Catalysis Science & Technology最新文献

{"title":"Carbon felt by acid treatment as a highly active metal-free electrocatalyst for the selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde†","authors":"Junli Sun, Yufang Ding, Daiping He, Xulin Qiu, Chengying Luo and Ping Jiang","doi":"10.1039/D4CY01407C","DOIUrl":"https://doi.org/10.1039/D4CY01407C","url":null,"abstract":"<p >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<small>⁻²</small>, 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 H<small>₂</small>O, 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.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2776-2782"},"PeriodicalIF":4.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913654","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, Ankit Kumar, Riya Javiya, Mukesh Kumar, Sudhanshu Sharma and Abinaya Sampath","doi":"10.1039/D4CY01379D","DOIUrl":"https://doi.org/10.1039/D4CY01379D","url":null,"abstract":"<p >Aqueous formic acid (FA) catalytic dehydrogenation to hydrogen (H<small>₂</small>) is a potential green H<small>₂</small> source under ambient conditions (in air). We show that commonly studied Pd nanoparticles supported on CeO<small>₂</small> provide low H<small>₂</small> selectivity and TOF (10%; 20 h<small>⁻¹</small>) against water (H<small>₂</small>O) 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 H<small>₂</small> 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–CeO<small>₂</small> decreases the H<small>₂</small> selectivity and promotes H<small>₂</small>O formation from the aqueous FA reaction at a temperature as low as 298 K. However, 0.5 PdAg–CeO<small>₂</small> (the atomic ratio of Pd and Ag is 0.5) catalysts provide a higher H<small>₂</small> selectivity (22%) and TOF (178 h<small>⁻¹</small>) when compared to Pd–CeO<small>₂</small> (10%; 20 h<small>⁻¹</small>) at 298 K. Despite the changes in H<small>₂</small> TOF and selectivity, Pd–CeO<small>₂</small> and 0.5 PdAg–CeO<small>₂</small> present the C–H bond activation of formate as a kinetically relevant step for H<small>₂</small> 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–CeO<small>₂</small> compared to Pd–CeO<small>₂</small>, and these electronic modifications of PdAg compared to Pd decrease the apparent activation barrier over 0.5 PdAg–CeO<small>₂</small> (8 ± 4 kJ mol<small>⁻¹</small>) compared to Pd–CeO<small>₂</small> (25 ± 3 kJ mol<small>⁻¹</small>) and increase the H<small>₂</small> TOF/selectivity from the FA reaction. Similar-sized PdAg nanoparticles on CeO<small>₂</small> and TiO<small>₂</small> provide comparable rates of H<small>₂</small> production from the FA reaction independent of the identity of the support due to negligible differences in the support basicity. The mechanistic insights of H<small>₂</small> 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 H<small>₂</small> production.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2809-2821"},"PeriodicalIF":4.4,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913657","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":"Mechanistic insights into the structure of CoCu bimetallic catalysts for CO2 hydrogenation into formate†","authors":"Ruijing Dong, Chao Wu, Truong-Giang Vo, San Hua Lim, Xun Cao, Jia'E Zheng, Xin Xiao, Wei Chu and Yan Liu","doi":"10.1039/D5CY00017C","DOIUrl":"https://doi.org/10.1039/D5CY00017C","url":null,"abstract":"<p >Direct hydrogenation of CO<small>₂</small> to valuable chemicals and fuels is a promising pathway for the valorization of detrimental CO<small>₂</small>. This study delves into the mechanistic insights of CO<small>₂</small> hydrogenation into formate over bimetallic cobalt–copper on silica support catalysts (Co<small>_<em>x</em></small>Cu/SiO<small>₂</small>, <em>x</em>: 0–2). CoCu/SiO<small>₂</small> with a Co and Cu molar ratio of 1 : 1 showed the best activity for CO<small>₂</small> hydrogenation into formate with a maximum yield of 2.3 mmol g<small>⁻¹</small> h<small>⁻¹</small>, and it exhibited 100% selectivity for formate and a turnover frequency (TOF) of 625.2 h<small>⁻¹</small> in NaOH media. The formate formation rate over CoCu/SiO<small>₂</small> was 2.5 times higher than the sum of those over monometallic Cu and Co catalysts. Combining X-ray absorption spectroscopy and transmission electron microscopy results provided insights into the active sites at the interface between cobalt and copper in CO<small>₂</small> hydrogenation into formate. Theoretical calculations clarified and highlighted that the rate determining step was the formation of a carbonate intermediate on the CoCu bimetallic composite during the CO<small>₂</small> conversion into formate. This work provides a theoretical reference for designing an efficient and cost-effective CoCu bimetallic catalyst for producing formate from CO<small>₂</small>.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2867-2877"},"PeriodicalIF":4.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy00017c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913688","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":"An efficient titanomaghemite MOF-derived catalyst for reverse water–gas shift†","authors":"Orxan Sayidov, Luis Garzon-Tovar, Javier Patarroyo, Giiaz Bekmukhamedov, Joseph A. Stewart, Bart D. Vandegehuchte, Nicolas Montroussier, Javier Ruiz-Martinez and Jorge Gascon","doi":"10.1039/D5CY00044K","DOIUrl":"https://doi.org/10.1039/D5CY00044K","url":null,"abstract":"<p >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 CO<small>₂</small> and H<small>₂</small> into valuable products. However, the requirement for high temperatures to achieve significant CO<small>₂</small> 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 CO<small>₂</small> 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 CO<small>₂</small> 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.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2908-2918"},"PeriodicalIF":4.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy00044k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913701","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":"Aerobic oxidative dehydrogenation of amines to nitriles catalyzed by Co@CsETS-10 catalyst†","authors":"Chaojie Zhu, Huili Liu, Yuanfeng Wu, Rong Meng, Lulu Ma, Xiaodong Wang and Cheng Wang","doi":"10.1039/D4CY01391C","DOIUrl":"https://doi.org/10.1039/D4CY01391C","url":null,"abstract":"<p >The C<img>N bond is an important moiety in many different types of significant organic molecules. A facile and green approach for the aerobic oxidative dehydrogenation of primary amines, with <small>CO@CSETS-10</small> as the bifunctional catalyst, to construct nitriles was developed. The electron-rich O in the –Ti–O–Ti– unit of ETS-10 was found to be able to activate the amines by interacting with two H atoms in the –NH<small>₂</small> group in the absence of a base or any additives. Under these facile conditions, a series of nitriles were prepared with up to 100% yield from the direct dehydrogenation of aliphatic, aromatic and heterocyclic amines. Gramscale synthesis also demonstrates the synthetic utility of this strategy.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2670-2676"},"PeriodicalIF":4.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913646","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":"Exploring the o-aryl halogen effects of α-diimine Pd(ii) catalysts on ethylene (co)polymerization†","authors":"Yan Wang ,&nbsp;Shengyu Dai","doi":"10.1039/d5cy00187k","DOIUrl":"10.1039/d5cy00187k","url":null,"abstract":"<div><div>Recently, we delved into the impact of <em>o</em>-aryl halogen effects on nickel α-diimine-catalyzed ethylene polymerization and uncovered some intriguing findings. Building on this work, we now further explore the influence of such substitution on the performance of palladium α-diimine catalysts on both the branching density and catalytic activity in ethylene (co)polymerization. To begin, we synthesized and characterized a range of dibenzhydryl α-diimine palladium catalysts, featuring a butyl backbone adorned with