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

The efficient catalysis nitrogen (N 2 ) into high-value N-containing products plays a crucial role in N economic cycle. However, weak N 2 adsorption and invalid N 2 activation remain two major bottleneck in rate-determining steps, leading to low N 2 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 2 /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 g bonding orbital of N 2 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 2 . Taking UiO-66 (C 48 H 28 O 32 Zr 6 ) and Mo 72 Fe 30 ([Mo 72 Fe 30 O 252 (CH 3 COO) 12 {Mo 2 O 7 (H 2 O)} 2 {H 2 Mo 2 O 8 (H 2 O)}(H 2 O) 91 ]·150H 2 O) as an example, Mo 72 Fe 30 @UiO-66 shows 2-fold enhanced adsorption of N 2 (250.5 cm 3 g -1 ) than UiO-66 (122.9 cm 3 g -1 ) at P/P 0 = 1. And, the HNO 3 yield of Mo 72 Fe 30 @UiO-66 is 702.4 μg g -1 h -1 , nearly 7 times and 24 times higher to UiO-66 and Mo 72 Fe 30 . Our work provides reliable value for the storage and relaying artificial N 2 fixation. This article is protected by copyright. All rights reserved.