Xu Yan-Tong, Ye Zi-Ming, Ye Jia-Wen, Cao Li-Ming, Huang Rui-Kang, Wu Jun-Xi, Zhou Dong-Dong, Zhang Xue-Feng, He Chun-Ting, Zhang Jie-Peng, Chen Xiao-Ming
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
MOE Key Laboratory of Functional Small Organic Molecule, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, China.
Angew Chem Int Ed Engl. 2019 Jan 2;58(1):139-143. doi: 10.1002/anie.201809144. Epub 2018 Dec 5.
Cobalt imidazolate frameworks are classical electrocatalysts for the oxygen evolution reaction (OER) but suffer from the relatively low activity. Here, a non-3d metal modulation strategy is presented for enhancing the OER activity of cobalt imidazolate frameworks. Two isomorphous frameworks [Co (MO )(eim) ] (M=Mo or W, Heim=2-ethylimidazole) having Co(eim) (MO ) units and high water stabilities were designed and synthesized. In different neutral media, the Mo-modulated framework coated on a glassy carbon electrode shows the best OER performances (1 mA cm at an overpotential of 210 mV in CO -saturated 0.5 m KHCO electrolyte and 2/10/22 mA cm at overpotential of 388/490/570 mV in phosphate buffer solution) among non-precious metal catalysts and even outperforms RuO . Spectroscopic measurements and computational simulations revealed that the non-3d metals modulate the electronic structure of Co for optimum reactant/product adsorption and tailor the energy of rate-determining step to a more moderate value.
咪唑钴框架是用于析氧反应（OER）的经典电催化剂，但活性相对较低。在此，提出了一种非3d金属调制策略来提高咪唑钴框架的OER活性。设计并合成了两种具有Co(eim) (MO )单元且水稳定性高的同构框架[Co (MO )(eim) ]（M = Mo或W，Heim = 2-乙基咪唑）。在不同的中性介质中，涂覆在玻碳电极上的Mo调制框架在非贵金属催化剂中表现出最佳的OER性能（在CO -饱和的0.5 m KHCO电解液中，过电位为210 mV时电流密度为1 mA cm ，在磷酸盐缓冲溶液中，过电位为388/490/570 mV时电流密度为2/10/22 mA cm ），甚至优于RuO 。光谱测量和计算模拟表明，非3d金属调节Co的电子结构以实现最佳的反应物/产物吸附，并将速率决定步骤的能量调整到更适中的值。
