Electrochemical Biomass Upgrading Coupled with Hydrogen Production under Industrial‐Level Current Density

Abstract As promising hydrogen energy carrier, formic acid (HCOOH) plays an indispensable role in building a complete industry chain of a hydrogen economy. Currently, the biomass upgrading assisted water electrolysis has emerged as an attractive alternative for co‐producing green HCOOH and H 2 in a cost‐effective manner, yet simultaneously affording high current density and Faradaic efficiency (FE) still remains a big challenge. Here, the ternary NiVRu‐layered double hydroxides (LDHs) nanosheet arrays for selective glycerol oxidation and hydrogen evolution catalysis are reported, which yield an industry‐level 1 A cm −2 at voltage of 1.933 V, meanwhile showing considerable HCOOH and H 2 productivities of 12.5 and 17.9 mmol cm −2 h −1 , with FEs of almost 80% and 96%, respectively. Experimental and theoretical results reveal that the introduced Ru atoms can tune the local electronic structure of Ni‐based LDHs, which not only optimizes hydrogen adsorption kinetics for HER, but also reduces the reaction energy barriers for both the conversion of Ni II into GOR‐active Ni III and carboncarbon (CC) bond cleavage. In short, this work highlights the potential of large‐scale H 2 and HCOOH productions from integrated electrocatalytic system and provides new insights for designing advanced electrocatalyst for low‐cost and sustainable energy conversion.