(Co,Ni) Se2/C@FeOOH中空笼状纳米结构的自旋调控加速水氧化催化研究

氢气作为一种清洁无污染的可再生能源,可以有效地解决全球能源危机和环境污染问题.低能耗水裂解制氢是公认的未来清洁制氢的有效途径之一.水裂解反应分为阳极上发生的析氧反应(OER)和阴极上发生的析氢反应,由于阳极半反应涉及四电子过程,反应动力学缓慢,进而导致整个水分解产氢效率低下,成为规模化水裂解制氢应用的瓶颈.贵金属Ir基和Ru基催化剂具有较好的OER催化性能,但其价格高昂和低储量极大地限制了其大规模应用.因此,设计出性能优良的非贵金属OER催化剂,对于促进电催化水裂解制氢领域的发展具有重要意义.自旋调控可以调节d-轨道电子与含氧物种之间的自旋占据态,进而改变含氧物种的吸附能,提升催化反应动力学.然而,自旋调控如何提升电催化水氧化及其内部的关联性鲜有报道.本文报道了一种(Co,Ni)Se₂/C@FeOOH笼状纳米结构的自旋调控工程以提升其析氧反应活性.以金属有机框架材料ZIF-67为前驱体,采用离子交换方法和化学气相沉积法合成了(Co,Ni)Se₂/C中空笼状纳米结构,接着通过化学水浴沉积法用FeOOH进行修饰,进一步提高了电催化反应动力学.磁化测试结果表明,(Co,Ni)Se₂/C@FeOOH样品的极化自旋数(μb=6.966μb/f.u)高于(Co,Ni)Se₂/C样品的极化自旋数(μb=6.398μb/f.u),从而有利于含氧中间体的吸附和脱附,这与表面价带谱的结果一致.与(Co,Ni)Se₂/C相比,(Co,Ni)Se₂/C@FeOOH样品具有更强的铁磁性,电磁感应促进了磁性粒子最外层电子的自旋.电子自旋的增加有利于(Co,Ni)Se₂/C@FeOOH样品最外层电子能级的跃迁,在3d-轨道上产生更多的空电子轨道和未成对电子,有利于电子转移和氧吸附.Ni,Co和Fe之间的π电子在界面处的局域化重组再分配优化了对含氧物种的吸附与脱附自由能,提升了OER催化性能.此外,所设计的中空笼状纳米结构和杂原子掺杂碳基体对提高OER活性也有重要作用.因此,在1.0 mol/L KOH碱性溶液中,(Co,Ni)Se₂/C@FeOOH催化剂展现出较好的析氧反应性能,在10 mA cm^-2电流下的过电位为241 mV,塔菲尔斜率为44 mV dec^-1,明显优于原先的(Co,Ni)Se₂/C催化剂.本文将为高效OER电催化剂的设计提供一种新的思路和方法.

Spin regulation on(Co,Ni)Se2/C@FeOOH hollow nanocage accelerates water oxidation

Spin engineering is recognized as a promising strategy that modulates the association between d‐orbital electrons and the oxygenated species,and enhances the catalytic kinetics.However,few efforts have been made to clarify whether spin engineering could make a considerable enhancement for electrocatalytic water oxidation.Herein,we report the spin engineering of a nanocage‐structured(Co,Ni)Se₂/C@FeOOH,that showed significant oxygen evolution reaction(OER)activity.Magnetization measurement presented that the(Co,Ni)Se₂/C@FeOOH sample possesses higher polarization spin number(μb=6.966μB/f.u.)compared with that of the(Co,Ni)Se₂/C sample(μb=6.398μB/f.u.),for which the enlarged spin polarization number favors the adsorption and desorption energy of the intermediate oxygenated species,as confirmed by surface valance band spectra.Consequently,the(Co,Ni)Se₂/C@FeOOH affords remarkable OER product with a low overpotential of 241 mV at a current of 10 mA cm^-2 and small Tafel slope of 44 mV dec^-1 in 1.0 mol/L KOH alkaline solution,significantly surpassing the parent(Co,Ni)Se₂/C catalyst.This work will trigger a solid step for the design of highly‐efficient OER electrocatalysts.