Synthesis · Operando Elucidation of Electrocatalytic and Redox Mechanisms on a 2D Metal Organic Framework Catalyst for Efficient Electrosynthesis of Hydrogen Peroxide in Neutral Media

7 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

S2 · Synthesis of Cu-HAB Powder

Metal precursorsCu(NO3)2.3H2O, 105 mg (0.43 mmol)

Linker precursorsHAB.3HCl, 50 mg (0.18 mmol) in 5 mL H2O

Solvents25 mL DMF, 20 mL water, plus 5 mL H2O linker solution

AdditivesAqueous NH4OH, 180 uL, 6 M (1.08 mmol, 6 equivalents to HAB)

Atmosphereopen air; stirred in air

Temperature75

Time2 h reaction after 15 min preheat

Oxidant / reductantAmbient O2 exposure; no separate oxidant added

Work-upFiltered; washed with water then acetone; dried under vacuum at 80 deg C for 2 h

ActivationVacuum drying at 80 deg C for 2 h

Scalability contextPrepared as direct analogue/comparison to Ni-HAB.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.3H2O	105 mg (0.43 mmol)	S2 · Synthesis of Cu-HAB Powder
Linker	HAB.3HCl	50 mg (0.18 mmol) · in 5 mL H2O	S2 · Synthesis of Cu-HAB Powder
Solvent	DMF	25 mL	S2 · Synthesis of Cu-HAB Powder
Solvent	water	20 mL + 5 mL	S2 · Synthesis of Cu-HAB Powder
Base	aqueous NH4OH	180 uL · 6 M	S2 · Synthesis of Cu-HAB Powder

Complete recipeSource: SI

Route 2: Drop Cast

S4 and S6 · Operando XAS Measurements; Bulk Electrolysis Experiments · Figure S28

Metal precursorspre-synthesised Ni-HAB powder

Linker precursorspre-synthesised Ni-HAB powder

Solventsethanol and Nafion solution (1:9 v:v) for XAS; ethanol or water and Nafion for bulk electrolysis

AdditivesNafion binder

AtmosphereO2 or Ar circulated during operando XAS; O2 purged/flowed during bulk electrolysis

Temperatureroom temperature / not specified

Substrate orientationplasma-treated carbon fibre paper working electrode

Oxidant / reductantelectrochemical potentials applied vs RHE during measurements

Work-upCatalyst suspension drop-cast onto CFP; electrode sealed with Kapton/acrylic faceplate for XAS or cut to about 1 cm2 for electrolysis

ActivationCFP plasma treated and heated at 700 deg C for 5 min before use; Nafion membrane cleaned before electrolysis

Scalability contextBulk electrolysis used about 1 cm2 active area in 5 mL H-cell.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-HAB catalyst suspension	400 uL for XAS; about 1 mg/cm2 loading for electrolysis · 10 ugcat/uL for XAS	S4 and S6 · Operando XAS Measurements; Bulk Electrolysis Experiments · Figure S28
Solvent	ethanol or water	Not specified	S4 and S6 · Operando XAS Measurements; Bulk Electrolysis Experiments · Figure S28
Additive	Nafion solution	1:9 v:v with ethanol/water	S4 and S6 · Operando XAS Measurements; Bulk Electrolysis Experiments · Figure S28
Other	carbon fibre paper	about 4 cm2 XAS piece; about 1 cm2 electrolysis piece	S4 and S6 · Operando XAS Measurements; Bulk Electrolysis Experiments · Figure S28

Complete recipeSource: SI

Route 3: Drop Cast

S5-S6 · EQCM Measurement · Figure S25

Metal precursorspre-synthesised Ni-HAB powder

Linker precursorspre-synthesised Ni-HAB powder

Solvents1:9 v:v Nafion solution with nanopure water

AdditivesNafion binder

AtmosphereAr-saturated or O2-saturated electrolyte during EQCM

Temperature25

Substrate orientation5 MHz chrome/gold QCM crystal

Oxidant / reductantelectrochemical cycling

Work-up137 uL of 1 mg/mL Ni-HAB suspension drop-cast to 100 ug/cm2 loading

ActivationEQCM calibrated by Ag plating/stripping

Scalability contextAnalytical EQCM electrode.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-HAB	137 uL suspension · 1 mg/mL	S5-S6 · EQCM Measurement · Figure S25
Additive	Nafion solution	1:9 v:v with water	S5-S6 · EQCM Measurement · Figure S25
Other	chrome/gold QCM crystal	1.37 cm2 active area · 5 MHz	S5-S6 · EQCM Measurement · Figure S25

Partial recipeSource: SI

Route 4: Other

S2-S3 · Synthesis of Ni-HAB Films · Figure S1

Metal precursorsNi(NO3)2.6H2O, 30 mg in 16 mL nanopure water

Linker precursorsHAB.3HCl, 10 mg in 16 mL nanopure water

Solventsnanopure water

AdditivesEDA, 10 uL added to nickel solution

AtmosphereSolutions degassed in nitrogen purge box, then removed under container-dependent oxygen exposure; direct air growth gives nanostructured morphology

