Catalysis Science & Technology最新文献_第5页

Synthesis of fluorinated biomimetic hydrophobic gas diffusion cathodes for catalytic hydrogen peroxide† 催化过氧化氢用氟化仿生疏水气体扩散阴极的合成

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d4cy01558d

Qi Yu , Zhexiu Liu , Jiefei Li

{"title":"Synthesis of fluorinated biomimetic hydrophobic gas diffusion cathodes for catalytic hydrogen peroxide†","authors":"Qi Yu , Zhexiu Liu , Jiefei Li","doi":"10.1039/d4cy01558d","DOIUrl":"10.1039/d4cy01558d","url":null,"abstract":"<div><div>The electrochemical synthesis of dispersed hydrogen peroxide (H2O2) in acidic solutions is of significant interest for the electro-Fenton (EF) process. However, the development of robust and cost-effective catalysts for the selective two-electron oxygen reduction reaction (2e-ORR) remains a challenge. In this study, inspired by the hydrophobic surface of natural rose petals and mimicking their microstructure, we utilized the high adhesion property of polytetrafluoroethylene (PTFE) to bind highly conductive acetylene carbon black (ACET) onto the surface of graphite felt wire mesh. This formed a low-surface-energy, fluorine-doped hydrophobic cathode with a rough and defect-rich surface, optimized for gas diffusion. The cathode demonstrated an impressive H2O2 generation rate of 46.21 mg h−1 cm−2, meeting the requirements for the EF process. In continuous operation, the electrode exhibited exceptional catalytic performance and stability. This can be attributed to the variations in electron distribution density induced by F/C doping and surface defects, where high-density electron domains attract oxygen molecules at the interfaces of hydrated hydrogen ion (H3O+) clusters, promoting the formation of the *OOH intermediate. The hydrophobicity of the interfaces weakly bind to *OOH, favouring desorption to enhance H2O2 generation and prevent the side reaction of hydrogen evolution on the wetted electrode surface and further reduction of generated H2O2 to H2O. This study provides a new strategy for designing efficient and stable cathodes to guide future catalyst discovery.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2888-2897"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911888","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}

引用次数: 0

Aerobic oxidative dehydrogenation of amines to nitriles catalyzed by Co@CsETS-10 catalyst† Co@CsETS-10催化剂†催化胺氧化脱氢制腈

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d4cy01391c

Chaojie Zhu , Huili Liu , Yuanfeng Wu , Rong Meng , Lulu Ma , Xiaodong Wang , Cheng Wang

引用次数: 0

Selective ketonization of propionic acid on Fe-MFI zeolites: crucial roles of acid strength and density† 丙酸在Fe-MFI沸石上的选择性酮化：酸强度和密度的关键作用

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d5cy00175g

Wenmin Yin , Zijun Yang , Zihao Liu , Chang-jun Liu , Qingfeng Ge , Xinli Zhu

{"title":"Selective ketonization of propionic acid on Fe-MFI zeolites: crucial roles of acid strength and density†","authors":"Wenmin Yin , Zijun Yang , Zihao Liu , Chang-jun Liu , Qingfeng Ge , Xinli Zhu","doi":"10.1039/d5cy00175g","DOIUrl":"10.1039/d5cy00175g","url":null,"abstract":"<div><div>The ketonization reaction offers a convenient approach to remove oxygen and increase the carbon chain length of carboxylic acids without consuming H2. Conventional zeolites with a strong Brønsted acid site (BAS) are very active for ketonization; however, they suffer from low ketone selectivity and fast deactivation owing to the facile secondary and tertiary reactions occurring on the strong BAS. Herein, a series of Fe-MFI zeolites (Si/Fe = 80–180) with a weaker BAS, i.e., Fe–OH–Si, than Al-MFI were prepared, characterized and tested for ketonization of propionic acid at 350 °C and atmospheric pressure. Compared with Al-MFI-180, although Fe-MFI-180 with its weaker BAS strength moderately reduces the activity for propionic acid ketonization (turnover frequency (TOF) of 6.97 and 3.80 min−1, respectively), it significantly reduces the activity of secondary (aldol condensation) and tertiary (aromatics formation) reactions (3-pentanone conversion TOF of 1.85 and 0.33 min−1, respectively), resulting in 3-pentanone as the dominant primary product as well as improved stability. The Fe-MFI zeolites not only showed high TOF (2.00–3.80 min−1) but also improved the selectivity for 3-pentanone and enhanced stability compared to Al-MFI with strong BAS. These results demonstrate a strategy for weakening the strength of BAS of zeolites to reduce the activity of the secondary and tertiary reactions and thereby improve the selectivity and stability of ketonization of carboxylic acids.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2677-2689"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911678","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}

