Catalysis Science & Technology最新文献

{"title":"Inhibitory effects of residual Cl− on the NO + CO reaction over a supported Pt catalyst†","authors":"Kaiqiang Wang ,&nbsp;Wenxiao Deng ,&nbsp;Rui Cai ,&nbsp;Jianming Gu ,&nbsp;Hong Yang ,&nbsp;Yubing Liu ,&nbsp;Yining Fan","doi":"10.1039/d4cy01545b","DOIUrl":"10.1039/d4cy01545b","url":null,"abstract":"<div><div>H₂PtCl₆·6H₂O is a widely used platinum precursor, but it can form residual chlorine on catalysts' surface. This study explores the effects of residual Cl⁻ on the NO + CO reaction and demonstrates that the presence of Cl⁻ is detrimental to the reaction performance of CeO₂-supported Pt catalysts. Residual Cl⁻ has negligible effect on the dispersion state of the catalytically active Pt component, and it exerts profound effects on tuning the NO dissociation and CO adsorption abilities of the Pt catalyst. The reduction of NO over the Cl-containing Pt catalyst (Cl–Pt/CeO₂) initiating at high temperature can be attributed to fewer oxygen vacancies on its surface, which are not conducive to the dissociation of NO, in contrast with the Pt/CeO₂ catalyst. In addition, CO interacts strongly with anchored Pt²⁺, and NO occupies fewer Pt²⁺ sites in the Cl–Pt/CeO₂ catalyst. Hence, fewer NO dissociation sites are present on the Cl–Pt/CeO₂ catalyst, deteriorating NO + CO reaction performance. This work paves a way to comprehensively understand the influence of residual Cl⁻ on the NO + CO reaction and can provide insights for selecting suitable metal precursors to avoid harmful interference from residues.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3238-3244"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090863","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":"Cu(i)-based metal–organic framework-derived core–shell composites for carbon dioxide conversion to oxazolidinones†","authors":"Xiaoci Zhang ,&nbsp;Ce Liu ,&nbsp;Yanxin Liu ,&nbsp;Rongrong Fan ,&nbsp;Feng Shi ,&nbsp;Xinjiang Cui","doi":"10.1039/d5cy00166h","DOIUrl":"10.1039/d5cy00166h","url":null,"abstract":"<div><div>Cu(<span>i</span>)-based catalysts have shown great potential for CO₂ conversion, though Cu(<span>i</span>) instability remains a significant hurdle. One promising approach is the encapsulation of Cu(<span>i</span>)-based nanoparticles within MOFs. This strategy not only protects the nanoparticles but also facilitates the preconcentration of substrates (<em>e.g.</em>, CO₂) and intermediates through steric confinement effects, thereby enhancing the catalytic rate and selectivity. In this study, a surfactant-assisted self-assembly strategy was employed to fabricate a Cu₂O@ZIF-8 composite with a high specific surface area (894.84 m³ g⁻¹). The ZIF-8 shell functions as a microchemical reactor, protecting the internal Cu₂O NPs while enabling localized CO₂ enrichment and activation, enhancing substrate interactions, and facilitating efficient transport. This composite enabled a one-pot synthesis of oxazolidinones with yields exceeding 99%, along with excellent stability and recyclability. This work offers valuable insights into stabilizing Cu(<span>i</span>) and designing efficient MOF-based catalysts for CO₂ conversion.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3092-3101"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090856","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":"Bifunctional Rh/Al-SBA-15 catalysed cascade hydroformylation and hydroxyalkylation of alkenes to fuel precursors†","authors":"Krishnan Ravi ,&nbsp;Hanuman Kachgunde ,&nbsp;Venkata D. B. C. Dasireddy ,&nbsp;Jim Mensah ,&nbsp;Adam F. Lee ,&nbsp;Ankush V. Biradar ,&nbsp;Karen Wilson","doi":"10.1039/d5cy00171d","DOIUrl":"10.1039/d5cy00171d","url":null,"abstract":"<div><div>Decarbonisation of hard-to-abate liquid transport fuels, notably used in the aviation and shipping sectors, requires new catalytic routes to valorise waste feedstocks. Here we report a bifunctional Rh/Al-SBA-15 catalyst for the one-pot, two step cascade hydroformylation of 1-alkenes with CO/H₂ to form linear and branched aldehydes, and their subsequent hydroxyalkylation (HAA) with 2-methylfuran to form oxygenated jet fuel precursors. A strong synergy between Rh and Al-SBA-15 is observed for hydroformylation, with the bifunctional catalyst significantly more active than Rh/SBA-15 for the first step of the cascade. Superior yields of desired HAA products are observed over Rh/Al-SBA-15 relative to a physical mixture of Rh/SBA-15 and Al-SBA-15. Under syngas (CO/H₂) at 30 bar and 80 °C, alkenes undergo Rh catalysed hydroformylation to aldehydes, and in a subsequent step under N₂, HAA of aldehydes over the solid acid sites of Al-SBA-15 gives an overall ∼60% yield of fuel range precursors.