Computational Modelling — CO2 Reduction to Methane and Ethylene on a Single-Atom Catalyst: A Grand Canonical Quantum Mechanics Study

10 measurement groups · 52 results

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

GCP-K adsorption-energy calculations and PDOS d-band-centre analysis for CuPc and CuO4 sites.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

Adsorption energies at zero bias and applied-potential trends; d-band centres from Figure S9.

Atmosphere: Implicit solvent for adsorption calculations.
Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d; Figure S9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
CO adsorption energy at first CuO4 site, zero external potential	-0.20 eV	—	—	Text Exact Reported	main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d
CO adsorption energy at second CuO4 site, zero external potential	-0.18 eV	—	—	Text Exact Reported	main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d
d-band centre for 2CO-CuO4 site	-2.92 eV	—	—	Text Exact Reported	main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure S9
d-band centre for CO-CuO4 site	-2.85 eV	—	—	Text Exact Reported	main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure S9
d-band centre for CO-CuPc siteMarked as a best value within this paper	-2.64 eV	—	—	Text Exact Reported	main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure S9
CO2 adsorption energy at PcCu catalytic center, zero external potential	-0.12 eV	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d
CO adsorption energy at PcCu catalytic center, zero external potential	-0.11 eV	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d
H adsorption energy at PcCu catalytic center, zero external potential	1.85 eV	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d

QM geometry optimisation of literature PcCu MOF cell.

Reoptimised pristine PcCu 2D MOF monolayer model cell · Model

Optimised monolayer with potassium counterions and S = 3/2 high-spin spin polarisation.

Geometry: Periodic monolayer cell.
Context: Pristine model system.
Measurement source: main p.8, article p.21326 · 3. Experimental Section

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Optimised cell parameter a	a = 18.17536 A	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section
Optimised cell angle alpha	alpha = 91.3834 deg	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section
Optimised cell parameter b	b = 18.17632 A	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section
Optimised cell angle beta	beta = 91.0939 deg	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section
Optimised cell parameter c	c = 20.20189 A	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section
Optimised cell angle gamma	gamma = 89.8539 deg	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section

Spin-polarised DFT in VASP with VASPsol implicit solvation, PBE functional, 500 eV plane-wave cutoff, Grimme D3(BJ), 1 x 1 x 1 Monkhorst-Pack k-point grid; single-point JDFTx at applied potentials with CANDLE implicit solvation; GCP-K/GC-QM Legendre transform.

Density functional theory

Reoptimised pristine PcCu 2D MOF monolayer model cell · Model

Geometry optimisations used 1.5 nm z-vacuum, force convergence 0.02 eV/A, electronic convergence 1e-5 eV; vibrational corrections at 298.15 K.

Temperature: 298.15
Atmosphere: Implicit water solvent; computational vacuum spacing normal to MOF.
Geometry: Periodic monolayer cell.
Context: Pristine model system.
Measurement source: main p.8, article p.21326 · 3. Experimental Section

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Geometry optimisation force convergence criterion	0.02 eV/A	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section
Plane-wave cutoff energy	500 eV	—	—	Text Exact Reported	main p.8, article p.21326 · 3. Experimental Section

DFT density of states and projected density of states (DOS/PDOS).

Density functional theory

Reoptimised pristine PcCu 2D MOF monolayer model cell · Model

Optimised pristine MOF monolayer model; electronic properties computed after geometry optimisation.

Geometry: Periodic monolayer cell.
Context: Pristine model system.
Measurement source: main p.3, article p.21321 · 2.1 Electronic Properties · Figure 1b,c

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Calculated semiconductor band gapMarked as a best value within this paper	~0.3 eV	—	—	Text Approximate	main p.3, article p.21321 · 2.1 Electronic Properties · Figure 1b
Pristine MOF total spin state	S = 3/2	—	—	Text Exact Reported	main p.3, article p.21321 · 2.1 Electronic Properties · Figure 1c

GCP-K free-energy pathway for ethylene formation through *(CH)CO.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

Computed at 298 K, neutral pH, and applied potential -1.2 V_RHE.

Temperature: 298
Atmosphere: Implicit solvent plus protonated four-water cluster.
Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: main p.5, article p.21323 · 2.3 Ethylene Formation Pathways · Figure 3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*Carbon-protonation branch RDS barrier via (CH2)COH**	0.82 eV	—	—	Text Exact Reported	main p.5, article p.21323 · 2.3 Ethylene Formation Pathways · Figure 3
*Relative energy of (CH)CO branch**	DeltaG = -4.69 eV	—	—	Text Exact Reported	main p.5, article p.21323 · 2.3 Ethylene Formation Pathways · Figure 3
*Relative energy of second (CH)CO branch**	DeltaG = -5.37 eV	—	—	Text Exact Reported	main p.5, article p.21323 · 2.3 Ethylene Formation Pathways · Figure 3
*Water-elimination branch RDS barrier via (CH)COH**	1.01 eV	—	—	Text Exact Reported	main p.5, article p.21323 · 2.3 Ethylene Formation Pathways · Figure 3

GCP-K free-energy pathway for ethylene formation through *(CHO)CO.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

Computed at 298 K, neutral pH, and applied potential -1.2 V_RHE.

