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Published on: March 19, 2017
Efficient electrosynthesis of ammonia from nitrate reduction over the perylene-3,4,9,10-tetracarboxylic diimide-based
Hongjun Fang1, Fang Fang1, Hongsheng Yang1
1Key Laboratory of Mesoscopic Chemistry, MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Abstract:
Electrochemical NO3- reduction reaction (eNO3-RR) has shown a promising prospect in both nitrate pollutant removal and NH3 production. However, the lack of novel electrocatalysts hinders its application. Herein, the perylene-3,4,9,10-tetracarboxylic diimide (PDI) based heterojunction electrocatalysts were prepared and used as a working electrode for highly efficient eNO3-RR. The developed 12 %-PDI/MgCo2O4 exhibited a high Faradaic efficiency (FE) of 98.60 % at -0.53 V vs. reversible hydrogen electrode (RHE) and an excellent NH3 production rate as high as 14.48 mg h-1 cm-2 at -0.83 V vs. RHE, the top performance among the systems reported. In-situ attenuated total reflection Fourier transformed infrared spectroscopy together with online differential electrochemical mass spectroscopy identified the reaction intermediates during eNO3-RR. The theoretical simulation manifested that the assembled 12 %-PDI/MgCo2O4 can not only suppress the hydrogen evolution reaction, but also reduces the energy barrier of *NO3 → *NO3H step (rate-determining step/RDS), thus boosting the electrocatalytic efficiency of the target reaction. Moreover, an assembled Zn-NO3- battery using 12 %-PDI/MgCo2O4 as cathode material exhibited a power density of 3.0 mW cm-2 with a remarkable NH3 production rate of 2646 μg h-1 cm-2. This work demonstrated the superiority of PDI in ameliorating eNO3-RR activity of the assembled heterojunction and provided guidance for the development of other PDI-based materials for efficient eNO3-RR towards NH3 generation.
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