Substrate orientationpetri dish/container; no substrate orientation reported

Oxidant / reductantOxygen diffusion varied by covered/sealed jar, perforated parafilm, or direct air exposure

Work-upnot specified

Activationnot specified

Scalability contextMorphology tunable by oxygen diffusion; direct air growth yielded typical nanostructured morphology used for measurement.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	30 mg · in 16 mL water	S2-S3 · Synthesis of Ni-HAB Films · Figure S1
Linker	HAB.3HCl	10 mg · in 16 mL water	S2-S3 · Synthesis of Ni-HAB Films · Figure S1
Additive	ethylenediamine (EDA)	10 uL	S2-S3 · Synthesis of Ni-HAB Films · Figure S1
Solvent	nanopure water	32 mL total · 18.2 Mohm cm	S2-S3 · Synthesis of Ni-HAB Films · Figure S1

Complete recipeSource: Both

Route 5: Solvothermal

S2 · Synthesis of Ni-HAB Powder

Metal precursorsNi(NO3)2.6H2O, 105 mg (0.36 mmol)

Linker precursorsHAB.3HCl, 50 mg (0.18 mmol) in 5 mL H2O; HAB linker itself prepared according to literature

Solvents25 mL DMF, 20 mL water, plus 5 mL H2O linker solution

AdditivesAqueous NH4OH, 180 uL, 6 M (1.08 mmol, 6 equivalents to HAB)

Atmosphereopen air; stirred in air

Temperature75

Time2 h reaction after 15 min preheat

Oxidant / reductantAmbient O2 participates in growth/oxidation of HAB; no separate oxidant added

Work-upFiltered; washed with water then acetone; dried under vacuum at 80 deg C for 2 h

ActivationVacuum drying at 80 deg C for 2 h; BET sample degassed separately at 100 deg C for 1.5 h

Scalability contextAir growth gives high-surface-area nanostructured powder suitable for electrocatalysis.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	105 mg (0.36 mmol)	S2 · Synthesis of Ni-HAB Powder
Linker	HAB.3HCl	50 mg (0.18 mmol) · in 5 mL H2O	S2 · Synthesis of Ni-HAB Powder
Solvent	dimethylformamide (DMF)	25 mL	S2 · Synthesis of Ni-HAB Powder
Solvent	water	20 mL + 5 mL	S2 · Synthesis of Ni-HAB Powder
Base	aqueous ammonium hydroxide (NH4OH)	180 uL · 6 M	S2 · Synthesis of Ni-HAB Powder

Complete recipeSource: SI

Route 6: Drop Cast

S3-S4 · Rotating Ring Disk Electrode Measurements

Metal precursorspre-synthesised Ni-HAB powder

Linker precursorspre-synthesised Ni-HAB powder

Solvents1:9 v:v Nafion solution in nanopure water

AdditivesNafion binder

Atmosphereelectrolyte bubbled with Ar or O2 depending on measurement

Temperatureroom temperature / not specified

Timesonication/shaking about 1 h before drop-casting

Substrate orientationRRDE disk

Work-up10 uL suspension dropped onto disk and spun at 700 rpm until dry film formed

ActivationRRDE ring conditioned by CV prior to selectivity measurements

Scalability contextSmall-area analytical electrode.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-HAB catalyst	approximately 3 ugcat/uL suspension; 10 uL used	S3-S4 · Rotating Ring Disk Electrode Measurements
Additive	Nafion solution	1 part in 1:9 v:v mixture · 5 wt.% stock	S3-S4 · Rotating Ring Disk Electrode Measurements
Solvent	nanopure water	9 parts in 1:9 v:v mixture	S3-S4 · Rotating Ring Disk Electrode Measurements

Complete recipeSource: SI

Route 7: Solvothermal

S2 · Synthesis of Ni-HITP Powder

Metal precursorsNi(NO3)2.6H2O, 105 mg (0.36 mmol)

Linker precursors2,3,6,7,10,11-hexaaminotriphenylene (HATP.6HCl), 95 mg (0.18 mmol) in 5 mL H2O

Solvents25 mL DMF, 20 mL water, plus 5 mL H2O linker solution

AdditivesAqueous NH4OH, 180 uL, 6 M (1.08 mmol, 6 equivalents to HATP)

Atmosphereopen air; stirred in air

Temperature75

Time2 h reaction after 15 min preheat

Oxidant / reductantAmbient O2 exposure; no separate oxidant added

Work-upFiltered; washed with water then acetone; dried under vacuum at 80 deg C for 2 h

ActivationVacuum drying at 80 deg C for 2 h

Scalability contextPrepared as Ni-N4 comparison material.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	105 mg (0.36 mmol)	S2 · Synthesis of Ni-HITP Powder
Linker	HATP.6HCl	95 mg (0.18 mmol) · in 5 mL H2O	S2 · Synthesis of Ni-HITP Powder
Solvent	DMF	25 mL	S2 · Synthesis of Ni-HITP Powder
Solvent	water	20 mL + 5 mL	S2 · Synthesis of Ni-HITP Powder
Base	aqueous NH4OH	180 uL · 6 M	S2 · Synthesis of Ni-HITP Powder