Zinnia Arora , Vasile I. Pârvulescu , Karine Philippot , Jérôme Durand , Maryse Gouygou
{"title":"Immobilization of a chiral rhodium catalyst on carbon nanotubes via non-covalent interaction for heterogeneous asymmetric hydrogenation†","authors":"Zinnia Arora , Vasile I. Pârvulescu , Karine Philippot , Jérôme Durand , Maryse Gouygou","doi":"10.1039/d4cy01457j","DOIUrl":"10.1039/d4cy01457j","url":null,"abstract":"<div><div>A new chiral rhodium complex containing a diphosphine ligand with a pyrene tag, Rh-(2<em>S</em>,4<em>S</em>)-PPM-pyrene, was synthesized. Its immobilization was achieved through non-covalent π–π stacking interaction between pyrene units of the ligand and multiwalled carbon nanotubes, leading to a hybrid material that was characterized by a set of analysis techniques. Strong adsorption of the complex onto the CNTs enabled an asymmetric hydrogenation of dimethyl itaconate under heterogeneous conditions. This hybrid catalyst showed reduced activity and enantioselectivity compared to its free complex but exhibited good stability for recycling.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3075-3081"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090854","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}
Eszter Fazekas , Carole A. Morrison , Jennifer A. Garden
{"title":"Cationic Zr catalysts for the sequential polymerisation of alkenes and cyclic oxygenated monomers†","authors":"Eszter Fazekas , Carole A. Morrison , Jennifer A. Garden","doi":"10.1039/d5cy00170f","DOIUrl":"10.1039/d5cy00170f","url":null,"abstract":"<div><div>Block copolymers (BCPs) featuring an apolar polyalkene and a polar polyester segment are attractive materials that can be synthesised through one-pot procedures with rare-earth metal catalysts, including those based on Sc. However, examples remain limited to the copolymerisation of conjugated olefins, such as isoprene and myrcene, with cyclic esters. While Zr is diagonally related to Sc in the periodic table, and Zr-based catalysts excel at non-conjugated olefin polymerisations, cationic Zr complexes remain unreported for apolar polyolefin/polar polyester BCPs. Here, we show that cationic Zr amine bisphenolate and zirconocene complexes are effective catalysts for the sequential polymerisation of various alkene and cyclic ester/ether monomers, yet deliver two separate homopolymers instead of copolymers. Mechanistic studies combined with DFT calculations suggest that the alkene monomer is polymerised <em>via</em> a coordination–insertion pathway, whereas ε-caprolactone polymerisation follows a cationic ring-opening mechanism under these conditions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3046-3052"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090848","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":"Bio-derived butadiene from cross-metathesis over silanol rich WO3 catalysts obtained from copper phyllosilicate†","authors":"Kanokwan Wengwirat , Kittisak Choojun , Pratya Promchana , Wanwisa Limphirat , Tawan Sooknoi","doi":"10.1039/d4cy01283f","DOIUrl":"10.1039/d4cy01283f","url":null,"abstract":"<div><div>Bio-butadiene can be produced from cross-metathesis of bioethanol-derived acetylene/ethylene over supported WO<sub>3</sub> on silanol-rich silica prepared with Cu-leached copper phyllosilicate (CuPS). 20CuPS and 30CuPS were preliminarily reduced before Cu-leaching under an acidic solution (1 M HCl). Compared with fumed SiO<sub>2</sub>, <sup>29</sup>Si CPMAS NMR spectroscopy showed an increase in surface silanols, particularly the isolated silanols (<em>Q</em><sub>3</sub>), from removing Cu<sup>2+</sup> octahedral sites (Cu<sup>2+</sup>(OSi)<sub>6</sub>) encapsulated within tetrahedral silica layers of CuPS. The surface silanols in fumed SiO<sub>2</sub>, 20CuPS-Le, and 30CuPS-Le adequately accommodate single-site and polymeric WO<sub>3</sub> species, leading to a similar 1,3-butadiene production rate (∼4.7 mmol h<sup>−1</sup> g<sub>cat</sub>) at 5 wt% loading. Only 30CuPS-Le sufficiently provides the exposed silanols to disperse 8 wt% WO<sub>3</sub> loading without bulk WO<sub>3</sub> formation. The cross-metathesis activity depends on the relative amounts of exposed silanols. Accordingly, the steady 1,3-butadiene production was obtained in the order of 8WO<sub>3</sub>/30CuPS-Le (6.3 mmol h<sup>−1</sup> g<sub>cat</sub>) > 8WO<sub>3</sub>/20CuPS-Le (5.1 mmol h<sup>−1</sup> g<sub>cat</sub>) > 8WO<sub>3</sub>/SiO<sub>2</sub> (2.5 mmol h<sup>−1</sup> g<sub>cat</sub>).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3009-3021"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090845","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}
