Catalysis Science & Technology最新文献

{"title":"(Trialkylsilyl-cyclopentadienyl)titanium(iv) dichloride complexes containing ketimide ligands, Cp′TiCl2(NCtBu2) (Cp′ = Me3SiC5H4, Et3SiC5H4), as efficient catalysts for ethylene copolymerisation with norbornene and tetracyclododecene†","authors":"Minaho Kawatsu ,&nbsp;Taiga Fujioka ,&nbsp;Simona Losio ,&nbsp;Incoronata Tritto ,&nbsp;Kotohiro Nomura","doi":"10.1039/d5cy00160a","DOIUrl":"10.1039/d5cy00160a","url":null,"abstract":"<div><div>Trialkylsilyl-substituted half sandwich titanium complexes containing ketimide ligands, (RC₅H₄)TiCl₂(NC^<em>t</em>Bu₂) (R = SiMe₃, SiEt₃), especially the SiEt₃ analogue, exhibited superior catalytic activities with efficient norbornene (NBE) incorporation (25 700–91 400 kg polymer per mol Ti h⁻¹; NBE 36.2–72.7 mol%) in the ethylene/NBE copolymerisation at 50 °C to afford high molecular weight copolymers with high NBE contents (NBE &gt; 60 mol%). These complexes also displayed superior capability for efficient synthesis of ethylene copolymers with tetracyclododecene (TCD) at 50 °C, and synthesis of high molar mass copolymers with high glass transition temperatures (<em>T</em>_g = 255 °C, TCD 52.3 mol%) has been achieved. Efficient synthesis of high molar mass cyclic olefin copolymers (COCs) possessing high <em>T</em>_g values has been demonstrated by using these catalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2757-2765"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911679","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":"Formic acid decomposition over supported Pd alloy catalysts: role of oxygen in hydrogen production†","authors":"Nandam Hemanth Kumar ,&nbsp;Ankit Kumar ,&nbsp;Riya Javiya ,&nbsp;Mukesh Kumar ,&nbsp;Sudhanshu Sharma ,&nbsp;Abinaya Sampath","doi":"10.1039/d4cy01379d","DOIUrl":"10.1039/d4cy01379d","url":null,"abstract":"<div><div>Aqueous formic acid (FA) catalytic dehydrogenation to hydrogen (H₂) is a potential green H₂ source under ambient conditions (in air). We show that commonly studied Pd nanoparticles supported on CeO₂ provide low H₂ selectivity and TOF (10%; 20 h⁻¹) against water (H₂O) formation from the aqueous FA reaction under ambient conditions. Further, this study explains how Ag alloying of Pd and interfacial sites affect the selective production of H₂ from FA with rates and apparent energy barrier measurements without promoters in the liquid phase under ambient conditions. The presence of a high surface coverage of oxygen on Pd–CeO₂ decreases the H₂ selectivity and promotes H₂O formation from the aqueous FA reaction at a temperature as low as 298 K. However, 0.5 PdAg–CeO₂ (the atomic ratio of Pd and Ag is 0.5) catalysts provide a higher H₂ selectivity (22%) and TOF (178 h⁻¹) when compared to Pd–CeO₂ (10%; 20 h⁻¹) at 298 K. Despite the changes in H₂ TOF and selectivity, Pd–CeO₂ and 0.5 PdAg–CeO₂ present the C–H bond activation of formate as a kinetically relevant step for H₂ production from FA over a formate covered surface. Even in the presence of an oxidative environment, Ag increases the surface coverage of reduced Pd on 0.5 PdAg–CeO₂ compared to Pd–CeO₂, and these electronic modifications of PdAg compared to Pd decrease the apparent activation barrier over 0.5 PdAg–CeO₂ (8 ± 4 kJ mol⁻¹) compared to Pd–CeO₂ (25 ± 3 kJ mol⁻¹) and increase the H₂ TOF/selectivity from the FA reaction. Similar-sized PdAg nanoparticles on CeO₂ and TiO₂ provide comparable rates of H₂ production from the FA reaction independent of the identity of the support due to negligible differences in the support basicity. The mechanistic insights of H₂ production from FA in the presence of surface oxygen on PdAg catalysts and the derived rate law will aid in the rational design of future catalysts for aerobic H₂ production.