Synthesis · A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Solvothermal

7 · Methods - Growth of NU-1000 thin films

Metal precursorszirconyl chloride octahydrate, 105 mg

Linker precursorsH4TBAPy, 0.5 mM pre-soak and 40 mg in growth solution

SolventsDMF

Additivesbenzoic acid, 2.7 g

Atmosphereair; sealed screw-thread vial in gravity convection oven

Temperature80 deg C preheat for 2 h; 90 deg C growth for 13 h

Time12 h H4TBAPy substrate soak; 2 h preheat; 13 h growth

Substrate orientationFTO conducting side facing down to the bottom of the vial

Work-upRemove backside precipitates and wash with DMF; HCl activation omitted.

ActivationNo HCl activation; benzoate-coordinated version retained.

Scalability contextSame thin-film growth as FTO_NU-1000, with acid activation omitted.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	105 mg	7 · Methods - Growth of NU-1000 thin films
Linker	H4TBAPy	40 mg plus 0.5 mM substrate pre-soak · 0.5 mM pre-soak	7 · Methods - Growth of NU-1000 thin films
Solvent	N,N-dimethylformamide (DMF)	8 ml	7 · Methods - Growth of NU-1000 thin films
Additive	benzoic acid	2.7 g	7 · Methods - Growth of NU-1000 thin films

Complete recipeSource: Both

Route 2: Electrochemical

9 · Supplementary Figure 11 · Supplementary Figure 11

Metal precursorsNiCl2, 10 mM

Solventswater

Additivesthiourea, 0.5 M sulfur source

Atmosphereaqueous three-electrode cell; atmosphere not specified

Temperatureroom temperature not explicitly stated

Time2 min deposition for EQCM comparison

Substrate orientationbenzoate-modified FTO_NU-1000 as working electrode

Oxidant / reductantelectrochemical reduction at -1.1 V vs Ag/AgCl

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	NiCl2	10 mM	9 · Supplementary Figure 11 · Supplementary Figure 11
Other	thiourea	0.5 M	9 · Supplementary Figure 11 · Supplementary Figure 11
Solvent	aqueous deposition bath	Not specified	9 · Supplementary Figure 11 · Supplementary Figure 11

Complete recipeSource: Main

Route 3: Solvothermal

7 · Methods - Growth of NU-1000 thin films

Metal precursorszirconyl chloride octahydrate, 105 mg

Linker precursorsH4TBAPy, 0.5 mM pre-soak and 40 mg in growth solution

SolventsDMF; acetone workup

Additivesbenzoic acid, 2.7 g; HCl/DMF activation solution

Atmosphereair; sealed screw-thread vial in gravity convection oven

Temperature80 deg C preheat for 2 h; 90 deg C growth for 13 h; 100 deg C activation for 4 days

Time12 h H4TBAPy substrate soak; 2 h preheat; 13 h growth; 96 h activation; 24 h acetone soak

Substrate orientationFTO conducting side facing down to the bottom of the vial

Work-upRemove backside precipitates, wash with DMF; after activation wash several times with acetone and soak in acetone for 1 day; dry in air.

ActivationBenzoate modulator removed by dilute HCl in DMF at 100 deg C for 4 days.

Scalability contextPrepared on 2.5 x 1.25 cm FTO substrates in 20 ml vials.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	zirconyl chloride octahydrate	105 mg	7 · Methods - Growth of NU-1000 thin films
Linker	H4TBAPy	40 mg plus 0.5 mM substrate pre-soak · 0.5 mM pre-soak	7 · Methods - Growth of NU-1000 thin films
Solvent	N,N-dimethylformamide (DMF)	8 ml growth solution; 13 ml and 49.95 ml activation dilutions	7 · Methods - Growth of NU-1000 thin films
Additive	benzoic acid	2.7 g	7 · Methods - Growth of NU-1000 thin films
Acid	hydrochloric acid aqueous solution	0.5 ml of 8 M HCl diluted; 0.05 ml stock used in 49.95 ml DMF · 8 M stock	7 · Methods - Growth of NU-1000 thin films
Solvent	acetone	several washes and 1 day soak	7 · Methods - Growth of NU-1000 thin films

Complete recipeSource: Both

Route 4: Electrochemical

7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1

Metal precursorsNiCl2, 10 mM

Solventswater

Additivesthiourea, 0.5 M sulfur source

Atmosphereaqueous three-electrode cell; atmosphere not specified

Temperatureroom temperature not explicitly stated

Timedeposition time not separately specified; same electrodeposition procedure as NU-1000_Ni-S

Substrate orientationbare FTO as working electrode

Oxidant / reductantelectrochemical reduction at -1.1 V vs Ag/AgCl

Scalability contextMOF-free control made in the same three-electrode electrodeposition bath.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	NiCl2	10 mM	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1
Other	thiourea	0.5 M	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1
Solvent	aqueous deposition bath	Not specified	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1

Complete recipeSource: Both

Route 5: Electrochemical

7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1

Metal precursorsNiCl2, 10 mM

Solventswater

Additivesthiourea, 0.5 M sulfur source

Atmosphereaqueous three-electrode cell; atmosphere not specified

Temperatureroom temperature not explicitly stated

Time2 min deposition for the main NU-1000_Ni-S samples

Substrate orientationFTO_NU-1000 as working electrode

Oxidant / reductantelectrochemical reduction at -1.1 V vs Ag/AgCl

Scalability contextElectrodeposition applied to supported MOF films/electrodes.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	NiCl2	10 mM	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1
Other	thiourea	0.5 M	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1
Solvent	aqueous deposition bath	Not specified	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1
Electrolyte	Ag/AgCl reference; FTO counter electrode	Not specified	7 · Methods - Electrodeposition of Ni-S · Supplementary Figure 1

Complete recipeSource: Main

Route 6: Other

7 · Methods - Proton conductivity measurements

Additivesconductive silver epoxy; tin-coated copper wires

AtmosphereH2O vapour at ambient temperature during measurement

Temperature60 deg C epoxy cure for 0.5 h

Time0.5 h epoxy cure

Work-upEach side of pellet coated with conductive silver epoxy and wired.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	conductive silver epoxy	Not specified	7 · Methods - Proton conductivity measurements
Other	tin-coated copper wires	Not specified	7 · Methods - Proton conductivity measurements