Catalysis Science & Technology最新文献

{"title":"The critical role of boron hybridization (sp3vs. sp2vs. sp) in hydrogenation mechanisms by boron-based Ru catalysts†","authors":"Chuanyi Xiong, Huayu Liang, Yinwu Li and Zhuofeng Ke","doi":"10.1039/D5CY00380F","DOIUrl":"https://doi.org/10.1039/D5CY00380F","url":null,"abstract":"<p >Boron–transition metal (B–TM) catalysts have emerged as promising systems for hydrogenation reactions due to their unique bifunctional reactivity. However, the electronic structure–activity relationships of B–TM systems with different boron hybridizations remain poorly understood. This study systematically investigates how the sp<small>³</small>, sp<small>²</small>, and sp hybridizations influence the catalytic mechanisms of B–Ru complexes in hydrogen activation and ethylene hydrogenation. For hydrogen activation, the sp<small>³</small>-B–Ru system follows a hydride mechanism (Δ<em>G</em> = 31.2 kcal mol<small>⁻¹</small>), while sp<small>²</small>/sp-B–Ru systems adopt a more efficient proton mechanism with lower barriers (15.3 and 20.8 kcal mol<small>⁻¹</small>, respectively). Orbital analysis demonstrates that the Ru contribution to bridging hydrides increases progressively from sp<small>³</small> (9.4%) to sp (13.9%) systems, correlating with enhanced catalytic activity. For the hydrogenation reaction, the 2c–2e terminal is more favorable than the 3c–2e bridging hydrogen mechanism. Moreover, in the bridging hydrogen mechanism, the metal oxidation state remains unchanged for the sp<small>²</small> and the sp systems, which is superior to that for the sp<small>³</small> system. These findings provide molecular-level insights for the rational design of B–TM catalysts with improved hydrogenation performance.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3906-3917"},"PeriodicalIF":4.4,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514483","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":"Regulating protonation paths for enhanced photocatalytic CO2 methanation by coupling Pt sites on WO2.9/TiO2†","authors":"Jiajun Du, Jun Deng, ChangAn Zhou, Hairong Yue, Chong Liu, Patrik Schmuki, Štěpán Kment and Xuemei Zhou","doi":"10.1039/D5CY00167F","DOIUrl":"https://doi.org/10.1039/D5CY00167F","url":null,"abstract":"<p >CO<small>₂</small> methanation <em>via</em> photocatalysis with water vapor is a sustainable technique for reducing CO<small>₂</small> emission but is challenged by the high energy barrier associated with the initial adsorption, activation and protonation of CO<small>₂</small> molecules. In this work, a substoichiometric WO<small>_2.9</small> thin film with strong Lewis acidity was coated on TiO<small>₂</small> microspheres, followed by the deposition of Pt cocatalysts on WO<small>_2.9</small> with controlled Pt single atoms and clusters (Pt–WO<small>_2.9</small>/TiO<small>₂</small>). The methane production rate reached 10.74 μmol h<small>⁻¹</small> g<small>⁻¹</small> with a selectivity of 99.8%, which was ∼40 times higher than that of bare TiO<small>₂</small> (0.27 μmol h<small>⁻¹</small> g<small>⁻¹</small>). The high methane production rate was attributed to the synergy of Pt sites on the WO<small>_2.9</small>/TiO<small>₂</small> heterojunction, where the Pt clusters facilitated water dissociation, thereby providing H* through hydrogen spillover on the surface, and the presence of a substoichiometric WO<small>_2.9</small> surface further enhanced the spillover process. The high density of active H* promoted the protonation pathway for CO<small>₂</small> activation (CO<small>₂</small> → COOH<small>⁺</small> → *COOH), which improved the adsorption of the essential intermediate *CO on Pt single atoms and displayed a significantly reduced energy barrier for the protonation reaction of C1 intermediates, resulting in a mixed reaction pathway. This work provides new insights into a mechanism to regulate the reaction path to facilitate efficient photocatalytic CO<small>₂</small> methanation.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 4002-4011"},"PeriodicalIF":4.4,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514485","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":"Enhancing CO2 hydrogenation via nitrogen-doped carbon nanospheres and in situ ruthenium nanoparticle synthesis†","authors":"Pradeep S. Murthy, Oliver J. Conquest, Lizhuo Wang, Xiaoyan Liu, Jian Liu, Catherine Stampfl and Jun Huang","doi":"10.1039/D5CY00368G","DOIUrl":"https://doi.org/10.1039/D5CY00368G","url":null,"abstract":"<p >As the excessive presence of CO<small>₂</small> continues to infiltrate the Earth's atmosphere, a crucial mitigation strategy is not merely capturing CO<small>₂</small> but converting it into more useful fuels and chemicals, such as CO and CH<small>₄</small>, through CO<small>₂</small> hydrogenation. This process is easily accelerated using a catalyst. A Ru/CNS nano-catalyst was studied, in which 1 wt% of ruthenium metal nanoparticles were dispersed