Synthesis · Defect Engineering to Tailor Metal Vacancies in 2D Conductive Metal-Organic Frameworks: An Example in Electrochemical Sensing

10 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Liquid Liquid Interface

3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Metal precursorsAgNO3, analogous aqueous metal solution

Linker precursorsBHT in chlorobenzene, analogous to Cu-BHT route

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesHCl adjusted to pH 0

Atmosphereambient conditions

Temperatureambient

Time1

Substrate orientationLangmuir-Schaefer transfer if deposited on substrate

Work-upWashed with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextPrepared by similar process to Cu-BHT; exact Ag precursor concentration/volume not restated.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Metal Source	AgNO3	not restated; similar process	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Partial recipeSource: Both

Route 2: Liquid Liquid Interface

3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Metal precursorsAgNO3, analogous aqueous metal solution

Linker precursorsBHT in chlorobenzene, analogous to Cu-BHT route

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesHCl adjusted to pH 1

Atmosphereambient conditions

Temperatureambient

Time1

Substrate orientationLangmuir-Schaefer transfer if deposited on substrate

Work-upWashed with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextPrepared by similar process to Cu-BHT; exact Ag precursor concentration/volume not restated.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Metal Source	AgNO3	not restated; similar process	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Partial recipeSource: Both

Route 3: Liquid Liquid Interface

3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Metal precursorsAgNO3, analogous aqueous metal solution

Linker precursorsBHT in chlorobenzene, analogous to Cu-BHT route

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesHCl adjusted to pH 2

Atmosphereambient conditions

Temperatureambient

Time1

Substrate orientationLangmuir-Schaefer transfer if deposited on substrate

Work-upWashed with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextPrepared by similar process to Cu-BHT; exact Ag precursor concentration/volume not restated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	AgNO3	not restated; similar process	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5
Linker	benzenehexathiol (BHT)	not restated; similar process · 0.1 mM in analogous Cu-BHT route	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Complete recipeSource: Both

Route 4: Liquid Liquid Interface

2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1

Metal precursorsCu(NO3)2.3H2O, 5 mL aqueous solution, 0.3 mM

Linker precursorsBHT in chlorobenzene, 15 mL, 0.1 mM

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesHCl used to set aqueous pH 0

Atmosphereambient conditions

Temperatureambient

Time1

Substrate orientationupside-upward or downside-upward transfer by Langmuir-Schaefer method

Work-upFilm washed carefully with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextComplete large-area thin films obtained when pH <= 2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	5 mL aqueous solution · 0.3 mM	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Linker	benzenehexathiol (BHT)	15 mL chlorobenzene solution · 0.1 mM	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Acid	HCl	10 mL initially; adjusted with Cu solution introduction · pH 0 final aqueous phase	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1

Complete recipeSource: Both

Route 5: Liquid Liquid Interface

2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1

Metal precursorsCu(NO3)2.3H2O, 5 mL aqueous solution, 0.3 mM

Linker precursorsBHT in chlorobenzene, 15 mL, 0.1 mM

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesHCl used to set aqueous pH 1

Atmosphereambient conditions

Temperatureambient

Time1

Substrate orientationupside-upward or downside-upward transfer by Langmuir-Schaefer method

Work-upFilm washed carefully with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextComplete large-area thin films obtained when pH <= 2.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	5 mL aqueous solution · 0.3 mM	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Linker	benzenehexathiol (BHT)	15 mL chlorobenzene solution · 0.1 mM	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Acid	HCl	10 mL initially; adjusted with Cu solution introduction · pH 1 final aqueous phase	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1

Complete recipeSource: Both

Route 6: Liquid Liquid Interface

2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1

Metal precursorsCu(NO3)2.3H2O, 5 mL aqueous solution, 0.3 mM

Linker precursorsBHT in chlorobenzene, 15 mL, 0.1 mM

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesHCl used to set aqueous pH 2

Atmosphereambient conditions

Temperatureambient

Time1

Substrate orientationupside-upward or downside-upward transfer by Langmuir-Schaefer method

Work-upFilm washed carefully with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextComplete large-area thin films obtained when pH <= 2; size and shape controlled by reaction vessel.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	5 mL aqueous solution · 0.3 mM	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Linker	benzenehexathiol (BHT)	15 mL chlorobenzene solution · 0.1 mM	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Solvent	chlorobenzene / water	15 mL chlorobenzene plus aqueous phase	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1
Acid	HCl	10 mL initially; Cu solution introduced into HCl · pH 2 final aqueous phase	2-3 · 1.2 Synthesis of Metal-BHT Films · Figure S1

