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Interface Engineering Modulation Combined with Electronic Structure Modification of Zn-Doped NiO Heterostructure for Efficient Water-Splitting Activity

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    Interface Engineering Modulation Combined with Electronic Structure Modification of Zn-Doped NiO Heterostructure for Efficient Water-Splitting Activity
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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2024, 7, 1, 214–229
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    https://doi.org/10.1021/acsaem.3c02519
    Published December 15, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Production of hydrogen at large scale requires development of non-noble, inexpensive, and high-performing catalysts for constructing water-splitting devices. Herein, we report the synthesis of Zn-doped NiO heterostructure (ZnNiO) catalysts at room temperature via a coprecipitation method followed by drying (at 80 °C, 6 h) and calcination at an elevated temperature of 400 °C for 5 h under three distinct conditions, namely, air, N2, and vacuum. The vacuum-synthesized catalyst demonstrates a low overpotential of 88 mV at −10 mA cm–2 and a small Tafel slope of 73 mV dec–1 suggesting relatively higher charge transfer kinetics for hydrogen evolution reactions (HER) compared with the specimens synthesized under N2 or O2 atmosphere. It also demonstrates an oxygen evolution (OER) overpotential of 260 mV at 10 mA cm–2 with a low Tafel slope of 63 mV dec–1. In a full-cell water-splitting device, the vacuum-synthesized ZnNiO heterostructure demonstrates a cell voltage of 1.94 V at 50 mA cm–2 and shows remarkable stability over 24 h at a high current density of 100 mA cm–2. It is also demonstrated in this study that Zn-doping, surface, and interface engineering in transition-metal oxides play a crucial role in efficient electrocatalytic water splitting. Also, the results obtained from density functional theory (DFT + U = 0–8 eV), where U is the on-site Coulomb repulsion parameter also known as Hubbard U, based electronic structure calculations confirm that Zn doping constructively modifies the electronic structure, in both the valence band and the conduction band, and found to be suitable in tailoring the carrier’s effective masses of electrons and holes. The decrease in electron’s effective masses together with large differences between the effective masses of electrons and holes is noticed, which is found to be mainly responsible for achieving the best water-splitting performance from a 9% Zn-doped NiO sample prepared under vacuum.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.3c02519.

    • Real-time water splitting, where a visible amount of hydrogen and oxygen gases evolved at the catalyst surface suggesting the promising ability of ZnNiO-Vac for commercial water-splitting applications (MP4)

    • Electrochemical measurements details; XRD patterns of ZnNiO catalysts; XPS survey spectra of ZnNiO catalysts; EDS mapping elemental spectra of ZnNiO catalysts; comparison of HER LSV polarization curves of ZnNiO catalysts with Pt/C, NiO, ZnO, and bare Ni-foam, and chronopotentiometry stability test of ZnNiO catalysts; comparison of OER LSV polarization curves of ZnNiO catalysts with IrO2, NiO, ZnO, and bare Ni-foam, and chronopotentiometry stability test of ZnNiO catalysts; electrochemical impedance spectroscopy (EIS) and computation of constant phase element (CPE); Nyquist plots for CPE in Rs (CPE·Rct) equivalent electrical circuits at different “n” values ranging from 1 to 0.8 and the corresponding depression of the center below the x-axis; Nyquist plots of ZnNiO-Air and ZnNiO-N2 at various HER potential values; Nyquist plots of ZnNiO-Air and ZnNiO-N2 catalysts at various OER potential values; Nyquist plots of ZnNiO-Air and ZnNiO-N2 catalysts at various OER potential values; CV curves of ZnNiO-Air and ZnNiO-N2 catalysts at various scan rates to determine the Cdl; variation of band gap values with different Zn-doping concentrations; band gap for Ni1–xZnx (x = 0.0, 0.05, 0.07, 0.09) O corresponds to the Ueff = 7.05 eV; Variation of effective mass of electrons (me*) and holes (mh*) calculated from the E versus k curves corresponding to the conduction band minimum (CBM) and valence band maximum (VBM), respectively. Plots are shown with different Zn-doping concentrations; computed values of the elements in equivalent electrical circuits from EIS data; OER and HER electrochemical measurement values; Average particle sizes derived from TEM analysis for ZnNiO Air, N2, and Vac samples (PDF)

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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2024, 7, 1, 214–229
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsaem.3c02519
    Published December 15, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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