over nitrogen-doped carbon nanospheres (CNSs) derived from resorcinol (Res) or 3-aminophenol (APF) and synthesized with or without a direct <em>in situ</em> mixing method. The generated C–N surface of the Ru/CNS-APF (<em>in situ</em>) catalyst not only possessed smaller, embedded, and well-dispersed Ru nanoparticles (2.38 nm), but also had a strong synergistic effect with the Ru species. The characterization and reaction test results indeed evidenced that this catalyst possessed the strongest activity (∼60% CO<small>₂</small> conversion and ∼85% CO selectivity at 600 °C and 3H<small>₂</small> : 1CO<small>₂</small> molar feed ratio). A 10 h stability test effectively demonstrated that the catalyst maintained its active and stable performance, with no major structural changes post-reaction. A density functional theory (DFT) model comprising a Ru nanostructure adsorbed on a C–N layer (graphene with substituted pyridinic-N) demonstrated easier CO<small>₂</small> capture on C–N before subsequent diffusion onto Ru. A strong electronic and material synergy between Ru and C–N was verified, and the preferred reaction intermediate was <em>trans</em>-COOH. The analysis proved both that a nitrogen-doped carbon nanosphere (CNS) support synthesized <em>via in situ</em> Ru incorporation enhances CO<small>₂</small> hydrogenation efficiency and that such Ru/C–N-based catalysts are highly capable towards addressing the global climate challenge.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3976-3990"},"PeriodicalIF":4.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514472","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":"Minimizing radiative and nonradiative energy leakage in red-light-absorbing supramolecular nanoassemblies to boost oxidative photocatalytic activity in water†","authors":"Aditya Singh, Manoj Kumar and Vandana Bhalla","doi":"10.1039/D5CY00131E","DOIUrl":"https://doi.org/10.1039/D5CY00131E","url":null,"abstract":"<p >Harnessing abundant red-light, which constitutes a significant portion of solar radiation, to energize oxidative transformations is an economic and eco-friendly strategy for sustainable chemistry. Given this consideration, red-light-absorbing J-type nanoassemblies based on a donor–acceptor–donor (D–A–D) building block (<strong>BrTPA-Py</strong>) with 4-bromo-<em>N</em>,<em>N</em>-diphenylaniline as the donor and pyrazino[2,3-b]pyrazine-2,3-dicarbonitrile as the acceptor have been developed in aqueous media. The strategic incorporation of bromine atoms at the periphery enhanced spin–orbit coupling and restricted nonradiative/radiative decay through bromine⋯bromine noncovalent interactions. Due to the synergistic effect of strong charge-transfer characteristics, presence of bromine atoms and restricted inter/intramolecular motion, rapid intersystem crossing (ISC) is facilitated in <strong>BrTPA-Py</strong> nanoassemblies, enabling the activation of aerial oxygen through type I (electron transfer) and/or type II (energy transfer) pathways upon irradiation by red-light. The remarkable photosensitization potential of <strong>BrTPA-Py</strong> nanoassemblies has been unveiled to catalyse the oxidation of phosphines and hydroxylation of arylboronic acids under red-light irradiation, which is unprecedented. This investigation presents a simple design strategy to propel advances in sustainable photocatalysis by regulating the dynamics of excited state under low-energy radiation through the incorporation of halogen atoms in the backbone of the building block with strong charge-transfer characteristics.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 4024-4036"},"PeriodicalIF":4.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514476","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":"Bioelectrocatalysis for solar fuels and sustainable energy","authors":"Rodrigo M. Iost, Senentxu Lanceros-Méndez and Frank N. Crespilho","doi":"10.1039/D5CY00177C","DOIUrl":"https://doi.org/10.1039/D5CY00177C","url":null,"abstract":"<p >Bioelectrocatalysis has emerged as an important area in the transition to sustainable energy, offering a green and efficient way for producing solar fuels, bioelectricity, and value-added chemicals. This review presents a comprehensive roadmap for bioelectrocatalytic systems, focusing on key enzymes, microorganisms, and bioelectrochemical processes that drive these technologies. Enzymes such as hydrogenases and nitrogenases play essential roles in hydrogen production and renewable nitrogen fixation, while photosynthetic microorganisms like cyanobacteria are suitable for biophotovoltaic applications. Recent advances in electrode materials, genetic engineering of biocatalysts, and nanomaterial integration have significantly improved electron transfer efficiency and biocatalyst stability. The use of bioelectrochemical systems, including mediated and direct electron transfer mechanisms, offers enhanced performance for applications ranging from microbial fuel cells to CO<small>₂</small> reduction and artificial photosynthesis. Despite the progress, challenges remain in optimizing biocatalyst stability, improving large-scale industrial applicability, and integrating bioelectrocatalysis with solar energy systems. This review highlights these advancements and addresses future directions, emphasizing the role of bioelectrocatalysis in developing a circular bio-economy and sustainable energy infrastructure.