Computational Modelling — Microscopic Origin of Electrochemical Capacitance in Metal-Organic Frameworks

6 measurement groups · 38 results

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

Mean squared displacement analysis of electrolyte self-diffusion

Cu3(HITP)2 QM/MM electrochemical interface model · Model

MSD of acetonitrile and ions at point of zero charge in Cu3(HITP)2 pores compared with Cu3(HHTP)2 pores and bulk electrolyte.

Temperature: 300
Atmosphere: computational
Geometry: hexagonal pore model
Context: model pristine frameworks with electrolyte
Measurement source: 14534 · Modulating the EDL Structure with MOF Composition · Supplementary Figures 32-33

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Anisotropy of in-pore electrolyte self-diffusion	parallel to hexagonal pores is two times larger than perpendicular to the pores	—	—	Text Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Supplementary Figures 32-33
Cu3(HHTP)2 in-pore electrolyte self-diffusion decrease vs bulk electrolyte	over 70% decreased self-diffusion coefficient compared to the bulk electrolyte	—	over	Text Approximate	14534 · Modulating the EDL Structure with MOF Composition · Supplementary Figures 32-33

DFT-CES electronic density of states and charge-density-difference analysis

Density functional theory

Cu3(HHTP)2 QM/MM electrochemical interface model · Model

Cu3(HHTP)2 electrochemical interface under charged conditions and PZC; counterion insertion and co-ion removal mechanisms compared.

Temperature: 300
Atmosphere: computational
Geometry: QM/MM electrode-electrolyte interface
Context: model pristine framework
Measurement source: 14532 · Polarization Phenomena of MOFs · Figure 4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Cu oxidation state in Cu3(HHTP)2 model/electrode window	Cu2+; 3d9 open-shell doublet configuration	—	—	Text Exact Reported	14532 · Polarization Phenomena of MOFs · Figure 4
Cu magnetic moment in Cu3(HHTP)2 potential window	0.6 uB	—	—	Text Exact Reported	14533 · Polarization Phenomena of MOFs · Figure 4b
Total magnetisation increase in Cu3(HHTP)2 simulation cell	0.05 uB from the PZC	—	—	Text Exact Reported	14533 · Polarization Phenomena of MOFs · Figure 4b
Cu3(HHTP)2 surface charge at DeltaU = -0.2 V, co-ion removal	-1.5 uC cm^-2	—	—	Text Exact Reported	14531-14532 · Polarization Phenomena of MOFs · Figure 3b
Cu3(HHTP)2 surface charge at DeltaU = -0.2 V, counterion insertion	-4.5 uC cm^-2	—	—	Text Exact Reported	14532 · Polarization Phenomena of MOFs · Figure 3c
Cu3(HHTP)2 surface charge at DeltaU = +0.2 V, co-ion removal	+4.5 uC cm^-2	—	—	Text Exact Reported	14532 · Polarization Phenomena of MOFs · Figure 3e
Cu3(HHTP)2 surface charge at DeltaU = +0.2 V, counterion insertion	+1.5 uC cm^-2	—	—	Text Exact Reported	14532 · Polarization Phenomena of MOFs · Figure 3d

DFT-CES density of states and magnetic moment analysis

Density functional theory

Cu3(HITP)2 QM/MM electrochemical interface model · Model

Cu3(HITP)2 electrochemical interface at varied surface charge densities.

Temperature: 300
Atmosphere: computational
Geometry: QM/MM electrode-electrolyte interface
Context: model pristine framework
Measurement source: 22 · Supplementary Fig. 21 · Supplementary Figure 21

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Cu oxidation state in Cu3(HITP)2 model	Cu maintained as 2+ independent of biased potential	—	—	Text Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Supplementary Figure 21
Cu magnetic moment in Cu3(HITP)2 model	0.6 uB	—	—	Caption Exact Reported	22 · Supplementary Fig. 21 · Supplementary Figure 21

QM/MM electrochemical interface calculation on graphite

Graphite electrochemical interface model · Model

Graphite surface charge density-biased potential curve with respect to ion-exchange ratio.

