Iron porphyrin with appended guanidyl group for significantly improved electrocatalytic carbon dioxide reduction activity and selectivity in aqueous solutions

doi:10.1016/S1872-2067(21)63957-8

Abstract

Abstract:

Iron porphyrins have high activity and selectivity for electrocatalytic CO₂ reduction reaction (CO₂RR) in nonaqueous solutions, but they usually display poor or moderate selectivity for CO₂RR in aqueous solutions because of the competitive hydrogen evolution reaction. Using water as the electrocatalytic reaction solvent is more favored because not only it is cheap, green and abundant but also it can sufficiently provide protons required for CO₂RR. Therefore, developing Fe porphyrins as electrocatalysts for efficient and selective CO₂RR in aqueous solutions is of both fundamental and practical significance. Herein, we report the design and synthesis of Fe porphyrin 1 with an appended guanidyl group and its electrocatalytic features for CO₂RR in both nonaqueous and aqueous solutions. In acetonitrile, Fe porphyrin 1 and its guanidyl-free analogue, tetrakis(3,4,5-trimethoxyphenyl)porphyrin 2, are both efficient for electrocatalytic CO₂-to-CO conversion, but the turnover frequency with 1 (3.9 × 10⁵ s^-1) is one order of magnitude larger than that with 2 (1.7 × 10⁴ s^-1), showing the critical role of the appended guanidyl group in improving electrocatalytic CO₂RR activity. More importantly, in 0.1 mol L^-1 KHCO₃ aqueous solutions, 1 showed very high selectivity for electrocatalytic CO₂-to-CO conversion with a Faradaic efficiency of 96%, while 2 displayed a Faradaic efficiency of 65% for the CO₂-to-CO conversion. This work is of significance to show the effect of appended guanidyl group on improving both activity and selectivity of Fe porphyrins for CO₂RR electrocatalysis.

Key words: CO₂ reduction, Molecular electrocatalysis, Iron porphyrin, Electrostatic interaction, Proton relay

Hongbo Guo, Zuozhong Liang, Kai Guo, Haitao Lei, Yabo Wang, Wei Zhang, Rui Cao. Iron porphyrin with appended guanidyl group for significantly improved electrocatalytic carbon dioxide reduction activity and selectivity in aqueous solutions[J]. Chinese Journal of Catalysis, 2022, 43(12): 3089-3094.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63957-8

https://www.cjcatal.com/EN/Y2022/V43/I12/3089

Figures/Tables 5

Fig. 1. (a) Molecular structure of Fe porphyrins 1 and 2; (b) Protonation of the appended guanidyl group of 1 in pH ≤ 7 aqueous solutions.

Fig. 2. HRMS of 1 (a) and 2 (b) measured in methanol; UV-vis (c) and infrared (d) spectra of 1 and 2.

Fig. 3. (a) CVs of 0.5 mmol L?1 1 and 2 in acetonitrile with a scan rate of 50 mV s-1 under argon. (b) CVs of 0.5 mmol L?1 1 under CO2 with and without 250 mmol L?1 H2O and under argon with 250 mmol L?1 H2O. (c) CVs of 0.5 mmol L?1 1 and 2 under CO2 with 250 mmol L?1 H2O. (d) TOF plots of 1 and 2 for CO2RR as determined from FOWA.

Fig. 4. (a) Diagram showing the preparation of 1/CNT; (b) SEM image of 1/CNT; (c) XPS spectrum of 1/CNT in the Fe 2p region.

Fig. 5. LSVs of 1/CNT and 2/CNT under argon (a) and CO2 (b); Faradaic efficiency for the production of CO and H2 with 1/CNT (c) and 2/CNT (d) under different applied potentials.

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