Morphological and electronic engineering of Co(OH)2/Ce(OH)3 electrocatalyst on ALD-enabled MgO modified carbon cloth electrode for glucose oxidation-coupled water splitting

• MgO functionalized carbon cloth directed growth of Co(OH) 2 /Ce(OH) 3 microstructures. • Microstructure-electron engineering synergism studied for glucose electrolysis. • Co(OH) 2 /Ce(OH) 3 −MgO@CC showed outstanding bifunctional glucose electrolysis activity. • Co(OH) 2 /Ce(OH) 3 microstructures ensured highly dense, fused, and accessible active sites. • Bimetallic and structural tuning lowered electrolysis voltage by 210 mV vs. water splitting. Exploration of advanced electrocatalyst design strategies and their development to propel the efficient glucose oxidation reaction (GOR) offers a feasible replacement for the stereotypical oxygen evolution reaction, unlocking a dual-benefit platform for sustainable hydrogen production and value-added biomass conversion. For the first time, this study presents the novel functionalization of carbon cloth (CC) fibers with a MgO interlayer to strategically direct the nucleation and growth of a catalytically dynamic Co(OH) 2 /Ce(OH) 3 system, while systematically exploring the influence of microstructural modulation and electron engineering towards enhancing bifunctional GOR-assisted water splitting activity. Among all the fabricated electrodes, the Co(OH) 2 /Ce(OH) 3 −MgO@CC delivers brilliant performance toward glucose electrolysis, driven by the synergistic interplay of densely packed, well-connected, and uniformly distributed three-dimensional Co(OH) 2 /Ce(OH) 3 microstructures, coupled with an optimized electron architecture established by bimetallic engineering tailored for proficient GOR. Impressively, the self-supporting Co(OH) 2 /Ce(OH) 3 −MgO@CC, when configured as a glucose electrolyzer, only demands a low operating potential of 1.65 V to achieve the high current density of 100 mA cm -2 , representing a 210 mV reduction compared to typical alkaline water electrolysis. Overall, this research establishes a new paradigm for innovative electrocatalyst design and paves the way for advancing next-generation materials tailored for efficient glucose oxidation electrocatalysis. Morphology and electronic-structure tailored Co(OH) 2 /Ce(OH) 3 anchored on ALD-derived MgO modified carbon cloth deployed as bifunctional electrocatalysts for glucose oxidation-assisted water splitting.