4.8 Article

Ingenious design of one mixed-valence dual-net copper metal-organic framework for deriving Cu2O/CuO heterojunction with highly electrocatalytic performances from NO3- to NH3

期刊

JOURNAL OF POWER SOURCES
卷 543, 期 -, 页码 -

出版社

ELSEVIER
DOI: 10.1016/j.jpowsour.2022.231832

关键词

Metal-organic frameworks; Copper oxides; Heterojunctions; Nitrate reduction reaction; Ammonium production

资金

  1. National Natural Science Foundation of China [21673177, 22171205]

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In this study, different structures of metal-organic framework (MOF) materials were synthesized and pyrolyzed to prepare CuxO/C heterojunction composites, which were used as catalysts for NO3- reduction to NH3. It was found that Cu2O/CuO@C exhibited the best NRA activity, and the abundant interfacial area and exposed active sites were crucial for the activity enhancement.
In the beginning, 1D chain MOF-ZX1 and 2D layer MOF-ZX2 are assembled from Cu(NO3)(2).3H(2)O with 1,4-bis (imidazole-1-yl)benzene (bib) and isophthalic acid (H2ipa), respectively. Then we ingeniously perceive a 1D/ 2D intercalated network MOF-ZX3 by one-pot reaction of Cu(NO3)2.3H2O with bib and H(2)ipa. Following, Cu2O@C and CuO@C are synthesized from fast microwave-assistant pyrolysis of MOF-ZX1 and MOF-ZX2 pre-cursors, respectively. Interestingly, MOF-ZX3 is a mixed-valence copper metal-organic framework, and it is liable to derive a Cu2O/CuO@C heterojunction. Significantly, we use such CuxO@C composites as catalysts for elec-trochemical NO3- reduction to NH3 (NRA). CuO@C shows the NO3- conversion rate of 31.84%, Faradaic effi-ciency of 68.83% and selectivity of 44.18%, while the NRA performance of Cu2O@C is promoted in some extends. For Cu2O/CuO@C, abundant interfacial areas and exposed active sites not only enhance electron transfer, but speed up reaction kinetics. Ultimately, Cu2O/CuO@C gives the best activity of NRA, including three outstanding indices: conversion rate (83.40%), Faradaic efficiency (93.05%) and selectivity (93.11%). Density functional theory calculations disclose Cu2O/CuO can tune d-band centers of active Cu sites, and thus favorably achieves fast conversion from NO3- to NH3. This work provides a novel idea to rationally design advanced electrocatalysts, and also fundamental investigation on heterojunction catalysts in NRA.

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