Journal of Catalysis最新文献

{"title":"Unveiling the structure of interfacial water and its role in acidic and alkaline hydrogen evolution reaction at Au electrode by electrochemical in-situ infrared spectroscopy and theoretical simulation","authors":"Bai-Quan Zhu ,&nbsp;Er-Fei Zhen ,&nbsp;Bing-Yu Liu ,&nbsp;Li-Dan Zhang ,&nbsp;Chen-Yu Zhang ,&nbsp;Zhi-Feng Liu ,&nbsp;Yan-Xia Chen","doi":"10.1016/j.jcat.2025.116021","DOIUrl":"10.1016/j.jcat.2025.116021","url":null,"abstract":"<div><div>Current for hydrogen evolution reaction (HER) in alkaline media has been generally found to be ca. one to two orders of magnitude smaller than that in acid. The origin is under hot debate. Different connectivity of the hydrogen bond networks in the electric double layer (EDL) has been recently proposed to play a significant role in the significant kinetic pH effect. To verify the generality of such an effect, the structure of Au/0.1 M HClO₄ and Au/0.1 M NaOH interfaces and its correlation to HER kinetics have been investigated by cyclic voltammetry, electrochemical <em>in-situ</em> infrared spectroscopy and theoretical simulation. Our results reveal that, i) the current density and corresponding apparent rate constants for HER at Au/HClO₄ are ca. 1 to 80 and 1 to 800 times higher than that at Au/NaOH interface at the same <span><math><mrow><msub><mrow><mi>E</mi></mrow><mrow><mi>R</mi><mi>H</mi><mi>E</mi></mrow></msub></mrow></math></span>, respectively, while the intrinsic rate constants for acidic and alkaline HER estimated after properly considering the EDL effect are comparable; ii) at potentials negative of the potential of zero charge, there is an enrichment of H₃O⁺ and Na⁺ near the surface, and the concentration of Na⁺ near Au surface is slightly higher than that of proton at the same <span><math><mrow><msub><mrow><mi>E</mi></mrow><mrow><mi>R</mi><mi>H</mi><mi>E</mi></mrow></msub></mrow></math></span> due to more free excess charge at Au/NaOH interface. Partial desolvation of hydrated Na⁺ occurs to balance the excess free charge; iii) water structure at Au/NaOH interface is more heterogeneous than that at Au/HClO₄ interface as evidenced by broader O–H stretching band with significant contribution at ca. 3590 cm⁻¹; iv) the superposition of the Onsager field induced by the enriched cations with the field generated by applied electrode potential across the electric double layer leads to a significantly higher Stark tuning rate for the O–H stretching vibration in the alkaline HER range compared to that under acidic conditions; v) instead of the difference in the connectivity of hydrogen bond networks and the dynamics of water reorganization, smaller electrochemical driving force as a result of lower electric potential at the reaction plane is the origin for the smaller current as well as the apparent rate constant for HER at Au in alkaline media than that in acid under mild HER condition.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116021"},"PeriodicalIF":6.5,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"NNN-Ru complexes catalyzed β-methylation of alcohols using methanol via borrowing hydrogen approach","authors":"Mengxuan Bai,&nbsp;Ziying Zhong,&nbsp;Zhiqiang Hao,&nbsp;Xiaoyan Li,&nbsp;Jin Lin","doi":"10.1016/j.jcat.2025.116026","DOIUrl":"10.1016/j.jcat.2025.116026","url":null,"abstract":"<div><div>The methyl groups-containing alcohols are important and valuable chemicals and pharmaceuticals. The development of efficient and sustainable methylation methods is highly desirable. Herein, the <em>β</em>-methylation of primary alcohols using methanol as a green and cost-effective methylating reagent has been successfully achieved with NNN-Ru complexes (<strong>Ru1-Ru5</strong>) as efficient catalysts. It was found that ligand electronics play a crucial role in catalyst activity. Overall, the complex <strong>Ru3</strong> bearing bis-OMe substituents displayed the highest catalytic reactivity. The present catalytic system proceeded <em>via</em> borrowing hydrogen (BH) approach and exhibited broad substrate scope. A variety of alcohols such as 2-arylethanols, 3-arylpropanols and aliphatic chain alcohols were selectively methylated, affording the corresponding products in good to excellent yields.