Synergistic Integrating of Thermocatalysis and Electrocatalysis.

ConspectusHigh-efficiency catalytic reactions are crucial to the development of a clean and sustainable society. Thermocatalysis specializes in large-scale continuous production, but certain specific thermocatalytic processes are highly endothermic and require high operating temperatures to achieve the desirable equilibrium conversion efficiency. With the rapid development of renewable energy, electrocatalysis has drawn extensive attention because it enables green and precise chemical synthesis. Nevertheless, the electrocatalytic reaction, which undergoes a multiple-electron transfer process and suffers from inherently sluggish kinetics, faces a critical challenge for large-scale application due to its high overpotential and mass transfer limitation.Recently, the synergistic integration of thermocatalysis and electrocatalysis proposed by our group has demonstrated a series of advantages in enabling efficient catalytic reactions, which have attracted widespread research interest. The integration of thermal and electrocatalysis offers a transformative strategy that circumvents thermodynamic limitations of conventional reactions, manipulates reaction energy barriers and pathways, and thereby significantly improves the reaction rates and selectivity. Beyond these benefits, it also simplifies product separation, thereby enhancing the overall process economics. In this Account, we systematically summarize recent progress in synergistic coupling of thermocatalysis and electrocatalysis, focusing on three main strategies: (1) room-temperature thermocatalytic-electrocatalytic coupling, which circumvents traditional high reaction energy barriers via the synergy of spontaneous nonelectrochemical and electrochemical processes; (2) tandem thermocatalytic-electrocatalytic reaction, which accurately addresses the shortcomings of electrocatalytic and thermocatalytic module to break through the conversion-selectivity trade-off; and (3) an integrated thermocatalytic-electrocatalytic pathway, in which the electrochemical procedures can break the thermodynamic equilibrium of the reaction and thereby improve the overall energy efficiency. Together, these approaches provide a versatile way for constructing a high-efficiency catalytic system by revealing the design criterion of the coupling reaction process.Additionally, we discuss the key challenges and prospects in this emerging field in terms of three aspects: (i) further improving the matching degree between thermocatalysis and electrocatalysis; (ii) elucidating the mechanism of reaction activity enhancement; and (iii) trying to scale up the system for industrial-scale level production. We hope this Account will guide the development of more efficient catalytic systems in the years ahead.