Computational Modelling — Mechanistic Evidence for Ligand-Centered Electrocatalytic Oxygen Reduction with the Conductive MOF Ni3(hexaiminotriphenylene)2

3 measurement groups · 15 results

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

DFT O2 binding calculations

Density functional theory

Ni3(HITP)(ISQ)3 DFT fragment · Model

B3LYP/6-31+G(d) with IEF-PCM implicit solvation in Q-Chem

Temperature: 298
Geometry: Ni3(HITP)(ISQ)3 fragment
Context: model system for pristine MOF
Measurement source: S12 · Computational details · Figure 6, Figure 7, Table S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Distance between distal O atom and imine proton	1.98 Angstrom	—	—	Text Exact Reported	7728 · Results and Discussion · Figure 6b
Chemical O2 binding to beta-C without electron transfer	uphill by 1.1 eV	—	—	Text Exact Reported	7728 · Results and Discussion · Figure 6
Electrochemical O2 binding to beta-C with 1e- transferMarked as a best value within this paper	endergonic by only 0.1 eV	—	—	Text Exact Reported	7729 · Results and Discussion · Figure 7
Chemical O2 binding to Ni centre	uphill free energy of 1.4 eV	—	—	Text Exact Reported	7728 · Results and Discussion · Figure 6
Electrochemical O2 binding to Ni sites	0.6 eV barrier	—	—	Text Exact Reported	7729 · Results and Discussion · Figure 7
Second electron transfer and HO2- release free energy	favorable by 1.2 eV	—	—	Text Exact Reported	7729 · Results and Discussion · Figure 7
Protonation of superoxide free energy	exergonic by 0.3 eV	—	—	Text Exact Reported	7729 · Results and Discussion · Figure 7
Calculated pKa of MOF fragment	pKa = 25	—	—	Text Exact Reported	S26 · Supplementary Notes
Spin-density plot isovalue for Ni3(HITP)2-O2- cluster	isovalue = 0.018; overall spin 0.5	—	—	Caption Exact Reported	S18 · Additional Figures · Figure S6
Calculated thermodynamic parameter table for Ni3(HITP)2 fragment	Table S4 reports vacuum energy, solvation energy, vibrational enthalpy, entropy and ZPE for Ni3(HITP)2, Ni3(HITP)2-O2(Cbeta-O2), Ni3(HITP)2-O2-(Cbeta-O2-), Ni3(HITP)2-O2H, and Ni3(HITP)2-O2-(Ni-O2-).	—	—	SI Table Exact Reported	S25 · Additional Figures · Table S4

Mulliken charge population analysis

Ni3(HITP)(ISQ)3 DFT fragment · Model

before versus after electrochemical O2 binding on numbered atoms in Ni3(HITP)2 model fragment

Geometry: Ni3(HITP)(ISQ)3 fragment
Context: model system for pristine MOF
Measurement source: S17 · Additional Figures · Figure S5, Table S2

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Mulliken population atom 4 after O2 binding	-0.73	—	—	SI Table Exact Reported	S17 · Additional Figures · Table S2
Mulliken population atom 4 before O2 bindingMarked as a best value within this paper	-1.01	—	—	SI Table Exact Reported	S17 · Additional Figures · Table S2
Mulliken populations for atoms 1-5 before/after O2 binding	Atom 1: 0.34 -> 0.33; atom 2: -0.78 -> -0.81; atom 3: 0.47 -> 0.26; atom 4: -1.01 -> -0.73; atom 5: 0.65 -> 0.82	—	—	SI Table Exact Reported	S17 · Additional Figures · Table S2

DFT molecular analogue calculations

Density functional theory

Ni(ISQ)2 molecular analogue · Powder

B3LYP/6-31+G(d), IEF-PCM, Q-Chem; HOMO and thermodynamic comparisons with Ni3(HITP)2 fragment

Temperature: 298
Geometry: Ni(ISQ)2 model
Context: molecular analogue/control
Measurement source: S12 · Computational details · Figure S10, Figure S11, Table S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Ni(ISQ)2 superoxide complex formation energy	endergonic by 0.7 eV at pH 13	—	—	Text Exact Reported	7730 · Results and Discussion · Figure S10
Calculated thermodynamic parameter table for Ni(ISQ)2 analogue	Table S4 reports Ni(ISQ)2: vacuum energy -2191.7560 Hartree, solvation -14.58 kcal/mol, vibrational enthalpy 142.50 kcal/mol, entropy 104.95 cal/mol, ZPE 136.86 kcal/mol; Ni(ISQ)2-O2(Cbeta-O2): -2342.0040 Hartree, -46.51 kcal/mol, 153.76 kcal/mol, 125.65 cal/mol, 145.80 kcal/mol; Ni(ISQ)2-O2-(Cbeta-O2-): -2342.1184 Hartree, -70.83 kcal/mol, 146.03 kcal/mol, 118.50 cal/mol, 138.81 kcal/mol.	—	—	SI Table Exact Reported	S25 · Additional Figures · Table S4