Unexpected Potential Dependent HER Behaviors of Cationic Phosphorus Doped WO3 Nanosheets
Authors: Kucukosman Oguz Kaan , Ma Qingquan , Young Joshua , Zhang Wen , He Huixin 
Published: September 2023

TMOs are generally considered as catalytically inert for hydrogen evolution reaction (HER).[1] This unique property has promoted a wide variety of applications of TMOs, such as aqueous-based lithium ionic batteries, electrochromic smart windows, electrocatalysts and/or catalyst supports. However, hydrogen evolution as an undesired side reaction is commonly observed when they are used in aqueous-based supercapacitors and battery applications.[2] The unexpected HER mechanism for intrinsic TMOs has not been studied until very recently by McKone and Mpourmpakis groups.[3] With careful theoretical calculations, they clearly demonstrated that intrinsic WO3 is not HER active. Bulk hydrogen (H) intercalation into WO3 is a prerequisite for its catalytic activity toward HER. Applying electrochemical potential to WO3 primarily sets the bulk H stoichiometry of thus formed hydrogen bronzes HxWO3. The level of intercalation (x), precisely to say, the density of the intercalated hydrogen in the WO3, in turn determines the formation of W-H*, the bonding strength of W-H*, and their consumption to H2 (HER). Significant HER is only seen at potentials negative enough when x > 0.5. Beyond this intercalation level, HER is no longer dictated by potential-dependent activation energies, instead, is controlled by the density of the hydrogen intercalation on the surface of WO3 catalysts. In line with this extensive theoretical study, Augustyn group very recently experimentally demonstrated the dependence of HER activity of WO3 materials on their electrochemical insertion characteristics.[4] By including crystal water between the WO3 sheets, proton intercalation is greatly facilitated likely with a Grotthuss mechanism. Accordingly, the HER kinetics is largely improved with a large positive shift of the HER on-set potential. On the other hand, by inclusion of molecular pillars in the WO3 lattice to physically block proton intercalation, the HER activity of WO3 was largely inhibited. Recently, we developed a facile approach to cationically dope WO3 nanosheets with red phosphorus. The proton interaction and the associated HER behavior as a function of electrochemical potentials were carefully studied with multiple electrochemical techniques. Interestingly, we found that proton interaction is largely suppressed even without including molecular pillars in the P-doped WO3 lattice. At lower intercalation levels before the so-called “potential independent regime”, the HER kinetics is largely decreased, as expected, compared to the non-doped WO3 control sample. While in the “potential independent regime”, the HER kinetics is largely enhanced. Furthermore, including alkaline metal ions into the electrolyte, the HER kinetics is further suppressed as demonstrated by largely negatively shifted onset potentials and the increased Tafel slopes. Interestingly, in the “potential independent regime”, the HER kinetics is further drastically enhanced. Extensive structural characterization and theoretical calculations are undergoing to reveal the mechanism behind these interesting tunable potential dependent - proton interaction and HER behavior, which will be reported in this work. Understanding how heteroatomic doping could modulate proton interaction and HER behaviors of TMOs at atomic levels would provide practical guidance for designing more efficient and selective electrochemical catalysts for various catalytic reduction reactions, such as carbon dioxide reductions and nitrogen/nitrate reductions to valuable compounds.

[1] Zhang, S.; Zhang, X.; Rui, Y.; Wang, R.; Li, X., Recent advances in non-precious metal electrocatalysts for pH-universal hydrogen evolution reaction. Green Energy & Environment
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6 (4), 458-478.

[2] Wang, R.; Mitchell, J. B.; Gao, Q.; Tsai, W.-Y.; Boyd, S.; Pharr, M.; Balke, N.; Augustyn, V., Operando Atomic Force Microscopy Reveals Mechanics of Structural Water Driven Battery-to-Pseudocapacitor Transition. ACS Nano
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12 (6), 6032-6039.

[3] Miu, E. V.; McKone, J. R.; Mpourmpakis, G., The Sensitivity of Metal Oxide Electrocatalysis to Bulk Hydrogen Intercalation: Hydrogen Evolution on Tungsten Oxide. Journal of the American Chemical Society
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144 (14), 6420-6433.

[4] Spencer, M. A.; Fortunato, J.; Augustyn, V., Electrochemical proton insertion modulates the hydrogen evolution reaction on tungsten oxides. The Journal of Chemical Physics
2022,
156 (6), 064704.

Figure 1