Defects-Induced Single-Atom Anchoring on Metal-Organic Frameworks for High-Efficiency Photocatalytic Nitrogen Reduction.
Angew Chem Int Ed Engl
; 63(2): e202314408, 2024 Jan 08.
Article
em En
| MEDLINE
| ID: mdl-37968240
ABSTRACT
Aiming to improve the photocatalytic activity in N2 fixation to produce ammonia, herein, we proposed a photochemical strategy to fabricate defects, and further deposition of Ru single atoms onto UiO-66 (Zr) framework. Electron-metal-support interactions (EMSI) were built between Ru single atoms and the support via a covalently bonding. EMSI were capable of accelerating charge transfer between Ru SAs and UiO-66, which was favorable for highly-efficiently photocatalytic activity. The photocatalytic production rate of ammonia improved from 4.57â
µmol g-1 h-1 to 16.28â
µmol g-1 h-1 with the fabrication of defects onto UiO-66, and further to 53.28â
µmol g-1 h-1 with Ru-single atoms loading. From the DFT results, it was found that d-orbital electrons of Ru were donated to N2 πâ¶-antibonding orbital, facilitating the activation of the N≡N triple bond. A distal reaction pathway was probably occurred for the photocatalytic N2 reduction to ammonia on Ru1 /d-UiO-66 (single Ru sites decorated onto the nodes of defective UiO-66), and the first step of hydrogenation of N2 was the reaction determination step. This work shed a light on improving the photocatalytic activity via feasibly anchoring single atoms on MOF, and provided more evidences to understand the reaction mechanism in photocatalytic reduction of N2 .
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MEDLINE
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En
Ano de publicação:
2024
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Article