Regulating the Coordination Environment of Mesopore-Confined Single Atoms from Metalloprotein-MOFs for Highly Efficient Biocatalysis

Abstract

Single-atom catalysts (SACs) exhibit unparalleled atomic utilization and catalytic efficiency, yet it is challenging to modulate SACs with highly dispersed single-atoms, mesopores, and well-regulated coordination environment simultaneously and ultimately maximize their catalytic efficiency. Here, a generalized strategy to construct highly active ferric-centered SACs (Fe-SACs) is developed successfully via a biomineralization strategy that enables the homogeneous encapsulation of metalloproteins within metal-organic frameworks (MOFs) followed by pyrolysis. The results demonstrate that the constructed metalloprotein-MOF-templated Fe-SACs achieve up to 23-fold and 47-fold higher activity compared to those using metal ions as the single-atom source and those with large mesopores induced by Zn evaporation, respectively, as well as up to a 25-fold and 1900-fold higher catalytic efficiency compared to natural enzymes and natural-enzyme-immobilized MOFs. Furthermore, this strategy can be generalized to a variety of metal-containing metalloproteins and enzymes. The enhanced catalytic activity of Fe-SACs benefits from the highly dispersed atoms, mesopores, as well as the regulated coordination environment of single-atom active sites induced by metalloproteins. Furthermore, the developed Fe-SACs act as an excellent and effective therapeutic platform for suppressing tumor cell growth. This work advances the development of highly efficient SACs using metalloproteins-MOFs as a template with diverse biotechnological applications.

Keywords: biocatalysis; enzymes; metal-organic frameworks; single atoms.