Synthesis · Charge Transfer-Induced Molecular Hole Doping into Thin Film of Metal-Organic Frameworks

6 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Hydrothermal

S2 · Experimental details, 1.1

Metal precursors0.344 mmol Co(NO3)2.3H2O in DMF

Linker precursors0.115 mmol 2,6-NDC (2,6-naphthalenedicarboxylic acid) in DMF

SolventsDMF

Atmospherenot reported

Temperature180

Time72

Work-upAll precipitate filtered, washed thoroughly with DMF, and dried at 50 deg C for 3 h.

ActivationDried at 50 deg C for 3 h

Scalability contextBulk powder used as feed/reference for both thin-film routes; scale limited to 0.344 mmol Co precursor in reported recipe.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.3H2O	0.344 mmol · in DMF	S2 · Experimental details, 1.1
Linker	2,6-NDC (2,6-naphthalenedicarboxylic acid)	0.115 mmol · in DMF	S2 · Experimental details, 1.1
Solvent	DMF	equal volumes of metal and linker solutions; exact volume not reported	S2 · Experimental details, 1.1

Complete recipeSource: SI

Route 2: Solution Shearing

S2 · Experimental details, 1.2

Metal precursorsPreformed bulk Co3(NDC)3 MOF powder

Linker precursorsNDC already incorporated in bulk Co3(NDC)3

Solvents2 mL ethanol and 1 mL deionised water

Additives0.05 g PEG binder

Atmospherenot reported

Temperature250 anneal

Time1 anneal

Substrate orientationNonconducting glass and ITO conducting glass substrates

Work-up0.5 g bulk MOFs ground with PEG/ethanol/water to proper viscosity, doctor-bladed onto substrates, annealed at 250 deg C for 1 h to decompose PEG.

ActivationAnnealed at 250 deg C for 1 h

Scalability contextDoctor-blade coating uses a paste from 0.5 g bulk MOF and is potentially area-scalable; blade gap and film thickness were not reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	bulk Co3(NDC)3 MOFs	0.5 g	S2 · Experimental details, 1.2
Additive	PEG	0.05 g	S2 · Experimental details, 1.2
Solvent	ethanol	2 mL	S2 · Experimental details, 1.2
Solvent	deionized water	1 mL	S2 · Experimental details, 1.2

Partial recipeSource: Both

Route 3: Other

18505 · Results and Discussion · Figure S10

Metal precursorsCo3(NDC)3 LbL layers on TiO2/FTO; Pt counter electrode

Linker precursorsNDC linkers in Co3(NDC)3

SolventsI-/I3- redox electrolyte; iodine-doping acetonitrile solution from SI route

AdditivesTiO2 mesoporous film, I2 dopant, Pt counter electrode, I-/I3- electrolyte

Atmospherenot reported

Temperature50 for iodine doping; other device steps not fully reported

Time2 h iodine doping; other device steps not fully reported

Substrate orientationDoctor-bladed mesoporous TiO2 film on FTO substrate

Oxidant / reductantI2 dopant and I-/I3- redox electrolyte

Work-upDoctor-bladed TiO2 mesoporous film on FTO was sensitised with Co3(NDC)3 layers by LbL, iodine doped, and assembled with Pt counter and I-/I3- electrolyte.

Activationnot reported

Scalability contextDevice assembly is a proof of concept; TiO2 doctor-blading conditions and electrolyte composition are not fully specified.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	FTO substrate	substrate	18505 · Results and Discussion · Figure S10
Other	TiO2 mesoporous film	doctor-bladed film	18505 · Results and Discussion · Figure S10
Electrolyte	I-/I3- redox electrolyte	cell electrolyte · not reported	18505 · Results and Discussion · Figure S10
Other	Pt counter electrode	counter electrode	18505 · Results and Discussion · Figure S10

Complete recipeSource: SI

Route 4: Other

S3 · Experimental details, 1.4

Metal precursorsPreformed Co3(NDC)3 doctor-blade film

Linker precursorsNDC linkers in preformed Co3(NDC)3

SolventsAcetonitrile

Additives0.1 M I2 molecular dopant

Atmospherenot reported

Temperature50

Time2

Substrate orientationCo3(NDC)3 doctor-blade film on glass or ITO

Oxidant / reductantI2 electron acceptor / oxidative dopant

Work-upFramework films dipped into 0.1 M I2 in acetonitrile for 2 h at 50 deg C; post-doping wash/dry not reported.

Activationnot reported

Scalability contextPost-synthetic solution doping applicable to doctor-bladed films.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Oxidant	I2	2 h dip · 0.1 M	S3 · Experimental details, 1.4
Solvent	acetonitrile	doping solution solvent	S3 · Experimental details, 1.4
Other	preformed Co3(NDC)3 film	framework film	S3 · Experimental details, 1.4

Complete recipeSource: SI

Route 5: Other

S3 · Experimental details, 1.4

Metal precursorsPreformed Co3(NDC)3 LbL film

Linker precursorsNDC linkers in preformed Co3(NDC)3

SolventsAcetonitrile

Additives0.1 M I2 molecular dopant

Atmospherenot reported

Temperature50

Time2

Substrate orientationCo3(NDC)3 LbL film on glass or ITO

Oxidant / reductantI2 electron acceptor / oxidative dopant

Work-upFramework films dipped into 0.1 M I2 in acetonitrile for 2 h at 50 deg C; post-doping wash/dry not reported.

Activationnot reported

Scalability contextPost-synthetic solution doping applicable to both LbL and DB films.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Oxidant	I2	2 h dip · 0.1 M	S3 · Experimental details, 1.4
Solvent	acetonitrile	doping solution solvent	S3 · Experimental details, 1.4
Other	preformed Co3(NDC)3 film	framework film	S3 · Experimental details, 1.4

Complete recipeSource: SI

Route 6: Other

S2 · Experimental details, 1.3

Metal precursors0.1 M Co(NO3)2.3H2O in DMF

Linker precursors0.1 M 2,6-naphthalenedicarboxylic acid in DMF

SolventsDMF; DMF wash

AdditivesAmine-functionalised glass or ITO substrate

Atmospherenot reported

Temperature120 for each dipping solution

Time20 cycles; each cycle has 1 h linker dip plus 1 h metal dip

Substrate orientationAmine-functionalised nonconducting glass and ITO glass substrates

Work-upEach cycle: dip substrate 1 h in 0.1 M 2,6-NDC/DMF at 120 deg C, wash by dipping in DMF, dip 1 h in 0.1 M Co(NO3)2.3H2O/DMF at 120 deg C, then wash again with DMF.

ActivationFinal DMF washing; no thermal activation reported for LbL route

Scalability contextRoute uses 20 sequential LbL cycles; film thickness not reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,6-naphthalenedicarboxylic acid	1 h dip per cycle · 0.1 M in DMF	S2 · Experimental details, 1.3
Metal Source	Co(NO3)2.3H2O	1 h dip per cycle · 0.1 M in DMF	S2 · Experimental details, 1.3
Solvent	DMF	solution solvent and wash	S2 · Experimental details, 1.3
Other	amine functionalized glass or ITO substrate	substrate	S2 · Experimental details, 1.3