The selective electrochemical reduction of CO₂ to value-added products is a useful strategy for the local storage of intermittent energy sources as chemical fuels and the recycling of industrial CO₂ waste into industrial feedstocks. This review highlights some of the recent research focused specifically on modulating substrate delivery and local catalyst environment to enhance reaction and product selectivity in the CO₂ reduction reaction by both solid-state materials and discrete molecular systems. We discuss recent studies that focus on (1) using nanostructured and mesoporous solid-state electrocatalysts to modulate local pH and CO₂ concentrations near active sites, (2) coating electrocatalysts with porous overlayers to directly control substrate delivery to the electrocatalyst surface, and (3) using polymer encapsulation to modify the coordination environment surrounding molecular electrocatalysts to enhance activity and selectivity for CO₂ reduction. We believe that increased research in controlling substrate delivery to enhance reaction and product selectivity for the CO₂ reduction reaction is a promising strategy for designing new electrocatalytic systems for the selective and efficient conversion of CO₂ to value-added products.

将CO ₂选择性电化学还原为高附加值产品是一种有用的策略，可用于局部存储作为化学燃料的间歇性能源以及将工业CO ₂废物回收为工业原料。这篇综述重点介绍了一些最近的研究，这些研究专门针对调节底物的输​​送和局部催化剂的环境，以提高固态材料和离散分子系统在CO ₂还原反应中的反应和产物选择性。我们讨论了最近的研究，这些研究集中于（1）使用纳米结构和介孔固态电催化剂来调节局部pH和CO ₂（2）用多孔覆盖层涂覆电催化剂以直接控制底物向电催化剂表面的输送，以及（3）使用聚合物包封改变分子电催化剂周围的配位环境以增强活性和CO ₂还原选择性。我们认为，增加对控制底物输送以增强反应和CO ₂还原反应的产物选择性的研究是设计新的电催化系统以选择性和有效地将CO ₂转化为增值产品的有前途的策略。