Electron effect regulation: A study on the influence of electron-donating and withdrawing group modification on the performance of metal-coordinated catalysts for electrochemical carbon dioxide reduction

IF 9.4 1区 化学 Q1 CHEMISTRY, PHYSICAL
Jiaqi Yu , Hongsen Zhang , Qi Liu , Jing Yu , Dalei Song , Chu-an Xiong , Ying Li , Rumin Li , Jun Wang
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Abstract

Electron effect regulation is a crucial factor influencing the activity and selectivity of Cu-based coordination compound catalysts in the electrochemical carbon dioxide reduction reaction (CO2RR). Despite significant progress, the structure–activity relationship and the underlying regulatory mechanisms warrant further in-depth investigation. In this study, three types of Cu-[ONNO] tetradentate coordination molecular catalysts with varying electron densities, namely Cu-N2O2, methoxy-modified Cu-N2O2 (Cu-EDG-N2O2), and nitro-modified Cu-N2O2 (Cu-EWG-N2O2), were prepared using a substituent regulation strategy. The prepared catalyst’s micromorphology and structural characteristics were analyzed using various characterization methods. Systematic electrocatalytic CO2RR experiments were conducted to evaluate the performance of these catalysts. Compared to the unmodified Cu-N2O2, the Cu-EDG-N2O2 catalyst exhibited superior reduction performance for CH4 and C2H4 products. At an applied potential of −1.7 V vs. the reversible hydrogen electrode, the Faradaic efficiencies for CH4 and C2H4 of Cu-EDG-N2O2 were 37.8 ± 2.2 % and 25.0 ± 0.5 %, respectively. In contrast, the Cu-EWG-N2O2 catalyst demonstrated higher activity towards the production of H2 as a by-product. The effects of electronic properties of substitutions on catalyst performance were revealed by combining experimental characterization and theoretical simulation. The results showed that the conjugation effect of the –OCH3 group facilitates faster electron transfer between Cu and CO2, thereby enhancing CO2RR activity. Additionally, the introduction of different substituents modulates the local microenvironment around the Cu active centers, significantly influencing the catalytic performance. This study provides valuable theoretical and experimental insights into the design of efficient Cu-N2O2-type metal coordination electrocatalysts for CO2RR processes.

Abstract Image

电子效应调控:供、吸电子基团修饰对电化学还原二氧化碳金属配位催化剂性能影响的研究。
在电化学二氧化碳还原反应(CO2RR)中,电子效应调控是影响铜基配位化合物催化剂活性和选择性的关键因素。尽管取得了重大进展,但结构-活性关系和潜在的调节机制值得进一步深入研究。本研究采用取代基调控策略制备了3种不同电子密度的Cu-[ONNO]四齿配位分子催化剂,分别为Cu- n2o2、甲氧基修饰Cu- n2o2 (Cu- edg - n2o2)和硝基修饰Cu- n2o2 (Cu- ewg - n2o2)。采用各种表征方法对制备的催化剂的微观形貌和结构特征进行了分析。通过系统的电催化CO2RR实验来评价这些催化剂的性能。与未改性的Cu-N2O2相比,Cu-EDG-N2O2催化剂对CH4和C2H4的还原性能更好。当电位为-1.7 V时,Cu-EDG-N2O2对CH4和C2H4的法拉第效率分别为37.8±2.2%和25.0±0.5%。相比之下,Cu-EWG-N2O2催化剂对H2作为副产物的生成具有更高的活性。通过实验表征和理论模拟相结合的方法揭示了取代基电子性质对催化剂性能的影响。结果表明,-OCH3基团的共轭作用促进了Cu和CO2之间更快的电子转移,从而增强了CO2RR活性。此外,不同取代基的引入调节了Cu活性中心周围的局部微环境,显著影响了催化性能。本研究为CO2RR过程中cu - n2o2型金属配位电催化剂的设计提供了有价值的理论和实验见解。
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来源期刊
CiteScore
16.10
自引率
7.10%
发文量
2568
审稿时长
2 months
期刊介绍: The Journal of Colloid and Interface Science publishes original research findings on the fundamental principles of colloid and interface science, as well as innovative applications in various fields. The criteria for publication include impact, quality, novelty, and originality. Emphasis: The journal emphasizes fundamental scientific innovation within the following categories: A.Colloidal Materials and Nanomaterials B.Soft Colloidal and Self-Assembly Systems C.Adsorption, Catalysis, and Electrochemistry D.Interfacial Processes, Capillarity, and Wetting E.Biomaterials and Nanomedicine F.Energy Conversion and Storage, and Environmental Technologies
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