Catalysis Science & Technology最新文献

{"title":"Modelling hydrogen peroxide adsorption on cerium dioxide: the effect of surface strain†","authors":"Sidra Munir ,&nbsp;Thomas Smith ,&nbsp;Khoa Minh Ta ,&nbsp;Lisa J. Gillie ,&nbsp;David J. Cooke ,&nbsp;Marco Molinari","doi":"10.1039/d5cy00589b","DOIUrl":"10.1039/d5cy00589b","url":null,"abstract":"<div><div>Ceria nanoparticles are nanozymes that can serve as important biomedical tools mimicking enzymes. The main issue with using metal oxide nanoparticles is the control of their surface speciation, which ultimately affects catalytic activity. Herein, we employ density functional theory calculations to unravel the adsorption of hydrogen peroxide and its dissociation products (hydroxyl, peroxide, superoxide and hydroperoxide) and the effect of strain on the absorption. Indeed, all nanoparticles are affected by intrinsic strain. We found that molecular H₂O₂ is unstable on the {100} surface at all strains, whereas hydroxyl radicals can be stabilized on reduced surfaces because of the electron transfer from surface Ce³⁺. Upon dissociation, the peroxide ion is not always the most stable adsorbed species on all surfaces, whether strained, unstrained, stoichiometric or reduced, and superoxide species may also occur under tensile strains. Our thermodynamic methodology connects atomic-level findings to particle morphology in relation to environmental factors such as temperature and vapor pressure. Regardless of the strain applied, the adsorption of hydrogen peroxide and its dissociation products fails to access nanoparticle shapes other than octahedral, which is not ideal for peroxidase activity considering the characteristics of the {111} surface which is less effective in anchoring the adsorbed species.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 5150-5166"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909488","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":"Solid micellar catalysts: exploring the stability of Ru(III) single-sites in amorphous silica†","authors":"Sara Santos ,&nbsp;Vitaly V. Ordomsky ,&nbsp;Frederik Tielens ,&nbsp;Mark Saeys","doi":"10.1039/d5cy00449g","DOIUrl":"10.1039/d5cy00449g","url":null,"abstract":"<div><div>Amorphous silica plays an important role as a catalyst support due to its structural and chemical properties, though its complexity poses challenges identifying and characterizing active sites. Computational models capturing the heterogeneity of amorphous silica-supported materials are crucial in understanding these systems and their catalytic behavior. Ru^(III)@MCM-41, the first example of a solid micellar catalyst, consists of Ru^(III) sites and silanoxo basic sites incorporated into the walls of amorphous MCM-41 and stabilized by quaternary ammonium surfactant molecules (CTA⁺) in the pores. To link structure and activity, computational models were developed to elucidate the nature and activity of these Ru^(III) single-sites. The amorphous silica framework offers a wide heterogeneity of sites where ruthenium can be located. To understand how site distribution affects the activity and stability of Ru^(III) sites, a periodic model of an amorphous hydroxylated silica surface was used. The model includes 27 potential Si-to-Ru^(III) exchange and multiple Ru^(III) grafting sites, from bulk-like Si(O)₄ to single and geminal silanol groups (Si(O)₃(OH) and Si(O)₂(OH)₂, respectively). The coordination environment, ring strain, and the hydrogen bonding interactions influence the stability and activity of the Ru^(III) single-sites. Incorporating Ru^(III) in amorphous silica is highly favorable, with Si-to-Ru^(III) exchange energies up to −248 kJ mol⁻¹ in the presence of the CTA⁺ surfactant. Replacing the surfactant counterion with H⁺ results in a less favorable incorporation of Ru^(III), with exchange energies up to −118 kJ mol⁻¹, highlighting the surfactant's stabilizing role. Grafting of Ru^(III) onto silanoxo groups is also favorable in the presence of surfactant. However, space restrictions and the limited availability of neighboring silanol groups at an optimal distance made the formation of Ru^(III)(O)₄ challenging, instead favoring less stable Ru^(III)(O)₂(OH)₂ species. Our calculations suggest that Ru^(III) is predominantly present as Ru^(III)(O)₄(H₂O)₂ or Ru^(III)(O)₃(OH)(H₂O)₂ at sites within large Si-membered rings near hydroxylated regions. Various Ru^(III)-hydride species were calculated, with formation energies ranging from +21 to −113 kJ mol⁻¹. Interestingly, some highly stable Ru^(III) sites also show favorable hydride formation, making them both synthesizable and active.