Pub Date : 2025-02-18DOI: 10.1016/j.jcat.2025.116031
Bin Zhu, Xin He, Lingze Liu, Jinglin Liu, Xiaomin Zhang, Ben W.-L. Jang
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 La0.8Sr0.2MnO3-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 (Ov). These features facilitate the generation of a large number of highly active and stable Pt0-Mn3+-Ov 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.
{"title":"Boosting low-concentration toluene oxidation by decorating ultrasmall Pt nanoparticles on La0.8Sr0.2MnO3-δ with hydrogen plasma treatment","authors":"Bin Zhu, Xin He, Lingze Liu, Jinglin Liu, Xiaomin Zhang, Ben W.-L. Jang","doi":"10.1016/j.jcat.2025.116031","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116031","url":null,"abstract":"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<sub>0.8</sub>Sr<sub>0.2</sub>MnO<sub>3-δ</sub> (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 (H<sub>2</sub>) plasma at low temperatures, which leads to the formation of high metallic Pt (Pt<sup>0</sup>), ultrasmall Pt nanoparticles (∼1.3 nm), and high concentration of oxygen vacancy (O<sub>v</sub>). These features facilitate the generation of a large number of highly active and stable Pt<sup>0</sup>-Mn<sup>3+</sup>-O<sub>v</sub> 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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"2 1","pages":""},"PeriodicalIF":7.3,"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}
Pub Date : 2025-02-18DOI: 10.1016/j.jcat.2025.116032
Na Zhu, Lingyu Yu, Lisen Hou, Siying Wang
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 deNOx 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 NOx 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.
{"title":"Insight into the role of Na distribution in Cu-SSZ-39 catalysts","authors":"Na Zhu, Lingyu Yu, Lisen Hou, Siying Wang","doi":"10.1016/j.jcat.2025.116032","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116032","url":null,"abstract":"Cu-SSZ-39 has garnered significant attention because of its outstanding NH<sub>3</sub>-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 NH<sub>4</sub>-SSZ-39. Comparative characterization of the Cu-SSZ-39 catalysts, derived from both Na-SSZ-39 and NH<sub>4</sub>-SSZ-39 exchanges demonstrated that the positioning of Na cations affected Cu distribution, and controlling Na distribution can enhance deNO<em><sub>x</sub></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><sub>x</sub></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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"1 1","pages":""},"PeriodicalIF":7.3,"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}
Pub Date : 2025-02-17DOI: 10.1016/j.jcat.2025.116028
Nikita F. Eremeev, Semon A. Hanna, Ekaterina M. Sadovskaya, Aleksandra A. Leonova, Olga A. Bulavchenko, Arcady V. Ishchenko, Igor P. Prosvirin, Vladislav A. Sadykov, Yuliya N. Bespalko
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 (D* 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.
{"title":"Catalysts for ethanol dry reforming based on high-entropy perovskites","authors":"Nikita F. Eremeev, Semon A. Hanna, Ekaterina M. Sadovskaya, Aleksandra A. Leonova, Olga A. Bulavchenko, Arcady V. Ishchenko, Igor P. Prosvirin, Vladislav A. Sadykov, Yuliya N. Bespalko","doi":"10.1016/j.jcat.2025.116028","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116028","url":null,"abstract":"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<sup>–12</sup> cm<sup>2</sup>/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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"18 1","pages":""},"PeriodicalIF":7.3,"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}
Pub Date : 2025-02-17DOI: 10.1016/j.jcat.2025.116008
Stepan M. Korobkov, Kirill P. Birin, Aslan Yu. Tsivadze
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 ptotocatalytic 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 ca. 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 gram-scale sulfoxidation is also successfully demonstrated.
