Synthesis evidence

Enhancing Proton Conductivity and Dimensional Stability of Nanofiber Proton Exchange Membranes through In Situ Growth of MOF-Modified PVDF Nanofibers

Sun J., Han D., Dong R. et al. · Energy and Fuels · 2024 · 7322-7330

8 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Drop Cast

p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Solvents1 mL N,N-dimethylacetamide added to 16 mL of 5% Nafion aqueous-alcohol solution

AdditivesNafion casting solution; 0.5 mol/L H2SO4 activation solution

Atmosphereambient drying; heat treatment atmosphere not specified

Temperatureroom temperature drying; 90; 100 hot-press; 130 heat treatment

Time12 h room temperature; 5 h at 90 C; 5 min hot-press; 3 h at 130 C; 12 h H2SO4 activation

Substrate orientationpolytetrafluoroethylene mould on level heating platform; nanofiber membrane placed into Nafion casting solution

Work-upwashed with deionised water to neutral pH after acid activation

Activationfully activated in 0.5 mol/L H2SO4 for 12 h, then washed with deionised water to neutral pH

Scalability contextSolution casting/hot pressing membrane fabrication with nanofibers controlled to 5 wt%; no scale-up discussed.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PVDF/UiO-66-NH2 NFM	nanofibers controlled to 5 wt % · 5 wt % nanofiber proportion	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Solvent	N,N-dimethylacetamide	1 mL	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Other	5% Nafion aqueous-alcohol solution	16 mL · 5%	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Acid	H2SO4	0.5 mol/L	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Complete recipeSource: Main

Route 2: Drop Cast

p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Solvents1 mL N,N-dimethylacetamide added to 16 mL of 5% Nafion aqueous-alcohol solution

AdditivesNafion casting solution; 0.5 mol/L H2SO4 activation solution

Atmosphereambient drying; heat treatment atmosphere not specified

Temperatureroom temperature drying; 90; 100 hot-press; 130 heat treatment

Time12 h room temperature; 5 h at 90 C; 5 min hot-press; 3 h at 130 C; 12 h H2SO4 activation

Substrate orientationpolytetrafluoroethylene mould on level heating platform; nanofiber membrane placed into Nafion casting solution

Work-upwashed with deionised water to neutral pH after acid activation

Activationfully activated in 0.5 mol/L H2SO4 for 12 h, then washed with deionised water to neutral pH

Scalability contextSolution casting/hot pressing membrane fabrication with nanofibers controlled to 5 wt%; no scale-up discussed.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	ammoniated PVDF NFM	nanofibers controlled to 5 wt % · 5 wt % nanofiber proportion	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Solvent	N,N-dimethylacetamide	1 mL	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Other	5% Nafion aqueous-alcohol solution	16 mL · 5%	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Acid	H2SO4	0.5 mol/L	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Partial recipeSource: Main

Route 3: Other

p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs

Solventsethylenediamine solution; solvent not further specified

Additivesethylenediamine

Atmospherereaction vessel; atmosphere not specified

Temperature150

Time20

Substrate orientationPVDF NFM wrapped with filter paper before immersion

Work-upreaction vessel cooled to room temperature; NFMs taken out and dried at room temperature

Scalability contextBatch immersion cross-linking route; no scale-up discussed.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PVDF NFM	Not specified	p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs
Additive	ethylenediamine	25% volume fraction · 25 vol%	p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs

Complete recipeSource: Main

Route 4: Drop Cast

p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Solvents1 mL N,N-dimethylacetamide added to 16 mL of 5% Nafion aqueous-alcohol solution

AdditivesNafion casting solution; 0.5 mol/L H2SO4 activation solution

Atmosphereambient drying; heat treatment atmosphere not specified

Temperatureroom temperature drying; 90; 100 hot-press; 130 heat treatment

Time12 h room temperature; 5 h at 90 C; 5 min hot-press; 3 h at 130 C; 12 h H2SO4 activation

Substrate orientationpolytetrafluoroethylene mould on level heating platform; nanofiber membrane placed into Nafion casting solution

Work-upwashed with deionised water to neutral pH after acid activation

Activationfully activated in 0.5 mol/L H2SO4 for 12 h, then washed with deionised water to neutral pH

