Li Yuan, Wu Hao-Ran, Yu Yue, Chen Miao-Ying, Zhao Kuang-Min, Li Wei-Dong, Rong Si-Yu, Xue Dong-Ping, Zhang Jia-Nan, Lu Bang-An
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450001, P. R. China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Small. 2025 Mar;21(11):e2411678. doi: 10.1002/smll.202411678. Epub 2025 Feb 9.
The development of platinum group metal-free catalysts for the oxygen reduction reaction (ORR) is critical to advancing sustainable energy conversion technologies. Manganese (Mn)-based catalysts, known for their reduced toxicity and promising durability, have traditionally exhibited lower ORR activity compared to state-of-the-art iron-nitrogen-carbon (Fe-N-C) catalysts. In this study, a highly efficient Mn-N-C-S catalyst is presented, engineered through a sulfur-mediated high-shell coordinated doping strategy, that markedly enhances ORR activity and stability. The Mn-N-C-S catalyst achieves a record-high half-wave potential of 0.94 V in alkaline media, among the highest values reported for Mn-based catalysts. Additionally, in acidic media, it exhibits a half-wave potential of 0.80 V, placing it among the top-performing M-N-C catalysts. The catalyst also demonstrates a high peak power density of 0.82 W cm in H-O fuel cells and 0.264 W cm in Zn-air batteries, outperforming previously reported Mn-based catalysts. Both experimental findings and theoretical computations suggest that the high-shell S-doping can increase the spin density of Mn sites, strengthen Mn-N bonds, and thereby improve the durability of Mn-N sites. This work underscores the effectiveness of high-shell sulfur doping and paving the way for their deployment in the cathodes of fuel cells and metal-air batteries.
开发用于氧还原反应（ORR）的无铂族金属催化剂对于推进可持续能源转换技术至关重要。锰（Mn）基催化剂以其较低的毒性和良好的耐久性而闻名，但传统上与最先进的铁氮碳（Fe-N-C）催化剂相比，其ORR活性较低。在本研究中，通过硫介导的高壳层配位掺杂策略设计了一种高效的Mn-N-C-S催化剂，该策略显著提高了ORR活性和稳定性。Mn-N-C-S催化剂在碱性介质中实现了创纪录的0.94 V半波电位，是报道的Mn基催化剂中的最高值之一。此外，在酸性介质中，它表现出0.80 V的半波电位，跻身性能最佳的M-N-C催化剂之列。该催化剂在氢氧燃料电池中还展示了0.82 W cm的高峰功率密度，在锌空气电池中为0.264 W cm，优于先前报道的Mn基催化剂。实验结果和理论计算均表明，高壳层S掺杂可以增加Mn位点的自旋密度，强化Mn-N键，从而提高Mn-N位点的耐久性。这项工作强调了高壳层硫掺杂的有效性，并为其在燃料电池和金属空气电池阴极中的应用铺平了道路。