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2809-2821"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911807","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":"Tailored support reduction of Cu/SrTiO3 catalysts for enhanced methanol production†","authors":"Chiara Pischetola ,&nbsp;Luca Artiglia ,&nbsp;Frank Krumeich ,&nbsp;Jeroen A. van Bokhoven","doi":"10.1039/d4cy01487a","DOIUrl":"10.1039/d4cy01487a","url":null,"abstract":"<div><div>Copper supported on strontium titanate is explored as a catalyst in the hydrogenation of carbon dioxide to methanol. We used combined H₂-TPR, O₂-TPO, XPS, and STEM-EDX to identify the support defects, tailored by the activation procedure. Strontium titanate forms oxygen vacancies under high-temperature reductive treatments. The extent of its reduction is a function of the copper content and of the pressure; the highest extent is achieved at 2 wt% copper and 20 bar hydrogen. The catalytic data agree with a direct relationship between the methanol selectivity and the concentration of the oxygen vacancies, with the best results being: 90% (10% towards carbon monoxide) and an associated methanol space time yield of 0.49 g_MeOH g_cat⁻¹ h⁻¹. The selectivity is higher than that achieved on a typical copper catalyst on zinc oxide alumina, while keeping the competitive productivity value, despite having thirty times lower copper content. <em>Post</em>-reaction characterisation suggests that these sites are stable under reaction conditions. We propose a dual-site surface mechanism based on oxygen vacancies formed at the copper–support interface and <em>via</em> long-distance hydrogen spillover.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2722-2732"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911796","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":"Carbon felt by acid treatment as a highly active metal-free electrocatalyst for the selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde†","authors":"Junli Sun ,&nbsp;Yufang Ding ,&nbsp;Daiping He ,&nbsp;Xulin Qiu ,&nbsp;Chengying Luo ,&nbsp;Ping Jiang","doi":"10.1039/d4cy01407c","DOIUrl":"10.1039/d4cy01407c","url":null,"abstract":"<div><div>Carbon felt by concentrated nitric acid treatment (CFn) was utilized directly as a metal-free electrode for electrochemical hydrogenation of cinnamaldehyde (CAL) for the first time. CFn shows high selectivity and Faradaic efficiency (FE) in converting CAL to hydrocinnamaldehyde (HCAL). At a constant current density of 20 mA cm⁻², CFn achieved 81.5% selectivity to HCAL with a FE of 85.7%. Compared with pristine carbon felt, CFn has more π electrons and carbonyl groups on its surface, which facilitate the adsorption of CAL and H₂O, and a larger electrochemical surface area and good electron transfer properties. These may be responsible for its excellent performance for selective hydrogenation of CAL to HCAL. This work provides a cost-effective metal-free catalyst for HCAL production.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2776-2782"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911799","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":"An efficient titanomaghemite MOF-derived catalyst for reverse water–gas shift†","authors":"Orxan Sayidov ,&nbsp;Luis Garzon-Tovar ,&nbsp;Javier Patarroyo ,&nbsp;Giiaz Bekmukhamedov ,&nbsp;Joseph A. Stewart ,&nbsp;Bart D. Vandegehuchte ,&nbsp;Nicolas Montroussier ,&nbsp;Javier Ruiz-Martinez ,&nbsp;Jorge Gascon","doi":"10.1039/d5cy00044k","DOIUrl":"10.1039/d5cy00044k","url":null,"abstract":"<div><div>In response to the escalating greenhouse gas (GHG) emission crisis, integrating the reverse water–gas shift (RWGS) reaction with Fischer–Tropsch synthesis (FTS) has been identified as a promising two-step approach for converting CO₂ and H₂ into valuable products. However, the requirement for high temperatures to achieve significant CO₂ conversion, along with the formation of undesired products (<em>e.g.</em>, methane) at high pressures during the RWGS step, presents challenges for integrating the RWGS reaction with FTS synthesis. In this context, developing a low-temperature RWGS catalyst that can suppress CO₂ methanation, even under high pressure, is paramount for facilitating energy integration between the two processes. In this study, we present an in-depth study of a metal–organic framework (MOF)-derived solid as a catalyst for the low temperature RWGS reaction. Our catalyst showed high activity and stability, achieving up to 97% CO selectivity at close to equilibrium CO₂ conversion levels at moderate temperatures and high pressures. A kinetic study of the resulting titanomaghemite catalyst was conducted to determine the kinetic parameters that describe the catalytic system and to facilitate future reactor and process design.