Abstract
Regulating the selectivity of catalysts in selective hydrogenation reactions at the atomic level is highly desirable but remains a grand challenge. Here we report a simple and practical strategy to synthesize a monolithic single-atom catalyst (SAC) with isolated Pd atoms supported on bulk nitrogen-doped carbon foams (Pd-SAs/CNF). Moreover, we demonstrate that the single-atom Pd sites with unique electronic structure endow Pd-SAs/CNF with an isolated site effect, leading to excellent activity and selectivity in 4-nitrophenylacetylene semi-hydrogenation reaction. In addition, benefiting from the great integrity and excellent mechanical strength, monolithic Pd-SAs/CNF catalyst is easy to separate from the reaction system for conducting the subsequent recycling. The cyclic test demonstrates the excellent reusability and stability of monolithic Pd-SAs/CNF catalyst. The discovery of isolated site effect provides a new approach to design highly selective catalysts. And the development of monolithic SACs provides new opportunities to advance the practical applications of single-atom catalysts.
摘要
原子级别调控催化剂在选择性加氢反应中的选择性是一个 巨大的挑战. 在本文中, 我们报告了一种简单实用的策略, 用于合成Pd单原子负载在氮掺杂碳纳米泡沫(Pd-SAs/CNF)上的整体型单原子催化剂. 此外, 我们证明独特电子结构的单原子Pd位点使得Pd-SAs/CNF产生孤立位点效应, 进而导致在4-硝基苯基乙炔半氢化反应中具有出色的活性和选择性. 此外, 得益于较高的完整性和良好的机械强度, 整体型Pd-SAs/CNF催化剂易与反应体系分离, 进一步有利于回收循环利用. 循环测试表明, 整体型Pd-SAs/CNF催化剂具有优异的可重复使用性和稳定性. 孤立位点效应的发现为设计高选择性催化剂提供了一种新方法. 整体式单原子催化剂的研究为推进单原子催化剂的实际应用提供了新的机会.
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Acknowledgements
This work was supported by the National Key R&D Program of China (2018YFA0702003), the National Natural Science Foundation of China (21890383, 21671117, 21871159 and 21901135), the National Postdoctoral Program for Innovative Talents (BX20180160), and the China Postdoctoral Science Foundation (2018M640113). We thank the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF) and 1W1B station for XAFS measurement in Beijing Synchrotron Radiation Facility (BSRF).
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Author contributions Li Y, Wang D and Chen Y conceived the idea, designed the research project and wrote the manuscript; Zhang Z designed the synthesis and controlled experiments, collected and analyzed the data, and wrote the manuscript; Zhou M and Wang H contributed to the computational results and wrote the manuscript; Liu S helped to perform XAFS data analysis; Zhang J helped with catalytic experiments; Ji S contributed to characterizations of samples and data analysis. All the authors commented on the manuscript and have given approval to the final version of the manuscript.
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Zedong Zhang received his BSc degree from the College of Chemical Engineering at Beijing University of Chemical Technology in 2019. He is now a PhD candidate in Prof. Dingsheng Wang’s group at the Department of Chemistry, Tsinghua University. His research interests focus on the explorations of the relationships between different configurations and the functions of isolated single-atom-site catalyst.
Min Zhou is currently a PhD student under the supervision of Prof. Hai-Feng Wang at the Centre for Computational Chemistry, East China University of Science and Technology (ECUST). Her research interests lie in the first-principle simulations of solid and interface structure, theoretical photo- and electro-catalysis, and first-principle simulations of catalytic reactions.
Yuanjun Chen received his BSc degree from the College of Chemical Engineering at Beijing University of Chemical Technology in 2015, and his PhD degree at the Department of Chemistry, Tsinghua University in 2020 under the supervision of Prof. Yadong Li. His research interests focus on the syntheses and applications of functional nanocatalysts and single-atom site catalysts.
Haifeng Wang received his PhD degree from ECUST in 2012, and is now a professor at ECUST. His research interests lie in theoretical catalysis and computational chemistry, with the focus on photoelectrocatalysis and rational design of heterogeneous catalyst driven by AI and ab initio kinetics.
Dingsheng Wang received his BSc degree from the Department of Chemistry and Physics, University of Science and Technology of China in 2004, and his PhD degree from the Department of Chemistry, Tsinghua University in 2009, under the supervision of Prof. Yadong Li. He did his postdoctoral research at the Department of Physics, Tsinghua University, with Prof. Shoushan Fan. He joined the faculty of the Department of Chemistry, Tsinghua University in 2012.
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Zhang, Z., Zhou, M., Chen, Y. et al. Pd single-atom monolithic catalyst: Functional 3D structure and unique chemical selectivity in hydrogenation reaction. Sci. China Mater. 64, 1919–1929 (2021). https://doi.org/10.1007/s40843-020-1579-7
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DOI: https://doi.org/10.1007/s40843-020-1579-7