{"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, Kirill P. Birin, Aslan Yu. Tsivadze","doi":"10.1016/j.jcat.2025.116008","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116008","url":null,"abstract":"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 ptotocatalytic 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 ca. 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 gram-scale sulfoxidation is also successfully demonstrated.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"35 1","pages":""},"PeriodicalIF":7.3,"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}
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 network 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 HClO<sub>4</sub> 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/HClO<sub>4</sub> are ca. 1 to 80 and 1 to 800 times higher than that at Au/NaOH interface at the same <span><span><math><msub is="true"><mi is="true">E</mi><mrow is="true"><mi is="true" mathvariant="normal">R</mi><mi is="true" mathvariant="normal">H</mi><mi is="true" mathvariant="normal">E</mi></mrow></msub></math></span><script type="math/mml"><math><msub is="true"><mi is="true">E</mi><mrow is="true"><mi mathvariant="normal" is="true">R</mi><mi mathvariant="normal" is="true">H</mi><mi mathvariant="normal" is="true">E</mi></mrow></msub></math></script></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 H<sub>3</sub>O<sup>+</sup> and Na<sup>+</sup> near the surface, and the concentration of Na<sup>+</sup> near Au surface is slightly higher than that of proton at the same <span><span><math><msub is="true"><mi is="true">E</mi><mrow is="true"><mi is="true" mathvariant="normal">R</mi><mi is="true" mathvariant="normal">H</mi><mi is="true" mathvariant="normal">E</mi></mrow></msub></math></span><script type="math/mml"><math><msub is="true"><mi is="true">E</mi><mrow is="true"><mi mathvariant="normal" is="true">R</mi><mi mathvariant="normal" is="true">H</mi><mi mathvariant="normal" is="true">E</mi></mrow></msub></math></script></span> due to more free excess charge at Au/NaOH interface. Partial desolvation of hydrated Na<sup>+</sup> occurs to balance the excess free charge; iii) water structure at Au/NaOH interface is more heterogeneous than that at Au/HClO<sub>4</sub> interface as evident by broader O–H stretching band with significant contribution at ca. 3590 cm<sup>−1</sup>; 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 network and the dynamics of water reorganization, smaller electrochemical driving f
{"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, Er-Fei Zhen, Bing-Yu Liu, Li-Dan Zhang, Chen-Yu Zhang, Zhi-Feng Liu, Yan-Xia Chen","doi":"10.1016/j.jcat.2025.116021","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116021","url":null,"abstract":"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 network 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 HClO<sub>4</sub> 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/HClO<sub>4</sub> are ca. 1 to 80 and 1 to 800 times higher than that at Au/NaOH interface at the same <span><span><math><msub is=\"true\"><mi is=\"true\">E</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">R</mi><mi is=\"true\" mathvariant=\"normal\">H</mi><mi is=\"true\" mathvariant=\"normal\">E</mi></mrow></msub></math></span><script type=\"math/mml\"><math><msub is=\"true\"><mi is=\"true\">E</mi><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">R</mi><mi mathvariant=\"normal\" is=\"true\">H</mi><mi mathvariant=\"normal\" is=\"true\">E</mi></mrow></msub></math></script></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 H<sub>3</sub>O<sup>+</sup> and Na<sup>+</sup> near the surface, and the concentration of Na<sup>+</sup> near Au surface is slightly higher than that of proton at the same <span><span><math><msub is=\"true\"><mi is=\"true\">E</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">R</mi><mi is=\"true\" mathvariant=\"normal\">H</mi><mi is=\"true\" mathvariant=\"normal\">E</mi></mrow></msub></math></span><script type=\"math/mml\"><math><msub is=\"true\"><mi is=\"true\">E</mi><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">R</mi><mi mathvariant=\"normal\" is=\"true\">H</mi><mi mathvariant=\"normal\" is=\"true\">E</mi></mrow></msub></math></script></span> due to more free excess charge at Au/NaOH interface. Partial desolvation of hydrated Na<sup>+</sup> occurs to balance the excess free charge; iii) water structure at Au/NaOH interface is more heterogeneous than that at Au/HClO<sub>4</sub> interface as evident by broader O–H stretching band with significant contribution at ca. 3590 cm<sup>−1</sup>; 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 network and the dynamics of water reorganization, smaller electrochemical driving f","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"2 1","pages":""},"PeriodicalIF":7.3,"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}
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.
