How can thermoelectric coupling catalysis be applied to facilitate biomass conversion into value-added products and hydrogen?

Abstract

Biomass conversion into fuels and chemicals holds great promise for sustainable development, yet its efficient valorization remains hindered by the intrinsic complexity of polymeric structures and oxygen-rich functionalities. While thermocatalysis specializes in depolymerization and electrocatalysis enables precise redox control, both face fundamental limitations when used alone. Thermoelectric catalysis has recently emerged as a transformative strategy to resolve this trade-off by synergistically integrating thermal and electrical energy. More than a simple integration of techniques, this strategy represents a paradigm shift in catalyst design: from creating static, heat-tolerant materials to engineering adaptive, field-responsive systems. In this framework, temperature is reimagined as a precision tool for modulating electronic structure and driving in situ catalyst evolution. This tutorial review systematically builds on this concept, starting from mechanistic fundamentals and a comparison of cascade and coupled architectures to highlight different design logics. We then present a multi-scale electrode design roadmap: from atomic-scale active sites to mesoscale transport control and intrinsically responsive materials, showcasing how these strategies can unlock energy-efficient pathways for the concurrent production of value-added chemicals and hydrogen. The review concludes by outlining critical challenges for industrial relevance, including control of fluid flow and heat/mass transfer in non-Newtonian electrolyte suspensions, the operational stability and durability of thermoelectrocatalytic reactors, and process integration and evaluation.