近日,中国科学院金属研究所刘洪阳团队实现了氨基巢型增强Pd/SiO2单原子催化剂用于乙炔的高效选择性半加氢反应。相关论文于2025年8月25日发表在《德国应用化学》杂志上。
乙炔选择性加氢制乙烯是提纯乙烯原料的关键工业过程。钯单原子催化剂(Pd SACs)在加氢反应中表现出优异的乙烯选择性。然而,它们孤立的活性位点显示出从富乙烯流中捕获和吸附微量乙炔分子的能力有限,导致相对较低的加氢活性。
为了克服这一限制,研究组在含有氨基巢(Pd1/SiO2-NH2)修饰的SiO2表面设计了Pd单原子催化剂。在这种结构中,钯单原子嵌入在SiO2-NH2载体表面的氨基巢中。结合实验和密度泛函理论(DFT)计算表明,氨基巢选择性地捕获和吸附富乙烯流中的乙炔分子,促进了关键的乙炔吸附步骤。在氨基巢和Pd原子之间形成的Pd─N键促进了氢的活化。
在190℃下,Pd1/SiO2-NH2催化剂实现了完全的乙炔转化,乙烯选择性为92%。值得注意的是,它的比活性为1900.36 molC2H2−1 molPd−1 min−1,超过了之前报道的所有SAC。这项工作为单原子催化剂建立了氨基巢辅助设计范例,实现了乙炔的高效、选择性半氢化。
附:英文原文
Title: Amino Nests Boost Pd/SiO2 Single-Atom Catalysts for Efficient Selective Semi-Hydrogenation of Acetylene
Author: Jingwang Zhang, Wan Wang, Jiawei Chen, Xiangbin Cai, Lini Yang, Mi Peng, Yue Wang, Yang Si, Feng Hong, Xiaowen Chen, Bo Sun, Jiangyong Diao, Li Jin, Guoqing Wang, Ding Ma, Hongyang Liu
Issue&Volume: 2025-08-25
Abstract: The selective hydrogenation of acetylene to ethylene is a critical industrial process for purifying ethylene feedstocks. Palladium single-atom catalysts (Pd SACs) exhibit exceptional ethylene selectivity in this hydrogenation reaction. However, their isolated active sites show limited ability to capture and adsorb trace acetylene molecules from ethylene-rich streams, resulting in relatively low hydrogenation activity. To overcome this limitation, we designed Pd single-atom catalyst on the SiO2 surface modified with amino nests (Pd1/SiO2-NH2). In this architecture, Pd single atoms are embedded within amino nests on the surface of SiO2-NH2 support. Combined experimental and density functional theory (DFT) calculations reveal that amino nests selectively capture and adsorb acetylene molecules from ethylene-rich streams, facilitating the key acetylene adsorption step. The Pd─N bonds formed between the amino nest and the Pd atom promote hydrogen activation. At 190 °C, the Pd1/SiO2-NH2 catalyst achieves complete acetylene conversion with the ethylene selectivity of 92%. Remarkably, it delivers a specific activity of 1900.36 mol C2H21 molPd1 min1, surpassing all previously reported SACs. This work establishes an amino nest-assisted design paradigm for single-atom catalysts, enabling efficient, selective semi-hydrogenation of acetylene.
DOI: 10.1002/anie.202515937
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202515937
Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:16.823
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx