The segregation (or exsolution) of nanoparticles (NPs) on the surface of perovskite oxide parents has emerged as an advanced technology to design functional materials for renewable energy. However, this process relies heavily upon lengthy reduction (800–1,200 K) in hydrogen-rich environments to facilitate the electron transfer from hydrogen to oxides, making this process costly. Here, we show that, in addition to thermal driving forces, photo-illumination can drive electron donation and facilitate the electron harvesting on perovskite directly. This results in segregation of NPs at room temperature with the assistance of trialkyl amine as a hole acceptor. A proton-coupled electron transfer catalytic cycle is suggested to explain this unusual electron transfer pathway, which is redox neutral and an intrinsically closed cycle. The practicality of this process is demonstrated by the improved performance in a trial electrocatalytic oxygen evolution reaction. This work suggests a promising design principle for perovskite functionalization.

钙钛矿氧化物母体表面上纳米颗粒（NPs）的分离（或析出）已成为一种设计可再生能源功能材料的先进技术。但是，此过程在很大程度上依赖于在富氢环境中的长时间还原（800-1,200 K），以促进电子从氢到氧化物的转移，从而使该过程成本很高。在这里，我们表明，除了热驱动力外，光照射还可以驱动电子捐赠，并直接促进钙钛矿上电子的收集。在三烷基胺作为空穴受体的辅助下，这导致NP在室温下分离。建议使用质子偶联的电子转移催化循环来解释这种不寻常的电子转移途径，该途径是氧化还原中性且本质上是封闭的循环。该方法的实用性通过试验的电催化氧放出反应中的改进性能证明。这项工作提出了钙钛矿功能化的有前途的设计原则。