Synthesis · Direct Electrodeposition of Electrically Conducting Ni3(HITP)2 MOF Nanostructures for Micro-Supercapacitor Integration

7 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Electrochemical

SI-3 · Experimental Procedures 1.3

Metal precursorsNi(OAc)2.4H2O, 0.014 mmol, 1.5 equiv. in 3 mL DMF

Linker precursorsHATP.6HCl, 0.0093 mmol, 1 equiv. in 1.5 mL deionised H2O

SolventsH2O-DMF-DMA: 1.5 mL H2O for linker, 3 mL DMF for Ni salt, 3 mL DMA, and 4 mL H2O for NaOAc solution

AdditivesNaOAc, 8.37 mmol, 900 equiv., 2 mol L-1 aqueous solution

Atmospheresolutions flushed with Ar; Ar flow passed continuously during electrodeposition

Temperatureroom temperature/not specified for electrodeposition

Timenot specified; potentiostatic or CV methods applied to optimisation endpoint

Substrate orientationelectrodes submerged in 3-neck flask closed by rubber septa; conducting substrate working electrode

Oxidant / reductantanodic electrochemical oxidation of HATP under Ar; O2 excluded from optimised electrodeposition bath

Work-upnot specified for aqueous route beyond electrodeposition

Activationnone reported

Scalability contextAqueous mixed-solvent bath gave crystalline films at optimised potential but organic pulsed route was selected for device integration.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP.6HCl	0.0093 mmol (1 equiv.)	SI-3 · Experimental Procedures 1.3
Metal Source	Ni(OAc)2.4H2O	0.014 mmol (1.5 equiv.)	SI-3 · Experimental Procedures 1.3
Base	NaOAc	8.37 mmol (900 equiv.) · 2 mol L-1 solution	SI-3 · Experimental Procedures 1.3
Solvent	deionized H2O	1.5 mL + 4 mL	SI-3 · Experimental Procedures 1.3
Solvent	dimethyl formamide (DMF)	3 mL	SI-3 · Experimental Procedures 1.3
Solvent	dimethyl acetamide (DMA)	3 mL	SI-3 · Experimental Procedures 1.3

Partial recipeSource: SI

Route 2: Other

SI-5 · Figure S1 · Figure S1

Metal precursorsNi(OAc)2.4H2O, 0.0197 mmol in SI air-reaction control

Linker precursorsHATP.6HCl, 0.0093 mmol, 1 equiv.

SolventsH2O-DMF-DMA (1.8:1:1 v/v)

AdditivesNaOAc, 8 mmol

Atmosphereambient air for reaction; argon control showed no reaction

Temperature65

Time2

Substrate orientationsolution reaction; no electrode substrate

Oxidant / reductantmolecular O2 from ambient air acts as oxidant

Work-upnot reported

Activationnot reported

Scalability contextControl experiment only; not the selected deposition route.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	HATP.6HCl	0.0093 mmol (1 equiv.)	SI-5 · Figure S1 · Figure S1
Metal Source	Ni(OAc)2.4H2O	0.0197 mmol	SI-5 · Figure S1 · Figure S1
Base	NaOAc	8 mmol	SI-5 · Figure S1 · Figure S1
Solvent	H2O-DMF-DMA	1.8:1:1 v/v	SI-5 · Figure S1 · Figure S1
Oxidant	O2 from ambient air	not quantified	SI-5 · Figure S1 · Figure S1

Complete recipeSource: Both

Route 3: Electrochemical

6 · Results and Discussion · Figure 5A

Metal precursorsNi(OAc)2.4H2O in MeOH-DMSO bath; Pt nanowire network substrate

Linker precursorsHATP.6HCl in MeOH-DMSO bath

SolventsMeOH-DMSO bath as in route_organic_meoh_dmso_pulsed_film

AdditivesNaOAc base as in route_organic_meoh_dmso_pulsed_film

AtmosphereAr-filled glovebox for organic electrodeposition route

Temperatureroom temperature/not specified

Timenot specified; pulsed deposition to applied charge density

Substrate orientationinterconnected Pt nanowire network working electrode

Oxidant / reductantanodic oxidation of HATP under pulsed potentiostatic conditions

