Aldehyde Directed In Situ Loading of Ag Nanodots Around the Open Metal Sites of MOFs for the Tandem Catalysis of Nitrate to Ammonia

Both spatial arrangement and intrinsic activity of electrocatalysts with dual-active sites are widely designed to match the coupling reaction between nitrate and water, in which most of the reactive intermediates can be optimized to achieve a high yield rate of ammonia. Herein, by introducing the aldehyde group inside metal-organic frameworks (MOFs) in advance, an aldehyde-induced method is achieved to direct the in situ nucleation of Ag nanodots depending on the mesopores of MOFs via a simple silver mirror reaction. The key point here is that the spatial arrangement between the aldehyde group and open metal sites is fixed end to end, which makes the aldehyde group a built-in redox-active site to drive the in situ nucleation of Ag nanodots next to the open metal sites of MOFs. Accordingly, by varying the metal sites of MOFs, a group of M-MOFs@Ag (M = Fe, Co, Ni, Cu, etc.) hybrids with dual active sites are acquired. Taking Ni-MOFs@Ag as an example, the interaction between Ni²⁺ and Ag sites makes it available for the tandem catalysis of nitrate-to-ammonia, in which the H· and NO₂⁻ generated on the open Ni²⁺ sites and Ag nanodots, respectively, can migrate to each other to evolve into ammonia.