Yun Gao, Dr. Chengdong Yang, Fenglei Sun, Prof. Daping He, Xinqiang Wang, Jian Chen, Dr. Xiaobo Zheng, Dr. Runcong Liu, Prof. Hongge Pan, Prof. Dingsheng Wang
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引用次数: 0
Abstract
Metal-organic hybrid catalysts with highly tunable single-sites are promising for oxygen-evolution reaction (OER), but molecular-scale understanding of underlying reaction mechanisms still remain elusive on these bulk materials. Herein, we report a direct construction of heterogenized molecular complexes stabilized on carbon substrates via coordinating Fe−Ni sites with four aromatic carboxylate ligands (FeNi-Lx). The ligands-tuning π-π stacking interaction between aromatic carboxylate ligands and carbon supports promote the oxidative charge accumulation on Fe−Ni sites via fast electron transferring, thus the optimized FeNi-Lx rendering a mass activity of 6680 A gFe/Ni−1 at 0.3 V overpotential. In situ characteristics and theoretical analysis demonstrate that the OH− nucleophilic attack on hypervalent iron sites induce the reconstruction of active Fe−O−Ni species, accompanying with fast valence increasing. Whereas, during OER, the unexpected valence reduction of Fe−O−Ni sites would be attributed to the oxygen-generating from OOH* intermediates. These findings would establish an essential understanding of the origin of active centers in molecular complexes catalysts for oxygen-evolution.
具有高度可调单位点的金属有机杂化催化剂在氧进化反应(OER)中大有可为,但对于这些块体材料的基本反应机理,分子尺度的理解仍是空白。在此,我们报告了通过将铁-镍位点与四个芳香族羧酸配体(FeNi-Lx)配位,直接构建稳定在碳基底上的异质化分子配合物。芳香族羧酸配体与碳衬底之间的配体调谐π-π堆叠相互作用通过快速电子传递促进了铁-镍位点上的氧化电荷积累,因此优化的 FeNi-Lx 在 0.3 V 过电位时的质量活性达到了 6680 A gFe/Ni-1。现场特征和理论分析表明,高价铁位点上的羟基亲核攻击会导致活性铁-氧-镍物种的重建,并伴随着价的快速增长。而在 OER 过程中,Fe-O-Ni 位点出乎意料的化合价降低将归因于 OOH* 中间体产生的氧。这些发现将使人们对氧演变分子复合物催化剂中活性中心的起源有一个基本的了解。
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.