Effects of Tin in La-Sn-Codoped Zn(O,S) Photocatalyst to Strongly Cleave the Azo Bond in Azobenzene with in Situ Generated Hydrogen

ACS Appl Mater Interfaces. 2020 Apr 8;12(14):16186-16199. doi: 10.1021/acsami.9b19885. Epub 2020 Mar 25.

Abstract

La-Sn-codoped Zn(O,S) catalysts were synthesized with different amounts (0%, 2.5%, 5%, and 10%) of Sn and a constant amount (10%) of La to improve the photocatalytic hydrogenation reaction (PHR) of azobenzene to aniline. The as-prepared catalysts were carefully characterized and tested for a hydrogenation reaction. The incorporation of Sn significantly enhanced the PHR activities since the incorporated Sn in the Zn(O,S) lattices could increase the conductivity of the catalysts to improve the charge transfer during the catalytic reaction as indicated with EIS measurement. Further measurement with a photoresponse of La-Sn-codoped Zn(O,S) catalysts also exhibited relatively higher intensities as compared to those of La-doped Zn(O,S) and Sn-doped Zn(O,S) catalysts. On the basis of the measurement results of EIS and transient photo current, the La-Sn-codoped Zn(O,S) with the best properties was further utilized for PHR to convert azobenzene to aniline. GC-MS measurement confirmed that 15 ppm azobenzene could be totally converted to aniline in only 60 min which was achieved with a catalyst that was prepared with 5%-Sn and 10%-La doping. The relatively short reaction time indicated that the as-prepared catalyst had a strong reduction capability able to cleave the strong bonding of N═N in azobenzene. The reaction kinetic of the N═N bond cleavage was elucidated based on solvation, adsorption, pinning, and photocatalytic hydrogenation processes on the catalyst surfaces.

Keywords: La−Sn-codoped Zn(O,S); N═N cleavage; aniline; azobenzene; photocatalytic hydrogenation reaction.