Hou Shujin, Xu Lili, Mukherjee Soumya, Zhou Jian, Song Kun-Ting, Zhou Zhenyu, Zhang Shengli, Ma Xiaoxin, Warnan Julien, Bandarenka Aliaksandr S, Fischer Roland A
Physics of Energy Conversion and Storage, School of Natural Sciences, Department of Physics, Technical University of Munich, James-Franck-Straße 1, Garching 85748, Germany.
Inorganic and Metal-Organic Chemistry, School of Natural Sciences, Department of Chemistry, Technical University of Munich, Lichtenbergstraße 4, Garching 85748, Germany.
ACS Catal. 2024 Jul 29;14(16):12074-12081. doi: 10.1021/acscatal.4c01907. eCollection 2024 Aug 16.
Structural metamorphosis of metal-organic frameworks (MOFs) eliciting highly active metal-hydroxide catalysts has come to the fore lately, with much promise. However, the role of organic ligands leaching into electrolytes during alkaline hydrolysis remains unclear. Here, we elucidate the influence of organic carboxylate anions on a family of Ni or NiFe-based hydroxide type catalysts during the oxygen evolution reaction. After excluding interfering variables, i.e., electrolyte purity, Ohmic loss, and electrolyte pH, the experimental results indicate that adding organic anions to the electrolyte profoundly impacts the redox potential of the Ni species versus with only a negligible effect on the oxygen evolution activities. In-depth studies demonstrate plausible reasons behind those observations and allude to far-reaching implications in controlling electrocatalysis in MOFs, mainly where compositional modularity entails fine-tuning organic anions.
引发高活性金属氢氧化物催化剂的金属有机框架(MOF)的结构转变近来备受关注,前景广阔。然而,在碱性水解过程中有机配体渗入电解质的作用仍不明确。在此,我们阐明了有机羧酸根阴离子在析氧反应过程中对一系列镍基或镍铁基氢氧化物型催化剂的影响。在排除干扰变量,即电解质纯度、欧姆损耗和电解质pH值后,实验结果表明,向电解质中添加有机阴离子对镍物种的氧化还原电位有深远影响,而对析氧活性的影响可忽略不计。深入研究揭示了这些观察结果背后的合理原因,并暗示了在控制MOF中的电催化方面的深远意义,主要是在组成模块化需要微调有机阴离子的情况下。