通过掺杂杂原子调整电子分布已成为改善镍单原子催化剂电化学二氧化碳还原（ECR）性能的一种有前途的策略。本文通过密度泛函理论计算（DFT）验证了在第一层外壳中掺杂磷原子可以调节镍中心的价态，提高外壳的电子密度，有利于中间体吸附、电子转移和降低反应能垒，从而获得优异的 ECR 性能。在理论计算结果的指导下，通过植酸改性和煅烧处理，成功制备了掺杂磷原子的非对称单原子镍催化剂。X 射线光电子能谱和 X 射线吸收精细结构能谱证明，掺杂磷原子后，镍的价态发生负迁移，成为富电子态，这与 DFT 计算结果一致。这种催化剂显示出卓越的 ECR 性能，在宽电位范围内一氧化碳远红外效率超过 90%，在流动池中 -1.0 V 电压下一氧化碳部分电流密度高达 -244.1 mA cm-2。不对称电子调节策略可应用于其他过渡金属单原子，以提高其催化性能。
{"title":"Construction of electron-rich nickel single atom catalyst by heteroatom doping for enhanced CO2 electroreduction","authors":"Jiale Sun, Kaiqi Li, Zhen Liu, Junwei Xu, Ping Gao, Meng Wang, Yifei Li, Rilong Zhu, Ivan P. Parkin, Zhongyuan Huang","doi":"10.1016/j.jcat.2025.116020","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116020","url":null,"abstract":"Adjustment of electron distribution by heteroatom doping has emerged as a promising strategy to improve the electrochemical CO<sub>2</sub> 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<sup>−2</sup> 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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"11 1","pages":""},"PeriodicalIF":7.3,"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}
Pub Date : 2025-02-15DOI: 10.1016/j.jcat.2025.116026
Mengxuan Bai, Ziying Zhong, Zhiqiang Hao, Xiaoyan Li, Jin Lin
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 β-methylation of primary alcohols using methanol as a green and cost-effective methylating reagent has been successfully achieved with NNN-Ru complexes (Ru1-Ru5) as efficient catalysts. It was found that ligand electronics play a crucial role in catalyst activity. Overall, the complex Ru3 bearing bis-OMe substituents displayed the highest catalytic reactivity. The present catalytic system proceeded via 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.
{"title":"NNN-Ru complexes catalyzed β-methylation of alcohols using methanol via borrowing hydrogen approach","authors":"Mengxuan Bai, Ziying Zhong, Zhiqiang Hao, Xiaoyan Li, Jin Lin","doi":"10.1016/j.jcat.2025.116026","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116026","url":null,"abstract":"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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"3 1","pages":""},"PeriodicalIF":7.3,"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}
Pub Date : 2025-02-15DOI: 10.1016/j.jcat.2025.116022
Mahsa Amiri, Majid Ahmadi, Nabil Khossossi, Prasad Gonugunta, Khatereh Roohi, Bart Kooi, Mahinder Ramdin, Prasaanth Ravi Anusuyadevi, Tanel Tätte, Nadezda Kongi, Alexander Vanetsev, Poulumi Dey, Peyman Taheri
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.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 up to 45 %. To elucidate the mechanism of photoelectrochemical CO2RR on TiO2-DTF, an in-situ attenuated total reflection Fourier-transform infrared spectroscopy (in-situ 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.
