Li He, Lin Cheng, Yang Yilong, Dong Chaoran, Min Yulin, Shi Xiaoqin, Wang Luyang, Lu Siyu, Zhang Kan
School of Materials Science and Engineering and School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China.
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai University of Electric Power, Shanghai, 200090, P. R. China.
Angew Chem Int Ed Engl. 2023 Jan 2;62(1):e202210804. doi: 10.1002/anie.202210804. Epub 2022 Dec 1.
Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4-electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H O and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter-facet edge (IFE) rich WO arrays in an electrolyte containing CO . Our results demonstrate that the IFE favors the adsorption of CO while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1-electron and indirect 2-electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 μmol h with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value-added product.
在各种太阳能燃料生产的发展中，水氧化反应仍有改进的空间，这是因为析氧反应的4电子转移过程在动力学上较为缓慢。在这项工作中，我们通过在含有CO 的电解质中使用富含晶面间边缘（IFE）的WO阵列，实现了活性氧物种（ROS）、H O和OH⋅的形成，总法拉第效率超过90%。我们的结果表明，IFE有利于CO 的吸附，同时降低OH⋅的吸附能，并通过直接1电子和间接2电子转移途径抑制表面空穴积累。最后，我们展示了通过原位使用生成的OH⋅对苯甲醇进行选择性氧化，其苯甲醛产率约为768 μmol h ，选择性接近100%。这项工作为在水性太阳能燃料系统中调节或控制氧化反应以实现高效和增值产品提供了一种有前景的方法。
