Constructing multifunctional 'Nanoplatelet-on-Nanoarray' electrocatalyst with unprecedented activity towards novel selective organic oxidation reactions to boost hydrogen production.

• 'Nanoplatelet-on-nanoarray' electrocatalyst is obtained from MOF nanoarrays. • The Electrochem-assisted transformation greatly increases the surface active sites. • Synergy between Ni/Co and unique structure contribute to superior anodic activity. • The electrode shows universal robustness towards oxidation of organic molecules. • HMF and bio-glycerol are upgraded to value-added FDCA and formate with high FE. Replacing oxygen evolution reaction with thermodynamically more favorable organic oxidation reactions is considered as attractive approach to enhance the energy conversion efficiency in electrochemical water splitting. Herein, 'Nanoplatelet-on-Nanoarray' NiCo hydroxide-based electrocatalysts (t-NiCo-MOF) fabricated from the facile transformation of bimetallic metal-organic framework nanoarrays is reported to exhibit rich surface active sites and unprecedented activity towards the oxidation of organic molecules including 5-hydroxymethylfurfural, urea, methanol and glycerol. Benefitting from the synergy between Ni/Co and unique nanostructure which facilitates the charge and mass transfer, the optimal electrode exhibits current densities of 600∼730 mA/cm2 at 1.4 V vs RHE and the Tafel slopes are in the range of 35∼58 mV/dec depending on the oxidized species. Value-added chemicals such as 2,5-furandicarboxylic acid and formate are produced from HMF and methanol/glycerol (main constituents of 'bio-glycerol') with high FE and superior stability, demonstrating its promises in high-throughput electrochemical biomass upgrading. [ABSTRACT FROM AUTHOR]