Filippo Franceschini , Catarina Fernandes , Koen Schouteden , Jon Ustarroz , Jean Pierre Locquet , Irene Taurino
{"title":"Tailoring the glucose oxidation activity of anodized copper thin films†","authors":"Filippo Franceschini , Catarina Fernandes , Koen Schouteden , Jon Ustarroz , Jean Pierre Locquet , Irene Taurino","doi":"10.1039/d4cy01248h","DOIUrl":"10.1039/d4cy01248h","url":null,"abstract":"<div><div>Glucose oxidation is a fundamental reaction in biosensing and energy conversion, and anodized copper electrodes have emerged as promising catalysts for its enhancement. This paper systematically investigates the link between anodization parameters and glucose oxidation on thin copper films, unraveling crucial insights into their optimization. By careful control of the anodization parameters, distinct species can be favoured, such as Cu<sub>2</sub>O, Cu(OH)<sub>2</sub>, and CuO, with varying catalytic activities. Applying a polarization in 1 M KOH at 0 V (<em>vs.</em> Ag|AgCl) results in the formation of a highly active surface CuO layer, which delivers significant performance improvements compared to the bare copper electrode. Namely, a 55% sensitivity gain in the 0.1–0.5 mM range, and a remarkable 73% gain in the 0.75–2 mM range. Furthermore, the manufactured electrodes display an extremely low limit of detection – only 0.004 mM. Such an exceptional result can be ascribed to the scalable and reproducible manufacturing done directly on cleanroom-compatible platforms. These insights not only clarify the effect of thin copper film anodization on glucose oxidation, but also chart a practical path towards improving the real-world efficiency of copper-based integrated systems for biosensing and energy conversion.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3022-3035"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090846","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}
Yue He , Ruiying Li , Fei Wang , Xiaodong Wen , Zhenhua Zhang
{"title":"Insight into the key factors governing the catalytic activity and stability of Ni/ZnO catalysts in CO2 hydrogenation†","authors":"Yue He , Ruiying Li , Fei Wang , Xiaodong Wen , Zhenhua Zhang","doi":"10.1039/d4cy01258e","DOIUrl":"10.1039/d4cy01258e","url":null,"abstract":"<div><div>The requirements for industrial catalysts are not only high efficiency but also excellent stability. Therefore, understanding the crucial factors governing the catalytic performance and long-term stability is fundamental yet challenging due to the structural complexity of heterogeneous catalysts. Herein, ZnO-supported Ni catalysts with different ZnO morphologies were used for CO<sub>2</sub> hydrogenation. The results revealed that catalytic activity and stability were strongly related to weak basic sites and Ni–ZnO interactions, respectively. The Ni/r-ZnO (nanorod) catalyst, which possessed a higher amount of weak basic sites responsible for the adsorption and activation of CO<sub>2</sub>, exhibited better catalytic activity. Nonetheless, r-ZnO, predominantly exposing nonpolar facets, was not conducive to Ni–r-ZnO interactions, which led to the agglomeration of supported Ni species during CO<sub>2</sub> hydrogenation and was the primary cause of the deactivation of the Ni/r-ZnO catalyst. Meanwhile, carbon deposition could be another minor factor affecting catalytic stability. Kinetic and <em>in situ</em> DRIFTS spectroscopy results demonstrated that the reaction proceeded through an H<sub>2</sub>-assisted associated mechanism, with the adsorption and activation of CO<sub>2</sub> as the rate-determining step. These results not only deepen the fundamental understanding of Ni-/ZnO-catalyzed CO<sub>2</sub> hydrogenation but also provide potential insights for developing highly active and stable catalysts for CO<sub>2</sub> hydrogenation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3053-3063"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090852","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}
Ying Ma , Mengyuan Huang , Ziyi Liu , Haowei Wang , Dongqi Wang , An-Hui Lu
