Phase engineering activation of low-cost iron-containing sulfide minerals for advanced electrocatalysis

doi:10.1016/j.jmst.2021.09.047

Abstract

Abstract:

Sustainable energy conversion and storage provide feasible approaches towards green energy solutions and carbon neutralization. The high cost and complex fabrication process of advanced energy nanomaterials, however, has impeded the practical application of emerging sustainable technologies. The direct use of earth-abundant natural minerals which contain active elements for effective catalysis and energy storage should be a promising approach to achieve affordable sustainable energy supply and green fuel generations. Herein, as typical examples of activating natural minerals for electrocatalysis, two common minerals, pyrite and chalcopyrite, are activated via a one-step phase transformation strategy. Through a facile thermal reduction process, the minerals are completely transformed into active pyrrhotite (FeS) and haycockite (Cu₄Fe₅S₈) phases. The thermal reduction resulting phase transformation can lead to significant surface disordering and can contribute to the catalytic activity by offering favourable electronic structure for intermediates adsorption, abundant surficial active centres, and substantial surface redox pairs. The activated minerals are examined for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysis. The obtained haycockite phase delivers the best performance towards acidic HER and alkaline OER. Further phase optimization is performed via loading a low percentage of iridium nanoclusters on the haycockite phase deposited onto a carbon cloth substrate, through which an overpotential as low as 310 mV for achieving 10 mA cm^-2 and a small Tafel slope of 55.6 mV dec^-1 are recorded for alkaline OER. This work demonstrates the feasibility of the direct use of cost-effective natural resources for addressing the current energy-related issues and paves a way to reach affordable practical emerging sustainable technologies.

Key words: Minerals, Phase transformation, Sulfides, Oxygen evolution, Electrocatalysis

Jun Mei, Qian Zhang, Hong Peng, Ting Liao, Ziqi Sun. Phase engineering activation of low-cost iron-containing sulfide minerals for advanced electrocatalysis[J]. J. Mater. Sci. Technol., 2022, 111: 181-188.

Figures/Tables 5

Scheme 1. Crystal structures and schematic illustration of phase transformations of iron-containing sulfide minerals.

Fig. 1. Morphology and crystal structure characterizations of pyrite mineral (FeS2) before and after thermal reduction. (a) SEM image and (b, c) the corresponding element mapping patterns, (d) TEM image, and (e) HR-TEM image of FeS2 mineral. (f) SEM image and (g, h) the corresponding element mapping patterns, (i) TEM image, and (j) HR-TEM image of FeS product. (k) XRD patterns and (l) Raman spectra of FeS2 mineral and FeS product. (m, n) High-resolution XPS spectra of Fe and S in FeS2 mineral and FeS product.

Fig. 2. Morphology and crystal structure characterizations of chalcopyrite mineral (CuFeS2) before and after thermal reduction. (a) SEM image and (b-d) the corresponding element mapping patterns, (e) TEM image, and (f) HR-TEM image of CuFeS2 mineral. (g) SEM image and (h-j) the corresponding element mapping patterns, (k) TEM image, and (l) HR-TEM image of Cu4Fe5S8 product. (m) XRD patterns and (n) Raman spectra of CuFeS2 mineral and Cu4Fe5S8 product. (o, p) High-resolution XPS spectra of Fe and S in CuFeS2 mineral and Cu4Fe5S8 product.

Fig. 3. Electrocatalytic hydrogen and oxygen evolution performance of FeS2, CuFeS2, FeS and Cu4Fe5S8 catalysts in acidic and alkaline electrolytes. (a) iR-corrected linear sweep voltammetry (LSV) curves for HER and (b) the corresponding Tafel slopes of FeS2, CuFeS2, FeS, and Cu4Fe5S8 catalysts in 0.5 mol/L H2SO4 at a scan rate of 5 mV s-1. (c) iR-corrected LSV curves for OER and (d) the corresponding Tafel slopes of FeS2, CuFeS2, FeS, and Cu4Fe5S8 catalysts in 1.0 mol/L KOH at a scan rate of 5 mV s-1. (e) Exposed surface states of FeS2, CuFeS2, FeS, and Cu4Fe5S8 structures.

Fig. 4. Structural and performance characterizations of Cu4Fe5S8/Ir-CC catalyst for OER in 1.0 mol/L KOH solution. (a) iR-corrected LSV curves for OER, (b) overpotential comparison at 10 mA cm-2, and (c) the corresponding Tafel slopes of Cu4Fe5S8-CC and Cu4Fe5S8/Ir-CC catalysts in 1.0 mol/L KOH at a scan rate of 5 mV s-1. (d) Cycling stability of Cu4Fe5S8/Ir-CC catalysts for OER at 10 mA cm-2 within 70 h in 1.0 mol/L KOH. (e) SEM image and the corresponding element mapping patterns for the Cu4Fe5S8/Ir-CC catalyst after OER. (f) Enlarged SEM image and the corresponding element distribution of Cu, Fe, S and O elements on the oxidized Cu4Fe5S8 surfaces after OER. (g) TEM and (h, i) HRTEM images of Cu4Fe5S8/Ir-CC catalyst after OER. Inset in (h) shows the HRTEM image of Ir species before OER. (j-l) High-resolution XPS spectra of Cu, Fe and S in the Cu4Fe5S8/Ir-CC catalyst after OER.

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