Li Jiayuan, Xia Zhaoming, Xue Qingyu, Zhang Mingkai, Zhang Sai, Xiao Hai, Ma Yuanyuan, Qu Yongquan
Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, 710072, China.
Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Small. 2021 Oct;17(39):e2103018. doi: 10.1002/smll.202103018. Epub 2021 Aug 18.
Despite the known efficacy of CeO as a promoter in alkaline hydrogen evolution reaction (HER), the underlying mechanism of this effect remains unclear. CoS , a pyrite-type alkaline HER electrocatalyst, suffers from sluggish HER kinetics and severe catalyst leaching due to its weak water dissociation kinetics and oxygen-related corrosion. Herein, it is demonstrated that the interfacial Lewis acid-base Ce∙∙∙S pairs in CeO -loaded CoS effectively improve the catalytic activity and durability. In CeO -loaded CoS nanowire array electrodes, these interfacial Lewis acid-base Ce∙∙∙S pairs with unique electronic and structural configurations efficiently activate water adsorptive dissociation and kinetically accelerate hydrogen evolution, delivering a low overpotential of 36 mV at 10 mA cm in alkaline media. Such Ce∙∙∙S pairs also weaken O adsorption on CoS , leading to undecayed activity over 1000 h. These findings are expected to provide guidance for the design of CeO -based electrocatalysts as well as other hybrid electrocatalysts for water splitting.
尽管已知CeO作为碱性析氢反应(HER)的促进剂具有功效,但其作用的潜在机制仍不清楚。CoS是一种黄铁矿型碱性HER电催化剂,由于其较弱的水解离动力学和与氧相关的腐蚀,存在HER动力学缓慢和严重的催化剂浸出问题。在此,证明了负载CeO的CoS中的界面路易斯酸碱Ce∙∙∙S对有效地提高了催化活性和耐久性。在负载CeO的CoS纳米线阵列电极中,这些具有独特电子和结构构型的界面路易斯酸碱Ce∙∙∙S对有效地激活了水的吸附解离,并在动力学上加速了析氢,在碱性介质中,在10 mA cm时提供了36 mV的低过电位。这种Ce∙∙∙S对也减弱了O在CoS上的吸附,导致在1000 h以上活性不衰减。这些发现有望为基于CeO的电催化剂以及其他用于水分解的混合电催化剂的设计提供指导。