Fluorine Induced In Situ Formation of High Valent Nickel Species for Ultra Low Potential Electrooxidation of 5‐Hydroxymethylfurfural

Abstract The Nickel‐based catalysts have a good catalytic effect on the 5‐hydroxymethylfurfural electrooxidation reaction (HMFOR), but limited by the conversion potential of Ni 2+ /Ni 3+ , 1.35 V versus RHE, the HMF electrooxidation potential of nickel‐based catalysts is generally greater than 1.35 V versus RHE. Considering fluorine has the highest Pauling electronegativity and similar atomic radius of oxygen, the introduction of fluorine into the lattice of metal oxides might promote the adsorption of intermediate species, thus improving the catalytic performance. F is successfully doped into the lattice structure of NiCo 2 O 4 spinel oxide by the strategy of hydrothermal reaction and low‐temperature fluorination. As is confirmed by in situ electrochemical impedance spectroscopy and Raman spectroscopy, the introduction of F weakens the interaction force of metal‐oxygen covalent bonds of the asymmetric M T ‐O‐M O backbone and improves the valence of Ni in tetrahedra structure, which makes it easier to be oxidized to higher valence active Ni 3+ under the action of electric field and promotes the adsorption of OH − , while the decrease of Co valence enhances the adsorption of HMF with the catalyst. Combining the above reasons, F‐NiCo 2 O 4 shows superb electrocatalytic performance with a potential of only 1.297 V versus RHE at a current density of 20 mA cm −2 , which is lower than the most catalyst.