Synthesis · Electrosynthesis of a Nickel-Based Conductive Metal-Organic Framework with Controlled Morphology for Enhanced Capacitance

5 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

S2-S3 · Preparation of Nickel Foam (NF) Electrodes

Metal precursorsNickel foam, >=99.8% Ni

Solventsacid etching solution; degassed water rinse

Additives5 mL glacial acetic acid, 3 mL concentrated nitric acid, 1 mL concentrated phosphoric acid, 1 mL concentrated sulfuric acid

Atmospheredegassed water rinse; used immediately

Temperatureroom temperature not explicitly stated

Time0.0167

Substrate orientationNF cut into 1.5 x 0.5 cm strips; 0.5 x 0.5 cm geometric area submerged for electrosynthesis.

Oxidant / reductantacid etching removes native metal oxide layer

Work-upRinsed with degassed water and used immediately.

Activationacid etch before electrochemistry/electrosynthesis

Scalability contextControl substrate preparation; insufficient etching can cause passivation and failure.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel foam	1.5 x 0.5 cm strips · >=99.8% Ni	S2-S3 · Preparation of Nickel Foam (NF) Electrodes
Acid	glacial acetic acid	5 mL	S2-S3 · Preparation of Nickel Foam (NF) Electrodes
Acid	concentrated nitric acid	3 mL · concentrated	S2-S3 · Preparation of Nickel Foam (NF) Electrodes
Acid	concentrated phosphoric acid	1 mL · concentrated	S2-S3 · Preparation of Nickel Foam (NF) Electrodes
Acid	concentrated sulfuric acid	1 mL · concentrated	S2-S3 · Preparation of Nickel Foam (NF) Electrodes

Complete recipeSource: SI

Route 2: Drop Cast

S3 · Bulk Ni-HHTP@NF Preparation

Metal precursorsBulk Ni-HHTP powder containing Ni nodes; pre-etched NF substrate.

Linker precursorsHHTP already incorporated in bulk Ni-HHTP powder.

Solvents75 uL ethanol

Additives0.4 mg Super P activated carbon; 6 uL of 5 wt% PTFE binder.

Atmospherenot reported

Temperature65

Time1

Substrate orientation20 uL ink injected into pre-etched NF electrode.

Oxidant / reductantnone reported

Work-upDried at 65 deg C for 1 h prior to use.

ActivationDrying at 65 deg C for 1 h.

Scalability contextComposite ink electrode prepared only as control; authors note binders/additives can obscure intrinsic MOF performance.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	bulk Ni-HHTP	0.8 mg	S3 · Bulk Ni-HHTP@NF Preparation
Additive	Super P activated carbon	0.4 mg	S3 · Bulk Ni-HHTP@NF Preparation
Additive	PTFE	6 uL · 5 wt%	S3 · Bulk Ni-HHTP@NF Preparation
Solvent	ethanol	75 uL	S3 · Bulk Ni-HHTP@NF Preparation
Other	ink aliquot	20 uL injected	S3 · Bulk Ni-HHTP@NF Preparation

Complete recipeSource: SI

Route 3: Solvothermal

S3 · Preparation of Bulk Ni-HHTP Powder

Metal precursorsNi(OAc)2 x 4 H2O, 10 mg

Linker precursorsHHTP, 7 mg

Solvents4 mL water

Additivesnone reported

Atmospherenot reported

Temperature85

Time12

Substrate orientation20 mL glass vial; no substrate.

Oxidant / reductantnone reported in bulk synthesis recipe

Work-upNavy-blue powder washed twice with water (10 mL) and twice with acetone (10 mL).

ActivationDried under vacuum at 60 deg C for 1 h.

Scalability contextPrepared as bulk powder control; no scale-up discussed.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2 x 4 H2O	10 mg	S3 · Preparation of Bulk Ni-HHTP Powder
Linker	HHTP	7 mg	S3 · Preparation of Bulk Ni-HHTP Powder
Solvent	water	4 mL	S3 · Preparation of Bulk Ni-HHTP Powder

Partial recipeSource: Both

Route 4: Electrochemical

51 · Results · Figure 2

Metal precursorsNickel foam working electrode/anode supplies Ni2+ by anodic dissolution.

Linker precursors5 mg reduced HHTP gives the disc morphology in 22 mL electrolyte; HHTP was reduced before use.

Solvents22 mL aqueous electrolyte; same electrosynthesis platform as flower route.

AdditivesKCl electrolyte and ammonium hydroxide base as in the optimised electrosynthesis; exact SI recipe is only fully written for the 3 mg flower condition.

AtmosphereElectrolyte nitrogen purge and HHTP nitrogen/glovebox handling as in SI general procedure.

Temperatureroom temperature not explicitly stated for electrosynthesis; electrodes dried at 65 deg C.

