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ZIF-12/Fe-Cu LDH Composite as a High Performance Electrocatalyst for Water Oxidation.

ABSTRACT: Layered double hydroxides (LDH) are being used as electrocatalysts for oxygen evolution reactions (OERs). However, low current densities limit their practical applications. Herein, we report a facile and economic synthesis of an iron-copper based LDH integrated with a cobalt-based metal-organic framework (ZIF-12) to form LDH-ZIF-12 composite (1) through a co-precipitation method. The as-synthesized composite 1 requires a low overpotential of 337 mV to achieve a catalytic current density of 10 mA cm^-2 with a Tafel slope of 89 mV dec^-1. Tafel analysis further demonstrates that 1 exhibits a slope of 89 mV dec^-1 which is much lower than the slope of 284 mV dec^-1 for LDH and 172 mV dec^-1 for ZIF-12. The slope value of 1 is also lower than previously reported electrocatalysts, including Ni-Co LDH (113 mV dec^-1) and Zn-Co LDH nanosheets (101 mV dec^-1), under similar conditions. Controlled potential electrolysis and stability test experiments show the potential application of 1 as a heterogeneous electrocatalyst for water oxidation.

SUBMITTER: Hameed A

PROVIDER: S-EPMC8264502 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Excess levels of nitrite ion in drinking water interact with amine functionalized compounds to form carcinogenic nitrosamines, which cause stomach cancer. Thus, it is indispensable to develop a simple protocol to detect nitrite. In this paper, a Cu-metal-organic framework (Cu-MOF) with graphene oxide (GO) composite was synthesized by ultrasonication followed by solvothermal method and then fabricated on a glassy carbon (GC) electrode for the sensitive and selective determination of nitrite contamination. The SEM image of the synthesized Cu-MOF showed colloidosome-like structure with an average size of 8 ?m. Interestingly, the Cu-MOF-GO composite synthesized by ultrasonic irradiation followed by solvothermal process produce controlled size of 3 ?m colloidosome-like structure. This was attributed to the formation of an exfoliated sheet-like structure of GO by ultrasonication in addition to the obvious influence of GO providing the oxygen functional groups as a nucleation node for size-controlled growth. On the other hand, the composite prepared without ultrasonication exhibited 6.6 ?m size agglomerated colloidosome-like structures, indicating the crucial role of ultrasonication for the formation of size-controlled composites. XPS results confirmed the presence of Cu(II) in the as-synthesized Cu-MOF-GO based on the binding energies at 935.5 eV for Cu 2p3/2 and 955.4 eV for Cu 2p1/2. The electrochemical impedance studies in [Fe(CN)6]3-/4- redox couple at the composite fabricated electrode exhibited more facile electron transfer than that with Cu-MOF and GO modified electrodes, which helped to utilize Cu-MOF-GO for trace level determination of nitrite in environmental effluent samples. The Cu-MOF-GO fabricated electrode offered a superior sensitive platform for nitrite determination than the Cu-MOF and GO modified electrodes demonstrating oxidation at less positive potential with enhanced oxidation current. The present sensor detects nitrite in the concentration range of 1 × 10-8 to 1 × 10-4 M with the lowest limit of detection (LOD) of 1.47 nM (S/N = 3). Finally, the present Cu-MOF-GO electrode was successfully exploited for nitrite ion determination in lake and dye contaminated water samples.

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ZIF-12/Fe-Cu LDH Composite as a High Performance Electrocatalyst for Water Oxidation.

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