Xu Lian-Hua, Wang Qichang, Hu Liangdong, Shen Dekui, Chu Sheng, Zhang Huiyan
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, 210096, China.
Joint International Research Laboratory of Biomass Energy and Materials, Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, Jiangsu, 210037, China.
Small. 2025 Feb;21(5):e2410290. doi: 10.1002/smll.202410290. Epub 2024 Dec 10.
The electrochemical reduction of oxygen is pivotal for advancing emerging energy technologies. Precise control over morphology and electronic structure is essential for enhancing catalytic activity and stability in the oxygen reduction reaction (ORR). In this study, a freestanding carbon electrode is developed by in-situ growth of carbon nanotube (CNT)-encapsulated bimetallic CoM (M = Ni, Fe, Mn, Cu) nanoparticles (NPs) within a hierarchical carbonized wood matrix (CoM@NWCC). The hierarchically porous architecture of the electrode promotes efficient mass transfer during the ORR. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analyses revealed that incorporating metals such as Ni, Fe, Mn, and Cu modulates the electronic structure of Co, specifically adjusting the distance between the d-band center (E) and the Fermi level (E), thus optimizing ORR kinetics. Among these, CoNi@NWCC, with its asymmetric electronic configuration, achieves an optimal balance between OH and OOH adsorption, significantly enhancing catalytic performance. This study demonstrates the potential of band structure engineering to precisely tailor catalyst properties, offering a cost-effective and high-performance solution for zinc-air batteries (ZABs) suitable for large-scale deployment.
氧的电化学还原对于推动新兴能源技术至关重要。精确控制形态和电子结构对于提高氧还原反应（ORR）中的催化活性和稳定性至关重要。在本研究中，通过在分级碳化木材基质（CoM@NWCC）中原位生长碳纳米管（CNT）包裹的双金属CoM（M = Ni、Fe、Mn、Cu）纳米颗粒（NPs），开发了一种独立的碳电极。电极的分级多孔结构促进了ORR过程中的高效传质。X射线光电子能谱（XPS）和密度泛函理论（DFT）分析表明，掺入Ni、Fe、Mn和Cu等金属会调节Co的电子结构，特别是调整d带中心（E）与费米能级（E）之间的距离，从而优化ORR动力学。其中，具有不对称电子构型的CoNi@NWCC在OH和OOH吸附之间实现了最佳平衡，显著提高了催化性能。本研究证明了能带结构工程精确调整催化剂性能的潜力，为适合大规模部署的锌空气电池（ZAB）提供了一种经济高效的高性能解决方案。
