Huang Sheng, Ouyang Ting, Zheng Bang-Feng, Dan Meng, Liu Zhao-Qing
School of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials/Guangzhou Key Laboratory for Clean Energy and Materials/Huangpu Hydrogen Innovation Center, Guangzhou University, Guangzhou Higher Education Mega Center, No. 230 Wai Huan Xi Road, 510006, Guangzhou, P. R. China.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9546-9552. doi: 10.1002/anie.202101058. Epub 2021 Mar 11.
The catalytic conversion of alcohols under mild conditions is a great challenge because it is constrained by low selectivity and low activity. Herein, we demonstrate a hollow nanotube Fe O /MoO heterojunction (FeMo-2) for the photoelectrocatalytic conversion of small-molecule alcohols. Experimental and theoretical analyses reveal that the optical carrier transfer rate is enhanced by constructing interfacial internal electric fields and Fe-O-Mo charge transfer channels. For the formox process, heterojunctions possess superior HCHO-selective reaction paths and free energy transitions, optimizing the selectivity of HCHO and enhancing the reactivity. FeMo-2 shows a greatly improved performance compared to single Fe O ; the photocurrent density of FeMo-2 reaches 0.66 mA cm , which is 3.88 times that of Fe O (0.17 mA cm ), and the Faraday efficiency of the CH OH-to-HCHO conversion is 95.7 %. This work may deepen our understanding of interfacial charge separation and has potential for the production of HCHO and for conversion reactions of other small-molecule alcohols at cryogenic temperatures.
在温和条件下实现醇类的催化转化是一项巨大挑战，因为它受到低选择性和低活性的限制。在此，我们展示了一种用于小分子醇类光电催化转化的中空纳米管FeO/MoO异质结（FeMo-2）。实验和理论分析表明，通过构建界面内电场和Fe-O-Mo电荷转移通道可提高光载流子转移速率。对于甲醛化过程，异质结具有优异的HCHO选择性反应路径和自由能跃迁，优化了HCHO的选择性并提高了反应活性。与单一FeO相比，FeMo-2表现出大大改善的性能；FeMo-2的光电流密度达到0.66 mA cm，是FeO（0.17 mA cm）的3.88倍，CHOH到HCHO转化的法拉第效率为95.7%。这项工作可能会加深我们对界面电荷分离的理解，并在低温下生产HCHO以及其他小分子醇类的转化反应方面具有潜力。