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3149-3156"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090877","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":"Efficient CeO2 and CeO2–Al2O3 supports for Ru as 3rd generation ammonia synthesis catalysts: enhanced kinetic mechanism over commercial Ru/CeO2†","authors":"Javier Arroyo-Caire ,&nbsp;Edgar S. Duran-Uribe ,&nbsp;Mayra Anabel Lara-Angulo ,&nbsp;Manuel Antonio Diaz-Perez ,&nbsp;Antonio Sepúlveda-Escribano ,&nbsp;Juan Carlos Serrano-Ruiz","doi":"10.1039/d5cy00122f","DOIUrl":"10.1039/d5cy00122f","url":null,"abstract":"<div><div>Ceria (CeO₂) has been previously reported as a functional support for ruthenium (Ru) as an ammonia synthesis catalyst. However, lab-synthesized ceria materials usually present low surface areas, thereby limiting the generation of oxygen vacancies and the ammonia synthesis activity as a result of weak metal–support interactions. With the aim of overcoming this issue, we prepared, by a simple impregnation method, high surface area ceria and ceria–alumina supported Ru catalysts with improved ammonia synthesis performance at moderate temperatures. In this sense, lab-synthesized Ru/CeO₂ (with higher specific surface area and lower crystallinity than commercial ceria) showed stronger metal–support interactions than the commercial sample, which resulted in a superior global ammonia synthesis kinetic mechanism with more positive hydrogen reaction orders (<em>i.e.</em>, more resistant to hydrogen inhibition) and significantly lower activation energies (46 <em>vs.</em> 61 kJ mol⁻¹). We found that the use of alumina as a structural support increased the surface area of ceria, thereby promoting the Ru–CeO₂ interaction and the catalytic performance. We analyzed the effect of the surface chemistry of two different commercial aluminas (acidic and basic) with similar surface areas. Basic alumina was found to increase the specific surface area of the catalyst to a larger extent as compared to acidic alumina. Thus, the Ru/CeO₂–Al₂O₃ catalyst with 50 wt% of basic alumina showed an ammonia synthesis activity of 1.9 mmol g⁻¹ h ⁻¹ at 400 °C and ambient pressure and an activation energy as low as 44.8 kJ mol⁻¹.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 2988-2998"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090843","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":"Highly active heterogeneous Fe-based catalysts synergistically enhanced by polyaniline and MoS2 for organic contaminant elimination†","authors":"ChengBo Qian ,&nbsp;Yuyuan Yao ,&nbsp;Hongliang Zhu","doi":"10.1039/d5cy00066a","DOIUrl":"10.1039/d5cy00066a","url":null,"abstract":"<div><div>Fe-based catalysts have garnered significant attention due to their high stability, low toxicity and cost-effectiveness, while the construction of highly active heterogeneous Fe-based catalysts through a simple method is still challenging in the environmental catalysis field. Herein, employing the synergistic enhancement effect of the conductive polymer polyaniline (PANI) and co-catalyst MoS₂, a highly active PANI-supported Fe-doped MoS₂ catalyst (PANI-Fe@MoS₂) was prepared <em>via</em> a facile one-step hydrothermal process. Surprisingly, PANI incorporation induced critical structural modifications, including reduced average particle size (1 μm), expanded interlayer spacing (1.09 nm), and enhanced sulfur vacancy density. Interestingly, PANI-Fe@MoS₂ achieved nearly 100% elimination of carbamazepine (CBZ) within 10 min, and its removal efficiency (<em>k</em>-value) surpassed most of those reported in the literature. Notably, PANI-Fe@MoS₂ exhibited a high removal of TOC (nearly 50%), a wide pH operating range (2–10), and outstanding removal efficiency for various contaminants. Additionally, the quenching and electron paramagnetic resonance (EPR) experiments revealed that singlet oxygen (¹O₂) and hydroxyl radicals (˙OH) were the main reactive oxygen species (ROSs) for degrading CBZ. Moreover, the potential degradation pathways were proposed based on the intermediates of CBZ. This work provides a strategic paradigm for designing efficient heterogeneous Fe-based catalysts for environmental remediation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3204-3215"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090860","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":"Improved