Strong Metal-Support Interaction – a Tool for Enhancing the Hydrogen Evolution Reaction Performance
Authors: Smiljanic Milutin , Panić Stefan , Bele Marjan , Ruiz-Zepeda Francisco , Pavko Luka , Gašparič Lea , Kokalj Anton , Gaberscek Miran , Hodnik Nejc 
Published: February 2024

Renewable and green energy transition and meeting ever-increasing energy demands are among modern society's most pressing challenges. Currently, the world's energy systems rely on fossil fuels, leading to significant environmental pollution, including anthropogenic CO2 emissions and subsequent climate changes. The concept of hydrogen economy was first proposed half a century ago as a way to overcome these challenges by using hydrogen as the primary energy carrier instead of fossils.1 However, hydrogen production remains one of the significant obstacles to realizing the hydrogen economy, as steam reforming of methane derived from natural gas is still the dominant method of industrial-scale production, contributing significantly to the undesired emissions. Water electrolysis powered by renewables such as wind and sun energy is a sustainable way to produce high-purity hydrogen. In electrolyzers, hydrogen is obtained at the cathode side through the electrochemical hydrogen evolution reaction (HER), while the oxygen evolution reaction (OER) occurs at the anode. The HER is one of the most intensely studied electrochemical processes as it is of paramount importance for both fundamental and applicable aspects of electrocatalysis and physical chemistry in general. Traditionally, Pt has been known as the best monometallic HER catalyst due to its close-to-optimal interaction with adsorbed hydrogen atoms, which are reaction intermediates.2 However, due to its scarcity and high price, significant research efforts are being invested in designing alternative Pt-free electrocatalysts for (not only) HER. While promising results have been reported with different abundant materials such as sulfides, nitrides, carbides, and phosphides, their applicability is still challenged by rather inferior activity with respect to Pt and rapid deactivation, especially in corrosive acidic media. Currently, state-of-the-art HER catalysts are based on Pt nanoparticles dispersed over high-surface-area carbon supports (Pt/C). The main downside of such composites is the weak interaction between carbon and Pt particles, which means that support cannot affect the intrinsic activity of Pt sites. Moreover, this weak interaction results in the degradation of Pt/C due to particle detachment, agglomeration, or coalescence during HER. Upgrading the overall performance of Pt/C may be achieved by employing alternative supports able to trigger strong metal-support interaction (SMSI). SMSI can alter the electronic structure of the metallic active sites and increase their activity, while also it can lead to the stronger anchoring of nanoparticles with the support, improving stability. Different materials, such as pre-functionalized carbons, carbides, and metal oxides, have been reported to be able to provide SMSI.

In this work, we investigated HER on a carbon-ceramic catalyst composed of Pt nanoparticles supported on titanium oxynitride (TiONx) embedded on reduced graphene oxide nanoribbons (Pt/TiONx).3 TiONx was obtained by incorporating nitrogen into TiO2 and provides the main merits of carbon supports, such as electrical conductivity and high surface area, combined with the ability to trigger SMSI. The screening of the electrocatalytic performance of the Pt/TiONx composite for HER revealed enhancement with respect to the Pt/C benchmark, which we ascribe to the effect of the TiONx substrate via SMSI. To confirm this, XPS was performed to compare the electronic states of Pt in Pt/TiONx and Pt/C catalysts, which revealed the ability of TiONx to trigger SMSI. DFT calculation provided additional confirmation of SMSI between the TiONx support and Pt nanoparticles and its impact on both HER activity and stability enhancement. The results presented in this work open up a perspective of using TiONx as an alternative support able to improve the catalytic performance of various active sites for different electrochemical reactions.

References

(1) Bockris, J. O. M. The Hydrogen Economy: Its History. Int J Hydrogen Energy
2013, 38 (6), 2579–2588. https://doi.org/10.1016/j.ijhydene.2012.12.026.

(2) Hansen, J. N.; Prats, H.; Toudahl, K. K.; Mørch Secher, N.; Chan, K.; Kibsgaard, J.; Chorkendorff, I. Is There Anything Better than Pt for HER? ACS Energy Lett
2021, 1175–1180. https://doi.org/10.1021/acsenergylett.1c00246.

(3) Smiljanić, M.; Panić, S.; Bele, M.; Ruiz-Zepeda, F.; Pavko, L.; Gašparič, L.; Kokalj, A.; Gaberšček, M.; Hodnik, N. Improving the HER Activity and Stability of Pt Nanoparticles by Titanium Oxynitride Support. ACS Catal
2022, 12 (20), 13021–13033. https://doi.org/10.1021/acscatal.2c03214.

Figure 1