Synthesis · Thousand-fold increase in O2electroreduction rates with conductive MOFs

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

SI p.S2 · Synthesis of the HITP MOFs

Metal precursorsCo(NO3)2.6H2O, 3 mL of 62.1 mM solution in DMF

Linker precursorsHATP.4HCl, 3 mL of 6.2 mM solution in DI water

SolventsDMF and DI water

AdditivesNaOAc, 4 mL of 2 M in DI water

Atmosphereair

Temperature65

Time2

Work-upWashed by centrifugation with methanol and DI water.

ActivationDried under vacuum; N2 adsorption samples activated at 100 C overnight.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	3 mL · 62.1 mM	SI p.S2 · Synthesis of the HITP MOFs
Linker	HATP.4HCl	3 mL · 6.2 mM	SI p.S2 · Synthesis of the HITP MOFs
Base	NaOAc	4 mL · 2 M	SI p.S2 · Synthesis of the HITP MOFs
Solvent	DMF	Not specified	SI p.S2 · Synthesis of the HITP MOFs
Solvent	DI water	Not specified	SI p.S2 · Synthesis of the HITP MOFs

Complete recipeSource: SI

Route 2: Solvothermal

SI p.S2 · Synthesis of the HITP MOFs

Metal precursorsCuSO4.5H2O, 3 mL of 9.3 mM solution in DMA

Linker precursorsHATP.4HCl, 3 mL of 6.2 mM solution in DI water

SolventsDMA and DI water

AdditivesNaOAc, 4 mL of 2 M in DI water

Atmosphereair

Temperature65

Time2

Work-upWashed by centrifugation with methanol and DI water.

ActivationDried under vacuum; N2 adsorption samples activated at 100 C overnight.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O	3 mL · 9.3 mM	SI p.S2 · Synthesis of the HITP MOFs
Linker	HATP.4HCl	3 mL · 6.2 mM	SI p.S2 · Synthesis of the HITP MOFs
Base	NaOAc	4 mL · 2 M	SI p.S2 · Synthesis of the HITP MOFs
Solvent	DMA	Not specified	SI p.S2 · Synthesis of the HITP MOFs
Solvent	DI water	Not specified	SI p.S2 · Synthesis of the HITP MOFs

Complete recipeSource: SI

Route 3: Drop Cast

SI pp.S3-S4 · Preparation of M3(HITP)2 GDEs · Figures S7-S8

SolventsIsopropanol

Additives5 v/v% Nafion 117 solution

Atmosphereambient laboratory atmosphere during casting; O2/N2 gases during electrochemistry

Temperature65

Time0.5

Substrate orientationAvCarb GDS2230 GDE placed on hotplate

Work-upCatalyst ink drop-cast one drop at a time to desired mass loading; solvent dried between drops; final drying at least 30 min.

Scalability contextA 1 cm^2 PET mask constrained the catalyst footprint to match the microfluidic cell body.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	M3(HITP)2 powder	2 mg · 1.35 mg mL^-1 dispersion	SI pp.S3-S4 · Preparation of M3(HITP)2 GDEs · Figures S7-S8
Solvent	isopropanol	Not specified	SI pp.S3-S4 · Preparation of M3(HITP)2 GDEs · Figures S7-S8
Additive	Nafion 117 solution	5 v/v%	SI pp.S3-S4 · Preparation of M3(HITP)2 GDEs · Figures S7-S8

Complete recipeSource: SI

Route 4: Drop Cast

SI p.S3 · Preparation of H-cell/RRDE measurements · Figure S5

SolventsIsopropanol

Additives5 v/v% Nafion 117 suspension

Atmosphereambient laboratory atmosphere during casting; O2 or N2 bubbled before electrochemistry

Temperature65

Time1

Substrate orientationPolished glassy-carbon disk electrode preheated on hotplate

Work-upDrop-cast 58.2 uL of suspension and dried at least 1 h.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni3(HITP)2 powder	58.2 uL suspension deposited · 1.35 mg mL^-1	SI p.S3 · Preparation of H-cell/RRDE measurements · Figure S5
Solvent	isopropanol	Not specified	SI p.S3 · Preparation of H-cell/RRDE measurements · Figure S5
Additive	Nafion 117	5 v/v%	SI p.S3 · Preparation of H-cell/RRDE measurements · Figure S5

