Catalysis Science & Technology最新文献

{"title":"Construction of a 0D/2D NixP/LaTiO2N Schottky junction photocatalyst for efficient visible-light-driven photocatalytic CO2 reduction†","authors":"Guoyu Xu ,&nbsp;Yanan Chen ,&nbsp;Peiling Lin ,&nbsp;Zizhong Zhang ,&nbsp;Tao Ji ,&nbsp;Wenyue Su","doi":"10.1039/d5cy00004a","DOIUrl":"10.1039/d5cy00004a","url":null,"abstract":"<div><div>Employing photocatalytic technology to transform CO₂ into valuable fuels is considered a promising solution for addressing the exacerbated greenhouse effect and energy crisis. The development of photocatalysts featuring superior charge separation efficiency is pivotal for the widespread implementation of photocatalytic CO₂ reduction technologies. Herein, zero-dimensional (0D) Ni_<em>x</em>P nanoparticles are anchored onto two-dimensional (2D) LaTiO₂N nanosheets by a photo-deposition method, and a Ni_<em>x</em>P/LaTiO₂N Schottky junction composite with excellent photocatalytic CO₂ reduction performance is constructed. The optimal Ni_<em>x</em>P/LaTiO₂N composite achieves CO and CH₄ yields of 9.39 and 4.15 μmol g⁻¹ h⁻¹, respectively, with the utilized photoelectron number (UPN) reaching 51.98 μmol g⁻¹, which is approximately 9.7 times higher than that of LaTiO₂N alone. The improved photocatalytic performance of the composites can be attributed to the formation of Schottky junctions, which effectively suppress the recombination of photogenerated carriers. This study provides a new idea for the development of 0D/2D Schottky junction photocatalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 2027-2033"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638049","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":"Preparation and modification of carbon based materials as efficient catalysts in the cycloaddition of carbon dioxide towards cyclic carbonates: a mini review","authors":"Jianhan Yang ,&nbsp;Jiangnan Huang ,&nbsp;Hao-Fan Wang ,&nbsp;Hongjuan Wang ,&nbsp;Hao Yu ,&nbsp;Yonghai Cao","doi":"10.1039/d4cy01408a","DOIUrl":"10.1039/d4cy01408a","url":null,"abstract":"<div><div>The preparation of carbonates <em>via</em> carbon dioxide (CO₂) cycloaddition is an important chemical process, which utilizes CO₂ and epoxides as raw materials. Nanocarbon materials, with their unique physical/chemical properties, make them ideal catalysts or carriers for CO₂ cycloaddition. In this process, the structure and surface features of nanocarbons are considered the key issues to facilitate the reaction, which has not been fully discussed. In this review, the preparation and modification of carbon based materials with unique surface features for CO₂ cycloaddition are summarized and fully discussed. The effect of intrinsic interactions between the co-catalyst and surface property of carbon based catalysts on the catalytic performance/reaction mechanism were fully discussed, and the state-of-the-art of CO₂ cycloaddition was highlighted.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 1771-1786"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637982","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":"The speciation of phosphates adsorbed on γ-alumina revealed by 31P NMR, AIMD and machine learning†","authors":"Adrian Hühn, Tao Jiang, Manuel Corral Valero, Mickaël Rivallan, Anne Lesage, Carine Michel and Pascal Raybaud","doi":"10.1039/D4CY01152J","DOIUrl":"https://doi.org/10.1039/D4CY01152J","url":null,"abstract":"<p >The chemical nature of adsorbed inorganic additives such as phophates used in the preparation of heterogeneous catalysts is suspected to impact their resulting activity. Predominant phosphate species located on the surfaces of the γ-alumina catalytic support are identified by using one-dimensional <small>³¹</small>P NMR spectra as the only experimental input. The detailed insight is made possible by combining machine learning (ML) <small>³¹</small>P chemical shift prediction and <em>ab initio</em> molecular dynamics (AIMD) to sample conformers of 10 representative possible structures and generate theoretical spectra, which were then used to decompose mathematically the broad experimental peak. At low P concentration, several types of monomeric species are found to co-exist on the γ-alumina (110) facets. Increasing the P concentration yields a marked increase in one monomeric species and one dimeric species both located on the (110) facets, whereas phosphates are mainly absent from the (100) facet. The NMR spectra broadening is interpreted by two levels of structural disorders: the various types of P species and the conformational distribution of each species. We finally propose some implications for the catalytic properties.