stereocontrol in reductive aminases through steric modification of residues around substrate and cofactor binding pockets†","authors":"Jake Gooderham ,&nbsp;Beatrice-Maria Zabava ,&nbsp;David D. Aleku ,&nbsp;Julie Vignot ,&nbsp;Zuoye Xie ,&nbsp;Ruth T. Bradshaw Allen ,&nbsp;Mario Prejanò ,&nbsp;Godwin A. Aleku","doi":"10.1039/d5cy00308c","DOIUrl":"10.1039/d5cy00308c","url":null,"abstract":"<div><div>Asymmetric reductive amination catalysed by reductive aminases (RedAms) provides a green and direct route to 2° and 3° chiral amines. Identifying residues or motifs in these enzymes that facilitate stereocontrol is essential for designing highly desirable enantiodivergent RedAm systems. In this work, we have identified key residues within both the cofactor and substrate binding pockets in a fungal reductive aminase (<em>Ma</em>RedAm) and a bacterial imine reductase (<em>Ao</em>IRED) that enable stereocontrol through steric modification. In <em>Ma</em>RedAm, removing steric bulk at the cofactor binding pocket <em>via</em> W33A or R35A mutation improved (<em>R</em>)-selectivity towards the synthesis of (<em>R</em>)-rasagiline, achieving up to 95% enantiomeric excess (e.e.). Conversely, the W211A mutation at the substrate binding pocket of <em>Ma</em>RedAm inverted the stereoselectivity, yielding (<em>S</em>)-rasagiline (42% e.e.). Likewise, varying steric bulk at position N241 in <em>Ao</em>IRED allowed for enantiodivergency. Notably, modifying the N241 position significantly improved <em>Ao</em>IRED's solution stability and storability. The wild-type enzyme typically precipitates out of solution within 8 h after purification, even when stored at 4 °C, whereas its N241H and N241Y variants remain in solution for up to &gt;1 week. Molecular dynamics (MD) simulations provided detailed insights into the effect of steric modification on stereoselectivity at the cofactor and substrate binding pockets. <em>Ma</em>RedAm W33A and W35A mutations induced reorganisation and downsizing of the active site, enhancing (<em>R</em>)-selectivity. In contrast, the W211A mutation enlarged the substrate binding pocket, increasing flexibility for substrate rotation. These findings contribute to the ongoing effort to establish the functional roles of key residues to allow efficient rational engineering of stereoselectivity in IREDs/RedAms.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3113-3121"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090865","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":"Experimental and computational optimisation of methanol dehydration to dimethyl ether†","authors":"Maciej G. Walerowski ,&nbsp;Stylianos Kyrimis ,&nbsp;Matthew E. Potter ,&nbsp;Alice E. Oakley ,&nbsp;Marina Carravetta ,&nbsp;Lindsay-Marie Armstrong ,&nbsp;Robert Raja","doi":"10.1039/d5cy00062a","DOIUrl":"10.1039/d5cy00062a","url":null,"abstract":"<div><div>Meeting the International Maritime Organization's net-zero target by 2050 necessitates the replacement of marine fossil fuels with sustainable alternatives, such as dimethyl ether (DME). Silicon-doped aluminophosphate (SAPO) solid acid catalysts, particularly the weakly-acidic SAPO-11, can catalyse the selective dehydration of methanol-to-DME with exceptional stability. Herein, we present a combined experimental, computational fluid dynamics, and design of experiments study to augment catalyst efficiency and DME production, and to support scale-up endeavours. Using a four-dimensional design surface, it was found that longer catalyst beds and higher operating temperature increase DME yields, with the catalyst bed length having a more pronounced influence. In contrast, the use of highly concentrated methanol reactant streams had a detrimental effect and this was ascribed to a saturation of the active sites in the SAPO-11 catalyst. Improved single-pass conversions and catalyst longevity on industrial scales can thus be achieved by optimising both the number of acid sites in SAPO-11 and reaction parameters.