Abstract
Combining the advantages of both heterogeneous and homogeneous catalysts, single-atom catalysts (SACs) with unique electronic properties have shown excellent catalytic properties. Herein, we report single-atom Pd dispersed on na-noscale TiO2 prepared by self-assembly method as efficient and selective catalysts for the hydrogenation of phenylacetylene to styrene. The catalysts were characterized by N2 adsorption/desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray absorption spectroscopy (XAS). 0.2Pd-TiO2(150°C) possessing dominant single-atom Pd species, exhibited a turnover frequency (TOF) of over 8000 h-1 with 91% selectivity towards styrene at room temperature. Further increasing Pd loading from 0.2% to 0.5% and 1.5% resulted in the decrease of activity probably due to the formation of Pd nanoparticles. Besides, the 0.2Pd-TiO2 prepared by self-assembly strategy showed better catalytic performance than commercial 10%Pd/C and 0.2Pd-TiO2 synthesized by using impregnation method.
近年
摘要单原子催化剂(SACs)兼具均相和非均相催化剂的优点, 具有 独特的电子结构, 在某些反应中呈现出优异的催化性能. 本文采用 自组装方法将单原子Pd分散于纳米级的TiO2载体上, 采用N2吸附/ 解吸、XRD、TEM、XPS、DRIFT和XAS对催化剂的结构进行了表征. 在苯乙炔选择加氢制苯乙烯中, 催化剂表现出优异的活性和 选择性. 在室温条件下, 单原子催化剂0.2 wt% Pd-TiO2(150°C)的 TOF达8000 h−1以上, 苯乙烯选择性维持在90%以上. 当Pd负载量增 加到0.5 wt%和1.5 wt%时, Pd物种聚集形成纳米颗粒, 从而使活性 下降. 该方法制备的单原子0.2Pd-TiO2催化剂催化性能显著高于商 品化10%Pd/C以及浸渍法制备的0.2Pd/TiO2催化剂.
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Acknowledgements
This work was supported by the National University of Singapore Flagship Green Energy Program (#R-279-000-553-646 and R-279-000-553-731), the National Natural Science Foundation of China (21908085), and the Natural Science Foundation of Jiangsu Province, China (BK20190961). We also thank Prof. Hiroyuki Asakura from Kyoto University for conducting X-ray absorption spectroscopy measurements.
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Author contributions Song H started the project and prepared the catalysts. Yang F carried out the catalyst synthesis, characterization and catalytic performance test. Yang F wrote the manuscript. Yan N and Ding S supervised the project and revised the manuscript. All authors contributed to the general discussion.
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Fu Yang received his PhD degree from Nanjing Tech University under the supervision of Prof. Yan Kong. During the PhD pursuing period, he worked with Prof. Ning Yan at the National University of Singapore as a China Scholarship Council (CSC) exchange student. After finishing his PhD, he joined Jiangsu University of Science and Technology as a lecturer. His research focuses on the development functional molecular sieve catalyst and nanostructural functional composite materials specific to heterogeneous selective catalytic oxidation/hydrogenation reaction and volatile organic compounds (VOCs) treatment.
Shipeng Ding received his BSc (2012) and MSc (2015) degrees in environmental engineering from Lanzhou University and Chinese Academy of Sciences, respectively. Since 2016, he has been pursuing his PhD in chemical engineering under the supervision of Prof. Ning Yan at the National University of Singapore, focusing on the synthesis, characterization and utilization of single-atom catalysts.
Ning Yan received BSc and PhD degrees in chemistry from Peking University working with Prof. Yuan Kou. After a Marie Curie Fellowship at the École Polytechnique Fédérale de Lausanne in Switzerland with Prof. Paul Dyson, he joined the Department of Chemical and Biomolecular Engineering at the National University of Singapore as an assistant professor in 2012 and was promoted to a tenured associate professor in 2018. Ning Yan works actively in advanced catalysis, renewable energy, and sustainable chemistry, for which he was duly recognized by recent awards from the Royal Society of Chemistry, American Chemical Society and National University of Singapore, among others.
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Yang, F., Ding, S., Song, H. et al. Single-atom Pd dispersed on nanoscale anatase TiO2 for the selective hydrogenation of phenylacetylene. Sci. China Mater. 63, 982–992 (2020). https://doi.org/10.1007/s40843-020-1271-x
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DOI: https://doi.org/10.1007/s40843-020-1271-x