Electrocatalytic volcano relations: surface occupation effects and rational kinetic models

doi:10.1016/S1872-2067(21)63890-1

Abstract

Abstract:

Electrocatalysis plays a vital role in technologies of energy and environment relevance, such as water electrolysis, fuel cells, synthesis of carbon and nitrogen-based fuels, etc. The volcano relations (VRs) are general and standard tools for predicting and understanding the activity trends of electrocatalysts. The modern electrocatalytic VRs are generally based on the kinetic models with the maximum free energy (ΔG⁰_max) of reaction steps as the rate-determining term (RDT), in which some important factors that crucially impact the reaction kinetics are missed, for examples, the surface structures and coverages of reaction intermediates and spectators, other free energy demanding steps than that associated with the ΔG⁰_max, and so on. In this perspective, we first give a brief introduction of the theoretical framework of current electrocatalytic VRs and the underlying problems in the oversimplified ΔG⁰_max-based kinetic models, and then provide an account of our effort in constructing more rational VRs for electrocatalytic reactions. We introduce a new theoretical framework of electrocatalytic VRs based on kinetic model with the so-called energetic span (δE) serving as RDT. Since the surface-coverage effects and multiple free energy-demanding steps are considered, the VRs thus obtained show several new features such as strong potential dependence, asymmetric ascending and descending branches, relatively flat tops, and so on. The effectiveness of the δE-based VRs is verified for hydrogen and oxygen electrocatalytic reactions. Finally, research directions to further rationalize the electrocatalytic VRs are discussed.

Key words: Electrocatalysi, Volcano relations, Energetic span, Hydrogen electrocatalytic reaction, Oxygen electrocatalytic reaction

Yongting Chen, Junxiang Chen, Shengli Chen. Electrocatalytic volcano relations: surface occupation effects and rational kinetic models[J]. Chinese Journal of Catalysis, 2022, 43(1): 2-10.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63890-1

https://www.cjcatal.com/EN/Y2022/V43/I1/2

Figures/Tables 5

Fig. 1. Volcano plots for different catalysts containing Pt overlayers: experimental ORR activity enhancement as a function of the *OH binding energy. Both of the variables are relative to pure Pt at 0.9 V (RHE) in acidic media (a) (Reproduced with permission from Ref. [14]. Copyright 2012, Royal Society of Chemistry) and alkaline media (c) (Reproduced with permission from Ref. [15]. Copyright 2015, Wiley-VCH). (b) VR of the ORR activity described by the *O binding energy based on the ΔG0max model (Reproduced with permission from Ref. [9]. Copyright 2004, American Chemical Soci ety).

Fig. 2. (a) Calculated adsorption isotherms for hydrogen (η~θ relationship curve); (b) Theoretical plots of j0 (in logarithmic form) as a function of the hydrogen adsorption energy ΔG*H(θ0) and the equilibrium coverage θ0; (c) Activity trend relative to θ0 (only the reactive Had is considered here) for the different Pt facets and nanoparticle edge. Reproduced with permission from Ref. [16]. Copyright 2011, American Chemical Society.

Fig. 3. (a) Surface phase diagram of Pt(111) under the ORR potential. (b) Theoretical Tafel relationship between the current density and electrode potential for the ORR on Pt(111) at potentials higher than 0.85 V; the green circles represent the experimental data. (a,b) Reproduced with permission from Ref. [22]. Copyright 2017, American Chemical Society. (c) The VR between the experimental onset potential and the calculated redox potential of Fe-N-C catalysts. Reproduced with permission from Ref. [28]. Copyright 2019, American Chemical Society.

Fig. 4. (a) The values of the relatively large 1/TOF terms using the ORR on iron phthalocyanine as an example; (b) Diagram of the activities as functions of the hydrogen adsorption free energy and electrode potential for the hydrogen electrode reactions; (c) Comparison between the activity VRs based on the δE and ΔG0max models for an oxygen electrode as a function of the *O adsorption free energy (ΔG*O). The values refer to the electrode potentials in V vs. RHE. Reproduced with permission from Ref. [30]. Copyright 2018, American Chemical Society.

Fig. 5. Application of the δE model in oxygen electrocatalysis: (a) phase diagrams of the TDI and TDTS for the oxygen electrode reactions. The red dashed lines indicate the optimal ΔG*O values of the volcano top at different electrode potentials; (b) Maps of the Tafel slopes (in mV/decade, as indicated by the values) as functions of the electrode potential and ΔG*O. Reproduced with permission from Ref. [30]. Copyright 2018, American Chemical Society.

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