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3793-3805"},"PeriodicalIF":4.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514439","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":"Advancements in transition metal iron-based catalysts: enhancing catalytic activity through electron transfer","authors":"Lu Huang, Weigang Zhu and Yunxin Wu","doi":"10.1039/D5CY00096C","DOIUrl":"https://doi.org/10.1039/D5CY00096C","url":null,"abstract":"<p >In this perspective, we aim to explore the latest advancements in a range of design improvements in iron-based catalysts, with a particular focus on electron transfer during catalytic processes. Up to now, various design improvements have been employed to enhance the catalytic activity of heterogeneous iron-based catalysts, including adjustment of microstructure, introduction of support materials, construction of core–shell structures, and incorporation of new components. The effectiveness of these adjustments is contingent upon enhancing the interfacial electron transfer capabilities of heterogeneous iron-based catalysts. Accelerating electron transfer is a fundamental measure to enhance the catalytic ability of the catalyst. Particularly, the activation of pollutants and oxidants during the electron transfer process will lead to different activation mechanisms, combinations, and transformations of activation pathways. Furthermore, considering the practical applications of iron-based composite catalysts, we have also provided future research directions, which address some challenging issues and possible solutions. These directions are crucial for guiding future efforts in catalyst development and optimization.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3784-3792"},"PeriodicalIF":4.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514478","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":"Influence of the supported ionic-liquid layer thickness on Z-selectivity in 1-alkyne hydrosilylation under continuous flow†","authors":"André Böth, Florian Kaltwasser, Christian Priedigkeit, Boshra Atwi, Wolfgang Frey, Michael R. Buchmeiser and Ulrich Tallarek","doi":"10.1039/D5CY00436E","DOIUrl":"https://doi.org/10.1039/D5CY00436E","url":null,"abstract":"<p >1-Butyl-3-methylimidazolium tetrafluoroborate containing different rhodium(<small>I</small>) N-heterocyclic carbene (NHC) complexes was immobilized as a supported ionic-liquid phase (SILP) inside the mesopores of a silica monolith to study the impact of SILP thickness (<em>d</em><small>_SILP</small>) from the thin-SILP-limit (<em>d</em><small>_SILP</small> ≈ 1 nm) to complete mesopore filling (<em>d</em><small>_SILP</small> ≈ 15 nm) on <em>Z</em>/<em>E</em>-selectivity in the rhodium-catalyzed hydrosilylation of phenylacetylene with dimethylphenylsilane. A coupled analytical platform allowed monitoring of both yield and selectivity of the produced isomer pattern online in continuous-flow experiments of 600 minutes using methyl <em>tert</em>-butyl ether as mobile phase. The approach provided new insights into the mechanistic aspects of the reaction under liquid confinement conditions created by the varied SILP thickness. With decreasing <em>d</em><small>_SILP</small>, the selectivity of a Rh-catalyst based on a chelating NHC is shifted towards the β(<em>Z</em>)-isomer, climaxing in a boost of the <em>Z</em>/<em>E</em>-ratio for <em>d</em><small>_SILP</small> = 1 nm by a factor of &gt;30, while the selectivity is mostly unaffected for catalysts based on nonchelating NHCs. The spatial dimension of 1 nm reflects the rigid part of the SILP characterized by a quasi-frozen morphology of the ionic liquid. It shapes a local, spatially as well as molecularly confined catalytic environment, which, together with a tailored catalyst, facilitates the predominant formation of the β(<em>Z</em>)-isomer under kinetic control. Contrariwise, the random, mobile part of the adjoining bulk SILP, emerging with increasing <em>d</em><small>_SILP</small>, generally favors the formation of the β(<em>E</em>)-isomer under thermodynamic control.