The photocatalytic hydroxylation of benzene to phenol using low-cost Fe-based materials is of great significance but remains a great challenge for the conversion of benzene in an efficient manner. Here we report a novel method to construct polymeric Fe-BTC-350 with highly dispersed coordinatively unsaturated (CUS) Fe centers by a simple pyrolysis of iron benzene tricarboxylic acid (Fe-BTC) coordination polymer. The CUS Fe centers in Fe-BTC-350 function as Lewis acid sites to accept both electrons and hydroxyl radicals, thus enhancing photocatalytic phenol generation. An optimal phenol yield of 22.7 % has been achieved over optimized Fe-BTC-350 which is 2.8 times that of the Fe-BTC. No evident decay in the activity was found after 4 cycles of consecutive reactions, indicating the robust stability of the photocatalyst. It is expected that the construction of CUS transition metal centers can also be utilized for other photocatalytic radical reactions.
Chunfeng Shao,Lingmin Wu,Yinghua Wang,Konggang Qu,Hailiang Chu,Lixian Sun,Jianshan Ye,Baitao Li,Xiujun Wang
Single-atom Fe catalysts are a promising substitute to Pt catalysts for oxygen reduction reaction (ORR). Adjusting metal energy level through direct atomic interface regulation can effectively improve catalytic performance but still in its infancy. Herein, highly active nitrogen and sulfur dual-coordinated asymmetric Fe center anchored in carbon nanoparticles were developed. Spontaneously absorbed OH ligand is steadily anchored in asymmetric atomic interface, constructing new FeN 3 S-OH moiety. Theoretical calculations reveal that the incorporated S atom combined with OH ligand as energy level modifier effectively activate Fe center by electronic modulation and d -band center shift, rendering improved ORR activity of FeNSC-2Fe with E 1/2 of 0.913 V in alkaline, 0.806 V in acidic and 0.711 V in neutral media. The FeNSC-2Fe-based device displays high power density of 306 mW cm −2 in Zn-air battery and 2485 mW m −2 in microbial fuel cell . This work provides a new perspective for the controllable synthesis and performance optimization for electrocatalysts.
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