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116026"},"PeriodicalIF":6.5,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultra-thin defective TiO2 films as photocathodes for selective CO2 reduction to formate","authors":"Mahsa Amiri ,&nbsp;Majid Ahmadi ,&nbsp;Nabil Khossossi ,&nbsp;Prasad Gonugunta ,&nbsp;Khatereh Roohi ,&nbsp;Bart Kooi ,&nbsp;Mahinder Ramdin ,&nbsp;Prasaanth Ravi Anusuyadevi ,&nbsp;Tanel Tätte ,&nbsp;Nadezda Kongi ,&nbsp;Alexander Vanetsev ,&nbsp;Poulumi Dey ,&nbsp;Peyman Taheri","doi":"10.1016/j.jcat.2025.116022","DOIUrl":"10.1016/j.jcat.2025.116022","url":null,"abstract":"<div><div>Titanium dioxide (TiO₂) has been widely used as a photocatalyst in CO₂ reduction reaction (CO₂RR) due to its low cost, high stability, and strong absorption in the close-to-visible ultra-violet (UV) range. However, TiO₂ films suffer from poor selectivity in CO₂ reduction due to their unfavorable electronic properties. In this work, we address this challenge by fabricating ultra-thin (14 nm) defective TiO₂ films (TiO₂-DTF) to enhance the selectivity of CO₂RR towards formate.</div><div>TiO₂ sol was prepared using a facile and reproducible sol-gel method and directly deposited onto the surface of the electrode, forming a uniform, ultra-thin TiO₂ layers with a high number of defects. The activity of the TiO₂-DTF catalyst was studied in both photochemical and photoelectrochemical CO₂RR, indicating that the applied potential increases both the yield and selectivity of CO₂RR to formate. The TiO₂-DTF photocathode exhibited remarkable formate production during CO₂ reduction, achieving exceptional Faradaic efficiencies of up to 45 %. To elucidate the mechanism of photoelectrochemical CO₂RR on TiO₂-DTF, an <em>in-situ</em> attenuated total reflection Fourier-transform infrared spectroscopy (<em>in-situ</em> ATR-FTIR) was used and experimental results were supported by density functional theory (DFT) calculations. This study demonstrates that ultra-thin highly defective TiO₂ film, prepared using the cost-effective and environmentally friendly sol-gel method, can be used as photoelectrocatalyst for CO₂ reduction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116022"},"PeriodicalIF":6.5,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Switchable ROS formation inhibits lignin β-O-4 models over-oxidation by CdS modified 2D g-C3N4 for highly efficient and selective producing aromatic monomers under visible light","authors":"Pengrui Zhang ,&nbsp;Chuan Wang ,&nbsp;Xuele Geng ,&nbsp;Jiyuan Xu ,&nbsp;Feng Song ,&nbsp;Hongchang Pei ,&nbsp;Ning-Ning Zhang ,&nbsp;Jian-Ping Zou ,&nbsp;Hongyou Cui ,&nbsp;Hongzi Tan","doi":"10.1016/j.jcat.2025.116007","DOIUrl":"10.1016/j.jcat.2025.116007","url":null,"abstract":"<div><div>Highly efficient and selective cleavage of the C–C linkages in lignin is highly pursued to obtain aromatic monomers but the actual yield is always lower than the theoretical value under photocatalysis. Under the catalysis of 2D <em>g</em>-C₃N₄, both ·O₂^– and ·OH radicals could be generated resulting in a decreased carbon recovery for aromatic monomers (CRAM). The maximum value of CRAM and total yield of aromatic monomers are 49.2 % and 62.6 %, respectively. ·O₂^– radicals take charge of the depolymerization of 2-phenoxy-1-phenylethanol into aromatic monomers by cracking C<em>_α</em>-C<em>_β</em> bonds, while ·OH radicals account for the mineralization of aromatic monomers and the repolymerization of ·C<em>_β</em> intermediates. Herein, a Type-II heterojunction of CdS/2D <em>g</em>-C₃N₄ with modified energy-band structure was rationally designed and successfully prepared, only permitting ·O₂^– generation and inhibiting ·OH formation owing to the lower redox potentials of its photogenerated carriers, which significantly increased the CRAM value and total yield of aromatic monomers (maximum value of CRAM: 91.1 %, total yield of aromatic monomers: 96.5 %). Under the identical conditions, the CRAM value and total yield of aromatic monomers over CdS/2D <em>g</em>-C₃N₄ have increased by 85.2 % and 54.2 % compared to 2D <em>g</em>-C₃N₄ sampling at the same point in time. Moreover, the generation mechanisms for permitting ·O₂^– permit and inhibiting ·OH over CdS/2D <em>g</em>-C₃N₄ were analyzed based on the