Atmosphere: computational
Geometry: graphite-electrolyte interface model
Context: non-MOF computational control
Measurement source: 10 · Supplementary Fig. 9 · Supplementary Figure 9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Graphite model differential capacitance	5-7 uF cm^-2	—	range	Caption Range	10 · Supplementary Fig. 9 · Supplementary Figure 9

Mean-field QM/MM DFT-CES electrochemical simulation using Quantum ESPRESSO and LAMMPS; capacitance from C = sigma/DeltaU

Density functional theory

Cu3(HHTP)2 QM/MM electrochemical interface model · Model

Cu3(HHTP)2 electrode at QM level with 1 M NEt4BF4 in acetonitrile; surface charge density from -4.5 to +4.5 uC cm^-2; X = 1 counterion insertion, X = 0 ion exchange, X = -1 co-ion removal.

Temperature: 300
Atmosphere: canonical ensemble MD
Geometry: cylindrical pore model; two-layer (1 x sqrt(3)) rectangular electrode cell
Context: model pristine framework with explicit electrolyte
Measurement source: 14535 · Computational Details · Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
DeltaU range for Cu3(HHTP)2 co-ion removal mechanism	-0.8 to 0.2 V as sigma changes from -4.5 to +4.5 uC cm^-2	—	range	Text Range	14530 · Electrochemical Interface and Differential Capacitance · Figure 2b
DeltaU range for Cu3(HHTP)2 counterion insertion mechanism	-0.3 to 0.5 V as sigma changes from -4.5 to +4.5 uC cm^-2	—	range	Text Range	14530 · Electrochemical Interface and Differential Capacitance · Figure 2b
Cu3(HHTP)2 simulated gravimetric capacitance, X=1, negative sigma	231 F g^-1	—	—	SI Table Exact Reported	36 · Supplementary Table 2 · Supplementary Table 2
Cu3(HHTP)2 simulated gravimetric capacitance, X=-1, positive sigmaMarked as a best value within this paper	308 F g^-1	—	—	SI Table Exact Reported	36 · Supplementary Table 2 · Supplementary Table 2
Cu3(HHTP)2 simulated capacitance, X=0.5, negative sigma range	12 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=0.5, positive sigma range	12 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=0 ion exchange, negative sigma range	8 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=0 ion exchange, positive sigma range	12 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=1 counterion insertion, negative sigma rangeMarked as a best value within this paper	18 uF cm^-2 for -4.5 < sigma < 0 uC cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=1 counterion insertion, positive sigma range	8 uF cm^-2 for 0 < sigma < +4.5 uC cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=-0.5, negative sigma range	7 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=-0.5, positive sigma range	11 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=-1 co-ion removal, negative sigma range	6 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulated capacitance, X=-1 co-ion removal, positive sigma rangeMarked as a best value within this paper	24 uF cm^-2	—	—	Table Exact Reported	14531 · Results and Discussion · Table 1
Cu3(HHTP)2 simulation cell Connolly surface area	1286 m2 g^-1	—	—	Caption Exact Reported	2 · Supplementary Fig. 1 · Supplementary Figure 1

Mean-field QM/MM DFT-CES electrochemical simulation; capacitance from inverse sigma-DeltaU slope

Density functional theory

Cu3(HITP)2 QM/MM electrochemical interface model · Model

Cu3(HITP)2 electrode model with 1 M NEt4BF4/acetonitrile; X parameter varied across counterion insertion, ion exchange and co-ion removal.

Temperature: 300
Atmosphere: canonical ensemble MD
Geometry: cylindrical pore model; (1 x sqrt(3)) rectangular unit cell
Context: model pristine framework with explicit electrolyte
Measurement source: 14534 · Modulating the EDL Structure with MOF Composition · Table 2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Cu3(HITP)2 simulated capacitance, X=0.5, negative sigma range	13 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=0.5, positive sigma range	24 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=0 ion exchange, negative sigma range	11 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=0 ion exchange, positive sigma range	23 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=1 counterion insertion, negative sigma range	17 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=1 counterion insertion, positive sigma rangeMarked as a best value within this paper	25 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=-0.5, negative sigma range	10 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=-0.5, positive sigma range	23 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=-1 co-ion removal, negative sigma range	9 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulated capacitance, X=-1 co-ion removal, positive sigma rangeMarked as a best value within this paper	25 uF cm^-2	—	—	Table Exact Reported	14534 · Modulating the EDL Structure with MOF Composition · Table 2
Cu3(HITP)2 simulation cell Connolly surface area	1333 m2 g^-1	—	—	Caption Exact Reported	21 · Supplementary Fig. 20 · Supplementary Figure 20