Computational Design and Experimental Validation of Enzyme Mimicking Cu-Based Metal-Organic Frameworks for the Reduction of CO into C Products: C-C Coupling Promoted by Ligand Modulation and the Optimal Cu-Cu Distance.

While extensive research has been conducted on the conversion of CO to C products, the synthesis of C products still strongly depends on the Cu electrode. One main issue hindering the C production on Cu-based catalysts is the lack of an appropriate Cu-Cu distance to provide the ideal platform for the C-C coupling process. Herein, we identify a lab-synthesized artificial enzyme with an optimal Cu-Cu distance, named MIL-53 (Cu) (MIL= Materials of Institute Lavoisier), for CO conversion by using a density functional theory method. By substituting the ligands in the porous MIL-53 (Cu) nanozyme with functional groups from electron-donating NH to electron-withdrawing NO, the Cu-Cu distance and charge of Cu can be significantly tuned, thus modulating the adsorption strength of CO that impacts the catalytic activity. MIL-53 (Cu) decorated with a COOH-ligand is found to be located at the top of a volcano-shaped plot and exhibits the highest activity and selectivity to reduce CO to CHCHOH with a limiting potential of only 0.47 eV. In addition, experiments were carried out to successfully synthesize COOH-decorated MIL-53(Cu) to prove its high catalytic performance for C production, which resulted in a -55.5% faradic efficiency at -1.19 V vs RHE, which is much higher than the faradic efficiency of the benchmark Cu electrode of 35.7% at -1.05 V vs RHE. Our results demonstrate that the biologically inspired enzyme engineering approach can redefine the structure-activity relationships of nanozyme catalysts and can also provide a new understanding of the catalytic mechanisms in natural enzymes toward the development of highly active and selective artificial nanozymes.