characterizations of catalyst structure and capture experiments of reaction oxygen species (ROS). The catalytic performances of both samples were also further verified with other lignin models and real lignin as reactants. Current work has not only provided a universal strategy for switchable ROS formation, but also developed an effective photocatalytic system for highly efficient and selective cracking C<em>_α</em>-C<em>_β</em> bonds in lignin <em>β</em>-O-4 linkages under mild conditions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116007"},"PeriodicalIF":6.5,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Borrowing hydrogen alkylation of indenes with alcohols by manganese pincer complex","authors":"Shuaihu Geng ,&nbsp;Jue Yang ,&nbsp;Aleksander A. Lugovski ,&nbsp;Weiping Liu","doi":"10.1016/j.jcat.2025.116011","DOIUrl":"10.1016/j.jcat.2025.116011","url":null,"abstract":"<div><div>Herein, we report a highly efficient and selective formal C3-alkylation of indenes with a wide range of primary and secondary alcohols catalyzed by PNP-manganese pincer complex. This transformation proceeds via a borrowing hydrogen strategy, utilizing sustainable and abundant alcohols as alkylating agents. The reaction offers good functional group tolerance and regioselectivity, providing a practical and straightforward approach to the synthesis of alkylated indenes. Preliminary mechanistic investigations indicate that the reaction proceeds via a multi-step pathway involving the dehydrogenation of the alcohol to a carbonyl intermediate, followed by cross-condensation, hydrogenation, and isomerization steps to afford the final product.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116011"},"PeriodicalIF":6.5,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Consequences of the co-existence of single-atom and nanoparticle catalysts","authors":"Muthuraja Velpandian ,&nbsp;Apurba Sinhamahapatra ,&nbsp;Suddhasatwa Basu","doi":"10.1016/j.jcat.2025.116012","DOIUrl":"10.1016/j.jcat.2025.116012","url":null,"abstract":"<div><div>Single-atom catalysts (SACs) have emerged as promising candidates for electrochemical conversion and storage applications due to their efficient atomic utilization and unique structure, wherein metal atoms are uniformly dispersed and anchored on a support material. This arrangement allows SACs to possess a high density of active sites, maximizing their exposure to reactants and consequently improving reaction rates and selectivity. In light of the growing global demand for renewable and sustainable energy sources, extensive research has been dedicated to designing and fabricating well-defined SAC-based electrocatalysts with optimized electronic structures and diverse compositions over the past decade. Given their exceptional activity and selectivity, particularly for small molecules or key intermediate conversions, the synergistic combination of SACs with nanoparticles (NPs) holds great potential for significantly enhancing performance in complex catalytic processes. In this mini-review, we provide a comprehensive overview of the various possibilities for the co-existence of SACs and nanoparticles, as well as the synthesis and characterization techniques employed in their preparation. Subsequently, we focus on the potential consequences of this co-existence, which has not been extensively explored in the literature, which can lead to improved selectivity towards desire products, thereby boosting the niche applications of these systems. We conclude by emphasizing the major challenges that need to be addressed and highlighting the emerging opportunities in the field of SAC-nanoparticle co-existence systems. By understanding and addressing these challenges, researchers can further advance the development and utilization of hybrid catalyst systems, thereby paving the way for the next generation of efficient and selective catalytic processes.