Work-uprinsed with MeOH and dried as general route; TEM samples dispersed in ethanol for analysis

Activationnone reported

Scalability contextDemonstrates conformal MOF growth on 3D conductive nanowire scaffold.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	0.014 mmol in base organic bath	6 · Results and Discussion · Figure 5A
Linker	HATP.6HCl	0.0093 mmol in base organic bath	6 · Results and Discussion · Figure 5A
Base	NaOAc	3 mmol in base organic bath	6 · Results and Discussion · Figure 5A
Other	Pt nanowire network	substrate	6 · Results and Discussion · Figure 5A

Complete recipeSource: SI

Route 4: Electrochemical

SI-3 · Experimental Procedures 1.4

Metal precursorsCr/Pt current collector; Ni(OAc)2.4H2O for MOF deposition

Linker precursorsHATP.6HCl for MOF deposition

SolventsMeOH-DMSO electrolyte for MOF deposition

AdditivesNaOAc base; Kapton tape mask; O2 plasma resist removal

AtmosphereMOF electrodeposition follows Ar-filled MeOH-DMSO route; lithography atmosphere not specified

Temperaturenot specified

Timenot specified; charge-controlled MOF deposition

Substrate orientationSi wafer with 50 nm Al2O3 insulating layer; Cr/Pt (3-50 nm) patterned interdigitated electrodes by photolithography and ion-beam milling

Oxidant / reductantanodic electrochemical oxidation of HATP in exposed interdigitated region

Work-upresidual resist removed by O2 plasma; chips masked with Kapton tape; MOF deposited on exposed interdigitated region

Activationnone reported

Scalability contextDemonstrates selected-area integration onto microfabricated current collectors.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Si wafer with Al2O3	50 nm Al2O3	SI-3 · Experimental Procedures 1.4
Metal Source	Cr/Pt current collector	3-50 nm	SI-3 · Experimental Procedures 1.4
Additive	Kapton tape mask	expose interdigitated region	SI-3 · Experimental Procedures 1.4
Linker	HATP.6HCl	as organic bath	SI-3 · Experimental Procedures 1.4
Metal Source	Ni(OAc)2.4H2O	as organic bath	SI-3 · Experimental Procedures 1.4
Base	NaOAc	as organic bath	SI-3 · Experimental Procedures 1.4

Complete recipeSource: Both

Route 5: Electrochemical

6 · Results and Discussion · Figure 5B

Metal precursorsNi(OAc)2.4H2O in MeOH-DMSO bath

Linker precursorsHATP.6HCl in MeOH-DMSO bath

SolventsMeOH-DMSO bath; polycarbonate template later dissolved (solvent not specified here for this template in main text)

AdditivesNaOAc base

AtmosphereAr-filled glovebox for organic electrodeposition route

Temperatureroom temperature/not specified

Timenot specified; pulsed deposition to total charge

Substrate orientationinterconnected track-etched polycarbonate membrane template, pore diameter 230 nm

Oxidant / reductantanodic oxidation of HATP under pulsed potentiostatic conditions

Work-uptemplate dissolved to reveal nanotube scaffold; analysis after dissolution

Activationnone reported

Scalability contextTemplate route gives 3D nanotube network with 15 um scaffold height.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	0.014 mmol in base organic bath	6 · Results and Discussion · Figure 5B
Linker	HATP.6HCl	0.0093 mmol in base organic bath	6 · Results and Discussion · Figure 5B
Base	NaOAc	3 mmol in base organic bath	6 · Results and Discussion · Figure 5B
Other	track-etched polycarbonate template	230 nm pore diameter	6 · Results and Discussion · Figure 5B

Complete recipeSource: Both

Route 6: Electrochemical

SI-3 · Experimental Procedures 1.2

Metal precursorsNi(OAc)2.4H2O, 0.014 mmol, 1.5 equiv.

