Ligand Hybridization for Electro‐reforming Waste Glycerol into Isolable Oxalate and Hydrogen

The electro‐reforming of glycerol is an emerging technology of simultaneous hydrogen production and biomass valorization. However, its complex reaction network and limited catalyst tunability restrict the precise steering toward high selectivity. Herein, we incorporated the chelating phenanthrolines into the bulk nickel hydroxide and tuned the electronic properties by installing functional groups, yielding tunable selectivity toward formate (max 92.7 %) and oxalate (max 45.3 %) with almost linear correlation with the Hammett parameters. Further combinatory study of intermediate analysis and various spectroscopic techniques revealed the electronic effect of tailoring the valence band that balances between C−C cleavage and oxidation through the key glycolaldehyde intermediate. A two‐electrode electro‐reforming setup using the 5‐nitro‐1,10‐phenanthroline‐nickel hydroxide catalyst was further established to convert crude glycerol into pure H2 and isolable sodium oxalate with high efficiency. Hybridizing chelating phenanthrolines with heterogeneous nickel hydroxides can efficiently tune the glycerol electrooxidation selectivities via controlling the catalyst electronic states. The selectivities almost linearly scale with the Hammett parameters of the functional groups on the phenanthrolines, creating new rationales for the design of selective catalysts.