Energy & Environ. Sci.: Near-Unity Electrochemical Conversion of Nitrate to Ammonia on Crystalline Nickel Porphyrin-based Covalent Organic Frameworks

time:2023-02-15Hits:10设置

Title:

Near-Unity Electrochemical Conversion of Nitrate to Ammonia on Crystalline Nickel Porphyrin-based Covalent Organic Frameworks

Authors:

Fang Lv1,2#, Mingzi Sun3#, Yongpan Hu1,2#, Jie Xu1,2, Wei Huang1,2, Na Han1,2*, Bolong Huang3,5* and Yanguang Li1,2,4*

Institutions:

1Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, 215123, China.

2Jiangsu Key Laboratory for Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, China.

3Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, China.

4Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa 999078, Macau SAR, China.

5Research Centre for Carbon-Strategic Catalysis, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, China

Abstract:

Electrochemical nitrate reduction, which has attracted rapidly increasing attention over recent years, can potentially enable the indirect fixation of atmospheric N2 as well as the efficient removal of nitrate from industrial wastewater. It is, however, limited by the lack of efficient and low-cost electrocatalysts available so far. To address this challenge, we here demonstrate a two-dimensional nickel porphyrin-based covalent organic framework (COF) as a potential candidate for the first time. The product has a highly ordered molecular structure with abundant square-shaped nanopores. In neutral solution, the reduction of nitrate ions at different concentrations from ammonia is realized with a great selectivity of 90% under a mild overpotential, a remarkable production rate of up to 2.5 mg h−1 cm−2, a turnover frequency of up to 3.5 s−1, and an intrinsic stability that is best delivered under pulse electrolysis. This cathodic reaction can also be coupled with the oxygen evolution reaction to enable full-cell electrolysis at high efficiency. Theoretical computations indicate that nickel centers can stably adsorb nitrate, and facilitate its subsequent reduction by lowering the energy barrier of the rate-determining step.

IF:

38.532

Link:

https://doi.org/10.1039/D2EE02647C



Editor: Guo Jia


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