Synthesis · Electronic Doping of Metal-Organic Frameworks for High-Performance Flexible Micro-Supercapacitors

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: Other

Experimental Section, Device fabrication

Metal precursorspreformed Cu3(BTC)2 thin film on Cu foil

Linker precursorsBTC framework retained; BQ electron acceptor introduced post-synthetically

Solventsanhydrous CH2Cl2 dispersion/solution for BQ loading

AdditivesBQ

Atmospherevacuum only specified for pre-immersion dehydration; immersion atmosphere not stated

Temperature180 C pre-immersion vacuum dehydration; immersion temperature not stated

Time0.5 h dehydration; 168 h immersion (7 days)

Substrate orientationCu3(BTC)2 thin film on Cu foil

Oxidant / reductantelectron acceptor doping; BQ accepts electrons from Cu3(BTC)2 according to CV energy-level analysis

Work-uprepeatedly washed at least 5 times with anhydrous CH2Cl2 to remove residual acceptor molecules

Activationcoordinated water removed by heating at 180 C for 30 min in vacuum before immersion

Scalability contextPost-synthetic molecular loading over 7 days with reported guest concentration and wash solvent.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Cu3(BTC)2 thin film	active material mass loading about 1 mg cm^-2	Experimental Section, Device fabrication
Additive	BQ	not reported as total mass used · 2 mg mL^-1	Experimental Section, Device fabrication
Solvent	anhydrous CH2Cl2	not reported	Experimental Section, Device fabrication
Solvent	anhydrous CH2Cl2	washed at least 5 times	Experimental Section, Device fabrication

Complete recipeSource: SI

Route 2: Other

Experimental Section, Assembling flexible micro-supercapacitors

Metal precursorsBQ@Cu3(BTC)2 thin film positive-electrode thin film on Cu foil; activated-carbon negative electrode on Cu foil

Linker precursorsBTC framework in MOF positive electrode where applicable

SolventsDMF for activated-carbon/Super P/PVDF slurry; deionised water for PVA/LiCl gel electrolyte

Additivesactivated carbon, Super P conductive additive, PVDF binder, PVA/LiCl gel electrolyte

Atmospherenot specified

Temperature80 C overnight drying of negative electrode; 85 C heating to clear PVA/LiCl gel dispersion

Timenegative electrode dried overnight; gel heated until clear; assembly time not specified

Substrate orientationpositive and negative electrodes tailored into interdigitated patterns and assembled on PET substrate

Oxidant / reductantnot applicable to device assembly

Work-uppositive film cut into interdigitated pattern; AC slurry pasted on cleaned Cu foil, dried, tailored, assembled on PET and drop-cast with gel electrolyte

Activationnone reported beyond electrode drying and gel preparation

Scalability contextInterdigitated geometry specified: finger width 1.5 mm, length 16 mm, electrode area 1.2 cm^2, interspace 0.5 mm.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	BQ@Cu3(BTC)2 thin film	positive electrode cut to interdigitated pattern; one electrode area 1.2 cm^2	Experimental Section, Assembling flexible micro-supercapacitors
Other	activated carbon	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	Super P	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	PVDF	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Solvent	DMF	used for negative-electrode slurry	Experimental Section, Assembling flexible micro-supercapacitors
Electrolyte	PVA/LiCl gel electrolyte	PVA 5 g; LiCl 2.12 g; deionised water 50 mL	Experimental Section, Assembling flexible micro-supercapacitors

Complete recipeSource: Both

Route 3: Drop Cast

Experimental Section, Device fabrication

Metal precursorsCu foil (10 um thick; cleaned, 3 cm x 4 cm for growth) supplies Cu2+ in situ; AgNO3 (300 mg) oxidises Cu and deposits Ag collector.

Linker precursorsH3BTC / 1,3,5-benzenetricarboxylic acid (300 mg)

SolventsDMSO (5 g) for H3BTC/AgNO3 coating solution; acetone and deionised water used during foil cleaning/workup

AdditivesAgNO3; dilute HCl (1 M) for copper-foil oxide removal before growth

Atmosphereair/ambient coating not explicitly stated; vacuum used for 180 C dehydration before acceptor loading

Temperature120 C during drop/spin coating; 60 C oven drying for 3 h; 180 C vacuum dehydration for 30 min before doping

TimeCu foil acetone sonication 30 min x 3; HCl dip 5 min; coating 5 min; drying 3 h; vacuum dehydration 0.5 h

Substrate orientationcleaned Cu foil on home-made rotary table; rotation speed 300 rpm; 1 mL solution drop-coated

Oxidant / reductantAg+ reacts with Cu foil: 2Ag+ + Cu = 2Ag + Cu2+

Work-uprepeatedly washed with acetone for 3 times; dried in oven at 60 C for 3 h

Activationfor doped films, coordinated water removed by heating at 180 C for 30 min in vacuum before molecule immersion

