Curved Surface Boosts Electrochemical CO2 Reduction to Formate via Bismuth Nanotubes in a Wide Potential Window
Curved Surface Boosts Electrochemical CO2 Reduction to Formate via Bismuth Nanotubes in a Wide Potential Window
复制标题
弯曲表面在宽电位范围内促进铋纳米管电化学二氧化碳还原成甲酸盐
DOI：
10.1021/acscatal.9b04516
复制
发表时间：
2020-01-03
期刊：
影响因子：
12.9
通讯作者：
Yu, Jiaguo
中科院分区：
文献类型：
--
作者：
Fan, Ke;Jia, Yufei;Yu, Jiaguo
电化学CO2还原反应（CO2RR）生成甲酸是增值燃料和化工生产中最有前途的途径之一。在广泛的电位范围内获得优异的活性和高的法拉第效率对于成熟的应用至关重要。为此，我们首先采用密度泛函理论模拟Bi纳米管和Bi纳米片对CO2RR的活性和对甲酸盐的选择性。理论热力学分析表明，CO2还原成HCOOH的极限势随着曲率的增大而减小，表明Bi纳米管形成甲酸盐的势窗更宽。然后，实验制备了具有高弯曲表面的Bi纳米管，在-1.1 V vs可逆氢电极（RHE）下具有较大的电流密度（-39.4 mA cm(-2)），可用于CO2还原，在-1.0 V vs可逆氢电极（RHE）下最大甲酸选择性为97%。更重要的是，与Bi纳米片相比，Bi纳米管对甲酸盐具有明显的选择性，其电位窗口明显更宽，接近600 mV（选择性bbb80 %）。该研究不仅提供了金属铋的CO2RR活性-表面结构关系，而且为合理设计具有高活性和选择性的电催化剂提供了有效的策略，有利于与各种类型的光伏和其他可再生能源的兼容应用。
Electrochemical CO2 reduction reaction (CO2RR) to formate is considered as one of the most promising routes for value-added fuels and chemical productions. The achievement of excellent activity and high Faradaic efficiency in a wide potential range is critical for mature applications. To this regard, we first employed density functional theory simulations to predict activity of Bi nanotubes and Bi nanosheets to CO2RR and selectivity toward formate. The theoretical thermodynamic analysis of the reaction energetics suggests that the limiting potential for CO2 reduction to HCOOH decreases with the increase of the curvature, suggesting a wider potential window of Bi nanotubes for formate formation. Then, Bi nanotubes with highly curved surface were experimentally prepared, showing a large current density (-39.4 mA cm(-2) at -1.1 V vs reversible hydrogen electrode (RHE)) for CO2 reduction and a maximum formate selectivity of 97% at -1.0 V vs RHE. More importantly, compared with Bi nanosheets, an appreciable selectivity for formate was achieved on Bi nanotubes in a significantly wider potential window of similar to 600 mV (selectivity > 80%). This research provides not only the CO2RR activity-surface structure relationship of metallic Bi but also an efficient strategy for the rational design of electrocatalysts with high activity and selectivity in a wide potential window for CO2RR, which is favorable for compatible application with varied types of photovoltaics and other renewable energy sources.