Synthesis · Efficient MOF-Sensitized Solar Cells Featuring Solvothermally Grown [100]-Oriented Pillared Porphyrin Framework-11 Films on ZnO/FTO Surfaces

8 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: Both

Route 1: Solvothermal

S-4 · Synthesis of Bulk PPF-11 Crystals

Metal precursorsZn(NO3)2.6H2O (90 mg, 0.3 mmol)

Linker precursorsTCPP (80 mg, 0.1 mmol); DMBPY (38 mg, 0.2 mmol)

SolventsDMF/ethanol 15/5 mL (main: 3:1, 20 mL)

Additives1 M HNO3/EtOH (0.2 mL)

Atmospheresealed screw-capped vial; atmosphere not specified

Temperature80

Time24

Work-upwashed several times/thoroughly with fresh DMF; stored in DMF

Activationnone for as-synthesised crystals; CH2Cl2 exchange and high-vacuum 120 C 24 h for CO2 sorption samples

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	90 mg, 0.3 mmol	S-4 · Synthesis of Bulk PPF-11 Crystals
Linker	TCPP	80 mg, 0.1 mmol	S-4 · Synthesis of Bulk PPF-11 Crystals
Linker	DMBPY	38 mg, 0.2 mmol	S-4 · Synthesis of Bulk PPF-11 Crystals
Solvent	DMF/Ethanol	15/5 mL	S-4 · Synthesis of Bulk PPF-11 Crystals
Acid	HNO3/EtOH	0.2 mL · 1 M	S-4 · Synthesis of Bulk PPF-11 Crystals

Complete recipeSource: Both

Route 2: Other

S-4 · Doping PPF-11 with C60

Linker precursorsas-synthesised PPF-11 crystals (~10 mg)

Solventstoluene

AdditivesC60 saturated solution (33 mg in 10 mL toluene)

Atmospherenot specified

Temperature60

Time168

Oxidant / reductantC60 electron acceptor guest

Work-upwashed with toluene (3 x 5 mL, ~10 s each) at room temperature

ActivationDMF-to-toluene solvent exchange before loading

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PPF-11 crystals	~10 mg	S-4 · Doping PPF-11 with C60
Additive	C60	33 mg in 10 mL · saturated in toluene	S-4 · Doping PPF-11 with C60
Solvent	toluene	Not specified	S-4 · Doping PPF-11 with C60

Complete recipeSource: SI

Route 3: Other

S-4 · Doping PPF-11 with C60

Linker precursorssolvothermally grown PPF-11/ZnO films

Solventstoluene

Additivessaturated C60 solution in toluene

Atmospherenot specified

Temperature60

Time96

Substrate orientation[100]-oriented PPF-11 film on ZnO-FTO

Oxidant / reductantC60 electron acceptor guest

Work-upwashed with fresh toluene to remove C60 adhered to surface

Activationsolvent exchange in toluene for 3 days, refreshed every 8-12 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PPF-11/ZnO films	Not specified	S-4 · Doping PPF-11 with C60
Additive	C60	saturated in toluene	S-4 · Doping PPF-11 with C60
Solvent	toluene	Not specified	S-4 · Doping PPF-11 with C60

Complete recipeSource: SI

Route 4: Drop Cast

S-5 · Drop-Cast PPF-11 Films

Linker precursorsPPF-11 crystal suspension

SolventsCHCl3

Atmosphereambient evaporation; not specified

Temperatureroom temperature

Substrate orientationTCPP-coated ZnO-FTO surface

Work-upallowed solvent to evaporate between drops

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	PPF-11 suspension in CHCl3	typically 10 drops	S-5 · Drop-Cast PPF-11 Films

Complete recipeSource: Both

Route 5: Solvothermal

S-5 · Solvothermal Growth

Metal precursorsZn(NO3)2.6H2O (8.9 mg, 0.03 mmol)

Linker precursorsTCPP (7.9 mg, 0.01 mmol); DMBPY (3.8 mg, 0.02 mmol)

SolventsDMF/EtOH 3/1 mL

Additives1 M HNO3/EtOH (20 uL)

Atmosphere14 mL screw-capped vial; atmosphere not specified

Temperature80

Time2 h nucleation plus 0.5 h film growth

Substrate orientationZnO layer facing down in slightly slanted slide; TCPP-precoated or bare ZnO-FTO

Work-upsoaked in fresh DMF, refreshed frequently for 3 days; kept in fresh DMF

Scalability contextOne slide per vial; uniform films only on ZnO-coated area.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.6H2O	8.9 mg, 0.03 mmol	S-5 · Solvothermal Growth
Linker	TCPP	7.9 mg, 0.01 mmol	S-5 · Solvothermal Growth
Linker	DMBPY	3.8 mg, 0.02 mmol	S-5 · Solvothermal Growth
Solvent	DMF/EtOH	3/1 mL	S-5 · Solvothermal Growth
Acid	HNO3/EtOH	20 uL · 1 M	S-5 · Solvothermal Growth
Other	TCPP-coated ZnO-FTO slide	one slide per vial	S-5 · Solvothermal Growth

Complete recipeSource: SI

Route 6: Other

S-5 · PV Device Construction and Measurements

Solventspropylene carbonate electrolyte solvent

AdditivesI-/I3- redox couple; 30 um surlyn sealant

Atmospherenot specified

Substrate orientationFTO-ZnO/PPF-11(or control)/electrolyte/Pt-FTO sandwich device

Oxidant / reductantI-/I3- redox electrolyte

Work-upelectrolyte injected by vacuum infiltration through drilled counter-electrode hole

Scalability contextPhotoactive area fixed at 0.2 cm2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	I-/I3- based electrolyte in propylene carbonate	Not specified	S-5 · PV Device Construction and Measurements
Other	Pt-coated FTO counter electrode	Not specified	S-5 · PV Device Construction and Measurements
Other	surlyn thermoplastic sealant	30 um	S-5 · PV Device Construction and Measurements

Complete recipeSource: SI

Route 7: Other

S-5 · Solvothermal Growth

Linker precursorsTCPP

Solventsethanol

Atmosphereambient; not specified

Temperatureroom temperature

Time18

Substrate orientationannealed ZnO-FTO soaked before MOF growth

Work-upwashed thoroughly to remove physisorbed ligands

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	TCPP	0.2 mM	S-5 · Solvothermal Growth
Solvent	EtOH	Not specified	S-5 · Solvothermal Growth

Complete recipeSource: SI

Route 8: Other

S-4 · Preparation of ZnO films

Metal precursorsZnO/EtOH suspension (40 wt%, particle size about 130 nm)

Solventsethanol in commercial ZnO suspension

Atmosphereair; programmable oven atmosphere not otherwise specified

Temperature350

Time0.5

Substrate orientationFTO glass exposed midsection between tape spacers

Work-upremove scotch tape; cool slowly to room temperature; cut slides into pieces

Activationannealing at 350 C for 30 min

Scalability contextUses spin coating on FTO-glass; rectangular area set by tape mask.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	FTO-glass slides	Not specified	S-4 · Preparation of ZnO films
Other	ZnO/EtOH suspension	40 wt%	S-4 · Preparation of ZnO films