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 4988-5003"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909468","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":"Electrooxidative C–H/O–H bond coupling via Ru catalysis: access to phthalides and naphtho[1,8-bc]furans†","authors":"Nilam Patil ,&nbsp;Ajay Dhapate ,&nbsp;Twinkle Bharadwaj ,&nbsp;Bhalchandra M. Bhanage","doi":"10.1039/d5cy00713e","DOIUrl":"10.1039/d5cy00713e","url":null,"abstract":"<div><div>We hereby report ruthenium-catalyzed electrooxidative coupling of acrylates with benzoic acids and naphthol for the synthesis of phthalide and naphthofuran derivatives. The process is particularly effective for activating weakly coordinating O–H bonds using ruthenium catalysts. This method is workable and well-organized for the activation of carbon–hydrogen and oxygen–hydrogen bonds, demonstrating moderate to good yields across a diverse set of over 26 readily available substrates. The method proceeds under oxidant- and additive-free conditions, significantly reducing the reaction time while retaining a broad substrate scope. Our approach provides a green and user-friendly method for synthesizing phthalides and naphthofurans <em>via</em> weak coordination O–H and C–H bond activation, leveraging electricity as an oxidant.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 4981-4987"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909467","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":"Coordinatively unsaturated Lewis acidic aluminum sites in zeolites for direct partial oxidation of methane†","authors":"Kazumasa Murata ,&nbsp;Natnicha Yotpanya ,&nbsp;Masato Sawada ,&nbsp;Nao Kondo ,&nbsp;Masakazu Koike ,&nbsp;Saiko Arai ,&nbsp;Ryo Manabe ,&nbsp;Saburo Hosokawa ,&nbsp;Takashi Yumura ,&nbsp;Junko N. Kondo ,&nbsp;Toshiyuki Yokoi","doi":"10.1039/d5cy00450k","DOIUrl":"10.1039/d5cy00450k","url":null,"abstract":"<div><div>In this study, we show that transition metal-free aluminosilicate-type zeolites (Al-zeolites) are active and highly selective for partial oxidation of CH₄ (POM) to CO at temperatures ranging from 600 to 800 °C by using O₂ as an oxidizing agent. Although the POM activities of Al-zeolites depend on their topologies, CO selectivity was high at around 80% even at CH₄ conversions above 20%, regardless of the topologies. CHA and Beta zeolites exhibit relatively high and stable catalytic performance over a reaction time of 6 h, while MFI zeolite was highly active at the initial period and then quickly deactivated with prolonged duration. MOR and FAU zeolites show low POM activity. The acid sites in Al-zeolites after the POM reaction were analyzed by infrared (IR) spectroscopy using CO as a molecular probe. The results illustrate that the Al-zeolites, with a greater abundance of coordinatively unsaturated Lewis acidic Al, result in higher POM activity. A mechanistic study demonstrates that the C−H bond was activated by a strong LAS derived from a coordinatively unsaturated Al atom <em>via</em> a four-centered transition state. Computational activation energy was revealed as 32 kcal mol⁻¹, being close to the experimental value (34 kcal mol⁻¹).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 5025-5037"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909471","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":"A quantitative analysis of the impact of SO2 on the activity of Cu-CHA catalysts for NH3-SCR†","authors":"Reza K. Abasabadi ,&nbsp;Ton V. W. Janssens ,&nbsp;Gloria Berlier","doi":"10.1039/d5cy00188a","DOIUrl":"10.1039/d5cy00188a","url":null,"abstract":"<div><div>Copper-exchanged chabazite (Cu-CHA) catalysts for selective catalytic reduction of NOx by ammonia (NH₃-SCR) in diesel exhausts deactivate in the presence of SO₂ at temperatures below 300 °C. In this article, we develop a descriptive model to evaluate a catalyst deactivation with respect to SO₂ tolerance, in terms of a disappearance of active catalyst. This leads to the SO₂ sensitivity, which can be interpreted as the loss of catalyst per mol SO₂ taken up by the catalyst, as a measure for the deactivation for that catalyst material. We have determined the SO₂ sensitivity for three Cu-CHA catalysts, namely 1.6 and 3.2 wt% Cu with a Si/Al ratio of 6.7 and 3.2 wt% Cu with a Si/Al ratio of 15. The 3.2 wt% Cu (Si/Al = 6.7) catalyst shows a lower SO₂ sensitivity at 200 °C, as compared to the other two catalysts. For all three catalysts, the SO₂ sensitivity is highest at low SO₂ uptake, and decreases linearly with the further uptake of SO₂. This means that small amounts of SO₂ cause a relatively strong deactivation, indicating that the deactivation is a consequence of a reaction of SO₂ with the active Cu.