Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO2 nanorod surface
Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO2 nanorod surface
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DOI：
10.1038/s41929-020-00550-5
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发表时间：
2020-12-14
期刊：
影响因子：
37.8
通讯作者：
Zhang, Sen
中科院分区：
文献类型：
--
作者：
Liu, Chang;Qian, Jin;Zhang, Sen
用于析氧反应（OER）的高效电催化剂对于清洁能源和燃料转化电化学装置的开发至关重要。然而，多相电催化剂的结构复杂性使得阐明表面催化位点和OER机制成为巨大挑战。在这里，我们报道了明确的板钛矿TiO2纳米棒（210）表面（Co-TiO2）中的催化单中心Co的转换频率是迄今为止报道的Co基多相催化剂中最高的，在300和400 mV过电势下分别达到6.6 +/- 1.2和181.4 +/- 28 s(-1)。基于大经典量子力学计算和通过原位和异位光谱探针验证的单点Co原子结构，我们建立了Co-TiO2催化反应动力学随施加电位函数的完整描述，揭示了OER的吸附质演化机制。计算预测的塔菲尔斜率和周转频率与实验表现出非常好的一致性。
Efficient electrocatalysts for the oxygen evolution reaction (OER) are paramount to the development of electrochemical devices for clean energy and fuel conversion. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the surface catalytic sites and OER mechanisms. Here, we report that catalytic single-site Co in a well-defined brookite TiO2 nanorod (210) surface (Co-TiO2) presents turnover frequencies that are among the highest for Co-based heterogeneous catalysts reported to date, reaching 6.6 +/- 1.2 and 181.4 +/- 28 s(-1) at 300 and 400 mV overpotentials, respectively. Based on grand canonical quantum mechanics calculations and the single-site Co atomic structure validated by in situ and ex situ spectroscopic probes, we have established a full description of the catalytic reaction kinetics for Co-TiO2 as a function of applied potential, revealing an adsorbate evolution mechanism for the OER. The computationally predicted Tafel slope and turnover frequencies exhibit exceedingly good agreement with experiment.