Synthesis · Electrochemical deposition and thermoelectric characterisation of a semiconducting 2-D metal-organic framework thin film

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: Electrochemical

4 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 onto Au/SiO2 substrates

Metal precursorsCuSO4 electrolyte for Cu@Au/SiO2 layer; electrodeposited Cu metal oxidised by anodic dissolution

Linker precursorsHHTP, 2.5 mM

Solvents80:20 EtOH:H2O for MOF deposition; 0.1 M HCl, DI water, acetone cleaning

AdditivesMTBS 0.02 M supporting electrolyte; KCl 0.1 M for Cu deposition

Atmospheresolutions degassed with Ar; substrates dried under Ar stream; final film dried in air at ambient temperature

Temperatureambient

Time1 h Cu deposition + 2 h MOF deposition

Substrate orientationAu/SiO2, 10 x 20 mm; exposed area about 1 cm2 for CV

Oxidant / reductantCu layer electrodeposited at -0.270 V vs SCE; anodic dissolution at +0.435 V vs SCE

Work-upAu/SiO2 cleaned ultrasonically in 0.1 M HCl, DI water, acetone for 15 min each; samples characterised by GIXRD, SEM and electrical measurements

Activationnone reported

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4	0.01 M	4 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 onto Au/SiO2 substrates
Electrolyte	KCl	0.1 M	4 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 onto Au/SiO2 substrates
Linker	HHTP	2.5 mM	4 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 onto Au/SiO2 substrates
Electrolyte	MTBS	0.02 M	4 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 onto Au/SiO2 substrates
Solvent	EtOH:H2O	80:20 solvent ratio	4 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 onto Au/SiO2 substrates

Complete recipeSource: Both

Route 2: Hydrothermal

3 · Methods - Solvothermal synthesis of Cu3(HHTP)2

Metal precursorsCu(NO3)2 3H2O, 127 mg (0.53 mmol)

Linker precursorsHHTP, 103 mg (0.30 mmol)

Solventsdistilled water, total 10.4 mL; ethanol and water washes

Additivesconcentrated NH4OH, 270 uL, 50 equivalents

Atmospheresealed reaction vessel; atmosphere not otherwise specified

Temperature80

Time24

Work-upsonicated 10 min; centrifuged 11000 rpm for 15 min; washed with ethanol (5 mL x 7) and water (5 mL x 7)

Activationnone reported

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2 3H2O	127 mg (0.53 mmol)	3 · Methods - Solvothermal synthesis of Cu3(HHTP)2
Linker	HHTP	103 mg (0.30 mmol)	3 · Methods - Solvothermal synthesis of Cu3(HHTP)2
Base	concentrated NH4OH	270 uL; 50 equivalent · 28.0-30.0% NH3 basis	3 · Methods - Solvothermal synthesis of Cu3(HHTP)2
Solvent	distilled water	2 mL + 8.4 mL	3 · Methods - Solvothermal synthesis of Cu3(HHTP)2
Solvent	ethanol	5 mL x 7 wash	3 · Methods - Solvothermal synthesis of Cu3(HHTP)2

Vague recipeSource: SI

Route 3: Other

18 · Figure S11 · Figure S11

Metal precursorsCu

Substrate orientationglass

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Metal Source	Cu	150 nm film	18 · Figure S11 · Figure S11

Complete recipeSource: Both

Route 4: Electrochemical

3 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 on Transparent Conducting Substrates

Metal precursorsCuSO4 electrolyte for Cu@FTO layer; electrodeposited Cu metal oxidised by anodic dissolution

Linker precursorsHHTP, 5 mM

Solvents80:20 EtOH:H2O for MOF deposition; HCl, IPA, acetone, deionised water cleaning

AdditivesMTBS 0.02 M supporting electrolyte; KCl 0.1 M for Cu deposition

Atmospheresolutions degassed with Ar; substrates dried under Ar stream

Temperatureambient

Time1 h Cu deposition + 1 h MOF deposition

Substrate orientationFTO glass, 15 ohm, 10 x 20 mm, exposed area 1 cm2

Oxidant / reductantCu layer electrodeposited at -0.8 V vs SCE; anodic dissolution at +0.435 V vs SCE

Work-upFTO cleaned ultrasonically in 1 M HCl, IPA, acetone, DI water 10 min each; Cu deposit rinsed with H2O and EtOH; MOF deposit washed with EtOH

Activationnone reported

Scalability contextMain text notes electrodeposition offers room-temperature formation, shorter synthesis times, low-cost equipment and easy scalability.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(SO)4 / CuSO4	0.01 M	3 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 on Transparent Conducting Substrates
Electrolyte	KCl	0.1 M	3 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 on Transparent Conducting Substrates
Linker	HHTP	5 mM	3 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 on Transparent Conducting Substrates
Electrolyte	MTBS	0.02 M	3 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 on Transparent Conducting Substrates
Solvent	EtOH:H2O	80:20 solvent ratio	3 · Two-Step Anodic Electrosynthesis of Cu3(HHTP)2 on Transparent Conducting Substrates

