Synthesis · Activating a Metallization Switch for Record Hydrogen Evolution in Single-Atom Modified Polar MOF Piezocatalysts

3 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

SI text lines 17-18 · Synthesis of Ni SAs@UiO-66-NH2(Hf)

Metal precursorsNi(NO3)2.6H2O (0.01 g)

Linker precursorsPreformed UiO-66-NH2(Hf) (0.20 g)

Solventsdeionized water (75 mL) and ethanol (25 mL)

Atmospherenot specified

Time1 h stirring plus 1 h irradiation

Oxidant / reductantPhotoinduction with 300 W Xe arc lamp, cutoff filter lambda > 400 nm, ca. 15 cm above suspension

Work-upRecover by filtration; thoroughly wash; dry under vacuum oven at 60 deg C for 12 h.

ActivationUiO-66-NH2 thermally activated at 120 deg C for 12 h before Ni addition.

Scalability contextSuspension photoinduction batch route; main text describes Ni precursor introduction into evacuated pores followed by stabilisation through amino coordination.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	UiO-66-NH2	0.20 g	SI text lines 17-18 · Synthesis of Ni SAs@UiO-66-NH2(Hf)
Metal Source	Ni(NO3)2.6H2O	0.01 g	SI text lines 17-18 · Synthesis of Ni SAs@UiO-66-NH2(Hf)
Solvent	deionized water	75 mL	SI text lines 17-18 · Synthesis of Ni SAs@UiO-66-NH2(Hf)
Solvent	ethanol	25 mL	SI text lines 17-18 · Synthesis of Ni SAs@UiO-66-NH2(Hf)

Complete recipeSource: SI

Route 2: Solvothermal

SI text lines 11-12 · Synthesis of UiO-66(Hf)

Metal precursorsHfCl4 (0.137 g)

Linker precursorsH2BDC / benzene-1,4-dicarboxylic acid (0.071 g)

SolventsDMF, 25 mL total (10 mL for HfCl4 and 15 mL for H2BDC)

Additivesdeionized water, 30 uL

Atmospherenot specified

Temperature120

Time24

Work-upCool to room temperature; collect white precipitate by centrifugation; wash three times with fresh DMF and ethanol.

ActivationDried under vacuum oven at 60 deg C for 12 h.

Scalability contextBatch solvothermal synthesis in a 50 mL Teflon-lined stainless-steel autoclave.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.137 g	SI text lines 11-12 · Synthesis of UiO-66(Hf)
Linker	H2BDC	0.071 g	SI text lines 11-12 · Synthesis of UiO-66(Hf)
Solvent	DMF	25 mL total	SI text lines 11-12 · Synthesis of UiO-66(Hf)
Additive	deionized water	30 uL	SI text lines 11-12 · Synthesis of UiO-66(Hf)

Complete recipeSource: SI

Route 3: Solvothermal

SI text lines 14-15 · Synthesis of UiO-66-NH2(Hf)

Metal precursorsHfCl4 (0.137 g)

Linker precursorsH2N-H2BDC / 2-amino-1,4-benzenedicarboxylic acid (0.078 g)

SolventsDMF, 25 mL total

Additivesdeionized water, 70 uL

Atmospherenot specified

Temperature120

Time24

Work-upNaturally cool to room temperature; recover white precipitate by centrifugation; wash three times with fresh DMF and ethanol.

ActivationDried under vacuum oven at 60 deg C for 12 h.

Scalability contextBatch solvothermal synthesis in a 50 mL Teflon-lined stainless-steel autoclave.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	HfCl4	0.137 g	SI text lines 14-15 · Synthesis of UiO-66-NH2(Hf)
Linker	H2N-H2BDC	0.078 g	SI text lines 14-15 · Synthesis of UiO-66-NH2(Hf)
Solvent	DMF	25 mL total	SI text lines 14-15 · Synthesis of UiO-66-NH2(Hf)
Additive	deionized water	70 uL	SI text lines 14-15 · Synthesis of UiO-66-NH2(Hf)