Directional Shunting of Photogenerated Carriers in Pom@Mof for Promoting Nitrogen Adsorption And Oxidation.

The efficient catalysis nitrogen (N ) into high-value N-containing products plays a crucial role in N economic cycle. However, weak N adsorption and invalid N activation remain two major bottleneck in rate-determining steps, leading to low N fixation performance. Herein, we highlight an effective dual active sites photocatalyst of polyoxometalates (POMs)-based metal-organic frameworks (MOFs) via altering coordination microenvironment and inducing directional shunting of photogenerated carriers to facilitate N /catalyst interaction and enhance oxidation performance. MOFs create more open unsaturated metal clusters sites with unoccupied d orbital possessing Lewis acidity to accept electrons from 3σ bonding orbital of N for storage by combining with POMs to replace bidentate linkers. POMs act as electron sponges donating electrons to MOFs, while the holes directional flow to POMs. The hole-rich POMs with strong oxidation capacity are easily involved in oxidizing adsorbed N . Taking UiO-66 (C H O Zr ) and Mo Fe ([Mo Fe O (CH COO) {Mo O (H O)} {H Mo O (H O)}(H O) ]·150H O) as an example, Mo Fe @UiO-66 shows 2-fold enhanced adsorption of N (250.5 cm g ) than UiO-66 (122.9 cm g ) at P/P = 1. And, the HNO yield of Mo Fe @UiO-66 is 702.4 μg g h , nearly 7 times and 24 times higher to UiO-66 and Mo Fe . Our work provides reliable value for the storage and relaying artificial N fixation. This article is protected by copyright. All rights reserved.