The sharp rise of CO₂ in the atmosphere has become a potential threat to global climate, which results from the massive utilization of fossil fuel since the industry revolution. CO₂ electroreduction provides us a new possibility of utilizing CO₂ as a carbon feedstock for fuel and commercial chemicals generation. In this article, a new method is developed for synthesizing CuInS2 hollow nanostructures through the Kirkendall effect. The CuInS₂ hollow nanostructures exhibit excellent catalytic activity for electrochemical reduction of CO₂ with particular high selectivity, achieving high faradaic efficiency for HCOOH of 72.8% at −0.7 V. To elucidate the mechanisms, operando electrochemical Raman spectroscopy is employed to examine the CO2 reduction process. This work provides new insights into the design of hollow nanostructures toward electrocatalytic CO2 conversion and offers us an effective and reliable way for real-time investigation of electrochemical CO2 reduction reaction processes.

自工业革命以来，由于对化石燃料的大量利用，大气中CO ₂的急剧上升已成为对全球气候的潜在威胁。CO ₂电还原为我们提供了一种新的可能性，即利用CO ₂作为碳原料来生产燃料和商业化学品。在本文中，开发了一种通过柯肯德尔效应合成CuInS2空心纳米结构的新方法。CuInS ₂中空纳米结构对电化学还原CO ₂表现出优异的催化活性具有特别高的选择性，在-0.7 V时HCOOH的法拉第效率高达72.8％。为阐明机理，采用操作电化学拉曼光谱法研究了CO2还原过程。这项工作为中空纳米结构向电催化CO2转化的设计提供了新的见识，并为我们提供了一种有效而可靠的方法，用于电化学CO2还原反应过程的实时研究。