Complete recipeSource: Both

Route 7: Other

3-4 · 1.3 Design and Fabrication of the Screen-Printed Sensor · Figure S2

Metal precursorsCu-BHT pH 2 film from route_cu_bht_ph2; Ag/AgCl conductive ink; conductive carbon ink

Linker precursorsCu-BHT pH 2 film

SolventsAcetone, ethanol, ultrapure water cleaning; measurement solution droplets

AdditivesLOR3A and S1813 photoresist; oxygen plasma etching

Atmosphereambient fabrication; oxygen plasma etching step

Temperature70 for printed-layer curing

Time0.1667 per printing cure step

Substrate orientationCu-BHT transferred to cover screen-printed PET substrate by Langmuir-Schaefer method.

Oxidant / reductantoxygen plasma used for etching

Work-upPET cleaned ultrasonically with acetone, ethanol, and ultrapure water for 5 min; printed layers cured at 70 C for 10 min after each printing; excess Cu-BHT etched to leave circular Cu-BHT film on working electrode.

ActivationNone reported.

Scalability contextScreen-printing described as suitable for mass production; low price less than 3 USD per sensor.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	flexible PET substrate	sensor dimension 4 x 1.0 x 0.05 cm	3-4 · 1.3 Design and Fabrication of the Screen-Printed Sensor · Figure S2
Other	Ag/AgCl conductive ink	printed reference electrode and connecting pads	3-4 · 1.3 Design and Fabrication of the Screen-Printed Sensor · Figure S2
Other	conductive carbon ink	printed working and counter electrodes	3-4 · 1.3 Design and Fabrication of the Screen-Printed Sensor · Figure S2
Other	LOR3A and S1813 photoresist	coated onto working electrode before oxygen plasma etching	3-4 · 1.3 Design and Fabrication of the Screen-Printed Sensor · Figure S2

Partial recipeSource: Both

Route 8: Liquid Liquid Interface

3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Metal precursorsNi(NO3)2.6H2O, analogous aqueous metal solution

Linker precursorsBHT in chlorobenzene, analogous to Cu-BHT route

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesNaCl in aqueous phase, 0.05 mM; HCl adjusted to pH 0

Atmosphereambient conditions

Temperatureambient

Time3

Substrate orientationLangmuir-Schaefer transfer if deposited on substrate

Work-upWashed with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextPrepared by similar process to Cu-BHT; exact Ni precursor concentration/volume not restated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	not restated; similar process	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5
Additive	NaCl	added to aqueous solution phase · 0.05 mM	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Partial recipeSource: Both

Route 9: Liquid Liquid Interface

3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Metal precursorsNi(NO3)2.6H2O, analogous aqueous metal solution

Linker precursorsBHT in chlorobenzene, analogous to Cu-BHT route

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesNaCl in aqueous phase, 0.05 mM; HCl adjusted to pH 1

Atmosphereambient conditions

Temperatureambient

Time3

Substrate orientationLangmuir-Schaefer transfer if deposited on substrate

Work-upWashed with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextPrepared by similar process to Cu-BHT; exact Ni precursor concentration/volume not restated.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	not restated; similar process	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5
Additive	NaCl	added to aqueous solution phase · 0.05 mM	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Partial recipeSource: Both

Route 10: Liquid Liquid Interface

3 · 1.2 Synthesis of Metal-BHT Films · Figure S5

Metal precursorsNi(NO3)2.6H2O, analogous aqueous metal solution

Linker precursorsBHT in chlorobenzene, analogous to Cu-BHT route

Solventschlorobenzene (C6H5Cl), aqueous HCl/water phase

AdditivesNaCl in aqueous phase, 0.05 mM; HCl adjusted to pH 2

Atmosphereambient conditions

Temperatureambient

Time3

Substrate orientationLangmuir-Schaefer transfer if deposited on substrate

Work-upWashed with deionized water three times and dried under ambient conditions.

ActivationNone reported.

Scalability contextPrepared by similar process to Cu-BHT; exact Ni precursor concentration/volume not restated.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	not restated; similar process	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5
Linker	benzenehexathiol (BHT)	not restated; similar process · 0.1 mM in analogous Cu-BHT route	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5
Additive	NaCl	added to aqueous solution phase · 0.05 mM	3 · 1.2 Synthesis of Metal-BHT Films · Figure S5