Li Wei, Liu Cong, Gu Chenkai, Choi Jin-Ho, Wang Song, Jiang Jun
Gusu Laboratory of Materials, Suzhou, Jiangsu 215123, People's Republic of China.
Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.
J Am Chem Soc. 2023 Mar 1;145(8):4774-4783. doi: 10.1021/jacs.2c13596. Epub 2023 Feb 17.
Single-atom catalysts with structure and activity tunability have attracted significant attention for energy and environmental applications. Herein we present a first-principles study of single-atom catalysis on two-dimensional graphene and electride heterostructures. The anion electron gas in the electride layer enables a colossal electron transfer to the graphene layer, with the degree of transfer being controllable by the selection of electride. The charge transfer tunes the d-orbital electron occupancy of a single metal atom, enhancing the catalytic activity of hydrogen evolution reactions and oxygen reduction reactions. The strong correlation between the adsorption energy and the charge variation Δ suggests that interfacial charge transfer is a critical catalytic descriptor for the heterostructure-based catalysts. The polynomial regression model proves the importance of charge transfer and accurately predicts the adsorption energy of ions and molecules. This study provides a strategy to obtain high-efficiency single-atom catalysts using two-dimensional heterostructures.
具有结构和活性可调性的单原子催化剂在能源和环境应用方面引起了广泛关注。在此，我们展示了对二维石墨烯和电子化物异质结构上单原子催化的第一性原理研究。电子化物层中的阴离子电子气能够实现向石墨烯层的大量电子转移，转移程度可通过电子化物的选择来控制。电荷转移调节单个金属原子的d轨道电子占据情况，增强析氢反应和氧还原反应的催化活性。吸附能与电荷变化Δ之间的强相关性表明，界面电荷转移是基于异质结构的催化剂的关键催化描述符。多项式回归模型证明了电荷转移的重要性，并准确预测了离子和分子的吸附能。本研究提供了一种利用二维异质结构获得高效单原子催化剂的策略。
