Computational Modelling — Electrically conductive Pt-MOFs for acidic oxygen reduction: Optimized performance via altering conjugated ligands

8 measurement groups · 44 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

Bader charge analysis

Pt3(C12N6O6)2 MOF monolayer model · Model

Charge transfer between Pt-X4 moieties, pyrazine rings and ORR intermediates for all three Pt-MOF monolayers.

Atmosphere: model system
Geometry: 2D monolayer models
Context: model pristine frameworks
Measurement source: p. 26-27 · Computational framework · Tables S10-S11

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Bader N-site in pyrazine ring charge for Pt3(C12N9H3O3)2	-2.28	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader Pt-site in Pt-X4 charge for Pt3(C12N9H3O3)2	0.91	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader Pt-X4 charge transfer for Pt3(C12N9H3O3)2	-2.25	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader pyrazine ring charge transfer for Pt3(C12N9H3O3)2	1.22	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader N-site in pyrazine ring charge for Pt3(C12N12H6)2	-2.61	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader Pt-site in Pt-X4 charge for Pt3(C12N12H6)2	0.67	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader Pt-X4 charge transfer for Pt3(C12N12H6)2	-2.21	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader pyrazine ring charge transfer for Pt3(C12N12H6)2	1.09	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader N-site in pyrazine ring charge for Pt3(C12N6O6)2	-2.2	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
*Bader Pt-active-site charge for O on Pt3(C12N6O6)2**	1.32	—	—	SI Table Exact Reported	p. 27 · Computational framework · Table S11
*Bader reactant charge for O on Pt-site of Pt3(C12N6O6)2**	-0.56	—	—	SI Table Exact Reported	p. 27 · Computational framework · Table S11
Bader Pt-site in Pt-X4 charge for Pt3(C12N6O6)2	1.0	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader Pt-X4 charge transfer for Pt3(C12N6O6)2	-2.7	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
Bader pyrazine ring charge transfer for Pt3(C12N6O6)2	1.38	—	—	SI Table Exact Reported	p. 26 · Computational framework · Table S10
*Bader Pt-active-site charge for OH on Pt3(C12N6O6)2**	0.31	—	—	SI Table Exact Reported	p. 27 · Computational framework · Table S11
*Bader reactant charge for OH on Pt-site of Pt3(C12N6O6)2**	-0.74	—	—	SI Table Exact Reported	p. 27 · Computational framework · Table S11
*Bader Pt-active-site charge for OOH on Pt3(C12N6O6)2**	1.21	—	—	SI Table Exact Reported	p. 27 · Computational framework · Table S11
*Bader reactant charge for OOH on Pt-site of Pt3(C12N6O6)2**	-0.43	—	—	SI Table Exact Reported	p. 27 · Computational framework · Table S11

DFT band structure and PDOS

Density functional theory

Pt3(C12N9H3O3)2 MOF monolayer model · Model

VASP; RPBE GGA; spin polarisation; 5x5x1 k-points; 520 eV cutoff; DFT-D3.

Geometry: 2D monolayer model
Context: model pristine framework
Measurement source: p. 8 · 3.3.1 · Fig. 5d

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
computed bandgap	0.17 eV	0.17 eV	—	Text Exact Reported	p. 8 · 3.3.1 · Fig. 5d

DFT band structure and PDOS

Density functional theory

Pt3(C12N12H6)2 MOF monolayer model · Model

VASP; RPBE GGA; spin polarisation; 5x5x1 k-points; 520 eV cutoff; DFT-D3; force convergence 0.05 eV A^-1.

Geometry: 2D monolayer model
Context: model pristine framework
Measurement source: SI text · 8.1. Calculation details · Fig. 5b

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
computed electronic character	metallic behavior with band dispersion through EF	—	—	Qualitative Qualitative	p. 8 · 3.3.1 · Fig. 5b

DFT band structure and PDOS

Density functional theory

Pt3(C12N6O6)2 MOF monolayer model · Model

VASP; RPBE GGA; spin polarisation; 5x5x1 k-points; 520 eV cutoff; DFT-D3.

Geometry: 2D monolayer model
Context: model pristine framework
Measurement source: p. 8 · 3.3.1 · Fig. 5f

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Pt-Pt distance in model	10.98 A	—	—	Text Rounded Reported	p. 8 · 3.3.1 · Fig. 5
computed electronic character	metallic behavior with band dispersion through EF	—	—	Qualitative Qualitative	p. 8 · 3.3.1 · Fig. 5f
computed pore size	17.01 A	—	—	Text Exact Reported	p. 8 · 3.3.1 · Fig. 5

DFT/CHE ORR free-energy modelling

Density functional theory

Pt3(C12N9H3O3)2 MOF monolayer model · Model

Four-electron ORR pathway using computational hydrogen electrode; Pt-site and pyridinic N-site active-site comparison.

