Deng Yuqiong, Fu Xionghui, Zhang Yuanming, Zhu Yi, Wei Yongge
Department of Chemistry, Jinan University, Guangzhou, Guangdong, 510632, P. R. China.
Guangdong Provincial Key Laboratory of Functional Supramolecular, Coordination Materials and Applications, Jinan University, Guangzhou, 510632, P. R. China.
Small. 2022 Jul;18(30):e2201410. doi: 10.1002/smll.202201410. Epub 2022 Jun 16.
The rate-determining step of the oxygen evolution reaction based on a semiconductor photoanode is the formation of the OO bond. Herein, polyethylene glycol (PEG)-modified BiVO photoanodes are reported, in which protons can be transferred quickly due to the high proton conductivity of PEG, resulting in the acceleration of the OO bond formation rate. These are fully demonstrated by different kinetic isotope effect values. Moreover, the open-circuit voltage (U ) further illustrates that PEG passivates the surface states and surface charge recombination is reduced. The composite photoanode can achieve a maximum photocurrent density of 3.64 mA cm at 1.23 V compared to 1.04 mA cm for pure BiVO , and an onset potential of 170 mV, which is a 230 mV negative shift compared to pure BiVO . This work provides a new strategy to accelerate water oxidation kinetics for photoanodes by speeding up the transfer of the proton and the OO bond formation rate.
基于半导体光阳极的析氧反应的速率决定步骤是OO键的形成。在此,报道了聚乙二醇(PEG)修饰的BiVO光阳极,其中由于PEG的高质子传导性,质子能够快速转移,从而加快了OO键的形成速率。不同的动力学同位素效应值充分证明了这一点。此外,开路电压(U)进一步表明PEG钝化了表面态并减少了表面电荷复合。与纯BiVO的1.04 mA cm相比,复合光阳极在1.23 V时可实现3.64 mA cm的最大光电流密度,起始电位为170 mV,与纯BiVO相比负移了230 mV。这项工作通过加快质子转移和OO键形成速率,为加速光阳极的水氧化动力学提供了一种新策略。