Journal of Catalysis最新文献

{"title":"Exhaustive reduction of aromatic esters and carboxylic acids with a homogeneous cobalt catalyst","authors":"Zi-Heng Zhang ,&nbsp;Rui Sun ,&nbsp;Yuan-Yuan Jiang ,&nbsp;Jin-Qing Lin ,&nbsp;Yan-Qiang Zhang ,&nbsp;Bao-Hua Xu","doi":"10.1016/j.jcat.2025.116034","DOIUrl":"10.1016/j.jcat.2025.116034","url":null,"abstract":"<div><div>A one-step procedure to exhaustively reduce aromatic esters and carboxylic acids to their corresponding tolyl derivatives is a significant transformation in organic synthesis, which remains challenging in homogeneous catalysis. In this study, it’s achieved by using the well-defined phosphinesulfonate chelated cobalt-based catalyst (Co(dppbsa)), along with NaBAr^F₄ as the basic additive and (MeO)₂MeSiH as the reductant. Particularly, this cobalt catalysis proceeds through ether intermediates. Experimental combined theoretical results support it follows an outer-sphere ionic hydrosilylation mechanism and the in situ formed cationic siloxane species are involved in the rate-limiting hydride transfer. The same system also enables the catalytic deoxygenation of aliphatic esters, aliphatic acids, and amides but terminating at the corresponding ethers, alkanols and secondary amines, respectively. These findings open up novel avenues for the catalytic application of phosphinesulfonate chelated complexes, potentially serving as the foundation for the exhaustive reduction of carboxylic skeletons with cobalt.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116034"},"PeriodicalIF":6.5,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462321","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":"The enhanced reactivity of graphitic supports for Pd catalyzed toluene hydrogenation","authors":"Alaba U. Ojo ,&nbsp;Deependra M. Shakya ,&nbsp;Julian Stetzler ,&nbsp;Musbau Gbadamosi ,&nbsp;Rahman Md. Masudur ,&nbsp;Narayan Acharya ,&nbsp;Nathan Thornburg ,&nbsp;John Tengco ,&nbsp;Santosh Kiran Balijepalli ,&nbsp;John R. Monnier ,&nbsp;Donna A. Chen ,&nbsp;John R. Regalbuto","doi":"10.1016/j.jcat.2025.116029","DOIUrl":"10.1016/j.jcat.2025.116029","url":null,"abstract":"<div><div>The hydrogenation of toluene to methylcyclohexane has recently been explored as a potential liquid hydrogen carrier system whereby methylcyclohexane can be safely and efficiently transported. Supported metal catalysts are currently being studied and optimized for this application. In this work, a pronounced support effect is demonstrated. Palladium catalysts on graphitic carbons were found to exhibit significantly enhanced toluene hydrogenation rates versus activated carbons and silica supports. Hydrogen temperature programmed desorption results appear to rule out the role of intercalated hydrogen. Using characterization by powder XRD, Raman and x-ray photoelectron spectroscopies, it is suggested that the enhancement in activity arises when a critical degree of crystallinity at the support surface enhances toluene adsorption and opens parallel reaction pathways.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116029"},"PeriodicalIF":6.5,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462322","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":"Divergent photoreduction of nitroaromatic compounds catalysed by dithienoquinoxaline","authors":"Zuzana Burešová ,&nbsp;Monika Grygarová ,&nbsp;Eva Prokopová ,&nbsp;Milan Klikar ,&nbsp;Oldřich Pytela ,&nbsp;Jiří Váňa ,&nbsp;Abul Mansur Muhammed Fahim ,&nbsp;Kanyashree Jana ,&nbsp;Ekaterina Zubova ,&nbsp;Jan Bartáček ,&nbsp;Jiří Tydlitát ,&nbsp;Zdeňka Růžičková ,&nbsp;Radek Cibulka ,&nbsp;Kirk S. Schanze ,&nbsp;Filip Bureš","doi":"10.1016/j.jcat.2025.116033","DOIUrl":"10.1016/j.jcat.2025.116033","url":null,"abstract":"<div><div>Nitroaromatic compounds can be conveniently reduced to anilines with the aid of a variety of chemical reductants. However, chemodivergent and chemoselective reduction of functionalized nitroaromatics into valuable nitroso, azo(xy), (hydr)azo and (hydroxyl)amino derivatives remains rather elusive. Electro- and photochemical strategies utilizing various catalytic systems and reaction media have been tested but most have been directed towards individual reduction products. Here, we present the photoredox-enabled chemodivergent reduction of nitroaromatics to nitroso, bis-(<em>N</em>,<em>O</em>-diacetyl)-<em>N</em>-arylhydroxylamine, azoxy, azo and amino derivatives. The developed protocol utilizes a novel photocatalyst, 6,9-dimethoxydithieno[2,3-<em>f</em>:3′,2′-<em>h</em>]quinoxaline-2,3-dicarbonitrile, and Hantzsch ester/triethanolamine as reductants. With the single organic photocatalyst, the reaction environment, temperature, time and catalyst loading can be varied to achieve chemodivergent photoreduction of nitroaromatics bearing various functional groups and to access a library of valuable products. The application of this methodology to multigram preparations of molecules of pharmaceutical and industrial relevance highlights its practical utility.