Computational Modelling — Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4

5 measurement groups · 24 results

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

DFT Gibbs free-energy profile for ECR-to-CH4 pathway

Density functional theory

Cu-O4 active-site DFT fragment · Model

Pathway *CO2 -> *COOH -> *CO -> *COH -> *CHOH -> *CH2OH -> *CH2 -> *CH3 -> *CH4; CHE model; U = 0 and onset-potential plots

Geometry: fragment models
Context: model systems
Measurement source: p007 · Discussion · Fig. 4d; Supplementary Figs. 35-39

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Cu-DBC Cu-O4 PDS free-energy barrierMarked as a best value within this paper	0.53 eV	—	—	Text Exact Reported	p007 · Discussion · Fig. 4d
Cu-PPCOF phthalocyanine Cu-N4 PDS free-energy barrier	1.80 eV	—	—	Text Exact Reported	p007 · Discussion · Fig. 4d
Cu-TTCOF porphyrin Cu-N4 PDS free-energy barrier	1.05 eV	—	—	Text Exact Reported	p007 · Discussion · Fig. 4d
onset potential used for downhill ECR profile: Cu-O4/Cu-DBCMarked as a best value within this paper	-0.53 V	—	—	Figure Axis Rounded Reported	p019-p020 text layer · Reviewer response · Supplementary Figs. 35-37
onset potential used for downhill ECR profile: phthalocyanine Cu-N4/Cu-PPCOF	-1.8 V	—	—	Figure Axis Rounded Reported	p019-p020 text layer · Reviewer response · Supplementary Figs. 35-37
onset potential used for downhill ECR profile: porphyrin Cu-N4/Cu-TTCOF	-1.05 V	—	—	Figure Axis Rounded Reported	p019-p020 text layer · Reviewer response · Supplementary Figs. 35-37
proposed ECR-to-CH4 pathway	CO2 -> COOH -> CO -> COH -> CHOH -> CH2OH -> CH2 -> CH3 -> *CH4	—	—	Text Qualitative	p007 · Discussion · Fig. 4d
*Cu-PPCOF CO -> COH barrier*	1.15 eV	—	—	Text Exact Reported	p007 · Discussion · Fig. 4d

DFT free-energy profiles for *H adsorption

Density functional theory

Cu-O4 active-site DFT fragment · Model

Comparison of *H adsorption on Cu-O4, porphyrin Cu-N4, and phthalocyanine Cu-N4 active-site models; U = 0 V unless stated

Geometry: fragment models
Context: model systems
Measurement source: p006-p007 · Discussion · Fig. 4c; Supplementary Fig. 32

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
HER H2 formation barrier on Cu-O4	1.27 eV	—	—	Text Exact Reported	p007 · Discussion · Supplementary Fig. 33

Löwdin population charge analysis

Cu-O4 active-site DFT fragment · Model

ORCA Löwdin population analysis for Cu-O4 and Cu-N4 systems

Geometry: fragment models
Context: model systems
Measurement source: p018 text layer · Supplementary Table 5 · Supplementary Table 5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Löwdin charge: Cu-O4	0.39	—	—	SI Table Exact Reported	p018 text layer · Supplementary Table 5 · Supplementary Table 5
Löwdin charge: Cu-O4H1	0.28	—	—	SI Table Exact Reported	p018 text layer · Supplementary Table 5 · Supplementary Table 5
Löwdin charge: Cu-O4H4	0.04	—	—	SI Table Exact Reported	p018 text layer · Supplementary Table 5 · Supplementary Table 5
Löwdin charge: Phthalocyanine Cu-N4	0.19	—	—	SI Table Exact Reported	p018 text layer · Supplementary Table 5 · Supplementary Table 5
Löwdin charge: Porphyrin Cu-N4	0.18	—	—	SI Table Exact Reported	p018 text layer · Supplementary Table 5 · Supplementary Table 5
Löwdin charge: Porphyrin Cu-N4H1	0.12	—	—	SI Table Exact Reported	p018 text layer · Supplementary Table 5 · Supplementary Table 5

DFT calculations with ORCA/B3LYP fragment models

Density functional theory

Cu-O4 active-site DFT fragment · Model

ORCA, RI approximation, B3LYP, def2-SVP geometry optimization, def2-TZVP single-point/energies for Cu/C/N/O/H, def2-TZVP/J, GRID4, TIGHT SCF, D3, frequency calculations, CHE model at 298.15 K

Temperature: 298.15
Geometry: fragment models
Context: model systems
Measurement source: p007-p008 text layer · Computational methods

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
functional	B3LYP with D3 dispersion	—	—	Text Qualitative	p007-p008 text layer · Computational methods
DFT model type	fragment models extracted from crystal structures; not periodic	—	—	Text Qualitative	p007-p008 text layer · Computational methods
Cu-DBC unit cell atom count	1408 atoms	—	—	Text Exact Reported	p009 text layer · Reviewer response · Fig. R2

simulated Raman spectrum from DFT fragment

Raman spectroscopy Density functional theory

Cu-O4 active-site DFT fragment · Model

Harmonic approximation on Cu-O4 site fragment; compared with experimental Raman of fresh/tested Cu-DBC

Geometry: fragment model
Context: model system
Measurement source: p015 text layer · Supplementary Fig. 15 text · Supplementary Fig. 15b

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
simulated Raman Peak 1 assigned to C fragment/D peak	~1380 cm-1	—	—	Text Approximate	p015 text layer · Supplementary Fig. 15 text · Supplementary Fig. 15b
simulated Raman Peak 2 assigned to C fragment/G peak	~1540 cm-1	—	—	Text Approximate	p015 text layer · Supplementary Fig. 15 text · Supplementary Fig. 15b
simulated Raman Peak 3 assigned to Cu-O vibration	~560 cm-1	—	—	Text Approximate	p015 text layer · Supplementary Fig. 15 text · Supplementary Fig. 15b
Supplementary Movie 1 content	stretching vibration of Peak 1	—	—	Text Qualitative	p001 · Description of Additional Supplementary Files · Supplementary Movie 1
Supplementary Movie 2 content	stretching vibration of Peak 2	—	—	Text Qualitative	p001 · Description of Additional Supplementary Files · Supplementary Movie 2
Supplementary Movie 3 content	stretching vibration of Peak 3	—	—	Text Qualitative	p001 · Description of Additional Supplementary Files · Supplementary Movie 3