Temperature: 298.15
Atmosphere: model acidic medium
Geometry: 2D monolayer model
Context: model pristine framework
Measurement source: p. 8-9 · 3.3.2 · Fig. 7; Fig. S18

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
ORR overpotential at pyridinic N-site	0.57 V	—	—	Text Exact Reported	p. 8 · 3.3.2 · Fig. S18b
ORR overpotential at Pt-site	0.47 V	—	—	Text Exact Reported	p. 8 · 3.3.2 · Fig. 7b
ORR limiting potential UL at pyridinic N-site	0.66 V	—	—	Calculated From Reported Exact Reported	p. 8 · 3.3.2 · Fig. S18b
ORR limiting potential UL at Pt-site	0.76 V	—	—	Calculated From Reported Exact Reported	p. 8 · 3.3.2 · Fig. 7b
DFT ORR DeltaG8 at U=1.23 V (N-site)	DeltaG8 (0.122) eV	—	—	SI Table Exact Reported	p. 20-26 · Computational framework · Table S7
DFT ORR DeltaG8 at U=1.23 V (Pt-site)	DeltaG8 (-0.643) eV	—	—	SI Table Exact Reported	p. 20-26 · Computational framework · Table S6

DFT/CHE ORR free-energy modelling

Density functional theory

Pt3(C12N12H6)2 MOF monolayer model · Model

Four-electron ORR pathway using computational hydrogen electrode; Pt-site and pyridinic N-site active-site comparison.

Temperature: 298.15
Atmosphere: model acidic medium
Geometry: 2D monolayer model
Context: model pristine framework
Measurement source: p. 8-9 · 3.3.2 · Fig. 7; Fig. S18

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
ORR overpotential at pyridinic N-site	about 0.69 V	—	—	Figure Axis Approximate	p. 18 · Computational framework · Figure S18a
ORR overpotential at Pt-site	about 0.62 V	—	—	Figure Axis Approximate	p. 9 · Fig. 7 · Fig. 7a
DFT ORR DeltaG8 at U=1.23 V (N-site)	DeltaG8 (0.384) eV	—	—	SI Table Exact Reported	p. 20-26 · Computational framework · Table S5
DFT ORR DeltaG8 at U=1.23 V (Pt-site)	DeltaG8 (-0.782) eV	—	—	SI Table Exact Reported	p. 20-26 · Computational framework · Table S4

DFT/CHE ORR free-energy modelling

Density functional theory

Pt3(C12N6O6)2 MOF monolayer model · Model

Four-electron ORR pathway; computational hydrogen electrode; Pt-site and pyridinic N-site active-site comparison.

Temperature: 298.15
Atmosphere: model acidic medium
Geometry: 2D monolayer model
Context: model pristine framework
Measurement source: p. 8 · 3.3.2 · Fig. 7; Fig. S18

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
ORR overpotential at pyridinic N-site	0.51 V	—	—	Text Exact Reported	p. 8 · 3.3.2 · Fig. S18c
ORR overpotential at Pt-siteMarked as a best value within this paper	0.36 V	0.36 V	—	Text Exact Reported	p. 8 · 3.3.2 · Fig. 7
ORR limiting potential UL at pyridinic N-site	0.72 V	0.72 V	—	Text Exact Reported	p. 8 · 3.3.2 · Fig. 7; Fig. S18
ORR limiting potential UL at Pt-siteMarked as a best value within this paper	0.87 V	0.87 V	—	Text Exact Reported	p. 8 · 3.3.2 · Fig. 7
DFT ORR DeltaG8 at U=1.23 V (N-site)	DeltaG8 (-0.183) eV	—	—	SI Table Exact Reported	p. 20-26 · Computational framework · Table S9
DFT ORR DeltaG8 at U=1.23 V (Pt-site)	DeltaG8 (-0.589) eV	—	—	SI Table Exact Reported	p. 20-26 · Computational framework · Table S8

DFTB/Lennard-Jones stacking-energy comparison

Pt3(C12N6O6)2 MOF monolayer model · Model

Ideal AA, slipped AA and AB stacking configurations for Pt3(C12N6O6)2 MOF.

Geometry: monolayer/stacking model
Context: model pristine framework
Measurement source: p. 5 · 2.8; 3.1 · Table 2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
AA total crystal stacking energy	49.45 kcal mol^-1	49.45 kcal/mol	—	Table Exact Reported	p. 5 · 3.1 · Table 2
AB total crystal stacking energy	94.15 kcal mol^-1	94.15 kcal/mol	—	Table Exact Reported	p. 5 · 3.1 · Table 2
monolayer DFTB energy	-243.0177 a.u.	—	—	Table Exact Reported	p. 5 · 3.1 · Table 2
slipped AA total DFTB energyMarked as a best value within this paper	-486.406628 a.u.	—	—	Table Exact Reported	p. 5 · 3.1 · Table 2
slipped AA total crystal stacking energyMarked as a best value within this paper	121.20 kcal mol^-1	121.2 kcal/mol	—	Table Exact Reported	p. 5 · 3.1 · Table 2