Bifunctional Cu–CoFe 2 O 4 Catalyst for Integrated Glucose Valorization and Green Hydrogen Cogeneration

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🔬研究者:Electrocatalysis researchers can explore the facet-dependent reactivity and core-shell design principles for other biomass valorization reactions.

🏢実務担当者:Companies in hydrogen production or biomass conversion can consider this catalyst for integrated DGFC systems to reduce energy costs.

Electrochemical biomass valorization is emerging as a promising route to produce renewable chemicals while simultaneously reducing the energetic and environmental cost associated with conventional hydrogen generation. Among biomass-derived molecules, glucose stands out as the most abundant monosaccharide, making it an attractive feedstock for paired electrochemical processes. However, designing a single catalytic platform capable of supporting both the glucose oxidation reaction (GOR) and the electrochemical hydrogenation of glucose (ECH) remains a fundamental challenge. This difficulty is mainly associated with the distinct pH, potential windows, and adsorption environments required for oxidative and reductive pathways. In this work, we introduce a Cu–CoFe 2 O 4 core–shell nanoarchitecture supported on CNT-modified carbon cloth, specifically engineered as a bifunctional electrocatalyst capable of operating in a Direct Glucose Fuel Cell (DGFC) configuration. This design enables the integration of glucose valorization reactions with in situ green hydrogen cogeneration, offering a unified approach for sustainable electrochemical conversion. The catalyst consists of a conductive Cu core that enhances charge transport and a CoFe 2 O 4 spinel shell rich in redox-active sites that modulate intermediate adsorption. This hierarchical architecture provides a unique synergy: Cu promotes electron mobility and stabilizes reductive intermediates, while the spinel layer facilitates oxidative dehydrogenation steps via accessible Co 2+ /Co 3+ and Fe 2+ /Fe 3+ redox couples. CNT-modified carbon cloth serves as a high-surface-area conductive scaffold that ensures uniform catalyst dispersion and efficient mass transport. The resulting electrode architecture displays excellent mechanical stability, wettability, and electrochemical accessibility of the catalytic surface. Under alkaline GOR conditions (1 M KOH, 10 mM glucose), the catalyst exhibits exceptional activity and selectivity. At 1.3 V vs RHE, it achieves 97.5% conversion of glucose and a Faradaic efficiency of 91.2% toward formic acid, markedly outperforming conventional Ni- and Co-based catalysts. Importantly, the catalyst effectively suppresses the oxygen evolution reaction, which commonly limits selectivity in alkaline systems. Chronoamperometry further demonstrates stable current densities over extended operation, confirming the robustness of the core–shell architecture. Gas chromatography simultaneously verifies 100% Faradaic efficiency toward H 2 production in the cathodic compartment of the DGFC, indicating full electron utilization in the paired oxidation–reduction process and validating its potential as a dual-function electrochemical platform. When transitioning to neutral conditions (0.1 M Na 2 SO 4 , 0.1 M glucose), the same catalyst exhibits a remarkable functional shift. Instead of oxidizing glucose, it selectively promotes its electrochemical hydrogenation to sorbitol, achieving a Faradaic efficiency of 87.5% at −0.4 V vs RHE. This ability to switch between oxidative and reductive behavior using the same material highlights the intrinsic bifunctionality of the Cu–CoFe 2 O 4 system. Switchable reactivity is especially relevant for DGFC configurations, where simultaneous oxidation at the anode and hydrogenation or hydrogen evolution at the cathode can be tuned depending on the target products. Density functional theory calculations provide insight into the origin of this dual behavior. The spinel-rich (111) surface stabilizes oxygen-bound intermediates such as gluconolactone and facilitates dehydrogenation steps characteristic of GOR, while the Cu-enriched (211) facet exhibits optimal binding energies for hydrogenated intermediates, favoring ECH pathways. This facet-dependent reactivity explains the catalyst’s ability to operate efficiently in both oxidative and reductive regimes simply by adjusting the electrolyte and applied potential. The theoretical predictions correlate strongly with experimental product distributions and electrochemical trends, confirming the cooperative functionality between the Cu core and the CoFe 2 O 4 shell. Overall, the Cu–CoFe 2 O 4 core–shell catalyst demonstrates an exceptional capacity to couple glucose oxidation with hydrogen evolution under alkaline conditions, while simultaneously enabling glucose hydrogenation under neutral conditions, using the same catalytic interface. Its high selectivity, stability, and operational flexibility establish it as a promising candidate for integrated electrochemical systems aimed at producing both green hydrogen and value-added chemicals from renewable feedstocks. This work positions bifunctional nanoarchitecture spinel–metal heterostructures as a versatile platform for sustainable electrochemical processes and highlights the potential of DGFC configurations as next-generation devices for simultaneous energy conversion and biomass upgrading. Figure 1

• semanticscholar https://doi.org/10.1149/ma2026-01552691mtgabsfirst seen 2026-07-21 05:23:46