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 5066-5075"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909481","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":"Computational insights into hydrogen adsorption energies on medium-entropy oxides","authors":"Haohong Song ,&nbsp;Vassiliki-Alexandra Glezakou ,&nbsp;Zili Wu ,&nbsp;De-En Jiang","doi":"10.1039/d5cy00583c","DOIUrl":"10.1039/d5cy00583c","url":null,"abstract":"<div><div>High entropy oxides (HEOs) have emerged as promising catalysts for several important chemical transformations including alkane activation. Hydrogen adsorption energy (HAE) has been used as a key descriptor for many reactions including methane C–H activation and hydrogen evolution reactions. Hence, understanding the relationship between HAEs and the surface chemistry of HEO surfaces could lay the foundation for meaningful correlations among methane C–H activation, HAE, and the complex, local environment of HEO surfaces. Here, we used a medium-entropy oxide as a prototypical system – Mg_0.25Ni_0.25Cu_0.25Zn_0.25O with a rock-salt structure – to interrogate these relationships. We sampled 2000 different surfaces of its (100) plane and calculated the HAEs at randomly chosen surface O sites using density functional theory (DFT). Our analysis of the 2000 data points reveals that the HAEs at the surface O sites are significantly influenced by the local environment around the adsorption sites, particularly the nature of the metal atom directly below the surface O site where H adsorbs. After comparing several popular graph-neural-network-based machine learning models, we found that the DimeNet++ model performed best achieving satisfactory accuracy in predicting HAEs for both Mg_0.25Ni_0.25Cu_0.25Zn_0.25O and slightly varied compositions. Our work underscores the promise of such models and the need for further refinement to address the complexity of HEOs.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 4937-4944"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909458","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":"Crude levulinic acid conversion to valeric acid over La–TiO2 supported Ni catalysts: an environmentally friendly route to fuel additive synthesis†","authors":"Ganga Bhavani Peddakasu ,&nbsp;Sasikumar Boggala ,&nbsp;Hari Padmasri Aytam ,&nbsp;Kalpana Manda ,&nbsp;Shirisha Varimalla ,&nbsp;Ashok Jangam ,&nbsp;Satyapaul A. Singh ,&nbsp;Venugopal Akula","doi":"10.1039/d5cy00578g","DOIUrl":"10.1039/d5cy00578g","url":null,"abstract":"<div><div>Transformation of biomass into energy or other valuable products is a sustainable route. This study encompasses the single step synthesis of valeric acid by hydrodeoxygenation of biomass derived crude levulinic acid using formic acid as a hydrogen source over different loadings of lanthanum modified TiO₂-supported Ni catalysts. Modification with La resulted in a comparatively low ratio of acid sites on the catalyst surface. Formic acid adsorbed IR studies revealed that 10 wt%Ni/3 wt%La–TiO₂ displayed a high proportion of surface basic sites, which were responsible for the high rate of valeric acid (∼56 × 10⁻⁸ mol g_cat⁻¹ s⁻¹) with a stable activity up to 48 h. Pyridine and acetone adsorbed IR results indicated an increase in the La loading from 1 to 5 wt% on TiO₂ and a decrease in the Lewis and Brønsted acidic sites and carbonyl interactions with the catalyst, respectively. Considering the probe (HCOOH, acetone, pyridine) adsorbed IR spectroscopic results, levulinic acid conversion and the product distribution, a plausible surface reaction mechanism has been proposed.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 4971-4980"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909466","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":"Rapid synthesis of dimethyl carbonate at room temperature catalyzed by a novel solid base 3-amino-1,2,4-triazole calcium†","authors":"Peixue Wang ,&nbsp;Shimin Liu ,&nbsp;Delong Han ,&nbsp;Wei Zhang ,&nbsp;Shuchao Jiang ,&nbsp;Xinjiang Cui ,&nbsp;Feng Shi","doi":"10.1039/d5cy00323g","DOIUrl":"10.1039/d5cy00323g","url":null,"abstract":"<div><div>Dimethyl carbonate (DMC) is a vital chemical compound with extensive applications, particularly as a solvent in lithium-ion battery electrolytes. In this study, a novel catalyst, 3-amino-1,2,4-triazole calcium [Ca(ATZ)₂], was synthesized, characterized, and applied for the efficient synthesis of DMC <em>via</em> the transesterification of ethylene carbonate (EC) and methanol. The catalyst demonstrated exceptional performance, achieving 73% EC conversion