Scalability contextCu foil squares/strips and 1 mL drop-coated solution are specified; growth is a short in situ coating process on copper foil.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper foil	3 cm x 4 cm, thickness 10 um for growth; cleaning initially used 3 cm x 3 cm squares	Experimental Section, Device fabrication
Oxidant	AgNO3	300 mg · in 5 g DMSO coating solution	Experimental Section, Device fabrication
Linker	H3BTC / 1,3,5-benzenetricarboxylic acid	300 mg · in 5 g DMSO coating solution	Experimental Section, Device fabrication
Solvent	DMSO	5 g	Experimental Section, Device fabrication
Acid	HCl	5 min copper-foil dip · 1 M	Experimental Section, Device fabrication
Solvent	acetone	sonication 30 min x 3; wash 3 times after growth	Experimental Section, Device fabrication

Complete recipeSource: SI

Route 4: Other

Experimental Section, Assembling flexible micro-supercapacitors

Metal precursorsundoped Cu3(BTC)2 thin film positive-electrode thin film on Cu foil; activated-carbon negative electrode on Cu foil

Linker precursorsBTC framework in MOF positive electrode where applicable

SolventsDMF for activated-carbon/Super P/PVDF slurry; deionised water for PVA/LiCl gel electrolyte

Additivesactivated carbon, Super P conductive additive, PVDF binder, PVA/LiCl gel electrolyte

Atmospherenot specified

Temperature80 C overnight drying of negative electrode; 85 C heating to clear PVA/LiCl gel dispersion

Timenegative electrode dried overnight; gel heated until clear; assembly time not specified

Substrate orientationpositive and negative electrodes tailored into interdigitated patterns and assembled on PET substrate

Oxidant / reductantnot applicable to device assembly

Work-uppositive film cut into interdigitated pattern; AC slurry pasted on cleaned Cu foil, dried, tailored, assembled on PET and drop-cast with gel electrolyte

Activationnone reported beyond electrode drying and gel preparation

Scalability contextInterdigitated geometry specified: finger width 1.5 mm, length 16 mm, electrode area 1.2 cm^2, interspace 0.5 mm.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	undoped Cu3(BTC)2 thin film	positive electrode cut to interdigitated pattern; one electrode area 1.2 cm^2	Experimental Section, Assembling flexible micro-supercapacitors
Other	activated carbon	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	Super P	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	PVDF	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Solvent	DMF	used for negative-electrode slurry	Experimental Section, Assembling flexible micro-supercapacitors
Electrolyte	PVA/LiCl gel electrolyte	PVA 5 g; LiCl 2.12 g; deionised water 50 mL	Experimental Section, Assembling flexible micro-supercapacitors

Complete recipeSource: Both

Route 5: Other

Experimental Section, Device fabrication

Metal precursorspreformed Cu3(BTC)2 thin film on Cu foil

Linker precursorsBTC framework retained; PMDI electron acceptor introduced post-synthetically

Solventsanhydrous DMF dispersion/solution for PMDI loading

AdditivesPMDI

Atmospherevacuum only specified for pre-immersion dehydration; immersion atmosphere not stated

Temperature180 C pre-immersion vacuum dehydration; immersion temperature not stated

Time0.5 h dehydration; 168 h immersion (7 days)

Substrate orientationCu3(BTC)2 thin film on Cu foil

Oxidant / reductantelectron acceptor doping; PMDI accepts electrons from Cu3(BTC)2 according to CV energy-level analysis

Work-uprepeatedly washed at least 5 times with anhydrous DMF to remove residual acceptor molecules

Activationcoordinated water removed by heating at 180 C for 30 min in vacuum before immersion

Scalability contextPost-synthetic molecular loading over 7 days with reported guest concentration and wash solvent.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Cu3(BTC)2 thin film	active material mass loading about 1 mg cm^-2	Experimental Section, Device fabrication
Additive	PMDI	not reported as total mass used · 4 mg mL^-1	Experimental Section, Device fabrication
Solvent	anhydrous DMF	not reported	Experimental Section, Device fabrication
Solvent	anhydrous DMF	washed at least 5 times	Experimental Section, Device fabrication

Complete recipeSource: SI

Route 6: Other

Experimental Section, Assembling flexible micro-supercapacitors

Metal precursorsPMDI@Cu3(BTC)2 thin film positive-electrode thin film on Cu foil; activated-carbon negative electrode on Cu foil

Linker precursorsBTC framework in MOF positive electrode where applicable

SolventsDMF for activated-carbon/Super P/PVDF slurry; deionised water for PVA/LiCl gel electrolyte

Additivesactivated carbon, Super P conductive additive, PVDF binder, PVA/LiCl gel electrolyte