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 4012-4023"},"PeriodicalIF":4.4,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy00436e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514489","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":"Silver enhanced oxidative coupling of methane over the Mn–Na2WO4/SiO2 catalyst†","authors":"Yilin Zhao, Fangwei Liu, Jingbo Hu, Yang Yang, Jianzhou Wu, Shihui Zou and Jie Fan","doi":"10.1039/D5CY00314H","DOIUrl":"https://doi.org/10.1039/D5CY00314H","url":null,"abstract":"<p >The Mn–Na<small>₂</small>WO<small>₄</small>/SiO<small>₂</small> catalyst for oxidative coupling of methane (OCM) is highly appealing and promising but its high light-off temperature (&gt;800 °C) hinders its industrial application. Engineering catalysts for efficient catalytic performance is attractive yet challenging. In this study, we demonstrate that the incorporation of small amounts of silver into the Mn–Na<small>₂</small>WO<small>₄</small>/SiO<small>₂</small> catalyst significantly improves its performance, achieving a C<small>₂</small> yield of up to 20% at 750 °C. Characterization results indicate that silver facilitates O<small>₂</small> activation and promotes C–H bond activation, thereby further enhancing CH<small>₄</small> conversion. The findings offer valuable insights into advancing the design concept of high-performance OCM catalysts.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3955-3960"},"PeriodicalIF":4.4,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514473","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":"Electrocatalytic oxidation of 5-hydroxymethylfurfural by MnO2 with tunable surface oxidation states†","authors":"Yongle Zhang, Yingyi Tu, Yunying Huo, Guang Pan, Qiao Zhang, Zhiting Liu, Guangxing Yang and Feng Peng","doi":"10.1039/D5CY00341E","DOIUrl":"https://doi.org/10.1039/D5CY00341E","url":null,"abstract":"<p >The electrochemical catalytic oxidation of 5-hydroxymethylfurfural (HMF) to generate high-value products like 2,5-furandicarboxylic acid (FDCA) has become a prominent research interest. In this work, an economical and efficient transition metal ε-MnO<small>₂</small> catalyst was used to electrocatalyze the oxidation of HMF in acidic environments. The results revealed a highly efficient HMF conversion rate of 92.95% and a FDCA yield of 23.03% under the specific conditions of 60 °C, 0.5 M H<small>₂</small>SO<small>₄</small> and 1.6 V (<em>vs.</em> RHE). Furthermore, the study outlined the oxidation pathway for HMF, which progresses through the following sequence: HMF → DFF → FFCA → FDCA. The apparent activation energies associated with each oxidation stage were found to be 25.52, 22.12 and 16.21 kJ mol<small>⁻¹</small>, respectively. Moreover, the findings indicated a favorable relationship between the electrocatalytic oxidation activity of HMF and the average surface oxidation state of ε-MnO<small>₂</small>.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3946-3954"},"PeriodicalIF":4.4,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514475","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":"Understanding alkali-metal driven hydrophosphorylation: mechanism and challenges in the Pudovik reaction†","authors":"Irina Bozhinovska, Gregori Ujaque, Matthias Westerhausen and Agustí Lledós","doi":"10.1039/D5CY00269A","DOIUrl":"https://doi.org/10.1039/D5CY00269A","url":null,"abstract":"<p >The addition of H–P(V) bonds of phosphane oxides across alkynes (hydrophosphorylation reaction) presents an effective synthetic strategy to generate alkenylphosphane oxides. This reaction requires a strong P-nucleophile, such as phosphinite, which can be generated by the reaction of a phosphane oxide with alkali metal amides, such as hexamethyldisilazanides (M-HMDS). Hydrophosphorylation exemplifies an important synthetic reaction facilitated by s-block metal bases. Extensive experimental studies have demonstrated the crucial impact of both the alkali cation and the P-bound substituent on reaction rates, product distribution, and the regio- and stereoselectivity of phosphane oxide addition. This study aims to provide a comprehensive mechanistic interpretation of the alkali metal-catalysed hydrophosphorylation reactions, employing density functional theory (DFT) calculations to clarify experimental findings. Our analysis focuses on two critical stages: 1) formation of the active alkali metal phosphinite species through the metalation–deprotonation of phosphane oxide by M-HMDS, and 2) the subsequent H–P addition onto the alkyne. Additionally, the study addresses side processes that may deactivate the active species by lowering its concentration in solution, potentially impacting the overall reaction efficiency. Computational modelling of reaction mechanisms involving s-block metal cations has been less explored than those with transition metal complexes and faces solvation and speciation as major challenges. This article also discusses the computational requirements necessary for accurate chemical modelling of these systems, as well as the limitations inherent in the employed approach.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 3888-3905"},"PeriodicalIF":4.4,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy00269a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514480","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}