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Interplay of electrochemical and electrical effects induces structural transformations in electrocatalysts

Abstract

The precise control of nanostructure and surface atomic arrangement can be used to tune the electrocatalytic properties of materials and improve their performance. Unfortunately, the long-term structural stability of electrocatalysts with complex nanoscale morphology, a necessary requirement for industrial implementation, often remains elusive. Here we study how electrochemical and complex current behaviours affect the nanoscale object and its structural stability during electrocatalysis. We find that metal electromigration can drive structural transformation during electrolysis to minimize current crowding in nanoscale geometric constrictions. This electrical phenomenon, acting in combination with electrochemically induced atomic migration, can result in specific structural transformations of the catalyst, with the extent and rate depending on the material, geometry and reaction. Using a series of nanostructure examples, we establish a general framework for evaluating the structural transformations in cathodic metal nanocatalysts and explain specific qualitative trends. In conjunction with catalyst design rules, this mechanistic framework will facilitate the development of nanostructured electrocatalysts with sufficient stability for sustainable applications.

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Fig. 1: Structural changes in gold nanoparticles during CO2RR.
Fig. 2: Effect of electrochemical reaction and catalyst material on the structural stability of CCs.
Fig. 3: Adsorbed reaction intermediate facilitation of atomic mobility on different crystallographic facets.
Fig. 4: Computed current-density distributions of various gold nanoshapes.
Fig. 5: Illustration of the factors driving atomic migration in electrocatalysts.

Data availability

Source data are provided with this paper. The data generated and/or analysed during the current study are available within the article and its Supplementary Information files or from the corresponding author upon reasonable request.

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Acknowledgements

We thank L. Nazar for help with the DFT calculations, S. Tatarchuk for help with FEM computing and O. Voznyy for fruitful discussions. F.L. is grateful for the Nanofellowship provided by the Waterloo Institute for Nanotechnology. Y.G. thanks the China Scholarship Council for the fellowship. A.K. is grateful to the University of Waterloo startup funding, the Discovery Grant and the Research Tools and Instruments funding provided by the Natural Sciences and Engineering Research Council of Canada, the Canada Foundation for Innovation John R. Evans Leaders Fund (award no. 38060) and the Ontario Research Fund: Small Infrastructure. H.T.-A. acknowledges the financial support from the Max Planck Society. A.A. acknowledges California State University Long Beach internal research funding.

Author information

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Authors

Contributions

A.K. conceived the idea, supervised the project and wrote the manuscript. F.L. designed and carried out the DFT calculations and the FEM simulations and assisted in manuscript writing. X.V.M. designed experiments and performed the nanoparticle synthesis, carried out the electrochemical experiments, conducted the SEM characterization and assisted in manuscript writing. J.J.M. performed electrochemical experiments and product analysis and conducted the literature survey summarized in Supplementary Tables 1–3. E.K. performed the nanoparticle synthesis and the electrochemical experiments. H.E. assisted with the nanoparticle synthesis and helped to organize the supplementary materials. S.C. assisted with the FEM simulations. J.J. assisted with the Joule heating simulations. A.A. assisted with running and analysing the FEM simulations. Y.G. assisted with the nanoparticle synthesis. A.L. assisted with data analysis. H.T.-A., A.A. and Y.P. contributed to data analysis and manuscript polishing. All authors discussed the results and assisted during manuscript preparation.

Corresponding author

Correspondence to Anna Klinkova.

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The authors declare no competing interests.

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Peer review information Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Electrochemical performance and stability of Au CCs and BNPs.

a-c, CO2 reduction activity of Au BNPs (a,b) and Au CCs (c) over time during potentiostatic electrolysis at −0.6 V (a,c) and −1.2 V (b) vs RHE in CO2-saturated 0.5 M KHCO3. d-g, Cyclic voltammograms of Au BNPs (d,e) and Au CCs (f,g) before and after 5 hours of potentiostatic electrolysis at −0.6 V vs RHE in CO2-saturated (d,f) or Ar-saturated 0.5 M KHCO3 (e,g). Current densities correspond to currents normalized by the geometric area of the electrode. For surface roughness analysis of these electrodes see Supplementary Table 5.

Extended Data Fig. 2 Structural stability of Pd CCs and BNPs under CO2 reduction conditions.

a-d, SEM images areas of Pd CCs before (a,c) and after (b,d) 300 min of CO2RR reaction at −1.2 V vs RHE at different magnifications. e-h, SEM images of Pd CCs with a more open wall morphology before (e,g) and after (f,h) 300 min of CO2RR reaction at −1.2 V vs RHE at different magnifications. i-n, SEM images of Pd BNPs before (i,l), after 120 min (j,m), and after 300 min (k,n) of CO2RR reaction at −1.2 V vs RHE at different magnifications.

Extended Data Fig. 3 Charge distribution profiles for different Ay facets with surface-bound intermediates *COOH or *H.

a–c, Side view of Au(111), Au(110) and Au(211). d-g, Top view of Au(111), Au(100), Au(110) and Au(211). Yellow and blue colors represent the charge accumulation and depletion, with an iso-surface value of 0.001 e/Å3 implemented.

Source data

Extended Data Fig. 4 Effects of geometry, material, and interelectrode distance on computed current density and E-field.

a, Computed current density distribution in Pd BNPs. b-d, average current density within the Debye length, Jelectrolyte (b), average current density within the electrode, Jmetal (c) and average E-field within the Stern layer (d), as the function of the distance between anode and cathode. e, Computed current density distribution in a Au CC tetramer with the geometry shown in the inset; three CCs in the front of the structure are hidden from the view to reveal the current distribution at the interfaces between the particles and at the particle-substrate interfaces. In (a) and (e) Jmetal is shown as colour maps, and Jelectrolyte at the nanostructure surface is shown as a group of yellow arrows, where the size and direction of each arrow represent the magnitude and direction of current at the spatial position of the arrow, respectively. Scale bars are 25 nm.

Supplementary information

Supplementary Information

Supplementary Notes 1–3, Methods, Tables 1–5, Figs. 1–30 and References.

Source data

Source Data Fig. 3

Optimized geometries for NEB and charge distribution calculations.

Source Data Extended Data Fig. 3

Optimized geometries for charge distribution calculations.

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Li, F., Medvedeva, X.V., Medvedev, J.J. et al. Interplay of electrochemical and electrical effects induces structural transformations in electrocatalysts. Nat Catal 4, 479–487 (2021). https://doi.org/10.1038/s41929-021-00624-y

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