Complete recipeSource: Both

Route 5: Electrochemical

3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO

Metal precursorsCuSO4 electrolyte for Cu@FTO layer; electrodeposited Cu metal oxidised by anodic dissolution

Linker precursorsHHTP, 5 mM

Solvents80:20 EtOH:H2O

AdditivesMTBS 0.02 M; KCl 0.1 M

AtmosphereAr-degassed electrolyte

Temperatureambient

Time1 h Cu deposition + 1 h MOF deposition

Substrate orientationFTO glass, 15 ohm, 10 x 20 mm, exposed area 1 cm2

Oxidant / reductantCu layer electrodeposited at -0.8 V vs SCE; anodic dissolution at +0.5 V vs SCE

Work-upwashed with EtOH after MOF deposition

Activationnone reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4	0.01 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Linker	HHTP	5 mM	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Electrolyte	MTBS	0.02 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Electrolyte	KCl	0.1 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO

Complete recipeSource: Both

Route 6: Electrochemical

3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO

Metal precursorsCuSO4 electrolyte for Cu@FTO layer; electrodeposited Cu metal oxidised by anodic dissolution

Linker precursorsHHTP, 5 mM

Solvents80:20 EtOH:H2O

AdditivesMTBS 0.02 M; KCl 0.1 M

AtmosphereAr-degassed electrolyte

Temperatureambient

Time1 h Cu deposition + 1 h MOF deposition

Substrate orientationFTO glass, 15 ohm, 10 x 20 mm, exposed area 1 cm2

Oxidant / reductantCu layer electrodeposited at -0.8 V vs SCE; anodic dissolution at +0.6 V vs SCE

Work-upwashed with EtOH after MOF deposition

Activationnone reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4	0.01 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Linker	HHTP	5 mM	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Electrolyte	MTBS	0.02 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Electrolyte	KCl	0.1 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO

Complete recipeSource: Both

Route 7: Electrochemical

3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO

Metal precursorsCuSO4 electrolyte for Cu@FTO layer; electrodeposited Cu metal oxidised by anodic dissolution

Linker precursorsHHTP, 5 mM

Solvents80:20 EtOH:H2O

AdditivesMTBS 0.02 M; KCl 0.1 M

AtmosphereAr-degassed electrolyte

Temperatureambient

Time1 h Cu deposition + 1 h MOF deposition

Substrate orientationFTO glass, 15 ohm, 10 x 20 mm, exposed area 1 cm2

Oxidant / reductantCu layer electrodeposited at -0.8 V vs SCE; anodic dissolution at +0.7 V vs SCE

Work-upwashed with EtOH after MOF deposition

Activationnone reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4	0.01 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Linker	HHTP	5 mM	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Electrolyte	MTBS	0.02 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO
Electrolyte	KCl	0.1 M	3 · Step 2. Electrodeposition of Cu3(HHTP)2@FTO

Complete recipeSource: Both

Route 8: Electrochemical

3 · Transferring method of electrodeposited Cu3(HHTP)2 thin films

Metal precursorsCuSO4 electrolyte for Cu@Au/SiO2 layer; electrodeposited Cu metal oxidised by anodic dissolution

Linker precursorsHHTP, 2.5 mM

Solvents80:20 EtOH:H2O for MOF deposition; chlorobenzene for PMMA suspension

AdditivesMTBS 0.02 M; PMMA 3.71 g in 10 mL chlorobenzene

AtmosphereAr-degassed electrolyte; dried in air; PMMA/MOF dried at 40 C

Temperatureambient deposition; 40 C PMMA drying

Time1 h Cu deposition + 2 h MOF deposition + overnight PMMA dissolution/drying in SI; main text states 12 h drying at 40 C

Substrate orientationAu/SiO2 substrate followed by PMMA transfer support

Oxidant / reductantCu layer electrodeposited at -0.270 V vs SCE; anodic dissolution at +0.435 V vs SCE

Work-upPMMA suspension drop cast onto film, heated at 40 C, cooled, peeled from Au/SiO2

Activationnone reported

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4	0.01 M	3 · Transferring method of electrodeposited Cu3(HHTP)2 thin films
Linker	HHTP	2.5 mM	3 · Transferring method of electrodeposited Cu3(HHTP)2 thin films
Electrolyte	MTBS	0.02 M	3 · Transferring method of electrodeposited Cu3(HHTP)2 thin films
Additive	poly(methyl methacrylate) (PMMA)	3.71 g · in 10 mL chlorobenzene	3 · Transferring method of electrodeposited Cu3(HHTP)2 thin films
Solvent	chlorobenzene	10 mL	3 · Transferring method of electrodeposited Cu3(HHTP)2 thin films