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2908-2918"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911809","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":"Accelerating the identification of the rate controlling steps by conducting microkinetic modeling on surrogate networks†","authors":"Hongyu Li, Jia Zhang, Zihao Yao and P. Hu","doi":"10.1039/D4CY01336K","DOIUrl":"https://doi.org/10.1039/D4CY01336K","url":null,"abstract":"<p >Identifying the rate-controlling steps in an unknown reaction network can be time-consuming due to its inherent complexity. Here we present a strategy to simplify this process by focusing expensive barrier calculations on significant elementary steps. The strategy is constructed by determining significant elementary steps using the degree of rate control data, which is derived from microkinetic modeling calculations performed on surrogate networks, which are a series of networks generated by assigning fictitious values to unknown barriers while all the reaction energies are computed using density functional theory. The barriers for significant elementary steps are then calculated iteratively to refine the network. We demonstrate this strategy for the reaction of Fischer–Tropsch synthesis, which has already been extensively studied in our previous work. Applying the strategy, we identified the most rate-controlling step, achieving a 77% reduction in the number of transition state calculations compared to traditional methods. Additionally, a detailed analysis of the strategy reveals the correlation between the parameters in the strategy and its performance. We validate the practicability of the strategy by applying it onto testing networks and the potential limitations of the strategy are also discussed.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2766-2775"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01336k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913653","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":"Accelerating the identification of the rate controlling steps by conducting microkinetic modeling on surrogate networks†","authors":"Hongyu Li ,&nbsp;Jia Zhang ,&nbsp;Zihao Yao ,&nbsp;P. Hu","doi":"10.1039/d4cy01336k","DOIUrl":"10.1039/d4cy01336k","url":null,"abstract":"<div><div>Identifying the rate-controlling steps in an unknown reaction network can be time-consuming due to its inherent complexity. Here we present a strategy to simplify this process by focusing expensive barrier calculations on significant elementary steps. The strategy is constructed by determining significant elementary steps using the degree of rate control data, which is derived from microkinetic modeling calculations performed on surrogate networks, which are a series of networks generated by assigning fictitious values to unknown barriers while all the reaction energies are computed using density functional theory. The barriers for significant elementary steps are then calculated iteratively to refine the network. We demonstrate this strategy for the reaction of Fischer–Tropsch synthesis, which has already been extensively studied in our previous work. Applying the strategy, we identified the most rate-controlling step, achieving a 77% reduction in the number of transition state calculations compared to traditional methods. Additionally, a detailed analysis of the strategy reveals the correlation between the parameters in the strategy and its performance. We validate the practicability of the strategy by applying it onto testing networks and the potential limitations of the strategy are also discussed.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2766-2775"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911880","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":"EDTA-Co(ii) complex functionalized magnetic nanoparticles: as a heterogeneous catalyst for the synthesis of 5-substituted 1H-tetrazoles","authors":"Chou-Yi Hsu ,&nbsp;Safia Obaidur Rab ,&nbsp;Farag M. A. Altalbawy ,&nbsp;Vicky Jain ,&nbsp;Soumya V. Menon ,&nbsp;Mamata Chahar ,&nbsp;Zahraa Ahmed Taha ,&nbsp;Wael Dheaa Kadhim","doi":"10.1039/d5cy00099h","DOIUrl":"10.1039/d5cy00099h","url":null,"abstract":"<div><div>In this study, we report the synthesis of an EDTA coordinated cobalt complex [EDTA-Co(<span>ii</span>)] immobilized on the surface of Fe₃O₄ magnetic nanoparticles (MNPs) <em>via</em> a three-step post-synthetic modification approach. The structure of the prepared catalytic nanocomposite was comprehensively characterized using a suite of spectroscopic, physical, morphological, and elemental analytical techniques. The catalytic efficiency of this nanocomposite was evaluated in the synthesis of 5-substituted 1<em>H</em>-tetrazoles <em>via</em> the [3 + 2] cycloaddition of sodium azide to nitriles at 120 °C in polyethylene glycol 400 (PEG-400) as a green solvent. This approach yielded the desired products with excellent yields and selectivity in short reaction times. Hot filtration, leaching and reusability studies confirmed the catalyst's high stability and recyclability with negligible loss of activity.