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Pyrite mesocrystals reconstruct into OER catalysts

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

Source

The formation of (NiFe)S<sub>2</sub> pyrite mesocrystals as efficient pre-catalysts for water oxidation

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

doi.org/10.1039/c7sc05452aRead the full paper ↗25 citationscc by

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.

What they did

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

What they found

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.

The limits

What it doesn't show

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

Key terms

Mesocrystal
Crystal of aligned nanocrystal building blocks with a common orientation.
OER
Oxygen evolution reaction, 4OH– → O2 + 2H2O + 4e– in alkali.
Pre-catalyst
As-synthesized phase that reconstructs into the true active material under anodic bias.
η10
Overpotential needed for 10 mA cm–2.
Pyrite
MS2 structure (Pa3) used here as (NiFe)S2.

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Growth mode of the PCs:

Common questions

How do the cubes grow?

Non-classical aggregation of <2 nm nickel sulfide clusters.

What is the working OER phase?

Amorphous S-doped metal (oxy)hydroxide after CV.

Role of Fe?

Lowers η10 and helps retain S under anodic conditions.

NiS2-only η10?

351 mV vs <260 mV with Fe.

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