The p-Orbital Delocalization of Main-Group Metals to Boost CO2 Electroreduction
The p-Orbital Delocalization of Main-Group Metals to Boost CO2 Electroreduction
复制标题
主族金属促进CO2电还原的p轨道离域
DOI：
10.1002/anie.201810538
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发表时间：
2018-12-03
影响因子：
16.6
通讯作者：
Peng, Huisheng
中科院分区：
文献类型：
--
作者：
He, Sisi;Ni, Fenglou;Peng, Huisheng
通过短的层间Bi-Bi键的层间偶联增强Bi催化剂（称为POD-Bi）的p轨道离域促进了CO2的中间体 *OCHO的吸附，从而提高了CO2还原反应（CO2 RR）到甲酸盐的速率。X射线吸收精细光谱表明，POD-Bi催化剂具有缩短的层间键后，催化剂被电化学还原原位从原始的BiOCl纳米片。玻碳电极上的催化剂在-1.16V vs. RHE下显示出57 mA cm（-2）的创纪录电流密度（是现有技术催化剂的两倍），甲酸法拉第效率（FE）为95%。该催化剂在流动电池系统中应用时，在100 mA cm（-2）的电流密度下具有79%的创纪录的半电池甲酸盐功率转换效率，具有93%的甲酸盐FE。报道的最高CO2 RR生产率（391 mgh（-1）cm（2））是在500 mA cm（-2）的电流密度下实现的，甲酸盐FE在高CO2压力下为91%。
Enhancing the p-orbital delocalization of a Bi catalyst (termed as POD-Bi) via layer coupling of the short inter-layer Bi-Bi bond facilitates the adsorption of intermediate *OCHO of CO2 and thus boosts the CO2 reduction reaction (CO2RR) rate to formate. X-ray absorption fine spectroscopy shows that the POD-Bi catalyst has a shortened inter-layer bond after the catalysts are electrochemically reduced insitu from original BiOCl nanosheets. The catalyst on a glassy carbon electrode exhibits a record current density of 57 mA cm(-2) (twice the state-of-the-art catalyst) at -1.16V vs. RHE with an excellent formate Faradic efficiency (FE) of 95%. The catalyst has a record half-cell formate power conversion efficiency of 79% at a current density of 100 mA cm(-2) with 93% formate FE when applied in a flow-cell system. The highest rate of the CO2RR production reported (391 mgh(-1) cm(2)) was achieved at a current density of 500 mA cm(-2) with formate FE of 91% at high CO2 pressure.