diverse <em>o</em>-aryl halogen substituents. These catalysts exhibited high activity (level of 10⁵ g mol⁻¹ Pd h⁻¹) in ethylene polymerization, yielding highly branched (70–83/1000C) polyethylenes with tunable molecular weights (0.9–44.2 kg mol⁻¹). Significantly, the molecular weight of the resultant polyethylene was critically influenced by the size of the <em>o</em>-aryl halogen substituent, wherein larger halogens contributed to a substantial increase. Interestingly, the effect of halogen substitution on both the branching density and catalytic activity was relatively subtle, likely due to the counteracting forces of steric hindrance and electronic effects. In the copolymerization of ethylene with MA, we observed similar trends with respect to the influence of <em>o</em>-aryl halogen substitution on the molecular weight and branching density. Furthermore, we discovered that bulkier halogens hindered MA incorporation, resulting in copolymers with lower MA insertion ratios, yet they surprisingly boosted the copolymerization activity.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2822-2828"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911802","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":"Achieving high CH4 selectivity in CO2 photoreduction via S-type MoO3/g-C3N4 heterojunction with Pt co-catalyst†","authors":"Tao Wang ,&nbsp;Jiangfeng Lu ,&nbsp;Jinshan Chen ,&nbsp;Chi Wang ,&nbsp;Kai Li ,&nbsp;Yi Mei","doi":"10.1039/d5cy00022j","DOIUrl":"10.1039/d5cy00022j","url":null,"abstract":"<div><div>A Pt-assisted MoO₃/g-C₃N₄ photocatalyst (Pt/5MoO₃/g-C₃N₄) was designed and synthesized for the selective photocatalytic reduction of CO₂ to CH₄. The structure, morphology, and chemical states of the catalyst were systematically analyzed using XRD, XPS, SEM, and TEM. The formation of an S-type heterojunction between MoO₃ and g-C₃N₄ effectively promoted charge separation and migration, enhancing photocatalytic efficiency. Pt, as a co-catalyst, facilitated charge transfer, reduced recombination, and improved CH₄ selectivity. The Pt/5MoO₃/g-C₃N₄ catalyst achieved a CH₄ production rate of 34.9 μmol g⁻¹ h⁻¹, 2.2 times higher than that of g-C₃N₄, with 100% CH₄ selectivity. <em>In situ</em> FTIR and XPS analyses confirmed that Pt⁰ acted as the primary catalytic site, while MoO₃ contributed to CO₂ adsorption and intermediate stabilization. Photoelectrochemical tests further demonstrated the synergistic effect of the S-type heterojunction and Pt co-catalyst, leading to enhanced charge separation and reduced interfacial charge transfer resistance. Moreover, Pt/5MoO₃/g-C₃N₄ exhibited excellent stability and recyclability. This study highlights the effectiveness of S-type heterojunction engineering and Pt co-catalysts in improving photocatalytic CO₂ reduction efficiency and selectivity.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2938-2949"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911801","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":"Catalytic static mixers enable the continuous hydrogenation of cannabidiol and tetrahydrocannabinol†","authors":"Stefano Martinuzzi, Felipe L. N. da Silva, Martin G. Schmid, Kurt Plöschberger, Rodrigo O. M. A. de Souza, Christopher A. Hone and C. Oliver Kappe","doi":"10.1039/D5CY00118H","DOIUrl":"https://doi.org/10.1039/D5CY00118H","url":null,"abstract":"<p >In this work, we investigated the catalytic hydrogenation of cannabidiol (CBD), delta-8-tetrahydrocannabinol (Δ<small>⁸</small>-THC) and delta-9-tetrahydrocannabinol (Δ<small>⁹</small>-THC) by using catalytic static mixer (CSM) technology within a shell-and-tube reactor. Hydrogenation of these compounds is typically reported in batch at milligram quantities and affords a mixture of products. We were interested in developing a robust preparative-scale synthesis of 8,9-dihydrocannabidiol (H2CBD) and tetrahydrocannabidiol (H4CBD) from CBD, and hexahydrocannabinol (HHC) from Δ<small>⁸</small>-THC and Δ<small>⁹</small>-THC. We examined the influence of different noble metal-based