Tuning Surface Chemistry and Self-Assembly to Increase Current Density in Bio-Inspired Hydrogen Fuel Cell Anodes with Ionomer
Authors: Coutard Nathan , Ghedjatti Ahmed , Lyonnard Sandrine , Okuno Hanako , Guetaz Laure , Artero Vincent , Chenevier Pascale 
Published: May 2020

Commercial proton exchange membrane fuel cells (PEMFCs) use platinum as the catalyst, a too scarce and precious metal for sustainable energy supply through PEMFCs. Pt-free catalysts are actively searched for, both at the cathode and at the anode. With huge advancements in current density, lower overpotential and higher stability in the past few years, molecular engineered bio-inspired catalysts hold promise for the next generation of PEMFC [1, 2]. Yet, their implementation in catalytic layers faces nanocomposite formulation issues [3]. Here, we use carbon nanotube immobilized DuBois nickel catalysts to exemplify how self-assembly at the mesoscale affects performances of H2 oxidation anodes.
Copied on the conserved functional features of the active site of hydrogenases, the nickel catalysts created by Dubois et al. [4] show impressive turn-over frequency with no over-potential for hydrogen oxidation in solution. Not only has the central part of the catalyst, but also its outer sphere has a strong influence on the catalytic capacity [5]. Modification of the outer sphere can be used to immobilize the catalyst on a conductive matrix [6-8], a requirement for further implementation in PEMFC [9].
However, long-term ion transport in PEMFC requires creating ion conductive paths in the electrode, a task usually fulfilled by the addition of an ionomer. Although it allowed us to assemble the first fully Pt-free PEMFC [3], the current density was very low when the anode contained ionomer. The electrode microstructure thus appears critical to the system performance, yet it was hardly studied. The figure includes a STEM picture of a carbon nanotube-ionomer mixture showing the thin film formed by the self-organized ionomer, and the schemes of the catalyst structure and of the ionomer structure. Here, we show that molecular engineering coupled with three-dimensional structuring of the carbon electrode plays a major role on the catalytic activity through enhancement of catalyst grafting and substrate/product diffusion inside the electrode.
In particular, we compare the effect of Nafion ionomer addition on the performances of bioinspired catalytic layers produced via three distinct surface chemistries [6-9]. We use microscopy as well as small angle neutron scattering techniques to characterize the self-assembly of the ionomer [10] with the carbon nanotubes/catalyst composite. A strong correlation appears between current drop in the presence of ionomer, and absence of ionomer hydrophilic/hydrophobic nanostructure. We propose a model that describes how the surface charge of the functionalized nanotubes drives the structuration of the Nafion ionomer and impacts diffusion of protons and gas to and from catalytic centres.
[1] N. Coutard, N. Kaeffer, V. Artero, Chem. Commun., 2016, 52, 13728-13748.
[2] F. Jaouen, D. Jones, N. Coutard, V. Artero, P. Strasser, A. Kucernak, Johnson Matthey Technology Review, 2018, 62, 231-255.
[3] P.D. Tran, A. Morozan, S. Archambault, J. Heidkamp, P. Chenevier, H. Dau, M. Fontecave, A. Martinent, B. Jousselme, V. Artero, Chem. Sci., 2015, 6, 2050-2053.
[4] M. Rakowski Dubois and D. L. Dubois, Acc. Chem. Res., 2009, 42, 1974–1982
[5] A. Dutta, J.A.S. Roberts, W.J. Shaw, Angew. Chem. Int. 2014, 53, 6487-6491
[6] A. Le Goff, V. Artero, B. Jousselme, P.D. Tran, N. Guillet, R. Metaye, A. Fihri, S. Palacin, M. Fontecave, Science, 2009, 326, 1384-1387.
[7] P.D. Tran, A. Le Goff, J. Heidkamp, B. Jousselme, N. Guillet, S. Palacin, H. Dau, M. Fontecave, V. Artero, Angew.
Chem. Int. Ed., 2011, 50, 1371-1374.
[8] T.N. Huan, R.T. Jane, A. Benayad, L. Guetaz, P.D. Tran, V. Artero, Energy Environ. Sci., 2016, 9, 940-947.
[9] S. Gentil, N. Lalaoui, A. Dutta, Y. Nedellec, S. Cosnier, W.J. Shaw, V. Artero, A. Le Goff, Angew. Chem. Int. Ed., 2017, 56, 1845-1849
[10] L. Rubatat, G. Gebel, O. Diat, Macromolecules 2004, 37, 7772

Figure 1