Time2

Substrate orientationThree-electrode cell with NF anode, Pt counter/cathode and Ag/AgCl reference; Figure 2 time-course marks +0.25 V.

Oxidant / reductantApplied potential +0.25 V vs Ag/AgCl in Figure 2; sodium hydrosulfite used to reduce HHTP before use.

Work-upSame electrode drying and detached-powder washing/drying methods as flower route when used for electrochemistry and characterisation.

ActivationDried at 65 deg C for 2 h for electrosynthesised electrodes; detached solid dried under vacuum at 60 deg C for 1 h.

Scalability contextDisc morphology is controlled by higher HHTP concentration; exceeding 5 mg HHTP causes adhesion loss rather than greater coverage.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel foam (NF) working electrode/anode	0.5 x 0.5 cm cross-section exposed in general procedure · >=99.8% Ni	51 · Results · Figure 2
Linker	HHTP	5 mg · in 22 mL electrolyte	51 · Results · Figure 2
Electrolyte	KCl aqueous electrolyte	22 mL in concentration screen · 1.17 mM in base electrosynthesis recipe	51 · Results · Figure 2
Base	ammonium hydroxide	7.25 equiv in base electrosynthesis recipe · 1 M in base electrosynthesis recipe	51 · Results · Figure 2
Reductant	sodium hydrosulfite for HHTP pre-reduction	7.68 g per 584 mg HHTP precursor batch	51 · Results · Figure 2

Complete recipeSource: Both

Route 5: Electrochemical

S3-S4 · Electrosynthesis of Ni-HHTP

Metal precursorsNickel foam working electrode/anode supplies Ni2+ by anodic dissolution; NF was >=99.8% Ni.

Linker precursors3 mg reduced HHTP; HHTP precursor was reduced from partially oxidised HHTP using sodium hydrosulfite before use.

Solvents22 mL deionized water electrolyte; HHTP pre-reduction used degassed 1:1 THF:water and ethyl acetate extraction.

Additives1.75 mg KCl; 86.2 uL (7.25 equiv) of 1 M ammonium hydroxide; NF acid etch used glacial acetic acid, concentrated nitric acid, concentrated phosphoric acid and concentrated sulfuric acid.

AtmosphereElectrolyte purged with nitrogen for 15 min; reduced HHTP stored in glovebox under nitrogen.

Temperatureroom temperature for electrosynthesis; electrodes dried at 65 deg C; detached solids dried at 60 deg C under vacuum where used for BET/XPS/EDS.

Time2

Substrate orientationThree-electrode cell: NF working electrode/anode clamped in PTFE holder with Pt contact, Pt counter electrode/cathode, Ag/AgCl reference; 0.5 x 0.5 cm NF cross-section exposed; gentle stirring at 60 RPM.

Oxidant / reductantApplied +0.25 V vs Ag/AgCl for anodic Ni dissolution; sodium hydrosulfite used to reduce HHTP precursor.

Work-upFor electrodes: dried 2 h at 65 deg C, rinsed with deionized water then acetonitrile. For detached powders: sonicated in water 3 min, centrifuged at 6000 RPM for 5 min, washed twice with water and twice with acetone, dried 1 h at 60 deg C under vacuum.

ActivationGentle drying at 65 deg C for 2 h before XRD or BET in the general procedure; vacuum drying at 60 deg C for 1 h after detachment.

Scalability contextMain text presents electrosynthesis as scalable and directly grown on targeted substrates, but no scale-up experiment is reported.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel foam (NF) working electrode/anode	1.5 x 0.5 cm strip; 0.5 x 0.5 cm exposed · >=99.8% Ni	S3-S4 · Electrosynthesis of Ni-HHTP
Linker	2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)	3 mg	S3-S4 · Electrosynthesis of Ni-HHTP
Electrolyte	KCl	1.75 mg in 22 mL water · 1.17 mM in main text	S3-S4 · Electrosynthesis of Ni-HHTP
Base	ammonium hydroxide	86.2 uL; 7.25 equiv · 1 M	S3-S4 · Electrosynthesis of Ni-HHTP
Acid	glacial acetic acid/nitric acid/phosphoric acid/sulfuric acid etch	5 mL / 3 mL / 1 mL / 1 mL for 60 s · concentrated nitric, phosphoric and sulfuric acids	S3-S4 · Electrosynthesis of Ni-HHTP
Reductant	sodium hydrosulfite for HHTP pre-reduction	7.68 g; 27 eq	S3-S4 · Electrosynthesis of Ni-HHTP
Solvent	degassed 1:1 THF:water for HHTP reduction	40 mL	S3-S4 · Electrosynthesis of Ni-HHTP
Solvent	ethyl acetate extraction solvent	2 x 80 mL	S3-S4 · Electrosynthesis of Ni-HHTP