastasiya V. Starozhitskaya and Anton L. Maximov","doi":"10.1039/D5CY00740B","DOIUrl":"https://doi.org/10.1039/D5CY00740B","url":null,"abstract":"<p >The catalytic properties of zeolite-based catalysts BEA/Al<small>₂</small>O<small>₃</small>, MCM-22/Al<small>₂</small>O<small>₃</small>, MRE/Al<small>₂</small>O<small>₃</small>, and MFI/Al<small>₂</small>O<small>₃</small> were compared in the conversion of dimethyl ether (DME) and methanol into hydrocarbons at 340 °C under 0.1 MPa (for DME) and 10.0 MPa (for methanol). Catalysts BEA/Al<small>₂</small>O<small>₃</small>, MCM-22/Al<small>₂</small>O<small>₃</small>, and MFI/Al<small>₂</small>O<small>₃</small> with comparable total acidity demonstrated similar activity. However, due to differences in zeolite structure, catalyst stability and product distribution varied. The MCM-22 zeolite with “super-cages” enabled a C<small>₅₊</small> liquid hydrocarbon yield of 62 wt% under atmospheric pressure. BEA/Al<small>₂</small>O<small>₃</small>, with a high fraction of mesopores, facilitated the formation of heavier hydrocarbons C<small>₁₄</small>–C<small>₁₆</small>, components of aviation fuel. The MRE-based catalyst exhibited the lowest acidity and activity but showed high selectivity towards C<small>₂</small>–C<small>₄</small> olefins and operational stability.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5772-5781"},"PeriodicalIF":4.2,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183992","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":"Advanced strategies for plastic upcycling: unlocking sustainable waste valorization pathways for a green and sustainable environment","authors":"Talaat Hassan Habeeb and Umar Farooq","doi":"10.1039/D5CY00477B","DOIUrl":"https://doi.org/10.1039/D5CY00477B","url":null,"abstract":"<p >The growing demand for plastic materials in different aspects of human life has created a serious burden on the environment due to the non-degradable nature of plastic wastes. Therefore, the growing concerns over sustainability and environmental pollution have driven a huge research curiosity for the upcycling of plastic wastes to essential chemical commodities and green fuels. To date, most of the plastic wastes are being upcycled using different conventional approaches like mechanical and thermal methods, which face a number of limitations including downcycling of plastics, low efficiency and production of inferior materials. Hence, to achieve efficient plastic upcycling, different alternative catalytic approaches are being explored, which include electrocatalysis, photocatalysis and photo-electrocatalysis. These approaches offer sustainable, efficient avenues for the upcycling of wastes to valuable chemicals. In this review article, we focus on advances made in the development of efficient catalyst materials for different upcycling processes with a special emphasis on their role in improving the stability, selectivity and efficiency of upcycling processes. Additionally, different approaches including doping, heterostructure formation and composite development employed for enhancing the efficiency of upcycling processes are discussed. Furthermore, insights into the mechanisms and challenges involved in various reported upcycling processes are discussed, highlighting the potential of diverse catalyst systems to be used in the future for achieving the goals of circular economy.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 19","pages":" 5602-5634"},"PeriodicalIF":4.2,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183935","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}