He Dongcheng, Li Teng, Dai Xingchao, Liu Shujuan, Cui Xinjiang, Shi Feng
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No. 18, Tianshui Middle Road, Lanzhou 730000, China.
University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing 100049, China.
J Am Chem Soc. 2023 Sep 27;145(38):20813-20824. doi: 10.1021/jacs.3c04576. Epub 2023 Sep 18.
Surface molecular imprinting (MI) is one of the most efficient techniques to improve selectivity in a catalytic reaction. Heretofore, a prerequisite to fabricating selective catalysts by MI strategies is to sacrifice the number of surface-active sites, leading to a remarkable decrease of activity. Thus, it is highly desirable to design molecular imprinting catalysts (MICs) in which both the catalytic activity and selectivity are significantly enhanced. Herein, a series of MICs are prepared by sequentially adsorbing imprinting molecules (nitro compounds, ) and imprinting ligand (1,10-phenanthroline, ) over the copper surface of Cu/AlO. The resulting Cu/AlO-N-L MICs not only offer promoted catalytic selectivity but also enhance catalytic activity for nitro compounds hydrogenation by an creating imprinting cavity derived from the presorption of and forming new active Cu-N sites at the interface of the copper sites and . Characterizations by means of various experimental investigations and DFT calculations disclose that the molecular imprinting effect (promoted activity and selectivity) originates from the formation of new active Cu-N sites and precise imprinting cavities, endowing promoted catalytic selectivity and activity on the hydrogenation of nitro compounds.
表面分子印迹（MI）是提高催化反应选择性的最有效技术之一。迄今为止，通过MI策略制备选择性催化剂的一个先决条件是牺牲表面活性位点的数量，导致活性显著降低。因此，非常需要设计一种分子印迹催化剂（MICs），使其催化活性和选择性都得到显著提高。在此，通过在Cu/AlO的铜表面依次吸附印迹分子（硝基化合物）和印迹配体（1,10-菲咯啉）制备了一系列MICs。所得的Cu/AlO-N-L MICs不仅具有更高的催化选择性，而且通过形成由预吸附产生的印迹空腔并在铜位点和的界面处形成新的活性Cu-N位点，提高了对硝基化合物氢化的催化活性。通过各种实验研究和DFT计算进行的表征表明，分子印迹效应（提高的活性和选择性）源于新活性Cu-N位点和精确印迹空腔的形成，赋予了对硝基化合物氢化更高的催化选择性和活性。
