二氧化碳還原反應的動態化學狀態與產物之間的相關性

Strong Correlation between Dynamic Chemical State and Product Profile of Carbon Dioxide Electroreduction

童敬維(Ching-Wei Tung) ； 王佳麗(Jiali Wang) ； 陳浩銘(Hao Ming Chen)

《化學》 80卷3期 (2022/06) Pp. 297-308

https://doi.org/10.6623/chem.202206_80(3).013

摘要

利用可再生電能將二氧化碳轉化為燃料和化學品，即二氧化碳電催化還原反應（CO_2RR），近年變得越來越重要，但依舊面臨著催化劑低活性問題和產物選擇性的挑戰。最近，越來越多的研究表示，在高負電壓的CO_2RR條件下，氧化的中間物質仍然可以在催化劑表面存活，並在發揮關鍵作用下影響催化的產物選擇性。然而，催化劑表面化學狀態的動態變化及其與產物選擇性的真正相關性仍有待釐清，且依舊是CO_2RR最具爭議的問題之一。在此，我們特別重新調查了最近的CO_2RR相關研究，這些研究均基於先進的臨場量測方法，旨在清楚地解釋工作條件下表面化學狀態的實際變化。內文整理了當前具有不同金屬中心於最先進催化劑中的最新發展，其中調控特定表面化學狀態能影響CO_2RR產物，這表示動態化學狀態與產物分佈之間存在令人強烈的關聯性。接下來，我們進一步整理了調節催化劑表面化學狀態的開發策略，並討論了在CO_2RR過程中化學狀態對產物分佈影響的爭論。最後，在以往成果的基礎上，提出CO_2RR催化過程中其產物分布之化學狀態的挑戰和觀點。

關鍵字

可再生能源 ； 電催化還原反應 ； 二氧化碳催化劑

並列摘要

Utilizing renewable electricity energy to convert CO_2 into fuels and chemicals, namely CO_2 electrocatalytic reduction reaction (CO_2RR), is becoming increasingly significant yet challenged by low activity and selectivity. Recently, a growing number of studies have demonstrated that oxidized species can be surprisingly survived on the catalyst surface under highly cathodic CO_2RR conditions and play crucial roles in affecting the product selectivity. However, dynamic evolutions of the surface chemical state together with its real correlation to the product selectivity are still unclear, which is one of the most controversial topics for CO_2RR. Herein, we particularly re-survey recent CO_2RR researches that are all based on advanced in situ/operando methodologies, aiming to clearly reveal the realistic variations in surface chemical state under the working conditions. Then, recent progress in the regulation of surface chemical state toward specific CO_2RR products in current state-of-the-art catalysts with varying metal centers is systematically summarized, which shows an impressive relation between dynamic chemical state and product profile. Next, we further highlight the developed strategies to regulate the surface chemical state in catalysts and discuss the debates over the effects of chemical state on product profile during CO_2RR. Finally, based on previous achievements, we present major challenges and some perspectives for exploring the imperative chemical state-sensitivity to product profile during CO_2RR.

並列關鍵字

Renewable energy ； Electrocatalytic reduction reaction ； Carbon dioxide catalyst