{"title":"Computational study of tailorable metal–support interactions in PtSn/γ-Al2O3via surface hydroxylation†","authors":"Ying Ma , Mengyuan Huang , Ziyi Liu , Haowei Wang , Dongqi Wang , An-Hui Lu","doi":"10.1039/d5cy00226e","DOIUrl":"10.1039/d5cy00226e","url":null,"abstract":"<div><div>Metal–support interactions (MSIs) are fundamental to the design and optimization of heterogeneous catalysts. In PtSn/γ-Al<sub>2</sub>O<sub>3</sub> catalysts, the tunable surface properties of γ-Al<sub>2</sub>O<sub>3</sub> provide opportunities to tailor MSIs for optimal catalytic performance, and calls for extensive study on the influence of surface hydroxylation of γ-Al<sub>2</sub>O<sub>3</sub> on MSIs. Herein, the influence of the surface hydroxylation mode and hydroxyl coverage on MSIs was investigated, and the results show that terminal hydroxyl groups can bind with the PtSn cluster to assist the anchoring of the cluster, while bridging hydroxyl groups repel the cluster from accessing the surface. A positive correlation between the Pt 5d band center and the support-to-metal charge transfer was established, and the charge of the supported metal cluster was proposed to be used as a descriptor to evaluate its reactivity in a catalytic reaction. This study provides insight into the rational design of tailored catalysts supported on hydroxylated surfaces.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3064-3074"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090853","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}
Wiktoria Dubiel , Anna Furgał , Andrzej Kowalczyk , Małgorzata Rutkowska , Włodzimierz Mozgawa , Irena Brunarska , Stanislaw Dzwigaj , Lucjan Chmielarz
{"title":"Influence of titanium species type in siliceous beta zeolites on their catalytic activity in the process of selective diphenyl sulphide oxidation with hydrogen peroxide","authors":"Wiktoria Dubiel , Anna Furgał , Andrzej Kowalczyk , Małgorzata Rutkowska , Włodzimierz Mozgawa , Irena Brunarska , Stanislaw Dzwigaj , Lucjan Chmielarz","doi":"10.1039/d5cy00009b","DOIUrl":"10.1039/d5cy00009b","url":null,"abstract":"<div><div>Siliceous beta zeolite containing titanium was evaluated as a catalyst for the selective oxidation of diphenyl sulphide (Ph<sub>2</sub>S) using hydrogen peroxide as the oxidising agent. Various titanium content was introduced into the SiBEA materials with vacant T-atom sites by post-synthetic methods, such as chemical vapour deposition and wet impregnation. Materials with diverse titanium loading were analysed in terms of their chemical composition using inductively coupled plasma optical emission spectrometry (ICP-OES), crystalline structure using X-ray diffraction (XRD), textural properties by low-temperature N<sub>2</sub> sorption and surface acidity by ammonia temperature-programmed desorption (NH<sub>3</sub>-TPD). The form and aggregation of catalytically active species were examined by UV-vis diffuse reflectance spectroscopy (UV-vis DRS). Titanium was incorporated into materials mainly in the form of tetrahedrally coordinated framework cations, except for the Ti<sub><em>x</em></sub>SiBEA-I samples, where anatase crystallites were identified. All the samples were characterised by high catalytic activity in the studied process. The influence of Ti(<span>iv</span>) framework species on Ph<sub>2</sub>S oxidation and selectivity towards diphenyl sulphone (Ph<sub>2</sub>SO<sub>2</sub>) were analysed and discussed.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3171-3182"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090857","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":"Optimization of nickel-based catalysts for hydrogenolysis of light paraffins using machine learning†","authors":"Mohamd Sebaa , Kirill Motaev , Maxim Molokeev , Nikita Azarapin , Alina Petrishena , Alexey Matigorov , Andrey Zagoruiko , Andrey Elyshev","doi":"10.1039/d5cy00024f","DOIUrl":"10.1039/d5cy00024f","url":null,"abstract":"<div><div>In this study, optimization of nickel-based catalysts for the hydrogenolysis of hydrocarbons using machine learning methods. A comprehensive dataset comprising 419 experiments was compiled on the basis of literature data, focusing on key parameters such as the catalyst composition, support type, surface area, reduction temperature, and reaction conditions. We employed a random forest model to predict the reaction rates, achieving a mean absolute error of 0.37 and an <em>R</em><sup>2</sup> value of 0.76. Two Ni/Al<sub>2</sub>O<sub>3</sub> and Ni/TiO<sub>2</sub> catalysts were synthesized following the model recommendations on the optimal synthesis parameters for Ni-based