Theory-guided synthesis of heterostructured Cu@Cu0.4W0.6 catalyst towards superior electrochemical reduction of CO2 to C2 products
Theory-guided synthesis of heterostructured Cu@Cu0.4W0.6 catalyst towards superior electrochemical reduction of CO2 to C2 products
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DOI：
10.1016/j.mtphys.2023.101045
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发表时间：
2023-03
影响因子：
11.5
通讯作者：
D. Xiang;Kunzhen Li;Manzhi Li;R. Long;Y. Xiong;D. Yakhvarov;Xiongwu Kang
中科院分区：
文献类型：
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作者：
D. Xiang;Kunzhen Li;Manzhi Li;R. Long;Y. Xiong;D. Yakhvarov;Xiongwu Kang
合理设计高性能的电催化剂用于电化学CO2还原（CO2 RR）制备C2产物仍然是一个巨大的挑战。本文在CO2 RR制C2产物理论计算的指导下，设计了一种异质结构的Cu@Cu0. 4 W 0. 6催化剂，并采用顺序反相微乳液-热还原法制备了该催化剂. X射线衍射（XRD）和透射电子显微镜（TEM）证实了Cu@Cu0.4W0.6催化剂的异质结构，其形貌为球形，尺寸为15.6 ± 0.5 nm。X射线光电子能谱（XPS）结果表明，与纯Cu 0. 4 W 0. 6相比，在异质结构Cu @ Cu 0. 4 W 0. 6催化剂中，Cu向W的电子转移更多.纯Cu 0. 4 W 0. 6催化剂主要用于CO2 RR中的析氢反应，而异质结构的Cu @ Cu 0. 4 W 0. 6催化剂对C2产物的选择性和活性显著提高，这与Cu/Cu 0. 4 W 0. 6的质量比密切相关，这归因于Cu/Cu 0. 4 W 0. 6界面。最终，Cu@Cu0.4W0.6champion催化剂显示出60.9%的法拉第效率（FE）和121.8 mA cm− 2的部分电流密度，在-1.0 V（vs. RHE）下，C2产物在碱性电解质中的CO2 RR中。计算结果表明，异质结构的Cu@Cu0. 4 W 0. 6抑制了析氢，有利于CO的生成和CO-CHO的不对称偶联，这归因于Cu/Cu 0. 4 W 0. 6界面上的电荷重新分布. W的高O亲合力有利于 * C2 H3 O中间体的C-O键断裂，促进乙烯的生成。原位拉曼光谱显示在2660 cm− 1处C2产物的桥接 *CO和 *CO-CHO中间体在Cu@Cu0.4W0.6上的高表面覆盖率，证实了CO-CHO偶联机制。这项工作突出了异质结构铜基催化剂在调整铜基材料的CO2 RR活性和选择性方面的重要性。
Rational design of high performance electrocatalyst towards electrochemical CO2reduction (CO2RR) to C2products remains a grand challenge. Herein, a heterostructured Cu@Cu0.4W0.6catalyst was designed under the guidance of theoretical calculation towards CO2RR to C2products and prepared by sequential reverse microemulsion and thermal reduction. The heterostructure of Cu@Cu0.4W0.6catalysts were corroborated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), which displayed spherical shape and a size of 15.6 ± 0.5 nm. X-ray photoelectron spectroscopy illustrated more electron transfer from copper (Cu) to tungsten (W) in heterostructured Cu@Cu0.4W0.6catalyst than that pure Cu0.4W0.6. The pure Cu0.4W0.6catalyst is dominated by hydrogen evolution in CO2RR, while heterostructured Cu@Cu0.4W0.6catalyst show much enhanced selectivity and activity towards C2products, which is strongly dependent on the mass ratio of Cu to Cu0.4W0.6, ascribing to the Cu/Cu0.4W0.6interface. Eventually, the Cu@Cu0.4W0.6champion catalyst displays a Faradaic efficiency (FE) of 60.9% and a partial current density of 121.8 mA cm−2at −1.0 V (vs. RHE) for C2products in CO2RR in alkaline electrolyte. Computational studies indicated that the heterostructured Cu@Cu0.4W0.6suppresses hydrogen evolution and favors the production of CO and asymmetrical CO–CHO coupling, ascribing to the charge redistribution at the Cu/Cu0.4W0.6interface. The high O affinity of W facilitates the rupture of C–O bond of *C2H3O intermediate and promotes the formation of ethylene. In-situ Raman spectroscopy revealed high surface coverage of bridging *CO and *CO–CHO intermediate for C2products at 2660 cm−1on Cu@Cu0.4W0.6, corroborating the CO–CHO coupling mechanism. This work highlights the importance of heterostructured Cu-based catalysts in tuning the CO2RR activity and selectivity of Cu-based materials.