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116033"},"PeriodicalIF":6.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451572","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":"Boosting low-concentration toluene oxidation by decorating ultrasmall Pt nanoparticles on La0.8Sr0.2MnO3-δ with hydrogen plasma treatment","authors":"Bin Zhu ,&nbsp;Xin He ,&nbsp;Lingze Liu ,&nbsp;Jinglin Liu ,&nbsp;Xiaomin Zhang ,&nbsp;Ben W.-L. Jang","doi":"10.1016/j.jcat.2025.116031","DOIUrl":"10.1016/j.jcat.2025.116031","url":null,"abstract":"<div><div>Perovskite is one of the most promising materials for catalytic oxidation of volatile organic compounds (VOCs) because of its special tunable structure and properties as well as high stability. However, it commonly suffers from relatively low catalytic activity due to the low specific surface area and limited numbers of active sites caused by high synthesis temperature required. To improve the<!--> <!-->reactivity of the perovskite catalyst, a promising strategy is to construct highly dispersed noble metal sites on surfaces perovskite. However, generating highly active metallic sites while exhibiting good thermal stability remains a formidable challenge. Here, it’s demonstrated that the construction of highly efficient and robust platinum (Pt) sites on La_0.8Sr_0.2MnO_3-δ (Pt/LSMO) for toluene oxidation resulted in an almost three-fold increase in toluene conversion with a good stability. The key to the construction of these Pt sites is treating the oxidized Pt species on LSMO with hydrogen (H₂) plasma at low temperatures, which leads to the formation of high metallic Pt (Pt⁰), ultrasmall Pt nanoparticles (∼1.3 nm), and high concentration of oxygen vacancy (O_v). These features facilitate the generation of a large number of highly active and stable Pt⁰-Mn³⁺-O_v sites on Pt/LSMO, which contribute to the activation of toluene and oxygen species and, therefore, the catalytic reaction. This investigation demonstrates a promising approach of using the cold plasma technique to design and construct high-performing noble-based perovskite catalysts for toluene oxidation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116031"},"PeriodicalIF":6.5,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443797","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":"Insight into the role of Na distribution in Cu-SSZ-39 catalysts","authors":"Na Zhu,&nbsp;Lingyu Yu,&nbsp;Lisen Hou,&nbsp;Siying Wang","doi":"10.1016/j.jcat.2025.116032","DOIUrl":"10.1016/j.jcat.2025.116032","url":null,"abstract":"<div><div>Cu-SSZ-39 has garnered significant attention because of its outstanding NH₃-SCR activity and hydrothermal stability. To facilitate commercial application of Cu-SSZ-39, it is crucial to streamline the synthesis process, adopt eco-friendly synthesis methods, enhance the catalytic performance, and explore the underlying catalytic mechanisms. Herein, ammonia exchange was skipped and Cu-SSZ-39 was directly synthesized via Cu-exchange of Na-SSZ-39. This approach yielded a Cu-SSZ-39 with superior catalytic performance compared to that prepared using the conventional NH₄-SSZ-39. Comparative characterization of the Cu-SSZ-39 catalysts, derived from both Na-SSZ-39 and NH₄-SSZ-39 exchanges demonstrated that the positioning of Na cations affected Cu distribution, and controlling Na distribution can enhance deNO<em>_x</em> activity. It was also found that while cation locations did not alter the reaction mechanism of Cu-SSZ-39 at low temperature, they did increase the concentration of active NO<em>_x</em> intermediates, thereby boosting catalytic performance. This study facilitates a more sustainable synthesis of Cu-SSZ-39 and provides deeper insights into how cations’ distribution in zeolites affects catalytic efficiency.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116032"},"PeriodicalIF":6.5,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443798","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":"Catalysts for ethanol dry reforming based on high-entropy perovskites","authors":"Nikita F. Eremeev ,&nbsp;Semon A. Hanna ,&nbsp;Ekaterina M. Sadovskaya ,&nbsp;Aleksandra A. Leonova ,&nbsp;Olga A. Bulavchenko ,&nbsp;Arcady V. Ishchenko ,&nbsp;Igor P. Prosvirin ,&nbsp;Vladislav A. Sadykov ,&nbsp;Yuliya N. Bespalko","doi":"10.1016/j.jcat.2025.116028","DOIUrl":"10.1016/j.jcat.2025.116028","url":null,"abstract":"<div><div>Ethanol dry reforming is a promising way to produce syngas and hydrogen due to utilization of carbon dioxide and ability to produce ethanol using renewable sources. Main problem associated with ethanol dry reforming reaction is coke formation. Coking