Scalability contextSolution casting/hot pressing membrane fabrication with nanofibers controlled to 5 wt%; no scale-up discussed.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PVDF/UiO-66-NH2-SO3H NFM	nanofibers controlled to 5 wt % · 5 wt % nanofiber proportion	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Solvent	N,N-dimethylacetamide	1 mL	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Other	5% Nafion aqueous-alcohol solution	16 mL · 5%	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Acid	H2SO4	0.5 mol/L	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Complete recipeSource: Main

Route 5: Drop Cast

p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Solvents1 mL N,N-dimethylacetamide added to 16 mL of 5% Nafion aqueous-alcohol solution

AdditivesNafion casting solution; 0.5 mol/L H2SO4 activation solution

Atmosphereambient drying; heat treatment atmosphere not specified

Temperatureroom temperature drying; 90; 100 hot-press; 130 heat treatment

Time12 h room temperature; 5 h at 90 C; 5 min hot-press; 3 h at 130 C; 12 h H2SO4 activation

Substrate orientationpolytetrafluoroethylene mould on level heating platform; nanofiber membrane placed into Nafion casting solution

Work-upwashed with deionised water to neutral pH after acid activation

Activationfully activated in 0.5 mol/L H2SO4 for 12 h, then washed with deionised water to neutral pH

Scalability contextSolution casting/hot pressing membrane fabrication with nanofibers controlled to 5 wt%; no scale-up discussed.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PVDF NFM	nanofibers controlled to 5 wt % · 5 wt % nanofiber proportion	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Solvent	N,N-dimethylacetamide	1 mL	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Other	5% Nafion aqueous-alcohol solution	16 mL · 5%	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1
Acid	H2SO4	0.5 mol/L	p003 / journal page 7324 · 2.2.3 Preparation of PVDF/UiO@Nafion NFPEMs · Figure 1

Complete recipeSource: Main

Route 6: Other

p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs

SolventsDMF/acetone

Atmosphererelative humidity 30-40%

Temperature60 C drying

Time12 h drying

Substrate orientationcollector distance 18 cm; 21# stainless steel needle

Work-upNFMs dried at 60 C for 12 h

Scalability contextElectrospinning feed rate reported as 0.8 mL/h; nanofiber preparation appears scalable by electrospinning but no scale-up is tested.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	PVDF	12 wt % · 12 wt % in DMF/acetone	p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs
Solvent	DMF	DMF/acetone mixture	p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs
Solvent	acetone	DMF/acetone mixture	p003 / journal page 7324 · 2.2.1 Preparation of Ammoniated PVDF NFMs

Complete recipeSource: Main

Route 7: Solvothermal

p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs

Metal precursorsZrCl4, 0.14 g

Linker precursorsBDC-NH2, 0.11 g

SolventsDMF, 10 mL for each separately dissolved precursor before mixing

Additivesacetic acid, 0.3 mL

Atmospheresealed reaction; atmosphere not specified

Temperature120

Time24

Substrate orientationaminated PVDF NFMs immersed in precursor solution

Work-upcool to room temperature; wash three times with DMF and ethanol; dry at 60 C for 12 h

Activationstored for later use; final membrane acid activation occurs after Nafion casting

Scalability contextIn situ growth on nanofiber membrane at 120 C/24 h; no batch size beyond reagent amounts reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	0.14 g	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Linker	BDC-NH2	0.11 g	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Solvent	DMF	10 mL	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Acid	acetic acid	0.3 mL	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Other	aminated PVDF NFMs	Not specified	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs

Complete recipeSource: Main

Route 8: Solvothermal

p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs

Metal precursorsZrCl4, 0.14 g

Linker precursorsBDC-NH2, 0.054 g; BDC-SO3H, 0.08 g

SolventsDMF, 10 mL for precursor solution

Additivesacetic acid, 0.3 mL

Atmospheresealed reaction; atmosphere not specified

Temperature120

Time24

Substrate orientationaminated PVDF NFMs immersed in mixed-linker precursor solution

Work-upcool to room temperature; wash three times with DMF and ethanol; dry at 60 C for 12 h

Activationstored for later use; final membrane acid activation occurs after Nafion casting

Scalability contextIn situ mixed-linker growth route; lower loading/yield is discussed qualitatively.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	0.14 g	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Linker	BDC-NH2	0.054 g	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Linker	BDC-SO3H	0.08 g	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Solvent	DMF	10 mL	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Acid	acetic acid	0.3 mL	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs
Other	aminated PVDF NFMs	Not specified	p003 / journal page 7324 · 2.2.2 Preparation of PVDF/UiO NFMs