Synthesis · Synergistic effect of Co/Ni bimetallic metal–organic nanostructures for enhanced electrochemical energy storage

13 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Solvothermal

SI text p001 · Experimental Section - Synthesis of Co-MOF

Metal precursorsCoCl2.6H2O (0.36 g, 1.5 mmol)

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol by same-as-Ni-MOF method)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol by analogy to Ni-MOF

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol) by analogy to Ni-MOF

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upSame reaction conditions as Ni-MOF; detailed workup implied as filtration/washing/drying but not restated.

ActivationDried at 50 C for 12 h by same-as-Ni-MOF method; no additional activation reported.

Scalability context25 mL autoclave batch inferred from same-as-Ni-MOF procedure; no scale-up reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	0.36 g, 1.5 mmol	SI text p001 · Experimental Section - Synthesis of Co-MOF
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol by same-as-Ni-MOF method	SI text p001 · Experimental Section - Synthesis of Co-MOF
Base	aqueous NaOH	10.5 mL, 2.1 mmol by same-as-Ni-MOF method · 0.2 mol/L	SI text p001 · Experimental Section - Synthesis of Co-MOF

Complete recipeSource: SI

Route 2: Solvothermal

SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Metal precursorsCoCl2.6H2O and NiCl2.6H2O with nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:1

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol by analogy to Ni-MOF

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol) by analogy to Ni-MOF

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upSame as Ni-MOF: cool, filter, wash with water and ethanol, dry at 50 C for 12 h.

ActivationDried at 50 C for 12 h; no additional activation reported.

Scalability context25 mL autoclave batch inferred from same-as-Ni-MOF procedure; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:1	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Metal Source	NiCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:1	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol by same-as-Ni-MOF method	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Base	aqueous NaOH	10.5 mL, 2.1 mmol by same-as-Ni-MOF method · 0.2 mol/L	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Partial recipeSource: SI

Route 3: Other

SI text p.3-4 · Experimental Section - Electrochemical measurements

Solventsnot specified for slurry

Additivesacetylene black; polytetrafluoroethylene binder

Atmosphereambient/room temperature electrochemical preparation; atmosphere not specified

Substrate orientationnickel foam, approximately 1 cm2

Work-upMix active MOF, acetylene black and PTFE at 80:15:5; grind to slurry; coat on nickel foam; press to thin foil at 10 MPa.

ActivationNo activation reported before electrochemistry.

Scalability contextSmall-area nickel foam electrode, approximately 1 cm2; active-mass loading not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co/Ni-MOF-1:1 active MOF material	80 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	acetylene black	15 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	polytetrafluoroethylene	5 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements

Complete recipeSource: SI

Route 4: Solvothermal

SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Metal precursorsCoCl2.6H2O and NiCl2.6H2O with nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:2

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol by analogy to Ni-MOF

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol) by analogy to Ni-MOF

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upSame as Ni-MOF: cool, filter, wash with water and ethanol, dry at 50 C for 12 h.

ActivationDried at 50 C for 12 h; no additional activation reported.

Scalability context25 mL autoclave batch inferred from same-as-Ni-MOF procedure; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:2	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Metal Source	NiCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:2	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol by same-as-Ni-MOF method	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Base	aqueous NaOH	10.5 mL, 2.1 mmol by same-as-Ni-MOF method · 0.2 mol/L	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Partial recipeSource: SI

Route 5: Other

SI text p.3-4 · Experimental Section - Electrochemical measurements

Solventsnot specified for slurry

Additivesacetylene black; polytetrafluoroethylene binder

Atmosphereambient/room temperature electrochemical preparation; atmosphere not specified

Substrate orientationnickel foam, approximately 1 cm2

Work-upMix active MOF, acetylene black and PTFE at 80:15:5; grind to slurry; coat on nickel foam; press to thin foil at 10 MPa.

ActivationNo activation reported before electrochemistry.