catalysts. Experiments demonstrated excellent agreement between predicted and observed reaction rates and, moreover, these catalysts appeared to be more active than all other Ni-based catalysts, considered at the model learning. This means that such a model is capable not only of interpolating existing information, but also of creating improved catalysts to some extent exceeding the current level of scientific achievements, though still remaining strictly within the existing knowledge set. The proposed approach may be helpful to researchers when they start working with a reaction or a catalyst which is unfamiliar to them. Another possible research application of the proposed approach is classification of catalysts, including indication of potentially promising new approaches.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3226-3237"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090862","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}
Yahaya Muhammad Abdullahi , Sani Abdullahi Zarewa , Aniz Chennampilly Ummer , Yahya Gambo , Niladri Maity , Ziyauddin S. Qureshi , Abdullah Bafaqeer , Nagendra Kulal , Bassam Elali
{"title":"ZnxCeO2 nanorod as active catalyst for CO2 conversion into carbamates†","authors":"Yahaya Muhammad Abdullahi , Sani Abdullahi Zarewa , Aniz Chennampilly Ummer , Yahya Gambo , Niladri Maity , Ziyauddin S. Qureshi , Abdullah Bafaqeer , Nagendra Kulal , Bassam Elali","doi":"10.1039/d4cy01438c","DOIUrl":"10.1039/d4cy01438c","url":null,"abstract":"<div><div>Carbon dioxide, as a non-toxic and commonly available gas, can be transformed into useful chemicals such as carbonates, carbamates, urethanes, substituted ureas, methanol, and hydrocarbons. We have found the cycloaddition of CO<sub>2</sub> and ethanolamine is a significant method for producing cyclic carbamates. The main aim of this study is to develop a stable and efficient catalyst that gives excellent selectivity for the direct synthesis of 2-oxazolidinone from CO<sub>2</sub> and ethanolamine. The CeO<sub>2</sub> nanorods (CeO<sub>2</sub> r) comprise a higher percentage of oxygen vacancies than the cubic and bulk forms of CeO<sub>2</sub>. The synthesized Zn<sub>0.1</sub>CeO<sub>2</sub> catalyst further improved the formation of oxygen vacancy sites and the surface reducibility of CeO<sub>2</sub> from Ce<sup>4+</sup> to Ce<sup>3+</sup> thereby facilitating the activation of CO<sub>2</sub> and amines. <em>In situ</em> FTIR has been used to examine the adsorption of ethanolamine and CO<sub>2</sub> on the catalyst as a function of temperature. Under the optimum reaction conditions, excellent conversion of ethanolamine (93.5%) and outstanding selectivity towards 2-oxazolidinone (98%) were achieved.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3082-3091"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090855","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}
Jiacheng Ji , Honglin Zhuang , Ling Zhou , Yi Zhang
{"title":"Effective conversion of glucose to 1,3-propanediol and ethanol via multifunctional iron foam catalysts†","authors":"Jiacheng Ji , Honglin Zhuang , Ling Zhou , Yi Zhang","doi":"10.1039/d5cy00041f","DOIUrl":"10.1039/d5cy00041f","url":null,"abstract":"<div><div>Hydrogenolysis of biomass-derived glucose to 1,3-propanediol (1,3-PDO) and ethanol (EtOH) is an important process for the sustainable production of value-added chemicals. In this work, hydrogenolysis of glucose to 1,3-PDO and EtOH was investigated over multifunctional iron foam (FF) catalysts <em>via</em> a continuous-flow fixed-bed reactor. The CoW/FF catalyst displays the highest 1,3-PDO selectivity (55.9%), and the Zr/CoW/FF catalyst exhibits the highest EtOH selectivity (48.0%) over a 20 h reaction. A range of characterization methods, including HR-TEM, XPS, NH<sub>3</sub>-TPD, Py-FTIR, and <em>operando</em> GLY-DRIFTS, were applied to reveal the nature of converting glucose into 1,3-PDO and EtOH. It is found that the interaction between CoWO<sub>4</sub> and Fe is beneficial to forming BAS and promoting glucose hydrogenolysis to 1,3-PDO. Besides, the added Zr promoter tunes this interaction and leads to a higher content of W<sup>5+</sup> LAS, which contributes to high EtOH selectivity on Zr/CoW/FF catalysts with the synergistic effects of Fe hydrogenation active sites.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3183-3194"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090858","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}