Skip to content

Mechanistic study of chemical looping reactions between solid carbon fuels and CuO

Evidence and attribution

Authority of statements

Prose summarizes the Combustion and Flame article identified by doi. Barrier values quoted below are taken from the abstract as reported in the corpus extract; confirm against the version of record if the galley text differs.

Summary

The work combines ReaxFF molecular dynamics and experiments on CuO–carbon mixtures to probe chemical-looping combustion (CLC)-relevant oxidation of n-butane and simplified solid fuels (lignite, anthracite) in contact with CuO nanoparticles. Activation energies from modeling are compared to flammability / flame speed measurements to argue for temperature-dependent competition between surface oxidation on CuO and O2-based pathways. The abstract frames CLC as a carbon conversion strategy where oxygen carriers such as CuO participate in fuel oxidation, motivating atomistic insight into CuO–hydrocarbon and CuO–char interfaces alongside flame measurements (abstract).

Methods

ReaxFF molecular dynamics (A/B)

  • Interaction model: ReaxFF for C/H/O hydrocarbon and solid-carbon oxidation in contact with CuO nanoparticle motifs (parameter lineage in the Combustion and Flame article).
  • Simulation setup: Supercells, ensembles, thermostats, and reaction-path sampling used to extract effective barriers for CuO-surface oxidation vs O\(_2\)-mediated channels—full numerical settings are in the VOR/SI (corpus file here is a proof PDF).

Experiments (integrated)

  • Observables: Thermal response, flammability, and flame speeds for CuO + carbon mixtures as summarized in the abstract.
  • Fuels: Gas-phase n-butane versus solid lignite / anthracite proxies to span volatile vs condensed carbon.

Kinetic analysis

  • Arrhenius plots and regime assignments connect modeled barriers to measured activation energies, including oxygen uncoupling from CuO nanoparticles for anthracite-like cases.

MD application (ReaxFF + solid fuel / CuO)

Engine / code: LAMMPS-style ReaxFF for C/H/O hydrocarbon/char in contact with CuO nanoparticle-like models as in Combust. Flame. 3D PBC supercell size, T program, timestep, ps/ns stages, and thermostat for sampling reaction barriers are in the VOR/SI (this galley path is for hash provenance). N/A — no NPT barostat or shock piston in the protocol summarized on this page unless the article states it; N/A — no static interfacial electric field; N/A — no replica/metadynamics beyond the reported RMD; Coulomb and QEq per VOR.

Findings

n-Butane (gas-phase surrogate)

CuO-surface oxidation carries a much lower barrier than O\(_2\) combustion in the quoted comparison (~9.2 vs ~53.3 kcal mol\(^{-1}\) in the abstract), so surface oxidation dominates in that framing.

Lignite (solid fuel)

O\(_2\) combustion vs CuO-surface reaction barriers are closer (~23.0 vs ~6.3 kcal mol\(^{-1}\) in the abstract), implying stronger competition between pathways.

Anthracite model and CuO decomposition

Arrhenius analysis shows two kinetic regimes; the crossover is associated with O\(_2\) release from CuO nanoparticles, aligning with experimental shifts in activation energy when CuO decomposition matters.

The authors connect simulated barriers to flammability / flame speed trends to argue which oxidation channel limits rate in different temperature windows, spanning volatile and condensed carbon CLC scenarios.

Limitations

Corpus PDF is an Elsevier proof; final pagination and SI tables should be checked against the version of record.

Relevance to group

van Duin-group ReaxFF on fuel oxidation with CuO and experimental validation.

Citations and evidence anchors