Scalability contextSmall-area nickel foam electrode, approximately 1 cm2; active-mass loading not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co/Ni-MOF-1:2 active MOF material	80 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	acetylene black	15 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	polytetrafluoroethylene	5 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements

Partial recipeSource: SI

Route 6: Other

SI text p003 · Figure S25 / ASC device details · Figure S25

Solvents3.0 M KOH aqueous electrolyte

Additivesacetylene black; polytetrafluoroethylene binder; activated carbon negative electrode

Atmosphereroom temperature; atmosphere not specified

Substrate orientationnickel foam positive and negative electrodes

Work-upFabricate positive and negative electrodes from active material or activated carbon, acetylene black and PTFE at 80:15:5; coat on nickel foam; press at 10 MPa; assemble two-electrode cell with mass ratio positive:negative = 1:2.8.

ActivationNo activation reported.

Scalability contextLaboratory two-electrode full cell; electrode area approximately 1 cm2; total active mass not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co/Ni-MOF-2:1 positive active material	positive:negative active mass ratio 1:2.8	SI text p003 · Figure S25 / ASC device details · Figure S25
Other	activated carbon	positive:negative active mass ratio 1:2.8	SI text p003 · Figure S25 / ASC device details · Figure S25
Electrolyte	KOH aqueous solution	3.0 M	SI text p003 · Figure S25 / ASC device details · Figure S25

Partial recipeSource: SI

Route 7: Other

SI text p001 · Experimental Section - Electrochemical measurements

Solventsnot specified for slurry

Additivesacetylene black; polytetrafluoroethylene binder

Atmosphereambient/room temperature electrochemical preparation; atmosphere not specified

Substrate orientationnickel foam, approximately 1 cm2

Work-upMix active MOF, acetylene black and PTFE at 80:15:5; grind to slurry; coat on nickel foam; press to thin foil at 10 MPa.

ActivationNo activation reported before electrochemistry.

Scalability contextSmall-area nickel foam electrode, approximately 1 cm2; active-mass loading not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co/Ni-MOF-2:1 active MOF material	80 wt% of electrode mixture	SI text p001 · Experimental Section - Electrochemical measurements
Additive	acetylene black	15 wt% of electrode mixture	SI text p001 · Experimental Section - Electrochemical measurements
Additive	polytetrafluoroethylene	5 wt% of electrode mixture	SI text p001 · Experimental Section - Electrochemical measurements

Complete recipeSource: SI

Route 8: Solvothermal

SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Metal precursorsCoCl2.6H2O and NiCl2.6H2O with nCo + nNi = 1.5 mmol; nominal Co:Ni = 3:1

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol by analogy to Ni-MOF

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol) by analogy to Ni-MOF

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upSame as Ni-MOF: cool, filter, wash with water and ethanol, dry at 50 C for 12 h.

ActivationDried at 50 C for 12 h; no additional activation reported.

Scalability context25 mL autoclave batch inferred from same-as-Ni-MOF procedure; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 3:1	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Metal Source	NiCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 3:1	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol by same-as-Ni-MOF method	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Base	aqueous NaOH	10.5 mL, 2.1 mmol by same-as-Ni-MOF method · 0.2 mol/L	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Partial recipeSource: SI

Route 9: Other

SI text p.3-4 · Experimental Section - Electrochemical measurements

Solventsnot specified for slurry

Additivesacetylene black; polytetrafluoroethylene binder

Atmosphereambient/room temperature electrochemical preparation; atmosphere not specified

Substrate orientationnickel foam, approximately 1 cm2

Work-upMix active MOF, acetylene black and PTFE at 80:15:5; grind to slurry; coat on nickel foam; press to thin foil at 10 MPa.

ActivationNo activation reported before electrochemistry.

Scalability contextSmall-area nickel foam electrode, approximately 1 cm2; active-mass loading not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Co/Ni-MOF-3:1 active MOF material	80 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	acetylene black	15 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	polytetrafluoroethylene	5 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements

Complete recipeSource: SI

Route 10: Solvothermal

SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Metal precursorsCoCl2.6H2O and NiCl2.6H2O with nCo + nNi = 1.5 mmol; nominal Co:Ni = 5:1

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol by analogy to Ni-MOF

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol) by analogy to Ni-MOF

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upSame as Ni-MOF: cool, filter, wash with water and ethanol, dry at 50 C for 12 h.

ActivationDried at 50 C for 12 h; no additional activation reported.