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 3","pages":" 878-884"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107427","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":"Perovskite-derived MnOx/LaMnO3 nanocomposites to boost CO oxidation activity†","authors":"Andrea Felli ,&nbsp;Alessandra Toso ,&nbsp;Andrea Braga ,&nbsp;Sara Colussi ,&nbsp;Marta Boaro ,&nbsp;Jordi Llorca ,&nbsp;Byron Truscott ,&nbsp;Christine Artner-Wallner ,&nbsp;Alessandro Trovarelli","doi":"10.1039/d4cy01418a","DOIUrl":"10.1039/d4cy01418a","url":null,"abstract":"<div><div>In this study, the impact of nitric acid treatment parameters, specifically acid concentration and exposure time, on the morphological, redox, and catalytic properties of LaMnO₃ for CO oxidation was thoroughly investigated. The samples were characterised by ICP analysis, N₂ adsorption/desorption measurements, XRD, H₂-TPR, XPS, HRTEM and HAADF-STEM. Acidic treatment of LaMnO₃ significantly increases the surface area, creating a new porous structure. Under mild treatment conditions, the composition, crystal structure and morphology are also modified, resulting in MnO_<em>x</em>/LaMnO₃ catalysts with various Mn oxide species forming needle-like structures segregated on a highly defective La_{1−<em>x</em>}MnO_{3−<em>δ</em>} perovskite. These MnO_<em>x</em>/LaMnO₃ nanocomposites exhibited superior CO oxidation activity, achieving 10% CO conversion (<em>T</em>₁₀) in the range of 375–396 K, compared to 459 K for the pristine perovskite. This enhanced performance is attributed not only to the increased surface area, but also to the exposure of reactive MnO_<em>x</em> species on the surface of the perovskite and, crucially, to the interfacial synergism between MnO_<em>x</em> and LaMnO₃. This synergy enhances oxygen exchange, and it improves the reducibility of the nanocomposite at low temperatures, providing a better thermal stability of active phases at elevated temperatures. However, the benefits of the acid treatment are lost under more severe conditions that transform LaMnO₃ into bulk Mn oxide phases (Mn₂O₃, Mn₃O₄), or pure MnO₂, highlighting the critical role of MnO_<em>x</em>/LaMnO₃ interface properties for CO oxidation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 1882-1893"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01418a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637993","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":"Oxygen vacancy-engineered In2O3@carbon catalysts from steam-pyrolyzed MOFs for photothermal CO2 hydrogenation†","authors":"Xinhuilan Wang ,&nbsp;Luis Garzon-Tovar ,&nbsp;Alejandra Rendón-Patiño ,&nbsp;Diego Mateo ,&nbsp;Jorge Gascon","doi":"10.1039/d4cy01515k","DOIUrl":"10.1039/d4cy01515k","url":null,"abstract":"<div><div>Photothermal CO₂ hydrogenation has attracted considerable attention as a promising approach to utilize carbon dioxide through the efficient conversion of solar energy into chemicals and fuels. In this study, we report a novel approach to improve the catalytic performance of indium oxide-based catalysts for the photothermal reverse water-gas shift (RWGS) reaction. Catalysts derived from the steam pyrolysis of the metal–organic framework MIL(In)-68 display a high density of oxygen vacancies and defect sites on the In₂O₃ surface. These features significantly enhance CO₂ adsorption and H₂ dissociation ability while maintaining the porosity of the material and enhancing its photothermal properties. Among the catalysts investigated, the Rb-promoted catalyst exhibited superior activity, achieving CO production rates of 53 mmol g_In₂O₃⁻¹ h⁻¹ with 100% selectivity without any external heating. Comprehensive characterization, including XPS and Raman spectroscopy, confirmed that steam-pyrolysis leads to extensive defective site formation, resulting in improved catalytic performance. These results highlight the potential of steam-pyrolyzed MOF materials as efficient and selective catalysts for photothermal CO₂ hydrogenation, offering a sustainable route to valuable chemical production.