Structural Reconstruction of Cu(2) O Superparticles toward Electrocatalytic CO(2) Reduction with High C(2+) Products Selectivity.
Structural Reconstruction of Cu(2) O Superparticles toward Electrocatalytic CO(2) Reduction with High C(2+) Products Selectivity.
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DOI：
10.1002/advs.202105292
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发表时间：
2022-05
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结构重构是铜基催化剂在电化学CO2还原中常见的一个过程。具有结构复杂性的Cu基预催化剂通常需要经过复杂的结构重构过程，这可能为提高多碳产品（C2+产品）的电合成提供机会，但由于在此过程中可能出现各种新的结构特征，因此在很大程度上仍然存在不确定性。在这项工作中，具有组装结构的Cu2O超颗粒在电化学还原条件下经历了复杂的结构演变，从而在电催化中实现了高选择性的co - to - C2+产物转化。电镜表征、原位X射线吸收光谱和拉曼光谱显示，超粒子内部的构建块融合产生许多晶界，而外壳中的构建块分离形成纳米隙结构，可以有效地限制OH -以诱导高局部ph。这种独特的结构特征与局部反应环境的结合为促进C - C耦合提供了两个重要因素。因此，Cu2O超粒子衍生的催化剂在C2H4和C2+产品上的法拉第效率分别达到53.2%和74.2%，超过了几何上更简单的Cu2O立方衍生催化剂和大多数报道的Cu电催化剂在可比条件下的性能。本研究为通过控制结构重构来合理设计高选择性CO2还原电催化剂提供了思路。实现多碳产品的电化学CO2减排是人们高度期望的，但也是具有挑战性的。在这里，通过Cu2O超粒子的结构重建，形成了一个独特的“行星-卫星”状的Cu结构，在电化学CO2还原中，乙烯的法拉第效率为53.2%，C2+产物的法拉第效率为74.2%。
Structural reconstruction is a process commonly observed for Cu‐based catalysts in electrochemical CO2 reduction. The Cu‐based precatalysts with structural complexity often undergo sophisticated structural reconstruction processes, which may offer opportunities for enhancing the electrosynthesis of multicarbon products (C2+ products) but remain largely uncertain due to various new structural features possibly arising during the processes. In this work, the Cu2O superparticles with an assembly structure are demonstrated to undergo complicated structure evolution under electrochemical reduction condition, enabling highly selective CO2‐to‐C2+ products conversion in electrocatalysis. As revealed by electron microscopic characterization together with in situ X‐ray absorption spectroscopy and Raman spectroscopy, the building blocks inside the superparticle fuse to generate numerous grain boundaries while those in the outer shell detach to form nanogap structures that can efficiently confine OH− to induce high local pH. Such a combination of unique structural features with local reaction environment offers two important factors for facilitating C−C coupling. Consequently, the Cu2O superparticle‐derived catalyst achieves high faradaic efficiencies of 53.2% for C2H4 and 74.2% for C2+ products, surpassing the performance of geometrically simpler Cu2O cube‐derived catalyst and most reported Cu electrocatalysts under comparable conditions. This work provides insights for rationally designing highly selective CO2 reduction electrocatalysts by controlling structural reconstruction. It is highly desired yet challenging to achieve electrochemical CO2 reduction toward multicarbon products. Here, a unique “planet–satellite”‐like Cu structure is formed through structural reconstruction from Cu2O superparticles to demonstrate high faradaic efficiencies of 53.2% for ethylene and 74.2% for C2+ products in electrochemical CO2 reduction.