Abstract
We propose several superiorities of applying some particular metal sulfides to the photocatalytic nitrate reduction in aqueous solution, including the high density of photogenerated excitons, high N2 selectivity (without over-reduction to ammonia). Indeed, ZnCr2S4 behaved as a highly efficient photocatalyst, and with the assistance of 1 wt% cocatalysts (RuOx, Ag, Au, Pd, or Pt), the efficiency was greatly improved. The simultaneous loading of Pt and Pd led to a synergistic effect. It offered the highest nitrate conversion rate of ~45 mg N/h together with the N2 selectivity of ~89%. Such a high activity remained steady after 5 cycles. The optimal apparent quantum yield at 380 nm was 15.46%. More importantly, with the assistance of the surface plasma resonance effect of Au, the visible light activity achieved 1.352 mg N/h under full arc Xe-lamp, and 0.452 mg N/h under pure visible light (λ > 400 nm). Comparing to the previous achievements in photocatalytic nitrate removal, our work on ZnCr2S4 eliminates the over-reduction problem, and possesses an extremely high and steady activity under UV-light, as well as a decent conversion rate under pure visible light.
Highlights
We propose several superiorities of applying some particular metal sulfides to the photocatalytic nitrate reduction in aqueous solution, including the high density of photogenerated excitons, high N2 selectivity
Heterogeneous photocatalysis over semiconductors allows the utilization of solar energy in various chemical reactions, among which overall water splitting is probably the most popular one owing to the global energy crisis[1,2,3,4]
They could be only active under UV-light excitation, the relatively negative conduction band (CB) potential allow the catalytic reduction of water, and the so-produced hydrogen would over-reduce the nitrate to ammonia[8,10,11,12,13,16,19,20,22,23,24,25,26,27,28,30,32,33,34,35,36,37,38,39,41,42,45,46,47,48]
Summary
We propose several superiorities of applying some particular metal sulfides to the photocatalytic nitrate reduction in aqueous solution, including the high density of photogenerated excitons, high N2 selectivity (without over-reduction to ammonia). The reasons include that it is very hard to find a suitable photocatalyst fulfilling both high efficiency and high N2 selectivity because NO3− is soluble and highly stable in aqueous solution, in addition, the rather complicity in mechanism of nitrate reduction[5,6,7,8,9,10,11,12,13], compared to water splitting, contributes to the less achievements in this research field. A recent study shows that the easy-oxidation problem of Ag nanoparticles on the surface lead to the fast degradation of the activity for Ag/TiO2 catalyst[39]
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