Synthesis · Nanostructured zinc-doped nickel/iron metal–organic framework electrode material for an efficient energy storage

7 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Other

SI rendered p.3 · Table S1 electrode preparation details · Table S1

Metal precursorsZn-doped Ni/Fe-MOF positive electrode material

Linker precursorsBDC-derived positive electrode material; activated carbon negative electrode

Solvents2 M KOH electrolyte

AdditivesWhatman separator

AtmosphereAmbient/room temperature operation

Temperatureroom temperature

Substrate orientationTwo-electrode asymmetric device

Work-upCharge-balanced assembly using m+/m- = 0.15; positive electrode 1.57 mg on 1.00 cm2, negative activated-carbon electrode 10.0 mg on 1.00 cm2; Whatman cellulose separator; 2 M KOH electrolyte; 0.0-1.8 V device window.

ActivationNo activation reported after ASC assembly; both electrodes were dried at 100 C for 10 h before use.

Scalability contextLaboratory ASC assembly; no device scaling described.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	KOH	2 M	SI rendered p.3 · Table S1 electrode preparation details · Table S1
Other	Zn-doped Ni/Fe-MOF positive electrode	1.57 mg active material; 1.00 cm2 · 90 wt% active / 10 wt% PVDF	SI rendered p.3 · Table S1 electrode preparation details · Table S1
Other	activated carbon negative electrode	10.0 mg active material; 1.00 cm2 · 90 wt% AC / 10 wt% PVDF	SI rendered p.3 · Table S1 electrode preparation details · Table S1
Other	Whatman cellulose separator	Not specified	SI rendered p.3 · Table S1 electrode preparation details · Table S1

Partial recipeSource: SI

Route 2: Other

SI rendered p.3 · Table S1 electrode preparation details · Table S1

Metal precursorsPrepared Zn-doped Ni/Fe-MOF-derived active material

Linker precursorsBDC-derived active material after MOF synthesis/post-treatment

SolventsNot specified for electrode slurry/dispersion

AdditivesPVDF binder

AtmosphereAir/oven drying; atmosphere not otherwise specified

Temperature100 drying

Time10 drying

Substrate orientationASC positive electrode area 1.00 cm2; current collector not specified

Work-upElectrode contained 1.57 mg active material at 1.57 mg cm-2; composition 90 wt% active / 10 wt% PVDF; dried at 100 C in an oven for 10 h.

ActivationNo separate activation after electrode drying reported.

Scalability contextLaboratory ASC electrode preparation; no scale-up data reported.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Zn-doped Ni/Fe-MOF active material	1.57 mg · 90 wt% of electrode composition	SI rendered p.3 · Table S1 electrode preparation details · Table S1
Additive	PVDF	10 wt% of electrode composition	SI rendered p.3 · Table S1 electrode preparation details · Table S1

Partial recipeSource: Main

Route 3: Solvothermal

main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF

Metal precursors382 mg FeCl3.6H2O

Linker precursors0.5 M BDC in DMF

Solvents50 mL DMF

AdditivesNone reported

AtmosphereNot specified

Temperature120

Timeovernight

Work-upCooling; red product collected; washed repeatedly; centrifuged at 3000 rpm; dried at 90 C for 4 h.

ActivationNone reported

Scalability contextBatch solvothermal autoclave method; no scale-up data reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	FeCl3.6H2O	382 mg	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF
Linker	BDC	0.5 M	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF
Solvent	DMF	50 mL	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF

Partial recipeSource: Main

Route 4: Solvothermal

main p.4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF

Metal precursors288 mg Ni(NO3)2.6H2O and 115 mg FeCl3.6H2O inferred from 'same procedure'; ZnCl2 omitted

Linker precursors498 mg terephthalic acid / BDC inferred from same procedure

Solvents60 mL DMF inferred from same procedure

AdditivesNaOH to pH 6 inferred from same procedure

AtmosphereIf post-treatment included, nitrogen; exact control post-treatment ambiguous

Temperature150 solvothermal; possible 600 pyrolysis if same procedure includes post-treatment

Time5 solvothermal; possible 3 pyrolysis

Work-upSame as Zn-doped route but without ZnCl2; exact text does not repeat workup.

