Rhodium-Based MOF-on-MOF Difunctional Core–Shell Nanoreactor for NAD(P)H Regeneration and Enzyme Directed Immobilization

An organometallic complex-catalyzed artificial coenzyme regeneration system has attracted widespread attention. However, the combined use of organometallic complex catalysts and natural enzymes easily results in mutual inactivation. Herein, we establish a rhodium-based metal-organic framework (MOF)-on-MOF difunctional core-shell nanoreactor as an artificial enzymatic NAD(P)H regeneration system. UiO67 as the core is used to capture rhodium molecules for catalyzing NAD(P)H regeneration. UiO66 as the shell is used to specifically immobilize His-tagged lactate dehydrogenase (LDH) and serve as a protection shield for LDH and [Cp*Rh(bpy)Cl]⁺ to prevent mutual inactivation. A variety of results indicate that UiO67@Rh@UiO66 has good activity in realizing NAD(P)H regeneration. Noteworthily, UiO67@Rh@UiO66@LDH maintains a high activity level even after 10 cycles. This work reports a novel NAD(P)H regeneration platform to open up a new avenue for constructing chemoenzyme coupling systems.