Synthesis · Electrochemical synthesis of metal organic framework films with proton conductive property

9 structured synthesis routes

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

Vague recipeSource: Main

Route 1: Unknown

5-7 · Stability; Proton conduction · Fig. 6B; Fig. 8d

Metal precursorsnot reported

Linker precursorsnot reported

Solventsnot reported

AdditivesPTA-free control

Atmospherenot reported

Substrate orientationnot reported

Oxidant / reductantnot reported

Work-upnot reported

Activationnot reported

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	PTA-free HKUST-1 control synthesis reagents not reported	Not specified	5-7 · Stability; Proton conduction · Fig. 6B; Fig. 8d

Complete recipeSource: Main

Route 2: Electrochemical

2-3 · Syntheses; Fig. 1 caption · Fig. 1

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time2

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant1.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextLow voltage produced scattered crystals rather than continuous optimal films.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	2-3 · Syntheses; Fig. 1 caption · Fig. 1
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	2-3 · Syntheses; Fig. 1 caption · Fig. 1
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	2-3 · Syntheses; Fig. 1 caption · Fig. 1
Solvent	ethanol	20 mL	2-3 · Syntheses; Fig. 1 caption · Fig. 1
Solvent	water	20 mL	2-3 · Syntheses; Fig. 1 caption · Fig. 1
Other	carbon rod cathode	not reported	2-3 · Syntheses; Fig. 1 caption · Fig. 1

Complete recipeSource: Main

Route 3: Electrochemical

4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time0.5

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant2.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextShort reaction already gave high coverage.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Solvent	ethanol	20 mL	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Solvent	water	20 mL	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Other	carbon rod cathode	not reported	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4

Complete recipeSource: Main

Route 4: Electrochemical

4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time1

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant2.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextThickness increased sharply from 0.5 h to 1 h.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Solvent	ethanol	20 mL	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Solvent	water	20 mL	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4
Other	carbon rod cathode	not reported	4-5 · Fig. 4 caption; Synthesis and characterizations · Fig. 4

Complete recipeSource: Main

Route 5: Electrochemical

2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time2

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant2.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextOptimal voltage for continuous film formation.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Solvent	ethanol	20 mL	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Solvent	water	20 mL	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Other	carbon rod cathode	not reported	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2

Complete recipeSource: Both

Route 6: Electrochemical

SI · Supporting Information · Figure S1

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time8

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant2.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextLonger times above 2 h caused only small additional thickness increase.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	SI · Supporting Information · Figure S1
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	SI · Supporting Information · Figure S1
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	SI · Supporting Information · Figure S1
Solvent	ethanol	20 mL	SI · Supporting Information · Figure S1
Solvent	water	20 mL	SI · Supporting Information · Figure S1
Other	carbon rod cathode	not reported	SI · Supporting Information · Figure S1

Complete recipeSource: Main

Route 7: Electrochemical

2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time2

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant5.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextHigher voltage accelerated nucleation/crystallisation and increased thickness.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Solvent	ethanol	20 mL	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Solvent	water	20 mL	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Other	carbon rod cathode	not reported	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2

Complete recipeSource: Main

Route 8: Electrochemical

2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2

Metal precursorscopper anode

Linker precursorsH3BTC, 2.78 mmol

Solventsethanol/water, 20 mL/20 mL

AdditivesPTA, 0.278 mmol

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time2

Substrate orientationcopper working electrode as anode, carbon rod as cathode

Oxidant / reductant8.0 V direct-current applied voltage

Work-upwashed with ethanol and water; dried overnight at room temperature

Activationnone beyond room-temperature drying

Scalability contextHigh voltage produced thick, compact films with large crystals.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Solvent	ethanol	20 mL	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Solvent	water	20 mL	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2
Other	carbon rod cathode	not reported	2-5 · Syntheses; Synthesis and characterizations · Fig. 1; Fig. 2

Complete recipeSource: Both

Route 9: Electrochemical

2 · Syntheses of NENU-3 films · Scheme S1

Metal precursorscopper working electrode/anode, 99.9% copper slice

Linker precursorsH3BTC (1,3,5-benzenetricarboxylic acid), 2.78 mmol

Solventsethanol (20 mL) and water (20 mL)

Additivesphosphotungstic acid (PTA), 0.278 mmol; acts as guest and electrolyte

Atmosphereair / not otherwise controlled

Temperatureroom temperature

Time0.5-8 depending on sample; common voltage series used 2 h

Substrate orientationcopper working electrode (2.5 x 2.5 cm2) immersed in reaction solution as anode; carbon rod as cathode

Oxidant / reductantelectrochemical oxidation of Cu0 anode to Cu2+ under applied direct-current voltage

Work-upAs-prepared MOF films washed thoroughly with ethanol and water to remove excess H3BTC and PTA.

ActivationDried at room temperature overnight; no further activation reported.

Scalability contextFacile room-temperature electrochemical film growth on conductive copper; applied voltage and time tune crystal size and film thickness.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper slice / copper working electrode	2.5 x 2.5 cm2 working electrode; copper slices 99.9%	2 · Syntheses of NENU-3 films · Scheme S1
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	2.78 mmol	2 · Syntheses of NENU-3 films · Scheme S1
Electrolyte	phosphotungstic acid (PTA)	0.278 mmol	2 · Syntheses of NENU-3 films · Scheme S1
Solvent	ethanol	20 mL	2 · Syntheses of NENU-3 films · Scheme S1
Solvent	water	20 mL	2 · Syntheses of NENU-3 films · Scheme S1
Other	carbon rod cathode	not reported	2 · Syntheses of NENU-3 films · Scheme S1