ActivationAmbiguous whether the 600 C N2 carbonisation was also applied to the control.

Scalability contextBatch control synthesis; no scale-up data reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	terephthalic acid (inferred from same procedure)	498 mg inferred	main p.4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF
Metal Source	Ni(NO3)2.6H2O	288 mg inferred	main p.4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF
Metal Source	FeCl3.6H2O	115 mg inferred	main p.4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF
Solvent	DMF	60 mL inferred	main p.4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF
Base	NaOH	pH adjusted to 6 inferred	main p.4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF

Partial recipeSource: Main

Route 5: Solvothermal

main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF

Metal precursors960 mg Ni(NO3)2.6H2O

Linker precursors1660 mg terephthalic acid (BDC)

Solvents140 mL DMF

AdditivesNaOH solution to adjust pH to 6

AtmosphereNot specified

Temperature150

Timenot reported

Work-upNatural cooling; solid precipitate separated; repeatedly washed with DMF; dried at 60 C for 3 h.

ActivationNone reported

Scalability contextBatch solvothermal autoclave method; no scale-up data reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	960 mg	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF
Linker	terephthalic acid (1,4-benzenedicarboxylic acid, BDC)	1660 mg	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF
Solvent	dimethylformamide (DMF)	140 mL	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF
Base	NaOH solution	pH adjusted to 6	main p.3 · 2.1.2 Synthesis of Ni-MOF and Fe-MOF

Partial recipeSource: Both

Route 6: Drop Cast

SI rendered p.3 · Table S1 electrode preparation details · Table S1

Metal precursorsPrepared MOF/MOF-derived sample dispersion

Linker precursorsNot applicable to electrode fabrication

SolventsDispersion solvent not specified

AdditivesPVDF binder; SI Table S1 composition 90 wt% active / 10 wt% PVDF

AtmosphereDrying in oven/vacuum oven at 50 C

Temperature50 drying

Time3 drying

Substrate orientationGlassy carbon working electrode, 3 mm diameter

Work-upPrepared sample dispersion drop-cast onto 3 mm glassy carbon surface; active material mass 0.50 +/- 0.02 mg; loading 0.14 mg cm-2; dried at 50 C for 3 h.

ActivationNo separate activation reported for electrode after drying.

Scalability contextAnalytical three-electrode preparation only.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	prepared active-material sample dispersion	0.50 +/- 0.02 mg active material	SI rendered p.3 · Table S1 electrode preparation details · Table S1
Other	glassy carbon electrode	3 mm diameter; 0.07065 cm2	SI rendered p.3 · Table S1 electrode preparation details · Table S1
Additive	PVDF	10 wt% of electrode composition	SI rendered p.3 · Table S1 electrode preparation details · Table S1

Complete recipeSource: Main

Route 7: Solvothermal

main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1

Metal precursors288 mg Ni(NO3)2.6H2O; 115 mg FeCl3.6H2O; 40 mg ZnCl2

Linker precursors498 mg terephthalic acid / BDC

Solvents60 mL DMF

AdditivesNaOH to pH 6

AtmosphereNitrogen during 600 C post-treatment

Temperature150 solvothermal; 600 pyrolysis

Time5 solvothermal; 3 pyrolysis

Work-upNatural cooling; precipitate collected; rinsed with DMF; dried at 60 C for 3 h; 500 mg powder pyrolysed in tubular furnace.

ActivationHeated to 600 C under N2 at 5 C min-1, held 3 h.

Scalability contextBatch autoclave plus furnace pyrolysis; no scale-up data reported.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	terephthalic acid (1,4-benzenedicarboxylic acid)	498 mg	main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1
Metal Source	Ni(NO3)2.6H2O	288 mg	main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1
Metal Source	FeCl3.6H2O	115 mg	main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1
Metal Source	ZnCl2	40 mg	main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1
Solvent	DMF	60 mL	main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1
Base	NaOH	pH adjusted to 6	main p.3-4 · 2.1.3 Synthesis of Ni/Fe-MOF and Zn-doped Ni/Fe-MOF · Fig. 1