CSMs (Pt/alumina, Pd/alumina, Pd-electroplated and Ru/alumina) and different operating conditions on the reaction performance. Pd/alumina CSMs were found to be unsuitable due to the formation of impurities, which partly arose due to double bond isomerization. Pd-electroplated CSMs displayed very low activity. Ru/alumina CSMs were observed to undergo rapid catalyst deactivation. Pt/alumina CSMs displayed high activity and good selectivity, even though signs of deactivation were still present at temperatures higher than 80 °C. We linked this deactivation to a combined influence of internal mass transfer limitation and accumulation of adsorbed molecules on the metal surface. After a careful fine-tuning of the operating conditions over Pt/alumina CSMs, we could obtain H2CBD, H4CBD and HHC in high yield from the corresponding cannabinoid derivative. Kinetic modeling and parameter fitting were successfully performed for the hydrogenation of CBD, which incorporated catalyst deactivation. Catalytic static mixer (CSM) technology is therefore demonstrated to be an industrially viable solution for the hydrogenation of cannabinoid derivatives.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2783-2793"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy00118h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913655","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":"Mechanistic insights into the structure of CoCu bimetallic catalysts for CO2 hydrogenation into formate†","authors":"Ruijing Dong ,&nbsp;Chao Wu ,&nbsp;Truong-Giang Vo ,&nbsp;San Hua Lim ,&nbsp;Xun Cao ,&nbsp;Jia'E Zheng ,&nbsp;Xin Xiao ,&nbsp;Wei Chu ,&nbsp;Yan Liu","doi":"10.1039/d5cy00017c","DOIUrl":"10.1039/d5cy00017c","url":null,"abstract":"<div><div>Direct hydrogenation of CO₂ to valuable chemicals and fuels is a promising pathway for the valorization of detrimental CO₂. This study delves into the mechanistic insights of CO₂ hydrogenation into formate over bimetallic cobalt–copper on silica support catalysts (Co_<em>x</em>Cu/SiO₂, <em>x</em>: 0–2). CoCu/SiO₂ with a Co and Cu molar ratio of 1 : 1 showed the best activity for CO₂ hydrogenation into formate with a maximum yield of 2.3 mmol g⁻¹ h⁻¹, and it exhibited 100% selectivity for formate and a turnover frequency (TOF) of 625.2 h⁻¹ in NaOH media. The formate formation rate over CoCu/SiO₂ was 2.5 times higher than the sum of those over monometallic Cu and Co catalysts. Combining X-ray absorption spectroscopy and transmission electron microscopy results provided insights into the active sites at the interface between cobalt and copper in CO₂ hydrogenation into formate. Theoretical calculations clarified and highlighted that the rate determining step was the formation of a carbonate intermediate on the CoCu bimetallic composite during the CO₂ conversion into formate. This work provides a theoretical reference for designing an efficient and cost-effective CoCu bimetallic catalyst for producing formate from CO₂.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2867-2877"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911882","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":"Lewis acid catalysis of phosphate-modified CaNb2O6 for xylose dehydration to furfural†","authors":"Zijian Wang ,&nbsp;Ryota Osuga ,&nbsp;Koichiro Endo ,&nbsp;Daniele Padovan ,&nbsp;Satoshi Suganuma ,&nbsp;Atsushi Fukuoka ,&nbsp;Hideki Kato ,&nbsp;Kiyotaka Nakajima","doi":"10.1039/d5cy00010f","DOIUrl":"10.1039/d5cy00010f","url":null,"abstract":"<div><div>Phosphate-modified CaNb₂O₆ was prepared using the amorphous metal complex method and tested as a solid catalyst for xylose dehydration to furfural. The orthorhombic CaNb₂O₆ consists of octahedral NbO₆ and square antiprismatic CaO₈, providing unique Lewis and Brønsted acid sites. These active sites exhibited a higher furfural yield compared to orthorhombic Nb₂O₅.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2665-2669"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911808","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}