Computational Modelling — Density Functional Theory Study of Synergistic Gas Sensing Using an Electrically Conductive Mixed Ligand Two-Dimensional Metal-Organic Framework

15 measurement groups · 112 results

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

Bader charge analysis and charge-density-difference (CDD) calculations

Co-HIB periodic multilayer DFT model · Model

Net gas charges and CDD isosurfaces after adsorption of H2S, NH3, NO and NO2 on the 2D-cMOF models.

Atmosphere: gas molecule adsorbed in periodic DFT model
Geometry: periodic multilayer model
Context: pristine model framework
Measurement source: PDF p4-p7 / article p3451-p3454 · Adsorption Energy and Charge Density Difference Calculation; Gas Adsorption Mechanism Analysis · Figure 6; Figure S8; Table S6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB adsorbed H2S net Bader charge qtotal	-0.0148 e at displacement (0.0, 0.0)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6
Co-HIB NH3 summed H atomic charge	1.134 e	—	—	Figure Axis Rounded Reported	SI p12 · Figure S9 · Figure S9
Co-HIB NH3 N atomic charge	-1.144 e	—	—	Figure Axis Rounded Reported	SI p12 · Figure S9 · Figure S9
Co-HIB adsorbed NH3 net Bader charge qtotal	-0.0098 e at displacement (0.0, 0.0)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6
Co-HIB adsorbed NO2 net Bader charge qtotal	-0.8876 e at displacement (0.0, 0.0)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6
Co-HIB adsorbed NO net Bader charge qtotal	-0.471 e at displacement (0.0, 0.0)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6

VASP 5.4.1 DFT; PBE-GGA; DFT-D3 zero damping; periodic SCF PES scan

Density functional theory

Co-HIB periodic multilayer DFT model · Model

Relaxed 2D-cMOF unit cell; interlayer displacement scanned along ab-plane from 0 to 4.2 Angstrom in 0.2 Angstrom increments where applicable; convergence 0.05 eV ionic force and 1e-5 eV electronic energy.

Atmosphere: periodic vacuum-free bulk multilayer computational cell
Geometry: periodic multilayer model
Context: pristine model framework
Measurement source: PDF p3-p4 / article p3450-p3451 · Computational Methods - DFT Settings; Structure Preparation and PES Construction · Figure 3; Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB lattice parameter a at displacement (0, 0)	13.42 Angstrom	—	—	SI Table Exact Reported	SI p2 · Table S1 · Table S1
Co-HIB lattice parameter b at displacement (0, 0)	13.42 Angstrom	—	—	SI Table Exact Reported	SI p2 · Table S1 · Table S1
Co-HIB lattice parameter c at displacement (0, 0)	6.54 Angstrom	—	—	SI Table Exact Reported	SI p2 · Table S1 · Table S1
Co-HIB pore diameter	9.32 Angstrom	—	—	Text Exact Reported	PDF p5 / article p3452 · Synergy Effect Analysis · Figure 1
Co-HIB global minimum PES energyMarked as a best value within this paper	-551.46 eV at AA stacking / (0, 0) Angstrom	—	—	Text Exact Reported	PDF p4 / article p3451 · Structural Analysis · Figure S1a
Co-HIB local minimum PES energy	-551.38 eV at AB coordinates (2.0, 4.2) and (4.2, 2.0) Angstrom	—	—	Text Exact Reported	PDF p4 / article p3451 · Structural Analysis · Figure S1a

DFT adsorption-energy calculation, Ead = |Etotal - (EMOF + Egas)|

Density functional theory

Co-HIB periodic multilayer DFT model · Model

Target gases H2S, NH3, NO and NO2 adsorbed on multilayer 2D-cMOF models at PES-predicted and selected displaced stacking coordinates; gas orientations and binding sites screened.

