Tunable-pH Environment Induced by Local Anchor Effect of High Lewis Basicity Conductive Polymers toward Glycerol Upgrading Assisted Hydrogen Evolution

Hybrid organic/inorganic composites with the organic phase tailored to modulate the local chemical environment at the transition metal-based catalyst surface arise as an enchanting category of catalysts for electrocatalysis. A fundamental understanding of how the conductive polymers of different Lewis basicities affect the reaction path is, however, still lacking to guide rational catalyst design. Herein, polyaniline (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT), and poly(vinyl alcohol) (PVA) manifesting different Lewis basicities are compared for their regulatory roles on the hydrogen evolution reaction (HER) and glycerol electrooxidation (GOR) pathways regarding local proton coverage. Concerted efforts from in situ Raman and DFT theoretical calculations unveil that conductive polymer/V 2 O 5 surface with tunable local pH regulated by Lewis acidity/basicity. As a result of the tailored chemical environment, the restructured V 2 O 5 /PANI/NF composite demonstrates a low overall potential of 1.55 V at the partial current density of 50 mA cm –2 for formate. The glycerol upgrading assisted hydrogen evolution device composed of V 2 O 5 /PANI/NF exhibits excellent electrochemical performance at a maximal Faraday efficiency of 82%, ranking among state of the art.