Interfacial Thermoconvection and Atomic Relay Catalysis Enable Equilibrium Shifting and Rapid Glucose‐to‐Fructose Isomerization

The aqueous glucose‐to‐fructose isomerization is controlled by thermodynamics to an equilibrium limit of ~50% fructose yield. However, here we report an in‐situ fructose removal strategy enabled by an interfacial local photothermal effect in combination with relay catalysis of geminal and isolated potassium single atoms (K SAs) on graphene‐type carbon (Ksg/GT) to effectively bypass the equilibrium limit and markedly speed up glucose‐to‐fructose isomerization. At 25 ºC, an unprecedented fructose yield of 68.2% was obtained over Ksg/GT in an aqueous solution without any additives under 30‐min solar‐like irradiation. Mechanistic studies expounded that the interfacial thermoconvection caused by the local photothermal effect of the graphene‐type carbon and preferable glucose adsorption on single‐atom K could facilitate the release of in‐situ formed fructose. The geminal K SAs were prone to form a stable metal‐glucose complex via bidentate coordination, and could significantly reduce the C–H bond electron density by light‐driven electron transfer toward K. This facilitated the hydride shift rate‐determining step and expedited glucose isomerization. In addition, isolated K SAs favored the subsequent protonation and ring‐closure process to furnish fructose. The integration of the interfacial thermoconvection‐enhanced in‐situ removal protocol and tailored atomic catalysis opens a prospective avenue for boosting equilibrium‐limited reactions under mild conditions.