清华大学李亚栋团队报道了p–n结整流连续调制单原子催化剂的电催化氧还原活性。相关研究成果发表在2022年11月15日出版的国际知名学术期刊《德国应用化学》。

在这样的原子尺度上，微调单原子催化剂（SACs）以超过其活性极限仍然具有挑战性。

该文中，利用具有与氮供体（MeN x）配位的金属中心的SAC的p型半导体特性，并通过n型半导体载体校正其局部电荷密度。使用酞菁铁（FePc）作为SAC模型，引入具有低功函数的n型一硫化镓在结界面上产生空间电荷区，并导致FeN4部分变形和Fe（II）中心的自旋态转变。该催化剂显示出比原始FePc高两倍以上的比氧还原活性。

研究人员进一步使用其他三种不同功函数的n型金属硫族化物作为载体，并发现负载的FeN4的活性与整流程度之间呈线性关系，这清楚地表明SACs可以通过这种整流策略连续调节。

附：英文原文

Title: Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single-atom Catalysts through p–n Junction Rectification

Author: Zechao Zhuang, Lixue Xia, Jiazhao Huang, Peng Zhu, Yong Li, Chenliang Ye, Minggang Xia, Ruohan Yu, Zhiquan Lang, Jiexin Zhu, Lirong Zheng, Yu Wang, Tianyou Zhai, Yan Zhao, Shiqiang Wei, Jun Li, Dingsheng Wang, Yadong Li

Issue&Volume: 2022-11-15

Abstract: Fine-tuning single-atom catalysts (SACs) to surpass their activity limit remains challenging at such an atomic scale. Herein, we exploit p-type semiconducting character of the SACs having metal center coordinated to nitrogen donors (MeN x ) and rectify their local charge density by an n-type semiconductor support. With iron phthalocyanine (FePc) as model SAC, introducing an n-type gallium monosulfide that features low work function generates a space-charged region across the junction interface, and causes distortion of the FeN4 moiety and spin state transition in the Fe(II) center. This catalyst shows an over two-fold higher specific oxygen-reduction activity than that of pristine FePc. We further employ other three n-type metal chalcogenides of varying work function as support, and discover a linear correlation between the activities of the supported FeN4 and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.

DOI: 10.1002/anie.202212335

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202212335