原子级Co掺杂纳米多孔RuO_(2)催化剂中金属-氧配体键的动态收缩加速酸性氧析出反应

Dynamic shrinkage of metal-oxygen bonds in atomic Co-doped nanoporous RuO_(2) for acidic oxygen evolution

设计在酸性介质中具有高活性和高稳定性的氧析出反应(OER)催化剂对能量转换和储存技术的发展具有重要意义.然而,在实际OER条件下催化剂的原子结构会发生变化,且目前对其动态活性结构的认识仍然不足.本文中,我们通过退火和蚀刻纳米多孔Co-Ru合金合成了具有优异酸性OER活性和稳定性的原子级Co掺杂纳米多孔Ru O_(2)催化剂.原位X射线吸收光谱证实:蚀刻策略可以在原子级Co掺杂纳米多孔Ru O_(2)的金属中心周围产生丰富的氧空位,从而在实际OER条件下产生收缩的金属-氧配体键.这种动态结构演变降低了催化活性位点在OER过程中的动力学势垒,因而催化剂的催化活性和稳定性大幅提高.本研究结果揭示了催化剂活性结构的原子细节以及它们的结构演化对催化活性的影响.

The design of highly active and stable catalysts for the oxygen evolution reaction(OER) in acidic media has become an attractive research area for the development of energy conversion and storage technologies. However, progress in this area has been limited by the poor understanding of the dynamic active structure of catalysts under realistic OER conditions. Here, an atomic Co-doped nanoporous Ru O_(2)electrocatalyst, which exhibited excellent OER activity and stability in acidic conditions, was synthesized through annealing and etching of a nanoporous Co-Ru alloy. Operando X-ray absorption spectroscopy results confirmed that the etching strategy produced abundant oxygen vacancies around the metal centers in the atomic Co-doped nanoporous Ru O_(2)electrocatalyst. These vacancies created contracted metaloxygen ligand bonds under realistic OER conditions. The dynamic structural evolution of the synthesized electrocatalyst allowed them to experience lower kinetic barriers during OER catalysis, resulting in enhanced catalytic activity and stability.This study also provided atomic details on the active structure of the electrocatalyst and the influence of their structural evolution on OER activity.