Li Peicai, Liu Xia, Guo Mingrui, Pi Yecan, Wang Ning, Bai Shuxing, Xu Yong, Sun Qi
Institute for Sustainable Energy and Resources, College of Chemistry and Chemical, Engineering, Qingdao University, Qingdao, 266071, China.
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, China.
Small Methods. 2023 Mar;7(3):e2201356. doi: 10.1002/smtd.202201356. Epub 2023 Jan 24.
Phase engineering of nanomaterials plays a crucial role for regulating the catalytic performance. Nevertheless, great challenges still remain for elucidating the structure-selectivity correlation. Herein, this study demonstrates that the body-centered cubic phase of PdCu (bcc-PdCu) can serve as a highly active and selective catalyst for 3-nitrostyrene (NS) hydrogenation under mild conditions. In particular, bcc-PdCu displays a 3-nitro-ethylbenzene (NE) selectivity of 93.8% with a turnover frequency (TOF) value of 4573 h at 30 °C in the presence of H . With the assistance of NH ∙BH , the selectivity of 3-amino-styrene (AS) reaches 94.5% with a TOF value of 13 719 h . Detailed experimental and theoretical calculations reveal that improved NE selectivity is ascribed to the selective adsorption of the CC bond and desorption of NE on bcc-PdCu. Moreover, the presence of NH ∙BH facilitates the selective hydrogenation of NO due to their strong interaction and thus leads to the formation of AS. This work provides an efficient selective catalyst for NS hydrogenation under mild conditions, which may attract immediate interests in the fields of materials, chemistry, and catalysis.
纳米材料的相工程在调节催化性能方面起着至关重要的作用。然而，在阐明结构-选择性相关性方面仍然存在巨大挑战。在此，本研究表明体心立方相的PdCu（bcc-PdCu）在温和条件下可作为3-硝基苯乙烯（NS）加氢反应的高活性和选择性催化剂。特别是，在30℃、有H存在的情况下，bcc-PdCu对3-硝基乙苯（NE）的选择性为93.8%，周转频率（TOF）值为4573 h⁻¹。在NH₃∙BH₃的辅助下，3-氨基苯乙烯（AS）的选择性达到94.5%，TOF值为13719 h⁻¹。详细的实验和理论计算表明，NE选择性的提高归因于bcc-PdCu上CC键的选择性吸附和NE的脱附。此外，NH₃∙BH₃的存在由于其强相互作用促进了NO₂的选择性加氢，从而导致AS的形成。这项工作为温和条件下NS加氢反应提供了一种高效的选择性催化剂，可能会立即引起材料、化学和催化领域的关注。