and 99% DMC selectivity under mild conditions (25 °C, 5 min). A unique feature of Ca(ATZ)₂ was its ability to transition from heterogeneous to homogeneous catalysis during the reaction. Initially, the reaction proceeded through heterogeneous catalysis, but as ethylene glycol (EG) was generated, the catalyst partially dissolved in EG, shifting to a homogeneous phase. This dual-phase mechanism significantly enhanced reaction efficiency. The effects of reaction conditions, alcohol structure, and catalyst reusability were systematically investigated, and a plausible catalytic mechanism was proposed. The results highlight the potential of Ca(ATZ)₂ as a sustainable and highly efficient catalyst for DMC production, offering a promising route for industrial applications. This work not only advances the field of catalytic chemistry but also contributes to the development of greener and more cost-effective chemical processes.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 5038-5045"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909472","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 surface chemistry drives speciation and reactivity of cationic Fe species in CO2 activation: a HERFD-XANES and valence-to-core XES study†","authors":"Matteo Aramini ,&nbsp;Rosa Arrigo","doi":"10.1039/d5cy00336a","DOIUrl":"10.1039/d5cy00336a","url":null,"abstract":"<div><div>While carbon-supported iron nanostructures are able to provide inexpensive frameworks where the dispersion of single-atom centres enables unique catalytic properties for carbon dioxide functionalization, detailed understanding of the structure of the transition metals is often prevented by the heterogeneous nature of the hosting C matrix and the variety of available sites, consequently hindering the understanding and development of CO₂ reduction chemistry. Herein, we report an experimental and computational spectroscopic investigation of few-layer graphene-based samples decorated with Fe atoms immobilised at the edges and in-plane defects of the graphene layers. We find that Fe–OH bound to N-terminated edge sites or in-plane defects of the graphene layers reacts with CO₂, forming bicarbonates. A similar reactivity is observed for Fe–OH bound to C-terminated edge sites, whereas Fe–OH coordinated to C-terminated in-plane defects remains unreactive towards CO₂. In stark contrast, FeN₄ sites in Fe–porphyrin present a direct, carbon-atom-mediated interaction with CO₂. These results provide insights into the local coordination environment of iron and its role in the reactivity towards CO₂ activation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 5046-5054"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909473","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":"Access to valuable 1,4- and 1,5-diketones through gold(i) catalysis in water: application to chemoenzymatic cascades†","authors":"Lorena Escot ,&nbsp;Sergio González-Granda ,&nbsp;Vicente Gotor-Fernández ,&nbsp;Iván Lavandera","doi":"10.1039/d5cy00107b","DOIUrl":"10.1039/d5cy00107b","url":null,"abstract":"<div><div>1,4- and 1,5-diketones are remarkable structures in different fields as they serve as precursors of many valuable derivatives such as heterocycles and they are also present in the skeleton of a wide variety of natural products and biologically active compounds. Herein, we propose a novel and general methodology that combines the use of both Weinreb and gold chemistries under mild conditions. Thus, starting from pent-4-ynoic or hex-5-ynoic acid, the corresponding Weinreb amides were efficiently obtained, and then after the reaction with a suitable Grignard reagent, a series of alk-4-yn-1-ones and alk-5-yn-1-ones were synthesized in high to excellent yields (74–94%). Later, these compounds were hydrated using the gold(<span>i</span>) catalyst JohnPhosAuCl and the additive NaBAr^F₄ at very low loadings in an aqueous medium and at mild temperature, affording the desired dicarbonylic derivatives at high extent (92–98%). This method was also applied to various aliphatic 1,ω-diynes, which were transformed into the corresponding diketones (88–93%). Due to the mildness of this reaction, it could be combined with different biocatalysts in a one-pot sequential or concurrent approach to access a valuable tetrahydropyridine (1 g scale, 94% isolated yield, &gt;99% ee) or a relevant diol (200 mg scale, 88% isolated yield, &gt;99% ee, &gt;99% de).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 17","pages":"Pages 5055-5065"},"PeriodicalIF":4.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909474","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}