Understanding surface charge effects in electrocatalysis. Part 2: Hydrogen peroxide reactions at platinum

doi:10.1016/S1872-2067(22)64138-X

Abstract

Abstract:

Electrocatalytic activity is influenced by the surface charge on the solid catalyst. Conventionally, our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reactant(s) in the local reaction zone. Taking H₂O₂ redox reactions at Pt(111) as a model system, we reveal a peculiar surface charge effect using ab initio molecular dynamics simulations of electrified Pt(111)-water interfaces. In this scenario, the negative surface charge on Pt(111) repels the O-O bond of the reactant (H₂O₂) farther away from the electrode surface. This leads to a higher activation barrier for breaking the O-O bond. Incorporating this microscopic mechanism into a microkinetic-double-layer model, we are able to semi-quantitatively interpret the pH-dependent activity of H₂O₂ redox reactions at Pt(111), especially the anomalously suppressed activity of H₂O₂ reduction with decreasing electrode potential. The relevance of the present surface charge effect is also examined in wider scenarios with different electrolyte cations, solution pHs, crystal facets of the catalyst, and model parameters. In contrast with previous mechanisms focusing on how surface charge influences the local reaction condition at a fixed reaction plane, the present work gives an example in which the location of the reaction plane is adjusted by the surface charge.

Key words: Electrocatalysis, Surface charge effect, Hydrogen peroxide reaction, Pt(111)-aqueous solution interface, Microkinetic-double-layer model

Jun Huang, Victor Climent, Axel Groß, Juan M. Feliu. Understanding surface charge effects in electrocatalysis. Part 2: Hydrogen peroxide reactions at platinum[J]. Chinese Journal of Catalysis, 2022, 43(11): 2837-2849.

Figures/Tables 5

Fig. 1. (a) Polarization curves of hydrogen peroxide reduction and oxidation at Pt(111) [47]. J?app represents the dimensionless apparent current density normalized to the diffusional limiting current density. The electrolyte solution was prepared with NaF/HClO4 mixtures and 1.7 mmol L-1 H2O2. The scan rate is 50 mV s-1 and the rotation rate is 2500 r min-1. The polarization curves are divided into four regions with descriptions detailed in the main text. (b) The absolute intrinsic kinetic current density (|J?int|) in the region 3 as a function of the surface charge density (σM) calculated from Eq. (2) with Cdl = 0.3 Fm-2, and Epzc,SHE = 0.30 VSHE.

Fig. 2. Snapshots of the configuration of charged Pt(111) - water interfaces with one H2O2 molecule in water: (a) the negatively charged Pt(111) with one Li+ cation in water; (b) the positively charged Pt(111) with one F- anion in water; (c) variation of the total energy with the simulation step for the two cases; (d) histograms of the medium distance of the two oxygen atoms of the H2O2 molecule away from the outermost layer of Pt atoms.

Fig. 3. Flowchart of solving the microkinetic-double-layer model.

Fig. 4. Model-based analysis of hydrogen peroxide reactions at Pt(111). (a) Model-based polarization curves at four pHs, see legends in (c), and the experimental polarization curve for pH = 2, marked as circles. (b) Model-based polarization curves for the case of χ = 0. (c) Surface charging behaviors at four pHs. (d) The forward reaction constant of the step H2O2 + 2■R ↔ 2OHadR at four pHs. (e) The forward reaction constant of the step H2O2 + ■O ↔ OOHadO + H+ + e at four pHs.

Fig. 5. Parametric analysis of the present model of hydrogen peroxide reactions at Pt(111). (a) Influence of EDL parameters on model-based polarization curves at pH = 2. The base line corresponds to the set of model parameters used in Fig. 4, namely, $\delta_{\mathrm{rp}}^{0}=3 \AA, \epsilon_{\mathrm{rp}}=6 \epsilon_{0}, \chi_{\mathrm{rp}}=-5 \times 10^{-10} \mathrm{~m}^{3} \mathrm{C}^{-1}, \mathrm{G}_{\mathrm{a}, 01}^{0}=0.66 \mathrm{eV}$. Other lines are obtained by varying a parameter with the modified value marked aside. (b) Influence of EDL parameters on surface charging relation at pH = 2. (c) Influence of $G_{\mathrm{a}, 01}^{0}$ on model-based polarization curves at pH = 2. (d) Influence of χrp on the surface charging relation.

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