Liu Wangxi, Wang Yuanqi, Huang Huiting, Wang Jun, He Gaoxiang, Feng Jianyong, Yu Tao, Li Zhaosheng, Zou Zhigang
National Laboratory of Solid State Microstructures, School of Physics, Nanjing University, Nanjing 210093, PR China.
Jiangsu Key Laboratory for Nano Technology, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, PR China.
J Am Chem Soc. 2023 Apr 5;145(13):7181-7189. doi: 10.1021/jacs.2c12182. Epub 2023 Mar 23.
Light-driven primary amine oxidation to imines integrated with H production presents a promising means to simultaneous production of high-value-added fine chemicals and clean fuels. Yet, the effectiveness of this strategy is generally limited by the poor charge separation of photocatalysts and uncontrolled hydrogenation of imines to secondary amines. Herein, a spatial decoupling strategy is proposed to isolate redox chemistry at distinct sites of photocatalysts, and CoP core-ZnInS shell (CoP@ZnInS) coaxial nanorods are assembled as the proof-of-concept photocatalyst. Directional and ultrafast carrier separation occurs between the CoP core and the ZnInS shell, as confirmed by in situ X-ray photoelectron spectroscopy, surface photovoltage spectroscopy, and transient absorption spectroscopy analyses. Toward the photoconversion of model substrate benzylamine to -benzylbenzaldimine, CoP@ZnInS exhibits a 48-time higher production rate and >99% selectivity when compared to ZnInS (ca. 20% selectivity), and the detailed reaction mechanism has been verified by in situ diffuse reflectance infrared Fourier transform spectroscopy.
光驱动的伯胺氧化为亚胺并伴有氢气生成，为同时生产高附加值精细化学品和清洁燃料提供了一种很有前景的方法。然而，这种策略的有效性通常受到光催化剂电荷分离不佳以及亚胺不受控制地氢化为仲胺的限制。在此，提出了一种空间解耦策略，以在光催化剂的不同位点隔离氧化还原化学，并组装了CoP核-ZnInS壳（CoP@ZnInS）同轴纳米棒作为概念验证光催化剂。原位X射线光电子能谱、表面光电压光谱和瞬态吸收光谱分析证实，CoP核与ZnInS壳之间发生了定向且超快的载流子分离。对于模型底物苄胺光转化为α-苄基苯甲亚胺，与ZnInS相比（选择性约为20%），CoP@ZnInS的产率高出48倍，选择性>99%，并且通过原位漫反射红外傅里叶变换光谱验证了详细的反应机理。
