Zhou Yin, Yin Kun, Huang Yingying, Li Jiapei, Zhu Anquan, Lin Dewu, Gan Guoqiang, Zhang Jianfang, Liu Kai, Zhang Tian, Liu Kunlun, Luan Chuhao, Yang Huawei, Chen Hou, Guo Shaojun, Zhang Wenjun, Hong Guo
Department of Materials Science and Engineering & Center of Super-Diamond and Advanced Films, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong SAR, 999077, China.
School of Chemistry and Materials Science, Shandong Key University Laboratory of High Performance and Functional Polymer, Ludong University, Yantai, 264025, China.
Nat Commun. 2025 Apr 9;16(1):3353. doi: 10.1038/s41467-025-58640-6.
Charge overpotential for oxygen evolution reaction is a crucial parameter for the energy conversion efficiency of lithium-oxygen (Li-O) batteries. So far, the realization of low charge overpotential via catalyst design is a grand challenge in this field, which usually exceeds 0.25 V. Herein, we report an orbital reconstruction strategy to significantly decrease the charge overpotential to the low 0.11 V by employing PdCo nanosheet catalyst under a low-loading mass (0.3 mg/cm) and capacity (0.3 mAh/cm). Experimental and theoretical calculations demonstrate that the precise d-d orbital coupling (d-d, d-d and d-d) between the low-electronegativity Co and Pd leads to the reconstruction of Pd 4 d orbitals in PdCo nanosheets, thereby resulting in a downward shift of all the three active Pd 4 d orbitals (d, d and d) relative to that of Pd nanosheets. Furthermore, the highest energy level of the Pd 4d orbital in PdCo is lower than the lowest energy levels of the Pd 4d and 4d orbitals in pure Pd, significantly decreasing the charge activation energy and achieving a highest energy conversion efficiency of 91%. This finding provides the orbital-level tuning into rational design of highly efficient electrocatalysts for Li-O batteries.
析氧反应的充电过电位是锂氧（Li-O）电池能量转换效率的关键参数。到目前为止，通过催化剂设计实现低充电过电位是该领域的一个巨大挑战，通常超过0.25V。在此，我们报道了一种轨道重构策略，通过在低负载质量（0.3mg/cm）和容量（0.3mAh/cm）下使用PdCo纳米片催化剂，将充电过电位显著降低至低至0.11V。实验和理论计算表明，低电负性的Co和Pd之间精确的d-d轨道耦合（d-d、d-d和d-d）导致PdCo纳米片中Pd 4d轨道的重构，从而导致所有三个活性Pd 4d轨道（d、d和d）相对于Pd纳米片向下移动。此外，PdCo中Pd 4d轨道的最高能级低于纯Pd中Pd 4d和4d轨道的最低能级，显著降低了电荷活化能，实现了91%的最高能量转换效率。这一发现为锂氧电池高效电催化剂的合理设计提供了轨道水平的调控。