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116012"},"PeriodicalIF":6.5,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418463","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Visible light-induced radical cascade hydroaminoalkylation involving two distinct alkenes","authors":"Zhu-Ming Qian ,&nbsp;Qin Zhang ,&nbsp;Ya-Nan Zhao ,&nbsp;Zhi Guan ,&nbsp;Chu-Sheng Huang ,&nbsp;Yan-Hong He","doi":"10.1016/j.jcat.2025.116010","DOIUrl":"10.1016/j.jcat.2025.116010","url":null,"abstract":"<div><div>This paper describes a visible-light-mediated three-component dicarbofunctionalization of alkenes via a tandem radical addition reaction of two different alkenes triggered by aminoalkyl radicals derived from <em>N</em>-phenyl glycines. This method allows for one-pot skeletal assembly, providing efficient and straightforward access to structurally complex γ-amino sulfone derivatives directly from readily available and simple starting materials. Beyond the convenience of the one-pot protocol, this method also demonstrates broad substrate scope, excellent functional group compatibility, mild reaction conditions, and ease of scalability.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116010"},"PeriodicalIF":6.5,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photo-induced aerobic deborohydroxylation of organoboron compounds in 1,3-dioxolane at room temperature","authors":"Mingjing Deng ,&nbsp;Ke Liu ,&nbsp;Zhaolun Ma ,&nbsp;Qingsheng Qi ,&nbsp;Longyang Dian","doi":"10.1016/j.jcat.2025.116006","DOIUrl":"10.1016/j.jcat.2025.116006","url":null,"abstract":"<div><div>We report herein a simple and efficient light-induced aerobic oxidation of organoboron compounds to obtain phenols in an air atmosphere at room temperature, without the use of any photocatalyst, oxidant or other reagent. This protocol utilizes inexpensive and commercially available 1,3-dioxolane as both the solvent and electron donor to activate the molecular oxygen in the air under 365 nm light, enabling the aerobic oxidation to occur under mild reaction conditions. A wide range of sensitive functional groups are well tolerated, resulting in the corresponding phenols in moderate to good yields.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116006"},"PeriodicalIF":6.5,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solvent-Free terminal alkyne hydrosilylation to β-(E)-vinylsilanes mediated by platinum(II) aminophosphine complexes","authors":"Hanna Stachowiak-Dłużyńska ,&nbsp;Marcin Gruszczyński ,&nbsp;Grzegorz Hreczycho","doi":"10.1016/j.jcat.2025.116027","DOIUrl":"10.1016/j.jcat.2025.116027","url":null,"abstract":"<div><div>This study presents a method for synthesizing β-(E)-vinylsilanes through the hydrosilylation of terminal alkynes with diverse secondary silanes, employing platinum(II) complexes with P,N-donor ligands. The method achieves selective hydrosilylation under solvent-free conditions, yielding up to 99% of alkenylhydrosilanes. It accommodates a wide range of aliphatic, aromatic, and heterocyclic alkynes, representing an advancement in platinum-based protocols by promoting mono-hydrosilylation with secondary silanes. The versatility of this approach is further demonstrated by subsequent transformations of β-(E)-vinylsilanes, indicating its broad applicability in organic synthesis and material chemistry.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116027"},"PeriodicalIF":6.5,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Access to SCF3-containing N-fused quinolines via photo-induced domino radical trifluoromethylthiolation","authors":"Congjun Zhu,&nbsp;Yangyang Shen,&nbsp;Zilong Wang,&nbsp;Jie Xu,&nbsp;Wendong Fang,&nbsp;Haofang Tian,&nbsp;Jinjie Li,&nbsp;Tao Guo","doi":"10.1016/j.jcat.2025.116005","DOIUrl":"10.1016/j.jcat.2025.116005","url":null,"abstract":"<div><div>Radical trifluoromethylthiolation under mild photoredox conditions, show unique utility in the preparation of SCF₃-containing organic skeleton. Here, we report an unprecedented domino radical trifluoromethylthiolation upon photocatalysis. With the established protocol, a wide spectrum of SCF₃-containing N-fused quinolines has been rapidly synthesized. Preliminary mechanistic investigations, including several control experiments and photochemistry measurements, shed light on the catalytic radical reaction mechanism. Sequential evaluated the photophysical properties for selected products is presented, which further underlines the value of this work.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116005"},"PeriodicalIF":6.5,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}