表面Co2CrO4电化学转化为CoOOH/CrOOH及其增强电催化析氧中的性能

以清洁能源发电为动力的水分解技术是一种很有应用前景的制氢方法,可以缓解日益增长的能源消耗和公众高度关注的环境问题.水分解的氧化过程,即析氧反应(OER),是一个四电子-质子耦合反应,其动力学缓慢,是实现高效电解水的技术难题.以RuO₂和IrO₂为代表的贵金属氧化物表现出极高的催化活性,但受限于储量低及价格昂贵,很难广泛应用.因此,迫切需要开发出具有高效和持久活性的非贵金属电催化剂以解决动力学迟缓问题.钴元素储量丰富、价格低廉,同时具有较高的催化活性,有望替代贵金属催化剂而在工业化电解水中大规模应用.尖晶石型氧化物(A₂BO₄)具有氧缺陷含量高,氧化态灵活,能形成氧化-还原对的特点,有利于提高催化剂的电化学活性.因此,Cr和Co合理协同制备A₂BO₄型催化剂可获得更好的催化剂性能.研究结果(Chem.Commun.,2018,54,4987?4990)表明,OER性能主要与催化剂表面OH?的吸收效率有关,过渡金属羟基氧化物(MOOH)是OER反应的主要活性物质.对A2BO4型催化剂进行阳极化处理,可以使其表面发生原子级相变,生成MOOH产物.因此,对电催化剂进行结构演化是提高其催化活性的一个重要策略.本文采用电化学阳极化处理,即在碱性环境下对Co₂CrO₄表面进行原位演化生成CoOOH/CrOOH,从而得到CoOOH/CrOOH-Co₂CrO₄.通过X-射线衍射、扫描电子显微镜、透射电子显微镜、X-射线光电子能谱和氮气吸附-脱附等方法对催化剂的结构和形貌进行表征.结果表明,阳极化处理后,光滑的Co₂CrO₄表面生成了CoOOH/CrOOH褶皱,CoOOH/CrOOH和Co₂CrO₄的协同效应可以暴露出更多活性位点并加快电子的传输,明显提升析氧反应性能.在1.0 M NaOH中进行CoOOH/CrOOH-Co₂CrO₄电催化性能测试,循环伏安曲线结果表明,电流密度达到20 mA cm^?2时,仅需过电位244 mV,转化频率是0.536 s^?1,说明催化剂催化析氧反应性能优异.多步计时电流曲线以及长时间电流曲线表明催化剂稳定性较高.

In situ evolution of surface Co2Cr O4 to Co OOH/Cr OOH byelectrochemical method: Toward boosting electrocatalytic wateroxidation

Developing non-noble-metal electrocatalyst with efficient and durable activity is a urgent task for addressing the sluggish reaction kinetics of electrochemical water oxidation. Structural evolution of the electrocatalyst is an important strategy for achieving enhanced performance. Herein, in situ evolution of surface Co2CrO4 to CoOOH/CrOOH (CoOOH/CrOOH-Co2CrO4) by an electrochemical method under alkaline conditions was designed for enhancing the electrocatalytic performance of water oxidation. The experiments demonstrated that the synergy between CoOOH/CrOOH and Co2CrO4 resulted in a marked increase in the number of active sites and improved the rate of charge transfer, which enhanced the activity for water oxidation. At a geometrical current density of 20 mA cm-2, the overpotential of the oxygen evolution reaction was 244 mV and the turnover frequency was 0.536 s-1 in 1.0 M NaOH.