Atmosphere: gas molecule adsorbed in periodic DFT model
Geometry: periodic multilayer model
Context: pristine model framework
Measurement source: PDF p4-p5 / article p3451-p3452 · Adsorption Energy and Charge Density Difference Calculation; Synergy Effect Analysis · Figures 4-5; Tables S3-S5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB H2S post-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB H2S pre-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB H2S adsorption energy at PES-predicted/favourable stacking	28.65 kJ/mol at displacement (0, 0)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB H2S gas-MOF nearest distance	approximately 3.198 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5
Co-HIB NH3 post-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB NH3 pre-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB NH3 adsorption energy at PES-predicted/favourable stacking	18.44 kJ/mol at displacement (0, 0)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB NH3 gas-MOF nearest distance	approximately 3.204 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5
Co-HIB NO2 post-adsorption interlayer Co-Co distance	3.299 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB NO2 pre-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB NO2 adsorption energy at PES-predicted/favourable stackingMarked as a best value within this paper	222.27 kJ/mol at displacement (0, 0)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB NO2 gas-MOF nearest distance	approximately 1.883 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5
Co-HIB NO post-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB NO pre-adsorption interlayer Co-Co distance	3.271 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB NO adsorption energy at PES-predicted/favourable stackingMarked as a best value within this paper	85.81 kJ/mol at displacement (0, 0)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB NO gas-MOF nearest distance	approximately 2.346 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5

Bader charge analysis and charge-density-difference (CDD) calculations

Co-HIB-HITP mixed-ligand periodic multilayer DFT model · Model

Net gas charges and CDD isosurfaces after adsorption of H2S, NH3, NO and NO2 on the 2D-cMOF models.

Atmosphere: gas molecule adsorbed in periodic DFT model
Geometry: periodic multilayer model
Context: mixed-ligand model framework
Measurement source: PDF p4-p7 / article p3451-p3454 · Adsorption Energy and Charge Density Difference Calculation; Gas Adsorption Mechanism Analysis · Figure 6; Figure S8; Table S6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB-HITP adsorbed H2S net Bader charge qtotal	-0.0807 e at displacement (3.0, 4.2)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6
Co-HIB-HITP NH3 summed H atomic chargeMarked as a best value within this paper	1.193 e	—	—	Figure Axis Rounded Reported	SI p12 · Figure S9 · Figure S9
Co-HIB-HITP NH3 N atomic charge	-1.198 e	—	—	Figure Axis Rounded Reported	SI p12 · Figure S9 · Figure S9
Co-HIB-HITP adsorbed NH3 net Bader charge qtotal	-0.0043 e at displacement (3.0, 4.2)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6
Co-HIB-HITP adsorbed NO2 net Bader charge qtotal	-0.8261 e at displacement (4.2, 1.2)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6
Co-HIB-HITP adsorbed NO net Bader charge qtotal	-0.2571 e at displacement (3.0, 4.2)	—	—	SI Table Exact Reported	SI p12 · Table S6 · Table S6

VASP 5.4.1 DFT; PBE-GGA; DFT-D3 zero damping; periodic SCF PES scan

Density functional theory

Co-HIB-HITP mixed-ligand periodic multilayer DFT model · Model

Atmosphere: periodic vacuum-free bulk multilayer computational cell
Geometry: periodic multilayer model
Context: mixed-ligand model framework
Measurement source: PDF p3-p4 / article p3450-p3451 · Computational Methods - DFT Settings; Structure Preparation and PES Construction · Figure 3; Table S1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB-HITP lattice parameter a at displacement (3.0, 4.2)	17.63 Angstrom	—	—	SI Table Exact Reported	SI p2 · Table S1 · Table S1
Co-HIB-HITP lattice parameter b at displacement (3.0, 4.2)	17.63 Angstrom	—	—	SI Table Exact Reported	SI p2 · Table S1 · Table S1
Co-HIB-HITP lattice parameter c at displacement (3.0, 4.2)	6.53 Angstrom	—	—	SI Table Exact Reported	SI p2 · Table S1 · Table S1
Co-HIB-HITP pore diameter	13.17 Angstrom	—	—	Text Exact Reported	PDF p5 / article p3452 · Synergy Effect Analysis · Figure 1
Co-HIB-HITP global minimum PES energyMarked as a best value within this paper	-813.23 eV at (1.2, 4.2) Angstrom; -813.22 eV at remaining global-minimum displacements	—	—	Text Exact Reported	PDF p4 / article p3451 · Structural Analysis · Figure 3
Co-HIB-HITP stable large-displacement regionMarked as a best value within this paper	3.6-4.2 Angstrom along the ab-plane	—	—	Text Range	PDF p4 / article p3451 · Structural Analysis · Figure 3

