Tailoring the selectivity at the electrode-electrolyte interface is one of the greatest challenges for heterogeneous electrocatalysis, and complementary strategies to catalyst structural designs need to be developed. Herein, we proposed a new strategy of controlling the electrocatalytic pathways by lateral adsorbate interaction for the bio-polyol oxidation. Redox-innocent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) anion possesses the alcoholic property that facilely adsorbs on the nickel oxyhydroxide catalyst, but is resistant to oxidation due to the electron-withdrawing trifluoromethyl groups. The alien HFIP adsorbents can compete with bio-polyols and form a mixed adsorbate layer that creates lateral adsorbate interaction via hydrogen bonding, which achieved a >2-fold enhancement of the oxalate selectivity to 55 % for the representative glycerol oxidation and can be extended to various bio-polyol substrates. Through in situ spectroscopic analysis and DFT calculation on the glycerol oxidation, we reveal that the hydrogen-bonded adsorbate interaction can effectively tune the adsorption energies and tailor the oxidation capabilities toward the targeted products. This work offers an additional perspective of tuning electrocatalytic reactions via introducing redox-innocent adsorbates to create lateral adsorbate interactions.
Keywords: Adsorbate Interaction; Bio-polyols; Biomass; Electrocatalysis; Hydrogen Production.
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