Linker precursorsHATP.6HCl, 0.0093 mmol, 1 equiv.

Solvents7.5 mL anhydrous methanol and 2.5 mL DMSO (MeOH-DMSO bath)

AdditivesNaOAc, 3 mmol, 322 equiv. vs HATP.6HCl

AtmosphereAr-filled glovebox, O2 and H2O below 1 ppm

Temperatureroom temperature/not specified

Timevariable; pulsed conditions often t_on = 1 min and t_off = 1 min; deposition to target charge density

Substrate orientationconducting substrate as working electrode in home-made 3-electrode cell; Pt wire counter electrode; Ag wire pseudo-reference

Oxidant / reductantcontrolled anodic electrochemical oxidation of HATP ligand; molecular O2 excluded

Work-upworking electrode rinsed with MeOH and dried

Activationnone reported

Scalability contextAuthors emphasise conformal deposition on versatile conducting substrates and micro/nanoarchitectures; exact scale-up not quantified.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-hexaiminotriphenylene hexahydrochloride (HATP.6HCl)	0.0093 mmol (1 equiv.)	SI-3 · Experimental Procedures 1.2
Metal Source	Ni(OAc)2.4H2O	0.014 mmol (1.5 equiv.)	SI-3 · Experimental Procedures 1.2
Base	NaOAc	3 mmol (322 equiv. with respect to HATP.6HCl)	SI-3 · Experimental Procedures 1.2
Solvent	anhydrous methanol (MeOH)	7.5 mL	SI-3 · Experimental Procedures 1.2
Solvent	dimethyl sulfoxide (DMSO)	2.5 mL	SI-3 · Experimental Procedures 1.2
Electrolyte	3-electrode electrochemical cell, Pt CE, Ag pseudo-RE	Not specified	SI-3 · Experimental Procedures 1.2

Complete recipeSource: SI

Route 7: Electrochemical

SI-4 · Experimental Procedures 1.6

Metal precursorsPt-DNS electrolyte for Pt deposition; Cr/Au layers on polycarbonate membrane

Linker precursorsnone for Pt template

SolventsPt-DNS electrolyte; dichloromethane for template dissolution

Additivessulphite-based Au electrolyte for Au reinforcement; Pt-DNS electrolyte pH about 1.5

Atmosphereambient air drying after template dissolution; deposition atmosphere not otherwise specified

Temperatureroom temperature/not specified

Timenot specified

Substrate orientationtrack-etched polycarbonate membranes with 80 nm pores interconnected at -25 and +25 degrees; circular entry 7 mm cell

Oxidant / reductantelectrodeposition at -0.7 V vs Ag/AgCl for Pt; Au reinforcement at -0.6 V vs Ag/AgCl

Work-uppolycarbonate membrane immersed in dichloromethane for a few minutes; Pt network dried under ambient air

Activationnone reported

Scalability contextTemplate fabrication creates 3D Pt nanowire network for subsequent MOF shell growth.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	track-etched polycarbonate membrane	80 nm diameter pores · volumetric porosity about 22%	SI-4 · Experimental Procedures 1.6
Metal Source	Pt-DNS electrolyte	not specified · pH about 1.5	SI-4 · Experimental Procedures 1.6
Metal Source	Cr adhesion layer	10 nm	SI-4 · Experimental Procedures 1.6
Metal Source	Au layer plus electroplated Au reinforcement	400 nm Au layer; 10 um thick Au layer · Gold-SF pH about 7.5	SI-4 · Experimental Procedures 1.6
Solvent	dichloromethane	few minutes immersion	SI-4 · Experimental Procedures 1.6