DFT adsorption-energy calculation, Ead = |Etotal - (EMOF + Egas)|

Density functional theory

Co-HIB-HITP mixed-ligand periodic multilayer DFT model · Model

Target gases H2S, NH3, NO and NO2 adsorbed on multilayer 2D-cMOF models at PES-predicted and selected displaced stacking coordinates; gas orientations and binding sites screened.

Atmosphere: gas molecule adsorbed in periodic DFT model
Geometry: periodic multilayer model
Context: mixed-ligand model framework
Measurement source: PDF p4-p5 / article p3451-p3452 · Adsorption Energy and Charge Density Difference Calculation; Synergy Effect Analysis · Figures 4-5; Tables S3-S5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB-HITP H2S post-adsorption interlayer Co-Co distance	4.937 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP H2S pre-adsorption interlayer Co-Co distance	4.958 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP H2S adsorption energy at PES-predicted/favourable stackingMarked as a best value within this paper	60.88 kJ/mol at displacement (3.0, 4.2)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB-HITP H2S gas-MOF nearest distance	approximately 2.59 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5
Co-HIB-HITP H2S adsorption-energy improvement versus best unmixed MOFMarked as a best value within this paper	158% improvement	—	—	Text Exact Reported	PDF p1 / article p3448 · Abstract
Co-HIB-HITP NH3 post-adsorption interlayer Co-Co distance	5.036 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP NH3 pre-adsorption interlayer Co-Co distance	4.958 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP NH3 adsorption energy at PES-predicted/favourable stackingMarked as a best value within this paper	64.78 kJ/mol at displacement (3.0, 4.2)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB-HITP NH3 gas-MOF nearest distance	approximately 1.985 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5
Co-HIB-HITP NH3 adsorption-energy improvement versus best unmixed MOFMarked as a best value within this paper	170% improvement	—	—	Text Exact Reported	PDF p1 / article p3448 · Abstract
Co-HIB-HITP NO2 post-adsorption interlayer Co-Co distance	4.974 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP NO2 pre-adsorption interlayer Co-Co distance	4.977 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP NO2 adsorption energy at PES-predicted/favourable stacking	128.74 kJ/mol at displacement (4.2, 1.2)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB-HITP NO2 gas-MOF nearest distance	approximately 1.847 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5
Co-HIB-HITP NO post-adsorption interlayer Co-Co distance	4.949 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP NO pre-adsorption interlayer Co-Co distance	4.958 Angstrom	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5; Figure S4
Co-HIB-HITP NO adsorption energy at PES-predicted/favourable stacking	46.41 kJ/mol at displacement (3.0, 4.2)	—	—	SI Table Exact Reported	SI p6 · Table S5 · Table S5
Co-HIB-HITP NO gas-MOF nearest distance	approximately 2.226 Angstrom from Figure S5 label	—	—	Visual Estimate Approximate	SI p7-p8 · Figure S5 · Figure S5

Spin-polarised DFT+U density of states and magnetic moment calculation; U = 3.3

Density functional theory

Co-HIB-HITP mixed-ligand periodic multilayer DFT model · Model

Pristine and gas-adsorbed models evaluated for magnetic moments and spin-polarised DOS near the Fermi level.

