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Effect of Nitrogen Doping and Oxidation of Graphene on the Deposition of Platinum from Trimethyl(methylcyclopentadienyl)platinum(IV)

Summary

Density functional theory examines how nitrogen doping and vacancy oxidation of graphene influence adsorption and stepwise demethylation of the Pt ALD precursor MeCpPtMe\(_3\), a common vapor-phase platinum source. Pyridinic nitrogen substitutions lengthen substrate–oxygen bonds at oxidized monovacancies, strengthening precursor–surface coupling, while nudged elastic band calculations compare reaction and activation enthalpies for methyl loss pathways on doped and undoped oxidized surfaces. Pt ALD on carbon supports underpins electrocatalysis electrodes; defect and N dopant patterns control nucleation density, so DFT surfaces here map precursor binding to likely island formation sites.

Methods

Canonical curation (same work): [[2022ian-e-campbell-j-phys-chem-effect-nitrogen]]. The corpus pdf_path is a galley-style J. Phys. Chem. C PDF—pagination and table labels should be checked against the VOR at the DOI.

1 — MD application (atomistic dynamics). N/A — no production MD trajectories are central to the published study; it is a 0 K DFT + NEB survey of MeCpPtMe\(_3\) on defect graphene.

2 — Force-field training. N/A.

3 — Static QM / DFT. Program: Quantum ESPRESSO-style planewave PBE-class DFT (see convergence: ecutwfc, charge density cutoff, a plain-text k-mesh / k-point mesh per slab class, and Fermi smearing in the article), with PBE+D3-or-equivalent dispersion and ultrasoft/PAW pseudopotentials as specified in J. Phys. Chem. C (rely on the VOR not the galley for final values). Structures include pristine graphene, monovacancy (MV), MV+2O, MV+3O oxides, and pyridinic N-substituted lattices (e.g. N@C1, N@C5, N@C13 in the paper’s nomenclature). Property work includes MeCpPtMe\(_3\) adsorption energies in several adsorption poses, and NEB reaction pathways for methyl cleavage and trapping to bridge / in-plane O; Bader/difference-density style plots in the PDF illustrate charge reorganization. Dipole-corrected slab vacuums are as documented in the Supplementary/Methods when present.

4 — Experiments. N/A — the paper is computation-forward; Pt ALD serves as context in the introduction/discussion.

Findings

Outcomes and mechanisms. O addition at the monovacancy is favorable thermochemically in the defect scenarios the authors treat; pyridinic N at the sites modeled lengthens C–O bonds at vacancy oxides relative to the N-free analogs, and tightens MeCpPtMe\(_3\) adsorption trends the authors use to discuss nucleation favorability. NEB-based reaction and activation enthalpies for the first demethylation stay endothermic on the oxidized graphenes sampled in the study, yet pyridinic N can lower both reaction endothermicity and the cited barrier for the first step and reorder exothermicity of subsequent CH\(_3\) sticking vs detachment in multi-O vacancy geometries—in some paths a net exothermic multistep sequence from precursor to O-saturated defects is reached for N-doped lattices, which they relate to enhanced Pt ALD nucleation on N-riched carbon.

Comparisons. Doped vs undoped defects, O-poor vs O-rich vacancy motifs, and multiple N-neighborhoods (see the VOR tables for concrete \(\Delta E\) and barrier data); N-doping is not reduced to Lewis-base-only effects—it restructures oxide local strain and electronic localization at the defects.

Sensitivity and levers. N location in the supercell and O coverage at the monovacancy are the main chemical knobs swept in the DFT sweep.

Corpus / KB honesty. Reproduce eV energies and barrier heights from the version-of-record; the corpus galley file is for manifest fingerprint only when it differs from VOR typography—see ## Limitations.

Limitations

Static 0 K DFT omits entropic and coverage effects of real ALD cycles; model vacancy/oxide motifs simplify actual N-doped carbon supports. Galley PDF in corpus may differ slightly from pagination and figure labels in the version of record at DOI 10.1021/acs.jpcc.2c04117. Coverage-dependent precursor competition and chlorine surface species from Pt chemistry are simplified in the static slab survey.

Relevance to group

Penn State collaboration with van Duin on organometallic adsorption at functionalized graphene for catalysis and ALD initiation.

Citations and evidence anchors