Yang Jianlong, Sun Ning, Zhang Ziqing, Bian Ji, Qu Yang, Li Zhijun, Xie Mingzheng, Han Weihua, Jing Liqiang
Key Laboratory of Western China's Environmental Systems (Ministry of Education), College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000, China.
Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, International Joint Research Center for Catalytic Technology, Heilongjiang University, Harbin 150080, China.
ACS Appl Mater Interfaces. 2020 Jun 24;12(25):28264-28272. doi: 10.1021/acsami.0c06892. Epub 2020 Jun 15.
It is a great challenge for achieving efficiently controllable conversion of chlorinated organics through BiVO-based photoelectrochemical methods by improving the selective adsorption of such organics and charge separation. Herein, we have successfully fabricated SnO/010 facet-exposed BiVO nanocomposites by a series of hydrothermal processes and further used as efficient photoanodes. The resulting photoanode exhibits about 6.3 times higher photoelectrochemical activity than bulk-BiVO, especially with the efficiently controllable conversion of 2,4-dichlorophenol (2,4-DCP) to the nontoxic valuable intermediates such as catechol and pyrogallol by preferential dechlorination. Based on the 2,4-DCP adsorption curves, in situ diffuse reflectance infrared spectra, transient-state surface photovoltage responses, and photocurrent action spectra, it was clearly confirmed that the exceptional performance could be mainly attributed to the promoted selective adsorption of 2,4-DCP for efficiently modulating holes by the strong coordination interactions between -Cl with lone-pair electrons in 2,4-DCP and Bi- with empty orbits on (010) facet-exposed BiVO nanoflakes and to the coupled nano-SnO for prolonging the charge lifetime of BiVO by acting as the high-energy-level electron-accepting platform. This work provides a feasible strategy to develop excellent BiVO-based photoelectrochemical methods for efficiently controlling the conversion of chlorinated organics simultaneously with energy production and recovery.
通过改善含氯有机物的选择性吸附和电荷分离，利用基于BiVO的光电化学方法实现含氯有机物的高效可控转化是一项巨大挑战。在此，我们通过一系列水热过程成功制备了暴露(010)晶面的SnO/BiVO纳米复合材料，并进一步用作高效光阳极。所得光阳极的光电化学活性比块状BiVO高约6.3倍，特别是能通过优先脱氯将2,4-二氯苯酚（2,4-DCP）高效可控地转化为儿茶酚和邻苯三酚等无毒有价值的中间体。基于2,4-DCP吸附曲线、原位漫反射红外光谱、瞬态表面光电压响应和光电流作用光谱，明确证实了这种优异性能主要归因于2,4-DCP通过其-Cl与(010)晶面暴露的BiVO纳米片上空轨道的Bi之间的强配位相互作用促进了对2,4-DCP的选择性吸附，从而有效地调节空穴，以及耦合的纳米SnO作为高能级电子接受平台延长了BiVO的电荷寿命。这项工作为开发基于BiVO的优异光电化学方法提供了一种可行策略，以在能量产生和回收的同时有效控制含氯有机物的转化。
