Tertiary amine-functionalized Co(II) porphyrin to enhance the electrochemical CO2 reduction activity
Tertiary amine-functionalized Co(II) porphyrin to enhance the electrochemical CO2 reduction activity
复制标题
叔胺功能化 Co(II) 卟啉增强电化学 CO2 还原活性
DOI：
10.1007/s10853-022-07303-8
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Xiaodong Zhuang
中科院分区：
文献类型：
--
作者：
Xiaodong Xuan;Kaiyue Jiang;Senhe Huang;Boxu Feng;Feng Qiu;Sheng Han;Jinhui Zhu;Xiaodong Zhuang
与过渡金属配位的卟啉基分子催化剂已广泛应用于电催化二氧化碳（CO2）还原活性。提高CO2吸附能力是提高CO2还原性能的有效策略，但由于制备困难，此类分子催化剂的设计报道很少。本工作通过卤代卟啉与二乙胺的Buchwald-Hartwig偶联反应合成了叔胺官能化卟啉。由于2,6-二甲基苯基的庞大空间效应，叔胺官能化的Co(II)卟啉(2NPorCo)具有与二(2,6-二甲基苯基)卟啉(PorCo)前体相似的电子结构。作为电催化剂，电压为 – 0.7 V vs.由于氨基增强了 CO2 吸附能力，RHE、2NPorCo 表现出更好的电催化 CO2 反应性能，包括 CO 法拉第效率（96.7% vs. 85.5%）和比 PorCo 高近三倍的周转频率（5433 h−1 vs. 1918 h−1）。 DFT计算还证实，叔胺的存在有利于*COOH的形成，从而导致CO生产的高性能。该研究为分子催化剂的改性实现助推电催化CO2RR带来了新的思路。胺功能化的Co(II)卟啉具有提高的CO2吸附能力，与未取代的Co(II)卟啉相比，其表现出更高的电催化CO2反应活性，包括96.7%的CO法拉第效率和5433 h−1的周转频率。
Porphyrin-based molecular catalysts coordinated with transition metals have been extensively applied in the electrocatalytic activity carbon dioxide (CO2) reduction. The enhancement of CO2 adsorption capacity is an efficient strategy to improve the CO2 reduction performance, however, it has few been reported for design of such molecular catalysts, due to difficulties in preparation. In this work, tertiary amine-functionalized porphyrin is synthesized by Buchwald-Hartwig coupling reaction of halogenated porphyrin with diethylamine. Owing to the bulky steric effect of 2,6-dimethylphenyl group, the tertiary amine-functionalized Co(II) porphyrin (2NPorCo) has the similar electronic structure with that of di(2,6-dimethylphenyl)porphyrin (PorCo) precursor. As the electrocatalyst at – 0.7 V versus. RHE, 2NPorCo exhibits a better electrocatalytic CO2 reaction performance including CO Faraday efficiency (96.7% versus. 85.5%) and a nearly three-times higher turnover frequency (5433 h−1 vs. 1918 h−1) than those of PorCo, owing to the enhanced CO2 adsorption capacity by amino group. DFT calculations also confirm that the presence of tertiary amines is beneficial to the formation of *COOH, leading to high performance of CO production. This study bring a new idea for the modification of molecular catalysts to achieve the boosting electrocatalytic CO2RR. Amine-functionalized Co(II) porphyrin possesses the improving the CO2 adsorption capacity, which exhibits a higher electrocatalytic CO2 reaction activity including a CO Faraday efficiency of 96.7% and a turnover frequency of 5433 h−1 than those of non-substituted Co(II) porphyrin.