Regulating the Selectivity of Nitrate Photoreduction for Purification or Ammonia Production by Cooperating Oxidative Half-Reactions
Shujie Shen, Ruimin Chen, Xin Li, Jielin Wang, Shuangshuang Yu, Jieyuan Li, Fan Dong
Abstract
The removal and conversion of nitrate (NO 3 – ) from wastewater has become an important environmental and health topic. The NO 3 – can be reduced to nontoxic nitrogen (N 2 ) for environmental remediation or ammonia (NH 3 ) for recovery, in which the tailoring of the selectivity is greatly challenging. Here, by construction of the CuO x @TiO 2 photocatalyst, the NO 3 – conversion efficiency is enhanced to ∼100%. Moreover, the precise regulation of selectivity to NH 3 (∼100%) or N 2 (92.67%) is accomplished by the synergy of cooperative redox reactions. It is identified that the selectivity of the NO 3 – photoreduction is determined by the combination of different oxidative reactions. The key roles of intermediates and reactive radicals are revealed by comprehensive in situ characterizations, providing direct evidence for the regulated selectivity of the NO 3 – photoreduction. Different active radicals are produced by the interaction of oxidative reactants and light-generated holes. Specifically, the introduction of CH 3 CHO as the oxidative reactant results in the generation of formate radicals, which drives selective NO 3 – reduction into N 2 for its remediation. The alkyl radicals, contributed to by the (CH 2 OH) 2 oxidation, facilitate the deep reduction of NO 3 – to NH 3 for its upcycling. This work provides a technological basis for radical-directed NO 3 – reduction for its purification and resource recovery.