引用次数: 0

Maximizing methanol selectivity over the microporous FeS-1 catalyst via aqueous-phase partial oxidation of methane with H2O2† 用H2O2†对甲烷进行水相部分氧化，使微孔FeS-1催化剂上甲醇选择性最大化

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d4cy01110d

Balashanmugam Venugopal , Niket S. Kaisare , Parasuraman Selvam

{"title":"Maximizing methanol selectivity over the microporous FeS-1 catalyst via aqueous-phase partial oxidation of methane with H2O2†","authors":"Balashanmugam Venugopal , Niket S. Kaisare , Parasuraman Selvam","doi":"10.1039/d4cy01110d","DOIUrl":"10.1039/d4cy01110d","url":null,"abstract":"<div><div>The conversion of methane to methanol faces challenges in liquid-phase systems due to lower methanol selectivity, often resulting in higher formic acid production. Previous studies have shown that iron-exchanged MFI zeolites, i.e., Fe–ZSM-5, tend to favor formic acid over methanol due to the indiscriminate decomposition of the oxidant. To address this, our study aims to identify the active sites responsible for such over-oxidation and develop methods to suppress these sites, thereby enhancing methanol selectivity. Hence, we have utilized hydrothermally synthesized microporous iron silicalite-1 (FeS-1) with an MFI structure and conducted a systematic comparison of its catalytic performance with FeZSM-5 and Fe–ZSM-5, which contain framework and extra-framework iron sites, respectively. This comparison highlights the relationship between active site distribution and methanol selectivity. Additionally, the analysis using DRUV-VIS and EPR spectroscopic techniques suggests that the yield of methanol and formic acid is found to vary monotonically with the amount of iron in framework and extra-framework sites, respectively, in the zeolitic matrix of fresh FeS-1. Therefore, selectively removing extra-framework iron and/or partially dissolving framework iron in MFI-based catalysts results in a significant reduction in formic acid yield, with only a small effect on methanol yield. Interestingly, in contrast to Fe–ZSM-5, both FeZSM-5 and FeS-1 maintain a significant amount of framework iron in the framework sites which results in a prominent enhancement in methanol selectivity (65%). Further investigation into FeS-1, FeZSM-5, and Fe–ZSM-5 underscored the importance of framework Si–O–Fe linkages in enhancing methanol selectivity.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2690-2705"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911803","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}

引用次数: 0

Catalytic static mixers enable the continuous hydrogenation of cannabidiol and tetrahydrocannabinol† 催化静态混合器使大麻二酚和四氢大麻酚†连续加氢

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d5cy00118h

Stefano Martinuzzi , Felipe L. N. da Silva , Martin G. Schmid , Kurt Plöschberger , Rodrigo O. M. A. de Souza , Christopher A. Hone , C. Oliver Kappe

{"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 , C. Oliver Kappe","doi":"10.1039/d5cy00118h","DOIUrl":"10.1039/d5cy00118h","url":null,"abstract":"<div><div>In this work, we investigated the catalytic hydrogenation of cannabidiol (CBD), delta-8-tetrahydrocannabinol (Δ8-THC) and delta-9-tetrahydrocannabinol (Δ9-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 Δ8-THC and Δ9-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.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2783-2793"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911804","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}

引用次数: 0

PCCP ligands with a semi-rigid backbone for chromium-catalyzed selective ethylene tri-/tetramerization† 具有半刚性骨架的PCCP配体用于铬催化选择性乙烯三/四聚体化†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d5cy00152h