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3216-3225"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090861","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":"Engineered In2O3 nanorods with abundant O vacancies significantly boost highly efficient photothermal CO2 hydrogenation into CO†","authors":"Chunyan Yang ,&nbsp;Buyun Shi ,&nbsp;Fenghao Xing ,&nbsp;Yawei Gu ,&nbsp;Chongqing Wang ,&nbsp;Yong Zhou ,&nbsp;Qiutong Han ,&nbsp;Yichang Pan","doi":"10.1039/d5cy00154d","DOIUrl":"10.1039/d5cy00154d","url":null,"abstract":"<div><div>Rising global demand for clean energy and carbon reduction challenges traditional CO₂ conversion. Photothermal catalytic CO₂ hydrogenation, powered by the combined force of light and heat, offers enhanced energy efficiency, lower reaction temperatures, and better product selectivity. Herein, a nanorod-shaped In₂O₃ catalyst rich in oxygen vacancies (Vos-In₂O₃) was synthesized. Compared to bulk In₂O₃, the rod-like structure effectively increases the catalyst's specific surface area, exposing more surface active sites. To facilitate reactant activation, oxygen defect engineering was implemented on the nanorod surface. The Vos-In₂O₃ exhibits a remarkable enhancement in the yield of photothermal CO₂ catalytic reduction to CO, CH₄, CH₃OH, and CH₃CH₂OH at lower heating temperatures and atmospheric pressure. Notably, the CO production rate at an initial C/H ratio of 3 in the filling gas mixture was close to 421.90 μmol g⁻¹ h⁻¹, which was 24.3 and 30.9 times higher than that of In₂O₃ and bulk In₂O₃, respectively. The product selectivity of CO for Vos-In₂O₃ reached an outstanding 98.96%. Introducing O vacancies accelerates reaction kinetics and thermodynamics, and strongly promotes the efficient progress of the photothermal CO₂ hydrogenation reaction.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3141-3148"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090876","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":"Designing molecular and two-dimensional metalloporphyrin catalysts for the electrochemical CO2 reduction reaction†","authors":"Amira Tasnima Uddin ,&nbsp;Rachel Crespo-Otero ,&nbsp;Devis Di Tommaso","doi":"10.1039/d5cy00156k","DOIUrl":"10.1039/d5cy00156k","url":null,"abstract":"<div><div>The electrochemical CO₂ reduction reaction (eCO₂R) is an important route toward the sustainable conversion of CO₂ to value-added chemicals. However, developing efficient catalysts with high selectivity and stability remains challenging. Metalloporphyrins (M–PORs) represent an attractive class of molecular catalysts because their structural framework offers a unique combination of tunability of the peripheral ligands, flexibility of the metal centre, and versatility of the oxidation state of the metal. These properties can be exploited to tailor the catalytic properties of M–PORs for the eCO₂R. Here, we present a comprehensive computational study using density functional theory to systematically explore M–POR catalysts with varying metal centers (Ni, Fe, Cu, Co), oxidation states, and anchoring ligands, aimed at enhancing the selective production of the C₁ products (carbon monoxide and formic acid). Thermodynamic and electrochemical stability analyses revealed neutral M–PORs to be significantly more stable than their charged counterparts, providing crucial guidelines for catalyst design. A mechanistic analysis of reaction pathways—proton-coupled electron transfer (PCET) <em>versus</em> sequential proton and electron transfer (PT–ET)—identified PCET as highly favourable, with predominant selectivity towards formic acid. This study identifies Fe–POR as the one showing superior catalytic performance. Importantly, integrating these optimal molecular catalysts into two-dimensional (2D) carbonaceous frameworks led to further enhancement of catalytic performance, identifying 2D Fe–POR as a highly promising material for selective C₁ product formation, thus providing a rational framework for designing effective molecular-to-framework electrocatalysts for the eCO₂R.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 10","pages":"Pages 3157-3170"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090878","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":"Correction: Surface analysis of thermally stable Pt loaded CeO2–ZrO2 using colloidal Pt for TWC application","authors":"Hiroki Tanaka, Yoshinori Endo and Masaaki Haneda","doi":"10.1039/D5CY90025E","DOIUrl":"https://doi.org/10.1039/D5CY90025E","url":null,"abstract":"<p >Correction for ‘Surface analysis of thermally stable Pt loaded CeO<small>₂</small>–ZrO<small>₂</small> using colloidal Pt for TWC application’ by Hiroki Tanaka <em>et al.</em>, <em>Catal. Sci. Technol.</em>, 2025, <strong>15</strong>, 1473–1481, https://doi.org/10.1039/D4CY01364F.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 9","pages":" 2950-2950"},"PeriodicalIF":4.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy90025e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913726","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}