Abstract
Interfacial engineering of synergistic catalysts is one of the keys to achieving multiple proton-coupled electron transfer processes in nitrate-to-ammonia conversion. Herein, by joining ultrathin nickel-based metal–organic framework (denoted Ni-MOF) nanosheets with few-layered hydrogen-substituted graphdiyne-supported copper single atoms and clusters (denoted HsGDY@Cu), a tandem catalyst of Ni-MOFs@HsGDY@Cu with dual-active interfaces was developed for the concerted catalysis of nitrate-to-ammonia. In such a system, the sandwiched HsGDY layer could serve as a bridge to connect the coordinated unsaturated Ni2+ sites with Cu single atoms/clusters in a limited range of 0 to 3.6 nm. From Ni2+ to Cu, via the hydrogen spillover process, the hydrogen radicals (H⋅) generated at the unsaturated Ni2+ sites could migrate across HsGDY to the Cu sites to participate in the transformation of *HNO3 to NH3. From Cu to Ni2+, bypassing the higher reaction energy for *HNO3 formation on the Ni2+ sites, the NO2− detached from the Cu sites could diffuse onto the unsaturated Ni2+ sites to form NH3 as well. The combined results make this hybrid a tandem catalyst with dual active sites for the catalysis of nitrate-to-ammonia conversion with improved Faradaic efficiency at lower overpotentials.
Original language | English |
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Article number | e202404819 |
Journal | Angewandte Chemie - International Edition |
Volume | 63 |
Issue number | 30 |
DOIs | |
State | Published - 22 Jul 2024 |
Keywords
- H-substituted graphdiyne
- Ni-MOFs
- clusters
- nitrate electroreduction
- single atoms