Complete recipeSource: SI

Route 5: Drop Cast

SI p.S7 · Sample Preparation for SECCM · Figure S23

SolventsIsopropanol; deionized water for substrate cleaning

AdditivesSilver paint and epoxy for electrical connection after drop-casting

AtmosphereDried in nitrogen stream after substrate cleaning; SECCM performed in N2 or ambient air

Substrate orientationITO-coated coverslip, 8-12 ohm/sq resistivity

Work-upITO cleaned by sonication in isopropanol then deionized water, dried under N2; Ni3(HITP)2 dispersion drop-cast and allowed to dry; mounted on 3D-printed holder.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni3(HITP)2 dispersion	1 mL · ~0.5 mg mL^-1	SI p.S7 · Sample Preparation for SECCM · Figure S23
Solvent	isopropanol	Not specified	SI p.S7 · Sample Preparation for SECCM · Figure S23
Other	ITO-coated coverslip	8-12 ohm/sq	SI p.S7 · Sample Preparation for SECCM · Figure S23
Additive	conductive silver paint	Not specified	SI p.S7 · Sample Preparation for SECCM · Figure S23

Complete recipeSource: SI

Route 6: Solvothermal

SI p.S2 · Synthesis of the HITP MOFs

Metal precursorsNi(OAc)2.4H2O, 32.4 mL of 2.33 mM solution

Linker precursorsHATP.6HCl, 10 mL of 5.8 mM solution; HATP ligand synthesised and deprotected as described previously

Solvents1:1 DMF/DMA for Ni source; DI water for HATP.6HCl and NaOAc

AdditivesNaOAc, 10.8 mL of 3 M in DI water

Atmosphereair

Temperature65

Time2

Work-upWashed by centrifugation with methanol and DI water.

ActivationDried under vacuum; N2 adsorption samples activated at 373 K under dynamic vacuum / 100 C overnight.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	32.4 mL · 2.33 mM	SI p.S2 · Synthesis of the HITP MOFs
Linker	HATP.6HCl	10 mL · 5.8 mM	SI p.S2 · Synthesis of the HITP MOFs
Solvent	DMF/DMA	1:1	SI p.S2 · Synthesis of the HITP MOFs
Solvent	DI water	Not specified	SI p.S2 · Synthesis of the HITP MOFs
Base	NaOAc	10.8 mL · 3 M	SI p.S2 · Synthesis of the HITP MOFs

Complete recipeSource: SI

Route 7: Drop Cast

SI p.S4 · Preparation of M3(HITP)2 GDEs · Figures S32-S34

SolventsIsopropanol

AdditivesPTFE powder; 1 v/v% Nafion 117 solution

Atmosphereambient laboratory atmosphere during casting; O2/N2 gases during electrochemistry

Temperature65

Time0.5

Substrate orientationAvCarb GDS2230 GDE placed on hotplate

Work-upPrepare PTFE suspension by sonicating 30 mg PTFE in 3 mL isopropanol for 10 min; mix 3 mg Ni3(HITP)2 with 30 uL of 10 mg mL^-1 PTFE suspension; dilute to 1.35 mg mL^-1 Ni3(HITP)2; add 1 v/v% Nafion; sonicate 3 min; prepare GDE as above.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni3(HITP)2 powder	3 mg · final 1.35 mg mL^-1	SI p.S4 · Preparation of M3(HITP)2 GDEs · Figures S32-S34
Additive	PTFE powder	30 mg to prepare stock; 30 uL stock added · 10 mg mL^-1 stock; 10 wt% in electrode	SI p.S4 · Preparation of M3(HITP)2 GDEs · Figures S32-S34
Solvent	isopropanol	3 mL for PTFE stock plus dilution	SI p.S4 · Preparation of M3(HITP)2 GDEs · Figures S32-S34
Additive	Nafion 117 solution	1 v/v%	SI p.S4 · Preparation of M3(HITP)2 GDEs · Figures S32-S34