Liu Yang, Shang Huishan, Zhang Bing, Yan Dongpeng, Xiang Xu
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, 100029, Beijing, P. R. China.
School of Chemical Engineering, Zhengzhou Key Laboratory of Advanced Separation Technology, Zhengzhou University, 450001, Zhengzhou, P. R. China.
Nat Commun. 2024 Sep 17;15(1):8155. doi: 10.1038/s41467-024-52161-4.
The C-C bond cleavage of biomass-derived glycerol to generate value-added C1 products remains challenging owing to its slow kinetics. We propose a surface fluorination strategy to construct dynamic dual hydrogen bonds on a semiconducting BiVO photoelectrode to overcome the kinetic limit of the oxidation of glycerol to produce formic acid (FA) in acidic media. Intensive spectroscopic characterizations confirm that double hydrogen bonds are formed by the interaction of the F-Bi-F sites of modified BiVO with water molecules, and the unique structure promotes the generation of hydroxyl radicals under light irradiation, which accelerates the kinetics of C-C bond cleavage. Theoretical investigations and infrared adsorption spectroscopy reveal that the double hydrogen bond enhances the C=O adsorption of the key intermediate product 1,3-dihydroxyacetone on the Bi-O sites to initiate the FA pathway. We fabricated a self-powered tandem device with an FA selectivity of 79% at the anode and a solar-to-H conversion efficiency of 5.8% at the cathode, and these results are superior to most reported results in acidic electrolytes.
由于生物质衍生甘油的C-C键裂解动力学缓慢，生成增值C1产物仍然具有挑战性。我们提出一种表面氟化策略，在半导体BiVO光电极上构建动态双氢键，以克服在酸性介质中将甘油氧化生成甲酸（FA）的动力学限制。密集的光谱表征证实，改性BiVO的F-Bi-F位点与水分子相互作用形成了双氢键，这种独特的结构促进了光照射下羟基自由基的产生，从而加速了C-C键裂解的动力学。理论研究和红外吸附光谱表明，双氢键增强了关键中间产物1,3-二羟基丙酮在Bi-O位点上的C=O吸附，从而启动了FA途径。我们制造了一种自供电串联装置，阳极处FA选择性为79%，阴极处太阳能到H的转换效率为5.8%，这些结果优于大多数在酸性电解质中报道的结果。