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2745-2756"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911884","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":"Sustainable copper nanocomposite for multicomponent synthesis of triazolo quinolines and triazolyl benzamide derivatives and their bioactivity study†","authors":"Nandini R. ,&nbsp;Byresh B. Kempegowda ,&nbsp;Sudhanva M. Srinivasa ,&nbsp;Umesh A. Kshirsagar ,&nbsp;Jan Grzegorz Malecki ,&nbsp;Siddappa A. Patil ,&nbsp;Shoyebmohamad F. Shaikh ,&nbsp;Manoj V. Mane ,&nbsp;Ramesh B. Dateer","doi":"10.1039/d4cy01225a","DOIUrl":"10.1039/d4cy01225a","url":null,"abstract":"<div><div>Herein, we report an efficient methodology for the preparation of a heterogeneous sustainable magnetically separable Cu@PANI@Fe₃O₄ nanocomposite, and its catalytic efficiency in multicomponent reactions for the synthesis of triazolo quinolines and triazolyl benzamide derivatives is investigated. The Cu@PANI@Fe₃O₄ nanocomposite is characterized by several analytical techniques such as PXRD, FE-SEM, ICP-OES, HR-TEM, XPS, VSM, and TG-DTA to understand its crystallinity, chemical composition, morphology, and magnetic properties. A series of triazolo quinolines and triazolyl benzamide derivatives are synthesized in good to excellent yields under greener reaction conditions. A detailed mechanistic investigation by control experiments and DFT calculations has been performed to validate the proposed mechanism. Additionally, anti-cancer studies of the synthesized triazolo quinoline derivatives were performed and they were screened against colon carcinoma cell lines (HCT116) and subjected to MTT assay, showcasing good activity against the cells with IC₅₀ of 28–45 μM. Further, gram-scale synthesis, recyclability of the nanocomposite and its utility in up to five consecutive cycles were deliberated.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2878-2887"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911887","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":"DBD plasma combined with Ni–Mn/SiO2 catalysts modified by myristic acid for methane oxidation in presence of water vapor","authors":"Chao Hu ,&nbsp;Minghui Li ,&nbsp;Runze Chen ,&nbsp;Yezheng Yu ,&nbsp;Changzhao Ye ,&nbsp;Yaoyao Xu ,&nbsp;Zelong Zhang ,&nbsp;Haitao Zhang","doi":"10.1039/d4cy01093k","DOIUrl":"10.1039/d4cy01093k","url":null,"abstract":"<div><div>Plasma catalysis is recognized as a promising technology for the elimination of methane. However, co-existence of moisture in flue gas reduces significantly the adsorption capacity of catalysts toward CH₄. Herein, Ni–Mn/SiO₂ catalysts were tuned by controlling the Ni/Mn molar ratio and subjected to hydrophobic treatment using myristic acid to promote methane oxidation under humid conditions. The plasma–catalytic system demonstrated a substantial improvement in CH₄ conversion and CO₂ selectivity compared to the plasma-only system owing to the synergistic effects of plasma and catalysis on methane degradation. The increase in the Mn/Ni molar ratio promotes the formation of Mn⁴⁺ on the catalyst surface and increases the specific surface area, facilitating the migration and adsorption of reactive oxygen species, which further improves the catalytic activity of methane oxidation reaction. In the presence of 5% water vapor, Ni–Mn(1 : 1)/SiO₂–MA exhibited the highest CH₄ conversion of 93.5% at 40 W. Due to the introduction of myristic acid with non-polar alkyl groups, a highly hydrophobic surface was obtained on modified catalysts, preventing the coverage of the active sites and promoting CH₄ adsorption. This study provides a new and viable solution to improve the performance of catalysts in methane oxidation under high-humidity conditions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2794-2808"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911806","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}