Ji Yuyao, Cheng Wendong, Li Chengbo, Liu Xingquan
School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 610054, China.
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, China.
Inorg Chem. 2022 Jan 10;61(1):28-31. doi: 10.1021/acs.inorgchem.1c02989. Epub 2021 Dec 22.
The electrochemical N reduction reaction (NRR) demonstrates a process of NH synthesis from N molecules under ambient conditions, which is environmentally friendly and recyclable. However, it requires an efficient electrocatalyst to activate inert N molecules, which is still difficult to satisfy. Recently, as an active NRR electrocatalyst and a typical metal oxide, CeO has featured ultrahigh thermal stability and the ability to apply heteroatom doping, which is an imperative approach importing oxygen vacancy by replacing metal ions with selective elements to greatly influence the activity of catalysts. Here, we analyze the unique properties of manganese dopants in modulating the activity of CeO nanospheres for NRR. It attains a larger NH yield of 27.79 μg h mg and a higher Faradaic efficiency of 9.1% than pure CeO at -0.30 V in 0.1 M HCl, with high electrochemical and structure stability. With calculations by density functional theory, the performance enhancement of Mn-doped CeO is also proved mathematically.
电化学氮还原反应(NRR)展示了在环境条件下由氮分子合成氨的过程,该过程环保且可循环利用。然而,它需要一种高效的电催化剂来活化惰性氮分子,而这一点目前仍难以实现。最近,作为一种活性NRR电催化剂和典型的金属氧化物,CeO具有超高的热稳定性以及进行杂原子掺杂的能力,这是一种通过用选择性元素取代金属离子来引入氧空位从而极大影响催化剂活性的必要方法。在此,我们分析了锰掺杂剂在调节CeO纳米球用于NRR的活性方面的独特性质。在0.1 M HCl中于-0.30 V时,它比纯CeO获得了更高的氨产率,达到27.79 μg h mg,法拉第效率也更高,为9.1%,同时具有高的电化学稳定性和结构稳定性。通过密度泛函理论计算,也从数学上证明了锰掺杂CeO的性能增强。