Scalability context25 mL autoclave batch inferred from same-as-Ni-MOF procedure; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 5:1	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Metal Source	NiCl2.6H2O	part of total nCo + nNi = 1.5 mmol; nominal Co:Ni = 5:1	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol by same-as-Ni-MOF method	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Base	aqueous NaOH	10.5 mL, 2.1 mmol by same-as-Ni-MOF method · 0.2 mol/L	SI text p.3 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Complete recipeSource: SI

Route 11: Solvothermal

SI text p001 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Metal precursorsCoCl2.6H2O and NiCl2.6H2O with nCo + nNi = 1.5 mmol; nominal Co:Ni = 1:2, 1:1, 2:1, 3:1 or 5:1

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol by analogy to Ni-MOF

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol) by analogy to Ni-MOF

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upSame as Ni-MOF: cool, filter, wash with water and ethanol, dry at 50 C for 12 h.

ActivationDried at 50 C for 12 h; no additional activation reported.

Scalability context25 mL autoclave batch inferred from same-as-Ni-MOF procedure; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CoCl2.6H2O	part of total nCo + nNi = 1.5 mmol; Co:Ni = 1:2, 1:1, 2:1, 3:1 or 5:1	SI text p001 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Metal Source	NiCl2.6H2O	part of total nCo + nNi = 1.5 mmol; Co:Ni = 1:2, 1:1, 2:1, 3:1 or 5:1	SI text p001 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol by same-as-Ni-MOF method	SI text p001 · Experimental Section - Syntheses of Co/Ni-MOF-x:y
Base	aqueous NaOH	10.5 mL, 2.1 mmol by same-as-Ni-MOF method · 0.2 mol/L	SI text p001 · Experimental Section - Syntheses of Co/Ni-MOF-x:y

Complete recipeSource: SI

Route 12: Solvothermal

SI text p001 · Experimental Section - Synthesis of Ni-MOF

Metal precursorsNiCl2.6H2O (0.36 g, 1.5 mmol)

Linker precursorsH2tdc = 2,5-thiophenedicarboxylic acid (0.26 g, 1.5 mmol)

SolventsDI water supplied through aqueous NaOH solution; wash solvents water and ethanol

AdditivesNaOH aqueous solution (0.2 mol/L, 10.5 mL, 2.1 mmol)

Atmospherenot specified; sealed Teflon-lined stainless-steel autoclave

Temperature180

Time61

Work-upCool to room temperature; filter; wash with water and ethanol; dry at 50 C for 12 h.

ActivationDried at 50 C for 12 h; no additional activation reported.

Scalability context25 mL Teflon-lined autoclave batch; no scale-up reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	NiCl2.6H2O	0.36 g, 1.5 mmol	SI text p001 · Experimental Section - Synthesis of Ni-MOF
Linker	H2tdc (2,5-thiophenedicarboxylic acid)	0.26 g, 1.5 mmol	SI text p001 · Experimental Section - Synthesis of Ni-MOF
Base	aqueous NaOH	10.5 mL, 2.1 mmol · 0.2 mol/L	SI text p001 · Experimental Section - Synthesis of Ni-MOF
Solvent	de-ionized water	not separately reported · 18 Mohm cm resistance	SI text p001 · Experimental Section - Synthesis of Ni-MOF

Partial recipeSource: SI

Route 13: Other

SI text p.3-4 · Experimental Section - Electrochemical measurements

Solventsnot specified for slurry

Additivesacetylene black; polytetrafluoroethylene binder

Atmosphereambient/room temperature electrochemical preparation; atmosphere not specified

Substrate orientationnickel foam, approximately 1 cm2

Work-upMix active MOF, acetylene black and PTFE at 80:15:5; grind to slurry; coat on nickel foam; press to thin foil at 10 MPa.

ActivationNo activation reported before electrochemistry.

Scalability contextSmall-area nickel foam electrode, approximately 1 cm2; active-mass loading not reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-MOF active MOF material	80 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	acetylene black	15 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements
Additive	polytetrafluoroethylene	5 wt% of electrode mixture	SI text p.3-4 · Experimental Section - Electrochemical measurements