Xing Zhao , Haojie Xie , Jing Zuo , Jihe Wang , Mei-Xin Zhao , Jun Zhang

{"title":"PCCP ligands with a semi-rigid backbone for chromium-catalyzed selective ethylene tri-/tetramerization†","authors":"Xing Zhao , Haojie Xie , Jing Zuo , Jihe Wang , Mei-Xin Zhao , Jun Zhang","doi":"10.1039/d5cy00152h","DOIUrl":"10.1039/d5cy00152h","url":null,"abstract":"<div><div>A series of semi-rigid PCCP ligands (R′′PhPC(CRR′)CH2PPhR′′′) containing a rigid olefinic moiety and a flexible methylene moiety within the ligand backbone was prepared, and their application to chromium-catalyzed selective ethylene tri-/tetramerization has been explored. These PCCP ligands could be easily modified at both the olefinic moiety and two P-substituents. Among the ligands bearing two PPh2 groups, L3, with a phenyl substituent at the olefinic site of the ligand backbone, in combination with chromium exhibited the highest activity (644 kg g−1 Cr h−1) and the highest 1-C6 selectivity, as well as the highest combined 1-C6/1-C8 selectivity at 60 °C. Complex , based on L3, also exhibited high thermal stability, giving a high activity of 1259 kg g−1 Cr h−1 at 100 °C. Complex , containing L4 with a PPhCy group adjacent to the rigid olefinic site, showed improved activity compared to its PPh2 counterpart . At 80 °C, complex exhibited a high combined 1-C6/1-C8 selectivity of 91.0 wt%, with almost no PE formation. The addition of hydrogen was shown to be capable of significantly improving the catalytic performance. In the presence of hydrogen, the catalytic activity increased 2.3–3.2-fold for and , giving a very high activity of up to 2160 kg g−1 Cr h−1 with significantly reduced PE formation (0.2 wt%).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2713-2721"},"PeriodicalIF":4.4,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911883","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}

引用次数: 0

Identification of hydrogen-evolving active sites by chemical probes 化学探针鉴定析氢活性位点

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-17 DOI: 10.1039/d5cy00054h

Tian Qiu , Mingpu Wu , Hanyue Jia , Xinlong Zhao , Liwen Xing

引用次数: 0

Modulating *CO coverage via the pyrrolic-N content on carbon for enhanced electrocatalytic CO2 reduction to CO† 通过碳上的吡咯- n含量调节*CO覆盖，以增强电催化CO2还原为CO†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-16 DOI: 10.1039/D5CY00100E

Fang Zhao, Yingzheng Zhang, Caiyue Wang, Jiatao Zhang and Di Zhao

{"title":"Modulating *CO coverage via the pyrrolic-N content on carbon for enhanced electrocatalytic CO2 reduction to CO†","authors":"Fang Zhao, Yingzheng Zhang, Caiyue Wang, Jiatao Zhang and Di Zhao","doi":"10.1039/D5CY00100E","DOIUrl":"https://doi.org/10.1039/D5CY00100E","url":null,"abstract":"The electrocatalytic CO2 reduction reaction (eCO2RR) is a new energy technology that shows a feasible way to achieve carbon neutrality and to produce valuable fuels and feedstocks with effective electrocatalysts. Nitrogen-doped carbon (NC) materials have become the most promising carbon-based electrocatalysts to produce CO and potential metal carriers to produce multi-carbon products due to their low cost, high activity, and ability to enhance metal–carrier interactions. However, aiming at high selectivity of CO, it is important to optimize the competing coverage of *CO and *H on the NC working electrocatalyst surface. Here, for the first time, we controllably adjusted the pyrrolic-N content on NC via a simple strategy of pyrrolic-N-abundant phthalocyanine-assisted pyrolysis of a common MOF precursor (ZIF-8), which then modulated the *CO and *H coverage for enhanced electrocatalytic CO2 reduction to CO with an FECO value of above 92% at −0.6 V vs. RHE. Mechanistic studies showed that the high content of pyrrolic-N of Pr-a-NC induced the surface coverage of *CO to be much higher than that of the control samples. Meanwhile, under the conditions of high *CO coverage, adsorbed *CO intermediates combined with the active *H generated the high-coverage intermediate *COH, which is one of the most common intermediates to generate multi-carbon products. So, this work not only provides an effective strategy for the future rational design of carbon electrocatalysts to generate CO, but also opens an avenue to engineer carbon–nitrogen coordination substrate-loaded metal electrocatalysts for the production of multi-carbon products from the eCO2RR.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2898-2907"},"PeriodicalIF":4.4,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913700","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}

引用次数: 0

Lewis acid catalysis of phosphate-modified CaNb2O6 for xylose dehydration to furfural† 磷酸修饰CaNb2O6的Lewis酸催化木糖脱水制糠醛†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-12 DOI: 10.1039/D5CY00010F

Zijian Wang, Ryota Osuga, Koichiro Endo, Daniele Padovan, Satoshi Suganuma, Atsushi Fukuoka, Hideki Kato and Kiyotaka Nakajima

引用次数: 0

Identification of hydrogen-evolving active sites by chemical probes 化学探针鉴定析氢活性位点

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-03-12 DOI: 10.1039/D5CY00054H

Tian Qiu, Mingpu Wu, Hanyue Jia, Xinlong Zhao and Liwen Xing

引用次数: 0