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 1814-1824"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01515k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638013","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":"Au–Ni synergy for enhanced electrochemical oxidation of ethanol over Au/Ni foam electrode†","authors":"Xing Tan, Ruixing Du, Qitong Zhong, Longfei Liao, Huanhao Chen, Zhenchen Tang, Dafeng Yan, Shiming Chen and Feng Zeng","doi":"10.1039/D4CY01490A","DOIUrl":"https://doi.org/10.1039/D4CY01490A","url":null,"abstract":"<p >Replacing the sluggish oxygen evolution reaction with ethanol oxidation can reduce the overpotential while generating value-added products. In this study, a highly active and stable catalyst was synthesized <em>via</em> electrochemical deposition, enabling the leaching of Ni and co-deposition of Au and Ni to form an Au–Ni alloy on Ni foam. The Au–Ni synergy enhances ethanol adsorption, tailors surface oxygen species, and shortens the distance between reaction intermediates, driving ethanol oxidation to acetate at low potentials and favoring acetaldehyde formation at higher potentials. The resulting electrode achieves 163 mA cm<small>⁻²</small> at 1.57 V <em>vs.</em> RHE and 209 mA cm<small>⁻²</small> at 1.90 V <em>vs.</em> RHE with excellent stability, offering a cost-effective alternative for the anode reaction in hydrogen production.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 3","pages":" 933-945"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107432","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":"The in situ structural evolution of Bi2O3 facilitates the electrocatalytic hydrogenation of oxalic acid to glycolic acid†","authors":"Donghai Chen ,&nbsp;Haolin Cheng ,&nbsp;Yan Fu ,&nbsp;Jinli Zhang","doi":"10.1039/d4cy01442a","DOIUrl":"10.1039/d4cy01442a","url":null,"abstract":"<div><div>Electrocatalytic hydrogenation (ECH) of oxalic acid (OX) as feedstock to generate glycolic acid (GA) with high added value has been considered to provide a feasible route for eco-friendly synthesis of GA. Herein, a Bi₂O₃-based electrocatalyst was reported for the first time in the selective ECH of OX to GA in acidic media. At −0.5 V <em>vs.</em> RHE, the selectivity toward GA reached 87% with an OX conversion of 82% in 0.05 M H₂SO₄. Notably, the Bi₂O₃ catalyst underwent a potential-driven reconstruction, resulting in a transformation from Bi₂O₃ particles into a dendrite-like Bi/Bi₂O₃ heterostructure. Kinetic studies demonstrated that the ECH of OX over the reconstituted Bi/Bi₂O₃ occurred through the Eley–Rideal (E–R) mechanism. The superior electrocatalytic efficiency originated from the Bi/Bi₂O₃ heterostructure with abundant defects that optimized the surface charge distribution and boosted the adsorption of the intermediate HOOCCO*, thereby exhibiting a notable selectivity for GA.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 1914-1925"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637995","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 efficient supported catalysts based on Zr-containing polyoxometalates and multiwalled carbon nanotubes for selective oxidation of thioethers with H2O2†","authors":"Vladimir A. Lopatkin ,&nbsp;Vasilii Yu. Evtushok ,&nbsp;Olga A. Stonkus ,&nbsp;Lidiya S. Kibis ,&nbsp;Olga Yu. Podyacheva ,&nbsp;Oxana A. Kholdeeva","doi":"10.1039/d4cy01526f","DOIUrl":"10.1039/d4cy01526f","url":null,"abstract":"<div><div>Zirconium-containing polyoxometalates (Zr–POM) with Lindqvist, Keggin, and Wells–Dawson structures have been irreversibly attached to the surface of nitrogen-free and nitrogen-doped multi-walled carbon nanotubes (CNT and N-CNT) using H⁺ or Zn²⁺ ions as immobilization agents. The supported catalysts were characterized using low temperature N₂ adsorption, thermogravimetric analysis, FT-IR spectroscopy, XPS, HRTEM and HAADF-STEM. Catalytic activity was assessed for the selective oxidation of thioethers to sulfoxides using methyl phenyl sulfide as model substrate and aqueous 30% H₂O₂ as green oxidant, and the relationships between the catalyst composition and its activity and selectivity have been established. Among the catalysts tested, Zr–POM of the Keggin structure [{PW₁₁O₃₉Zr(μ-OH)}₂]⁸⁻ (PW₁₁Zr) immobilized on N-CNT (1.8 at% N) using Zn²⁺ (18 wt% PW₁₁Zr/Zn–N-CNT) exhibited superior performance in terms of turnover frequency (TOF 10 200 h⁻¹ in acetonitrile at room temperature) and H₂O₂ utilization efficiency (90%). Sulfoxide selectivity depends on the solvent nature and varies from 88% (acetonitrile) to 98% (ethanol) at 80–83% substrate conversion attained with only one equiv. of H₂O₂ and 0.1 mol% of PW₁₁Zr. The reaction can proceed successfully even with 0.01 mol% of the catalyst, achieving turnover number of 9360 with retention of the Zr–POM structure. Hot filtration tests confirmed the heterogeneous nature of the catalysis. The catalyst showed excellent reusability over, at least, five cycles without degradation and was resistant to Zr–POM and Zn leaching, even when using the highly polar protic solvent ethanol. The catalyst 18 wt% PW₁₁Zr/Zn–N-CNT was able to accomplish sulfoxidation of the practically important omeprazole sulfide with 98% selectivity at 95% conversion.