Proton reduction in the presence of oxygen by iron porphyrin enabled with 2 nd sphere redox active ferrocenes

doi:10.1016/S1872-2067(20)63761-5

Abstract

Abstract:

Hydrogen evolution in the presence of atmospheric level of oxygen is a significant barrier in the quest for an alternative, sustainable and green source of energy to counter the depleting fossil fuel sources and increasing global warming due to fossil fuel burning. Oxygen reduction is thermodynamically more favourable than proton reduction and it often produces reactive oxygenated species upon partial reduction which deactivates the catalyst. Thus, catalyst development is required for efficient proton reduction in the presence of oxygen. Here, we demonstrate an iron porphyrin having triazole containing 2 ^nd sphere hydrogen bonding residues appended with redox active ferrocene moieties (α₄-Tetra-2-(3-ferrocenyl-1,2,3-triazolyl)phenylporphyrin (FeFc₄)) as a bifunctional catalyst for fast and selective oxygen reduction to water and thus, preventing the proton reduction by the same catalyst from oxidative stress. Fe(0) is the active species for proton reduction in these iron porphyrin class of complexes and it is observed that the kinetics of proton reduction at Fe(0) state occurs at much faster rate than O₂ reduction and thus, paving the way for selective proton reduction in the presence of oxygen.

Key words: Iron porphyrin, Hydrogen evolution reaction, Oxygen tolerance, Electrocatalysis, Kinetics

Biswajit Mondal, Pritha Sen, Abhishek Dey. Proton reduction in the presence of oxygen by iron porphyrin enabled with 2 ^nd sphere redox active ferrocenes[J]. Chinese Journal of Catalysis, 2021, 42(8): 1327-1331.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63761-5

https://www.cjcatal.com/EN/Y2021/V42/I8/1327

Figures/Tables 6

Scheme 1. (a) Strategies to obtain oxygen-tolerant proton reduction catalytic system; (b) The iron porphyrin (FeFc4) used in this study; (c) Chemical structure of FeFc4. Usually, the oxygen reduction starts at MIII/II state whereas, hydrogen evolution occurs either at MI or M0 depending on the metal and ligand environment.

Fig. 1. Heterogeneous electrocatalysis: (a) Linear sweep voltammetry (LSV) of FeFc4. LSV of FeFc4 in the presence of air with catalyst physisorbed on pyrolytic graphite electrode; (b) Rotating ring disk electrochemistry (RRDE) of FeFc4 in the presence of Air. RRDE of FeFc4 in the presence of air with catalyst physisorbed on pyrolytic graphite electrode, Pt and AgCl/Ag are used as counter and reference electrodes, respectively. Scan rate = 50 mV s-1, rotation speed is 300 rpm and Pt is held at 1.1 V.

Fig. 2. Rotating ring disk electrochemistry (RRDE) of FeEs4 in the Presence of Air. RRDE of FeEs4 in the presence of air with catalyst physiadsorbed on pyrolytic graphite electrode, Pt and AgCl/Ag are used as counter and reference electrodes, respectively. Scan rate = 50 mV s-1, rotation speed is 300 rpm and Pt is held at 1.1 V.

Fig. 3. Charge vs. time plot for HER with FeFc4 at varied N2:O2 mixtures and the corresponding FY values are tabulated. Charge vs. time plot for FeFc4 at different ratios of N2 and O2 mixtures; catalyst physisorbed on pyrolytic graphite and applied a constant -1.3 V at the working electrode, Pt and AgCl/Ag are used counter and reference electrode, respectively.

Fig. 4. Reaction of Fe(0)Fc4 with weak acid, PhOH and the corresponding UV-Vis kinetics. (a) UV-Vis spectra of Fe(0)Fc4 (green) and its reaction with PhOH (red); (b) UV-Vis kinetics of the reaction of Fe(0)Fc4 with weak acid PhOH, 1M (red dots).

Scheme 2. Proposed pathway for O2-tolerant proton reduction.

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