Substantially Updating Photocatalytic Reaction by In-Situ Generated SO4− Through Directly Exciting SO42−
JOURNAL OF WATER PROCESS ENGINEERING（2022）
Nanjing Univ Informat Sci & Technol
Abstract
In photocatalytic oxidation reaction, sulfate radicals (SO4-center dot) as active oxidative species is investigated rarely and is not fully understanded. In this work, the generation process of SO4-center dot and its effect on photodegradation reaction are mainly investigated. The pre-adsorption of Na2SO4 on Bi2O2CO3 is performed (named as Na2SO4-BOC). It is found that after irradiation for 70 min under ultraviolet light (lambda < 400 nm), 61% and 15% of RhB are degraded by Na2SO4-BOC and pristine BOC (Bi2O2CO3 without pre-adsorption of Na2SO4), respectively. The apparent reaction kinetic rate constant (k(a)) for Na2SO4-BOC (0.048 min(-1)) has increased by 11 times, compared to that of BOC (0.004 min(-1)). Besides, Na2SO4 is also directly added in photoreaction system to compare. The results show that 87% of RhB is degraded at 70 min, which is significantly higher than BOC; the k(a) (0.036 min(-1)) of the reaction with adding Na2SO4 has increased by 8 times, compared to BOC. The greatly enhanced photocatalytic activity is mainly attributed to the SO4-center dot, as proved by electron spin resonance (ESR) spectrum. It is found that SO42- anions can be converted to SO4-center dot radicals by ultraviolet light irradiation directly, (OH)-O-center dot radicals and holes. The newly generated SO4-center dot (redox potential 2.6 V), combined with (OH)-O-center dot radicals and holes, synergistically improves the photocatalytic reaction. The results for TiO2 (P25) system also confirm the substantially updated degradation ability by SO4-center dot through directly exciting SO42-. This work provides a simple, low-cost method to improve conventional photoreaction.
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Key words
SO4-center dot radical,Active oxidation species,Photocatalytic reaction,Synergistic effect
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