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 1825-1838"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638014","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":"Regulation of the oxygen vacancies of WOx for highly efficient catalytic epoxidation of cyclooctene†","authors":"Yunwei Wang ,&nbsp;Yingyong Wang ,&nbsp;Zhimin Yin ,&nbsp;Xincheng Li ,&nbsp;Xianmo Gu ,&nbsp;Ruiyi Wang ,&nbsp;Zhanfeng Zheng","doi":"10.1039/d4cy01422g","DOIUrl":"10.1039/d4cy01422g","url":null,"abstract":"<div><div>Oxygen vacancies of the WO_<em>x</em> catalyst play a critical role in the epoxidation of cyclooctene. However, the main factor restricting the industrial application of oxygen vacancy-enriched tungsten oxide is deactivation due to oxidation of oxygen vacancies. Herein, WO_<em>x</em> with tunable oxygen vacancies was prepared through simple reduction and regeneration of inactivated WO_2.72, which exhibited 97.3% conversion of cyclooctene and 99.0% selectivity toward epoxyoctane. The catalytic performance of the catalyst was not significantly reduced after five repeated regeneration cycles. SEM, XRD and XPS characterization presented the variation in the morphology, structure and component of a series of WO_<em>x</em> regenerated with different reduction temperatures and times and verified the regeneration of WO_2.72 and the presence of abundant oxygen vacancies. <em>In situ</em> DRIFTS demonstrated that appropriate oxygen vacancies improved the adsorption and activation of H₂O₂ to the hydroperoxide-coordinated HOO–WO_<em>x</em> species, which greatly promoted the performance of cyclooctene epoxidation. This paper not only provides a simple, green, and cost-effective approach for the regeneration of the WO_2.72 catalyst as an industrial catalyst using oxygen vacancy-enriched tungsten oxide but also sheds light on the mechanism of olefin epoxidation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 2008-2015"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638043","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 comprehensive mechanistic investigation of sustainable carbene N–H insertion catalyzed by engineered His-ligated heme proteins†","authors":"Rahul L. Khade ,&nbsp;Ronald Daisuke Adukure ,&nbsp;Xinyi Zhao ,&nbsp;Carolyn Wang ,&nbsp;Rudi Fasan ,&nbsp;Yong Zhang","doi":"10.1039/d4cy00999a","DOIUrl":"10.1039/d4cy00999a","url":null,"abstract":"<div><div>Engineered heme proteins possess excellent biocatalytic carbene N–H insertion abilities for sustainable synthesis, and most of them have His as the Fe axial ligand. However, information on the basic reaction mechanisms is limited, and ground states of heme carbenes involved in the prior computational mechanistic studies are under debate. A comprehensive quantum chemical reaction pathway study was performed for the heme model with a His analogue as the axial ligand and carbene from the widely used precursor ethyl diazoacetate with aniline as the substrate. The ground state of this heme carbene was calculated by the high-level complete active space self-consistent field (CASSCF) approach, which shows a closed-shell singlet that is consistent with many experimental works. Based on this, DFT calculations of ten main reaction pathways were compared. Results showed that the most favorable pathway involved the initial formation of the metal-bound ylide, followed by a concerted rearrangement/dissociation transition state to form the free enol, which then underwent a water-assisted proton transfer process to yield the final N–H insertion product. This computational prediction was validated <em>via</em> new experimental data using His-ligated myoglobin variants with different types of carbenes. Overall, this is the first comprehensive computational mechanistic study of heme carbene N–H insertions, particularly for neutral His ligated heme proteins and the first high-level CASSCF confirmation of the ground state of the used heme carbene. The experimental results are also the first in this field. Overall, these results build a solid basis for the proposed reaction mechanism to facilitate future biocatalytic carbene N–H insertion studies.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 6","pages":"Pages 1802-1813"},"PeriodicalIF":4.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11771221/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062606","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}