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Electrochemistry

Pyrite mesocrystals reconstruct into OER catalysts

Ni B, He T, Wang JO, et al. · Chemical science · 2018

Open access · cc by · source: Europe PMC

Oleylamine-grown (NiFe)S2 porous cubes form by cluster aggregation; Fe-doped samples reach η10 < 260 mV after converting to S-doped (oxy)hydroxides.

Study at a glance

Design
Other — NiFeS2 pyrite mesocrystal growth and OER pre-catalyst evaluation
N
Materials synthesis and electrocatalysis — no sample N
Population
Fe-doped NiS2 pyrite mesocrystals on GCEs
Outcome
OER overpotential and post-CV transformation to active (oxy)hydroxide

Structured fields used in claim comparison tables when every cited study has a complete layer.

Key findings

40–50 nm nearly single-crystalline porous cubes grow from <2 nm clusters at 180 °C. Fe-doped PCs have η10 < 260 mV vs 351 mV for NiS2. After CVs the real catalyst is amorphous S-doped metal (oxy)hydroxide; Fe helps retain S.

Methodology

Authors heated Ni(NO3)2/TAA in oleylamine, doped Fe, used TEM/SAED to map mesocrystal growth, then measured OER and post-CV spectroscopy.

Limitations

Atomic OER cycle on the reconstructed surface is not solved; GCE η10 is not a device metric.

How this study connects

Role on claims

Each row is a claim on a concept or method page where this paper supports, challenges, or qualifies the statement. Roles are hand-checked — not a model guess.

  • TEM/SAED of a pre-catalyst can disagree with the working catalyst. Fe-doped NiFeS₂ pyrite mesocrystals grow as 40–50 nm nearly single-crystalline porous cubes from <2 nm clusters at 180 °C, with η₁₀ < 260 mV versus 351 mV for NiS₂. After CVs the real OER catalyst is an amorphous S-doped metal (oxy)hydroxide; Fe helps retain S. The cubes TEM imaged are not the surface that evolves oxygen.

    Evidence for the claim as stated.

  • A TEM image of the as-made solid can be characterisation while the mechanism lives elsewhere. Pyrite mesocrystal cubes (40–50 nm, SAED nearly single-crystalline) reconstruct into amorphous (oxy)hydroxide under OER CVs; SAXS, not TEM, clocks PISA nucleation at 9–10 min. Treating the first image as the operating structure is the disagreement between those papers and a simple 'TEM showed the catalyst/morphology' sentence.

    Evidence for the claim as stated.

Open questions

Tensions this paper is part of

From concept pages' “where studies disagree.” Disagreement means the same question; scope means different assays, populations, or outcomes.

  • Scope difference — different assays, populations, or outcomes

    A TEM image of the as-made solid can be characterisation while the mechanism lives elsewhere. Pyrite mesocrystal cubes (40–50 nm, SAED nearly single-crystalline) reconstruct into amorphous (oxy)hydroxide under OER CVs; SAXS, not TEM, clocks PISA nucleation at 9–10 min. Treating the first image as the operating structure is the disagreement between those papers and a simple 'TEM showed the catalyst/morphology' sentence.

    Also on this tension

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