Gao Yang, Xue Yurui, He Feng, Li Yuliang
CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Science Center for Material Creation and Energy Conversion, Institute of Frontier and Interdisciplinary Science, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Proc Natl Acad Sci U S A. 2022 Sep 6;119(36):e2206946119. doi: 10.1073/pnas.2206946119. Epub 2022 Aug 29.
Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in seawater electrolysis reactions. In this report, the heterostructures of graphdiyne-RhO-graphdiyne (GDY/RhO/GDY) were constructed by in situ-controlled growth of GDY on RhO nanocrystals. A double layer interface of -hybridized carbon-oxide-Rhodium (-C∼O-Rh) was formed in this system. The microstructures at the interface are composed of active sites of -C∼O-Rh. The obvious electron-withdrawing surface enhances the catalytic activity with orders of magnitude, while the GDY outer of the metal oxides guarantees the stability. The electron-donating and withdrawing -C∼O-Rh structures enhance the catalytic activity, achieving high-performance overall seawater electrolysis with very small cell voltages of 1.42 and 1.52 V at large current densities of 10 and 500 mA cm at room temperatures and ambient pressures, respectively. The compositional and structural superiority of the GDY-derived -C-metal-oxide active center offers great opportunities to engineer tunable redox properties and catalytic performance for seawater electrolysis and beyond. This is a typical successful example of the rational design of catalytic systems.
总体而言，海水电解是氢能转换发展的一个重要方向。关键问题包括如何在海水电解反应中实现高选择性、活性和稳定性。在本报告中，通过在RhO纳米晶体上原位控制生长石墨二炔，构建了石墨二炔-RhO-石墨二炔（GDY/RhO/GDY）异质结构。在该体系中形成了一个由杂化的碳-氧化物-铑（-C∼O-Rh）组成的双层界面。界面处的微观结构由-C∼O-Rh的活性位点组成。明显的吸电子表面将催化活性提高了几个数量级，而金属氧化物外部的GDY则保证了稳定性。供电子和吸电子的-C∼O-Rh结构增强了催化活性，在室温和常压下，分别在10和500 mA cm的大电流密度下，以非常小的电池电压1.42和1.52 V实现了高性能的整体海水电解。由GDY衍生的-C-金属-氧化物活性中心的组成和结构优势为设计用于海水电解及其他领域的可调氧化还原性质和催化性能提供了巨大机遇。这是催化体系合理设计的一个典型成功案例。