suppression can be achieved in a few ways including use of catalysts possessing required oxygen transport properties. High entropy oxides are of interest in application as catalysts for ethanol dry reforming and other reactions due to their structural stability, disordering features and tunability of functional properties. In this work, the catalysts based on Ni and multiple doped La manganites are studied. The oxides are synthesized by modified Pechini and citrate techniques, and the catalysts are prepared by wetness impregnation. The samples are characterized by XRD, TEM with EDX analysis, XPS. Oxygen transport and redox properties are studied by temperature-programmed isotope exchange of oxygen and reduction. According to structural and morphological studies, the samples are nanosized and form perovskite-like structure. The surface features of samples were characterized by XPS. The samples demonstrate a moderate oxygen mobility (<em>D*</em> up to ∼10^–12 cm²/s at 700 °C) required for catalytic operation and coking suppression. Tests in ethanol dry reforming demonstrated fine performance and good stability in the reaction conditions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116028"},"PeriodicalIF":6.5,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435366","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":"Supremely high turnover numbers with a simple porphyrin photosensitizer: Kinetic and mechanistic insights into the oxidation of sulfides with singlet oxygen","authors":"Stepan M. Korobkov ,&nbsp;Kirill P. Birin ,&nbsp;Aslan Yu. Tsivadze","doi":"10.1016/j.jcat.2025.116008","DOIUrl":"10.1016/j.jcat.2025.116008","url":null,"abstract":"<div><div>The evaluation of the porphyrin-sensitized photocatalytic sulfoxidation mechanism with kinetic studies and DFT calculations is reported. The precise evaluation of the factors, determining the observed efficiency of the photocatalytic process, namely the photostability of the sensitizer, its loading, origin of the solvent, was performed. The revealed insights into the reaction mechanism allowed the development of the photooxidation protocol exceeding the turnover number (TON) values of typical porphyrin sensitizers by <em>ca</em>. two orders of magnitude reaching values up to<!--> <!-->830<!--> <!-->000 using a simple tetrapyrrolic sensitizer (5,10,15,20-tetraphenylporphyrin, TPP). The scope of the developed protocol is proved by preparation of a series of sulfoxides bearing substituents of different electronic nature. The applicability of the developed protocol is a gram-scale sulfoxidation which was also successfully demonstrated.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116008"},"PeriodicalIF":6.5,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435398","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":"Construction of electron-rich nickel single atom catalyst by heteroatom doping for enhanced CO2 electroreduction","authors":"Jiale Sun ,&nbsp;Kaiqi Li ,&nbsp;Zhen Liu ,&nbsp;Junwei Xu ,&nbsp;Ping Gao ,&nbsp;Meng Wang ,&nbsp;Yifei Li ,&nbsp;Rilong Zhu ,&nbsp;Ivan P. Parkin ,&nbsp;Zhongyuan Huang","doi":"10.1016/j.jcat.2025.116020","DOIUrl":"10.1016/j.jcat.2025.116020","url":null,"abstract":"<div><div>Adjustment of electron distribution by heteroatom doping has emerged as a promising strategy to improve the electrochemical CO₂ reduction (ECR) performance of nickel single atom catalysts. Herein, density functional theory calculation (DFT) verifies that the doping of phosphorus atoms in the first shell regulates the valence state of the nickel centre and facilitates higher electron density in the outer shell, which is beneficial to intermediate adsorption, electron transfer and the decrease of reaction energy barrier, resulting in outstanding ECR performance. Guided by the theoretical calculation results, the asymmetrical nickel single atom catalyst doped with phosphorus atom was successfully fabricated by phytic acid modification and calcination treatment. X-ray photoelectron spectroscopy and X-ray absorption fine structure spectroscopy prove that the valence state of nickel exhibits a negative shift and makes them electron-rich after doping phosphorus atom, which is consistent with DFT results. Such catalyst displays superior ECR performance with CO faradaic efficiency above 90 % at a wide potential range and a high CO partial current density of −244.1 mA cm⁻² at −1.0 V in flow cell. The asymmetric electron regulation strategy can be potentially applied to the other transition metal single atoms to enhance their catalytic performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116020"},"PeriodicalIF":6.5,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418439","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":"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}