The role of proton dynamics on the catalyst-electrolyte interface in the oxygen evolution reaction

doi:10.1016/S1872-2067(21)63909-8

Abstract

Abstract:

The development of non-precious metal catalysts that facilitate the oxygen evolution reaction (OER) is important for the widespread application of hydrogen production by water splitting. Various perovskite oxides have been employed as active OER catalysts, however, the underlying mechanism that occurs at the catalyst-electrolyte interface is still not well understood, prohibiting the design and preparation of advanced OER catalysts. Here, we report a systematic investigation into the effect of proton dynamics on the catalyst-electrolyte interfaces of four perovskite catalysts: La_0.5Sr_0.5CoO_3-δ (LSCO), LaCoO₃, LaFeO₃, and LaNiO₃. The pH-dependent OER activities, H/D kinetic isotope effect, and surface functionalization with phosphate anion groups were investigated to elucidate the role of proton dynamics in the rate-limiting steps of the OER. For oxides with small charge-transfer energies, such as LSCO and LaNiO₃, non-concerted proton-coupled electron transfer steps are involved in the OER, and the activity is strongly controlled by the proton dynamics on the catalyst surface. The results demonstrate the important role of interfacial proton transfer in the OER mechanism, and suggest that proton dynamics at the interface should carefully be considered in the design of future high-performance catalysts.

Key words: Electrocatalysis, Water oxidation, Oxygen evolution reaction, Kinetic isotope effect, Proton-coupled electron transfer, Reaction mechanism

Huiyan Zeng, Yanquan Zeng, Jun Qi, Long Gu, Enna Hong, Rui Si, Chunzhen Yang. The role of proton dynamics on the catalyst-electrolyte interface in the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2022, 43(1): 139-147.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63909-8

https://www.cjcatal.com/EN/Y2022/V43/I1/139

Figures/Tables 7

Fig. 1. Powder XRD and Rietveld refinements of the as-synthesized LSCO (a), LaCoO3 (b), LaNiO3 (c), and LaFeO3 (d) samples. The insets show their crystal structures.

Table 1 Crystal structures, lattice parameters, and BET surface areas of the perovskites used in this study.

Compound	Space group	a (Å)	b (Å)	c (Å)	V_unit-cell (Å^-3)	BET (m² g^-1)
La_0.5Sr_0.5CoO_3-_δ	R -3 c H	5.423	5.423	13.250	338.58	1.2
LaCoO₃	R -3 c H	5.444	5.444	13.094	336.11	0.7
LaNiO₃	P b n m	5.556	7.855	5.561	242.76	1.4
LaFeO₃	R -3 c H	5.456	5.456	13.150	338.96	0.9

Fig. 2. OER performances of the perovskite catalysts. (a) Linear sweeping voltammograms of the as-synthesized LSCO, LaNiO3, LaCoO3, and LaFeO3 samples in 0.1 M KOH solution; (b) Tafel plots of the perovskites catalysts; (c) Comparison between the OER activities at an overpotential of 370 mV.

Fig. 3. pH dependence of the OER activities. (a) CV curves of the as-synthesized LSCO, LaNiO3, LaCoO3, and LaFeO3 samples in KOH solutions with pH values ranging from 12.5 to 14 at a scan rate of 10 mV s-1; (b) Tafel plots of the perovskites catalysts at the different pH values; (c) A comparison between the current densities measured at 1.6 V vs. RHE with an increase in the pH from 12.5 to 14.

Fig. 4. H/D isotope effect measurement. (a) The OER activities of the LSCO, LaNiO3, LaCoO3, and LaFeO3 perovskite catalysts in 0.1 M KOH dissolved in H2O or D2O; (b) Comparison between the OER activities (at 0.9 V vs. Ag/AgCl) in H2O and D2O. The insets illustrate the -OOH deprotonation and O-O bond formation processes on the catalyst-electrolyte interface of the perovskite.

Fig. 5. Enhancing the interfacial proton dynamics of the perovskite catalysts by surface functionalization with Pi groups. (a) The OER activities of the LSCO, LaNiO3, LaCoO3, and LaFeO3 perovskite catalysts in 0.1 M KOH with and without Pi functionalization; (b) Comparison between the OER activities of the different perovskite catalysts at 1.6 V vs. RHE in a pH = 13 KOH solution in the presence and absence of 0.1 M K3PO4. The insets illustrate the -OOH deprotonation process by the Pi coating and the O-O bond formation process on the catalyst-electrolyte interface of the perovskite.

Fig. 6. The effect of interfacial proton transfer on the OER activities of different perovskite catalysts. (a) The different charge-transfer energy (Δ) definitions for the perovskite oxides; (b) The concerted PCET and non-concerted PCET steps of the O-O bond formation and -OOHads deprotonation processes; (c) The experimental overpotentials obtained at 0.5 mA cm-2disk for the different perovskite oxides versus the charge transfer energies derived from DFT calculations [41]. Oxides with low charge-transfer energies, such as LSCO and LaNiO3, have high OER activities, but the RLS is determined by proton transfer, thus the OER kinetics is regulated or influenced to a large extent by the interfacial proton transfer kinetics. For LaFeO3, the charge-transfer energy is large, thus, the OER occurs through an electron-limited pathway, with the kinetics less affected by interfacial proton transfer.

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