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Boosting Cobalt Porphyrin for Selective Nitrate Electroreduction
Bulin Chen1, Jie Zao1, Yirong Tang1
1State Key Laboratory of Quantum Functional Materials, Shenzhen Key Laboratory of Printed Organic Electronics, Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, China.
Abstract:
The electrocatalytic reduction of nitrate (NO3 -) to ammonia (NH3) offers a sustainable pathway for NH3 synthesis. Metal porphyrins are promising electrocatalysts for the NO3 - reduction reactions (NO3RR) due to their tunable molecular structures, yet effective strategies for enhancing their performance are still lacking. Herein, we develop an efficient composite electrocatalyst based on cobalt tetraphenylporphyrin (CoTPP) for electrochemical NH3 synthesis by mitigating hydroxide (OH-) interference and optimizing active hydrogen supply. CoTPP is identified as a superior catalyst with a strong affinity for NO3 - adsorption, and neutral condition is adopted to suppress the competitive OH- adsorption. Poly(benzodifurandione) (PBFDO) is further introduced as an active hydrogen support cocatalyst. The optimized composite catalyst of CoTPP+carbon nanotube (CNT)+PBFDO shows high Faradaic efficiencies (FEs) of NH3 near 100% across a broad potential range, and a high NH3 yield rate (5.3 mg h-1 cm-2) is achieved, increasing by fivefold when compared to the catalyst without PBFDO. This work provides mechanistic insights into enhancing the activity of molecular electrocatalysts for the conversion of NO3 - to NH3.
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