Temperature: 298
Atmosphere: Implicit solvent plus protonated four-water cluster.
Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: main p.6, article p.21324 · 2.3 Ethylene Formation Pathways · Figure 4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*Stabilisation on CO coupling into CHO to form (CHO)CO*Marked as a best value within this paper	DeltaG = -0.93 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
*Preferred (CHO)CO pathway RDS barrier**Marked as a best value within this paper	0.42 eV	—	—	Text Exact Reported	main p.6, article p.21324 · 2.3 Ethylene Formation Pathways · Figure 4

GCP-K free-energy pathway for methane formation from CO2 on PcCu MOF.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

Free energies in eV at 298 K; neutral pH; applied potential -1.2 V_RHE unless noted.

Temperature: 298
Atmosphere: Implicit solvent plus protonated four-water cluster.
Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
CO to CHO activation barrier	0.22 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
Methane binding energy on surface	DeltaG = 0.01 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
Initial CO2 adsorption free energy	DeltaG = -0.12 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
CO2 bending activation barrier	0.32 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
*CO binding energy	DeltaG = -0.11 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
*Overall stability of CO relative to free CO2**	DeltaG = -2.27 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
Final methane formation free energy relative to gas-phase CO2	DeltaG = -8.78 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
*First proton-electron transfer barrier to HOCO**	0.75 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2
*Methane-pathway rate-determining barrier to CHOH**	0.92 eV	—	—	Text Exact Reported	main p.4, article p.21322 · 2.2 Methane Formation Pathway · Figure 2

GCP-K potential-dependent free energies for selected intermediates and transition states.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

Applied-potential series compared with prior experimental FE trends; Figure 5.

Atmosphere: Implicit solvent.
Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*CHOH-formation barrier at -1.0 V_RHE	1.00 eV	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5a
*CHOH-formation barrier at -1.6 V_RHE	0.74 eV	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5a
CHOH energy relative to CHO at -1.0 V_RHE	0.40 eV higher	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5a,c
CHOH energy relative to CHO at -1.6 V_RHE	0.14 eV	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5a,c
*Applied potential where CHOH population exceeds CHO*	-1.96 V	—	—	Text Exact Reported	main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5c

Optimised intermediate geometry; tabulated Cu-C and C-N distances.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

Different intermediates at -1.2 V.

Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: SI p.S13 · Supporting Information · Table S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
*Cu-C distance for CCH intermediate**	Cu-C = 1.91 A	—	—	Text Exact Reported	main p.6, article p.21324 · 2.3 Ethylene Formation Pathways · Figure 4; Table S4
*C-N distance for CCHOH stabilised structure**	1.44 A	—	—	Text Exact Reported	main p.6, article p.21324 · 2.3 Ethylene Formation Pathways · Figure 4; Table S4
*CH C-N distance	1.39 A	—	—	SI Table Exact Reported	SI p.S13 · Supporting Information · Table S4
*CH Cu-C distance	1.94 A	—	—	SI Table Exact Reported	SI p.S13 · Supporting Information · Table S4
*(CH)CO Cu-C distances	1.98/1.90 A	—	—	SI Table Exact Reported	SI p.S13 · Supporting Information · Table S4
*(CHO)CO Cu-C distance	1.94 A	—	—	SI Table Exact Reported	SI p.S13 · Supporting Information · Table S4

GCP-K quadratic free-energy parameter extraction.

PcCu 2D MOF reaction model with adsorbates and water cluster · Model

GCP parameters a, b, c, differential capacitance, and potential of zero charge for investigated intermediates.

Geometry: Periodic monolayer reaction model.
Context: Adsorbate-bearing model system.
Measurement source: SI p.S15 · Supporting Information · Table S6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Cu-MOF GCP parameter a	0.1612960 V/e	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
Cu-MOF differential capacitanceMarked as a best value within this paper	3.09989 F	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
Cu-MOF potential of zero chargeMarked as a best value within this paper	-0.92623 V vs. SHE	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
*(CH)CO potential of zero charge	-0.98136 V vs. SHE	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
*CHO potential of zero charge	-0.90669 V vs. SHE	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
*(CHO)CO potential of zero charge	-1.12833 V vs. SHE	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
*CHOH potential of zero charge	-0.94594 V vs. SHE	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6
*CO2 potential of zero charge	-1.18529 V vs. SHE	—	—	SI Table Exact Reported	SI p.S15 · Supporting Information · Table S6