Atmosphere: periodic DFT model before and after gas adsorption
Geometry: periodic multilayer model
Context: mixed-ligand model framework
Measurement source: PDF p3 and SI p13-p15 · Computational Methods - DFT Settings; Supporting Information DOS discussion · Table S7; Figure S10

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB-HITP average total magnetic moment alteration at PES-predicted stackingMarked as a best value within this paper	1.642 uB	—	—	Text Exact Reported	PDF p7 / article p3454 · Gas Adsorption Mechanism Analysis · Table S7
Co-HIB-HITP total magnetic moment (bulk)	6.276 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB-HITP pristine DOS metallic behaviour	spin-polarised DOS crosses the Fermi level	—	—	Qualitative Qualitative	SI p15 · DOS discussion · Figure S10
Co-HIB-HITP total magnetic moment (H2S)	5.273 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB-HITP total magnetic moment (NH3)	6.282 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB-HITP total magnetic moment (NO2)	2.099 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB-HITP total magnetic moment (NO)	4.883 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7

DFT monolayer surface adsorption calculation

Density functional theory

Co-HIB-HITP mixed-ligand periodic multilayer DFT model · Model

Monolayer 2D-cMOF surface models with 20 Angstrom vacuum; target gases placed on top-metal/top-linker sites and compared with infinite z-stacked linker-site calculations.

Atmosphere: isolated monolayer slab with 20 Angstrom vacuum and adsorbed gas
Geometry: monolayer surface model
Context: mixed-ligand model framework
Measurement source: SI p9-p10 · Supporting Information - monolayer surface adsorption · Figure S6; Figure S7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB-HITP H2S monolayer surface adsorption energy	19.55 kJ/mol	—	—	Text Exact Reported	SI p9 · Monolayer surface adsorption discussion · Figure S7
Average MOF-type difference in monolayer surface adsorption energy for NH3	4.55 kJ/mol average difference	—	—	Text Exact Reported	SI p9-p10 · Monolayer surface adsorption discussion · Figure S7
Average MOF-type difference in monolayer surface adsorption energy for NO	3.65 kJ/mol average difference	—	—	Text Exact Reported	SI p9-p10 · Monolayer surface adsorption discussion · Figure S7
Average MOF-type difference in monolayer surface adsorption energy for NO2	3.54 kJ/mol average difference	—	—	Text Exact Reported	SI p9-p10 · Monolayer surface adsorption discussion · Figure S7

Spin-polarised DFT+U density of states and magnetic moment calculation; U = 3.3

Density functional theory

Co-HIB periodic multilayer DFT model · Model

Pristine and gas-adsorbed models evaluated for magnetic moments and spin-polarised DOS near the Fermi level.

Atmosphere: periodic DFT model before and after gas adsorption
Geometry: periodic multilayer model
Context: pristine model framework
Measurement source: PDF p3 and SI p13-p15 · Computational Methods - DFT Settings; Supporting Information DOS discussion · Table S7; Figure S10

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB average total magnetic moment alteration at PES-predicted stacking	0.484 uB	—	—	Text Exact Reported	PDF p7 / article p3454 · Gas Adsorption Mechanism Analysis · Table S7
Co-HIB total magnetic moment (bulk)	6.906 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB pristine DOS metallic behaviour	spin-polarised DOS crosses the Fermi level	—	—	Qualitative Qualitative	SI p15 · DOS discussion · Figure S10
Co-HIB total magnetic moment (H2S)	5.695 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB total magnetic moment (NH3)	6.79 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB total magnetic moment (NO2)	5.475 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7
Co-HIB total magnetic moment (NO)	7.728 uB	—	—	SI Table Exact Reported	SI p13 · Table S7 · Table S7

DFT monolayer surface adsorption calculation

Density functional theory

Co-HIB periodic multilayer DFT model · Model

Monolayer 2D-cMOF surface models with 20 Angstrom vacuum; target gases placed on top-metal/top-linker sites and compared with infinite z-stacked linker-site calculations.

Atmosphere: isolated monolayer slab with 20 Angstrom vacuum and adsorbed gas
Geometry: monolayer surface model
Context: pristine model framework
Measurement source: SI p9-p10 · Supporting Information - monolayer surface adsorption · Figure S6; Figure S7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Co-HIB H2S monolayer surface adsorption energy	19.46 kJ/mol	—	—	Text Exact Reported	SI p9 · Monolayer surface adsorption discussion · Figure S7