Joint Center for Artificial Photosynthesis and †Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
J Am Chem Soc. 2013 Nov 13;135(45):16977-87. doi: 10.1021/ja407115p. Epub 2013 Oct 30.
Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.
客观评价水氧化电催化剂的活性对于开发有前途的能量转换技术至关重要,这些技术包括集成太阳能水分解装置、水电解槽和锂空气电池。然而,目前用于评估析氧催化剂的方法没有标准化,这使得难以比较这些材料的活性和稳定性。我们报告了一种评估电沉积析氧电催化剂的活性、稳定性和法拉第效率的方案。特别是,我们专注于确定电化学活性表面积的方法以及在与集成太阳能水分解装置相关的条件下测量电催化活性和稳定性的方法。我们的主要评价标准是达到 10 mA cm(-2)每几何面积所需的过电势,这大约是 10%高效太阳能到燃料转换装置的预期电流密度。利用上述表面积测量,可以确定电催化剂的转换频率。该报道的方案用于在酸性和碱性溶液中检查以下系统的析氧活性:CoO(x)、CoPi、CoFeO(x)、NiO(x)、NiCeO(x)、NiCoO(x)、NiCuO(x)、NiFeO(x)和 NiLaO(x)。还研究了电沉积 IrO(x)催化剂的析氧活性进行比较。通过比较所研究的 OER 催化剂的催化性能,可以得出两个一般观察结果:(1)在碱性溶液中,每个非贵金属系统在 0.35 至 0.43 V 的相似工作过电势下达到 10 mA cm(-2)的电流密度,(2)除了 IrO(x)之外,每个系统在酸性溶液中的氧化条件下都是不稳定的。