Alloying Gold with Copper Makes for a Highly Selective Visible-Light Photocatalyst for the Reduction of Nitroaromatics to Anilines

作者：Xiao, Qi; Sarina, Sarina; Waclawik, Eric R.; Jia, Jianfeng; Chang, Jin; Riches, James D.; Wu, Haishun; Zheng, Zhanfeng; Zhu, Huaiyong^*

来源：ACS Catalysis, 2016, 6(3): 1744-1753.

DOI：10.1021/acscatal.5b02643

• Au-Cu alloy
• photocatalysis
• reduction
• reaction pathways
• visible light

Finely control of product selectivity is an essential issue in organic chemical production. In the synthesis of functionalized anilines via reduction of the corresponding nitroarenes, the challenge is to selectively reduce only the nitro group in the presence of other reducible functional groups in nitroarene molecules at a high reaction rate. Normally, the nitroarene is reduced stepwise through a series of intermediates that remain as byproducts, increasing the aniline synthesis cost. Here we report that alloying small amounts of copper into gold nanoparticles can alter the reaction pathway of the catalytic reduction under visible-light irradiation at ambient temperature, allowing nitroaromatics to be transformed directly to anilines in a highly selective manner. The reasons for the high efficiency of the photocatalytic reduction under these comparatively benign conditions as well as the light-excited reaction mechanisms are discussed. This photocatalytic process avoids byproducts, exhibits a high reaction rate and excellent substituent tolerance, and can be used for the synthesis of many useful functionalized anilines under environmentally benign conditions. Switching of the reaction pathway simply by tailoring the bimetallic alloy NPs of the photocatalysts is effective for engineering of product chemoselectivity.

• 出版日期2016-3
• 单位山西师范大学; 中国科学院山西煤炭化学研究所