{"title":"Ultra-thin defective TiO2 films as photocathodes for selective CO2 reduction to formate","authors":"Mahsa Amiri, Majid Ahmadi, Nabil Khossossi, Prasad Gonugunta, Khatereh Roohi, Bart Kooi, Mahinder Ramdin, Prasaanth Ravi Anusuyadevi, Tanel Tätte, Nadezda Kongi, Alexander Vanetsev, Poulumi Dey, Peyman Taheri","doi":"10.1016/j.jcat.2025.116022","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116022","url":null,"abstract":"Titanium dioxide (TiO<sub>2</sub>) has been widely used as a photocatalyst in CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) due to its low cost, high stability, and strong absorption in the close-to-visible ultra-violet (UV) range. However, TiO<sub>2</sub> films suffer from poor selectivity in CO<sub>2</sub> reduction due to their unfavorable electronic properties. In this work, we address this challenge by fabricating ultra-thin (14 nm) defective TiO<sub>2</sub> films (TiO<sub>2</sub>-DTF) to enhance the selectivity of CO<sub>2</sub>RR towards formate.TiO<sub>2</sub> 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 TiO<sub>2</sub> layers with a high number of defects. The activity of the TiO<sub>2</sub>-DTF catalyst was studied in both photochemical and photoelectrochemical CO<sub>2</sub>RR, indicating that the applied potential increases both the yield and selectivity of CO<sub>2</sub>RR to formate. The TiO<sub>2</sub>-DTF photocathode exhibited remarkable formate production during CO<sub>2</sub> reduction, achieving exceptional Faradaic efficiencies up to 45 %. To elucidate the mechanism of photoelectrochemical CO<sub>2</sub>RR on TiO<sub>2</sub>-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 TiO<sub>2</sub> film, prepared using the cost-effective and environmentally friendly sol-gel method, can be used as photoelectrocatalyst for CO<sub>2</sub> reduction.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"195 1","pages":""},"PeriodicalIF":7.3,"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}
Pub Date : 2025-02-15DOI: 10.1016/j.jcat.2025.116007
Pengrui Zhang , Chuan Wang , Xuele Geng , Jiyuan Xu , Feng Song , Hongchang Pei , Ning-Ning Zhang , Jian-Ping Zou , Hongyou Cui , Hongzi Tan
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 g-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 Cα-Cβ bonds, while ·OH radicals account for the mineralization of aromatic monomers and the repolymerization of ·Cβ intermediates. Herein, a Type-II heterojunction of CdS/2D g-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 g-C3N4 have increased by 85.2 % and 54.2 % compared to 2D g-C3N4 sampling at the same point in time. Moreover, the generation mechanisms for permitting ·O2– permit and inhibiting ·OH over CdS/2D g-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 Cα-Cβ bonds in lignin β-O-4 linkages under mild conditions.
{"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 , Chuan Wang , Xuele Geng , Jiyuan Xu , Feng Song , Hongchang Pei , Ning-Ning Zhang , Jian-Ping Zou , Hongyou Cui , 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>-C<sub>3</sub>N<sub>4</sub>, both ·O<sub>2</sub><sup>–</sup> 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. ·O<sub>2</sub><sup>–</sup> radicals take charge of the depolymerization of 2-phenoxy-1-phenylethanol into aromatic monomers by cracking C<em><sub>α</sub></em>-C<em><sub>β</sub></em> bonds, while ·OH radicals account for the mineralization of aromatic monomers and the repolymerization of ·C<em><sub>β</sub></em> intermediates. Herein, a Type-II heterojunction of CdS/2D <em>g</em>-C<sub>3</sub>N<sub>4</sub> with modified energy-band structure was rationally designed and successfully prepared, only permitting ·O<sub>2</sub><sup>–</sup> 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>-C<sub>3</sub>N<sub>4</sub> have increased by 85.2 % and 54.2 % compared to 2D <em>g</em>-C<sub>3</sub>N<sub>4</sub> sampling at the same point in time. Moreover, the generation mechanisms for permitting ·O<sub>2</sub><sup>–</sup> permit and inhibiting ·OH over CdS/2D <em>g</em>-C<sub>3</sub>N<sub>4</sub> 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><sub>α</sub></em>-C<em><sub>β</sub></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}
Pub Date : 2025-02-15DOI: 10.1016/j.jcat.2025.116011
Shuaihu Geng, Jue Yang, Aleksander A. Lugovski, Weiping Liu
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.
{"title":"Borrowing hydrogen alkylation of indenes with alcohols by manganese pincer complex","authors":"Shuaihu Geng, Jue Yang, Aleksander A. Lugovski, Weiping Liu","doi":"10.1016/j.jcat.2025.116011","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116011","url":null,"abstract":"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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"13 1","pages":""},"PeriodicalIF":7.3,"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}
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