Atmospherenot specified

Temperature80 C overnight drying of negative electrode; 85 C heating to clear PVA/LiCl gel dispersion

Timenegative electrode dried overnight; gel heated until clear; assembly time not specified

Substrate orientationpositive and negative electrodes tailored into interdigitated patterns and assembled on PET substrate

Oxidant / reductantnot applicable to device assembly

Work-uppositive film cut into interdigitated pattern; AC slurry pasted on cleaned Cu foil, dried, tailored, assembled on PET and drop-cast with gel electrolyte

Activationnone reported beyond electrode drying and gel preparation

Scalability contextInterdigitated geometry specified: finger width 1.5 mm, length 16 mm, electrode area 1.2 cm^2, interspace 0.5 mm.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PMDI@Cu3(BTC)2 thin film	positive electrode cut to interdigitated pattern; one electrode area 1.2 cm^2	Experimental Section, Assembling flexible micro-supercapacitors
Other	activated carbon	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	Super P	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	PVDF	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Solvent	DMF	used for negative-electrode slurry	Experimental Section, Assembling flexible micro-supercapacitors
Electrolyte	PVA/LiCl gel electrolyte	PVA 5 g; LiCl 2.12 g; deionised water 50 mL	Experimental Section, Assembling flexible micro-supercapacitors

Complete recipeSource: Both

Route 7: Other

Experimental Section, Device fabrication

Metal precursorspreformed Cu3(BTC)2 thin film on Cu foil

Linker precursorsBTC framework retained; TCNQ electron acceptor introduced post-synthetically

Solventsanhydrous CH2Cl2 dispersion/solution for TCNQ loading

AdditivesTCNQ

Atmospherevacuum only specified for pre-immersion dehydration; immersion atmosphere not stated

Temperature180 C pre-immersion vacuum dehydration; immersion temperature not stated

Time0.5 h dehydration; 168 h immersion (7 days)

Substrate orientationCu3(BTC)2 thin film on Cu foil

Oxidant / reductantelectron acceptor doping; TCNQ accepts electrons from Cu3(BTC)2 according to CV energy-level analysis

Work-uprepeatedly washed at least 5 times with anhydrous CH2Cl2 to remove residual acceptor molecules

Activationcoordinated water removed by heating at 180 C for 30 min in vacuum before immersion

Scalability contextPost-synthetic molecular loading over 7 days with reported guest concentration and wash solvent.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	preformed Cu3(BTC)2 thin film	active material mass loading about 1 mg cm^-2	Experimental Section, Device fabrication
Additive	TCNQ	not reported as total mass used · 4 mg mL^-1	Experimental Section, Device fabrication
Solvent	anhydrous CH2Cl2	not reported	Experimental Section, Device fabrication
Solvent	anhydrous CH2Cl2	washed at least 5 times	Experimental Section, Device fabrication

Complete recipeSource: SI

Route 8: Other

Experimental Section, Assembling flexible micro-supercapacitors

Metal precursorsTCNQ@Cu3(BTC)2 thin film positive-electrode thin film on Cu foil; activated-carbon negative electrode on Cu foil

Linker precursorsBTC framework in MOF positive electrode where applicable

SolventsDMF for activated-carbon/Super P/PVDF slurry; deionised water for PVA/LiCl gel electrolyte

Additivesactivated carbon, Super P conductive additive, PVDF binder, PVA/LiCl gel electrolyte

Atmospherenot specified

Temperature80 C overnight drying of negative electrode; 85 C heating to clear PVA/LiCl gel dispersion

Timenegative electrode dried overnight; gel heated until clear; assembly time not specified

Substrate orientationpositive and negative electrodes tailored into interdigitated patterns and assembled on PET substrate

Oxidant / reductantnot applicable to device assembly

Work-uppositive film cut into interdigitated pattern; AC slurry pasted on cleaned Cu foil, dried, tailored, assembled on PET and drop-cast with gel electrolyte

Activationnone reported beyond electrode drying and gel preparation

Scalability contextInterdigitated geometry specified: finger width 1.5 mm, length 16 mm, electrode area 1.2 cm^2, interspace 0.5 mm.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TCNQ@Cu3(BTC)2 thin film	positive electrode cut to interdigitated pattern; one electrode area 1.2 cm^2	Experimental Section, Assembling flexible micro-supercapacitors
Other	activated carbon	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	Super P	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Additive	PVDF	AC:Super P:PVDF = 8:1:1 by mass	Experimental Section, Assembling flexible micro-supercapacitors
Solvent	DMF	used for negative-electrode slurry	Experimental Section, Assembling flexible micro-supercapacitors
Electrolyte	PVA/LiCl gel electrolyte	PVA 5 g; LiCl 2.12 g; deionised water 50 mL	Experimental Section, Assembling flexible micro-supercapacitors