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具有高效析氧反应的钙钛矿结构K(x≈0.25)IrO2催化剂

Hollandite Structure K(x≈0.25)IrO2 Catalyst with Highly Efficient Oxygen Evolution Reaction.

作者信息

Sun Wei, Song Ya, Gong Xue-Qing, Cao Li-mei, Yang Ji

机构信息

State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Processes, School of Resources and Environmental Engineering and ‡Key Laboratory for Advanced Materials, Center for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology , 130 Meilong Road, Shanghai 200237, P.R. China.

出版信息

ACS Appl Mater Interfaces. 2016 Jan 13;8(1):820-6. doi: 10.1021/acsami.5b10159. Epub 2015 Dec 31.

Abstract

Oxygen evolution reaction (OER) catalysts with high activity are of particular importance for renewable energy production and storage. Here, we prepare Kx≈0.25IrO2 catalyst that exhibits an excellent OER activity compared to IrO2, which is univerally acknoweledged as a state-of-the-art OER catalyst. The prepared catalyst reflects a small overpotential 0.35 V at a current density of 10 mA cm(-2) and a lower Tafel slope (65 mV dec(-1)) compared to that for IrO2 (74 mV dec(-1)). The performed X-ray photoelectron spectroscopy (XPS) and X-ray adsorption (XAS) experiments indicate that the Ir-site of Kx≈0.25IrO2 has a lower valence and more Ir-5d occupied states, suggesting more electrons on the Ir site. The extra electrons located on the Ir site and distorted IrO6 octahedral symmetry have a significant effect on the 5d orbital energy distribution which is verified by our DOS calculation. The performed DFT calculations state that the Kx≈0.25IrO2 essentially obtains good OER performance because it has a lower theoretical overpotential (0.50 V) compared to IrO2 (0.61 V).

摘要

具有高活性的析氧反应(OER)催化剂对于可再生能源的生产和存储尤为重要。在此,我们制备了Kx≈0.25IrO2催化剂,与被公认为最先进的OER催化剂IrO2相比,该催化剂表现出优异的OER活性。制备的催化剂在电流密度为10 mA cm(-2)时显示出0.35 V的小过电位,并且与IrO2(74 mV dec(-1))相比具有更低的塔菲尔斜率(65 mV dec(-1))。进行的X射线光电子能谱(XPS)和X射线吸收(XAS)实验表明,Kx≈0.25IrO2的Ir位点具有更低的价态和更多的Ir-5d占据态,这表明Ir位点上有更多电子。位于Ir位点上的额外电子和扭曲的IrO6八面体对称性对5d轨道能量分布有显著影响,这通过我们的态密度(DOS)计算得到了验证。进行的密度泛函理论(DFT)计算表明,Kx≈0.25IrO2本质上获得了良好的OER性能,因为与IrO2(0.61 V)相比,它具有更低的理论过电位(0.50 V)。

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