Synthesis · Metal-Organic Framework Glass Catalysts from Melting Glass-Forming Cobalt-Based Zeolitic Imidazolate Framework for Boosting Photoelectrochemical Water Oxidation

9 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

4 · Preparation of Co-agZIF-62/BiVO4 and Co-agZIF-62/NiO/BiVO4 array

Metal precursorsCo-ZIF-62/BiVO4 photoanode

Linker precursorsIm/bIm in Co-ZIF-62

Solventsmethanol spin-coating dispersion, 2 mg/mL before melt-quench

AtmosphereAr protection

Temperature400-450

Time0.0167

Substrate orientationBiVO4 photoanode

Work-upheated at 10 C min-1, held 1 min, cooled to room temperature naturally

Activationmelt quenching forms Co-agZIF-62 glass

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	Co-ZIF-62/BiVO4 photoanode	Not specified	4 · Preparation of Co-agZIF-62/BiVO4 and Co-agZIF-62/NiO/BiVO4 array

Complete recipeSource: SI

Route 2: Other

4 · Preparation of Co-agZIF-62/BiVO4 and Co-agZIF-62/NiO/BiVO4 array

Metal precursorsCo-ZIF-62/NiO/BiVO4 photoanode

Linker precursorsIm/bIm in Co-ZIF-62

Solventsmethanol spin-coating dispersion, 2 mg/mL before melt-quench

AtmosphereAr protection

Temperature400-450

Time0.0167

Substrate orientationNiO/BiVO4 photoanode

Work-upheated at 10 C min-1, held 1 min, cooled to room temperature naturally

Activationmelt quenching forms Co-agZIF-62 glass

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	Co-ZIF-62/NiO/BiVO4 photoanode	Not specified	4 · Preparation of Co-agZIF-62/BiVO4 and Co-agZIF-62/NiO/BiVO4 array

Partial recipeSource: SI

Route 3: Other

4 · Preparation of Fe2O3 and Co-agZIF-62/NiO/Fe2O3 photoanodes

Metal precursorsFe2O3 photoanode from previous reported method; NiO and Co-ZIF-62 procedure same as BiVO4 based photoanodes

Linker precursorsIm/bIm in Co-ZIF-62

Solventsmethanol dispersion for Co-ZIF-62; NiSO4 electrolyte for NiO

AdditivesNaOH for NiO electrolyte pH adjustment

AtmosphereN2 purge before electrodeposition; Ar protection during annealing/melt-quench

Temperature300 for NiO anneal; 400-450 for Co-ZIF-62 melt-quench

Time0.5 NiO anneal; 0.0167 melt-quench hold

Substrate orientationFe2O3 photoanode

Work-upsame procedure as BiVO4 based photoanodes

Activationmelt quenching forms Co-agZIF-62 glass

Partial recipeSource: SI

Route 4: Other

4 · Preparation of WO3 and Co-agZIF-62/NiO/WO3 photoanodes

Metal precursorsWO3 photoanode from previous reported method; NiO and Co-ZIF-62 procedure same as BiVO4 based photoanodes

Linker precursorsIm/bIm in Co-ZIF-62

Solventsmethanol dispersion for Co-ZIF-62; NiSO4 electrolyte for NiO

AdditivesNaOH for NiO electrolyte pH adjustment

AtmosphereN2 purge before electrodeposition; Ar protection during annealing/melt-quench

Temperature300 for NiO anneal; 400-450 for Co-ZIF-62 melt-quench

Time0.5 NiO anneal; 0.0167 melt-quench hold

Substrate orientationWO3 photoanode

Work-upsame procedure as BiVO4 based photoanodes

Activationmelt quenching forms Co-agZIF-62 glass

Partial recipeSource: SI

Route 5: Drop Cast

4 · Preparation of Co-agZIF-62/BiVO4 and Co-agZIF-62/NiO/BiVO4 array

Metal precursorsas-prepared Co-ZIF-62 sample

Linker precursorsIm/bIm in Co-ZIF-62

Solventsmethanol dispersion, 2 mg/mL

Substrate orientationBiVO4 photoanode surface

Work-upspin-coated onto BiVO4

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Solvent	methanol	2 mg/mL Co-ZIF-62 dispersion	4 · Preparation of Co-agZIF-62/BiVO4 and Co-agZIF-62/NiO/BiVO4 array

Complete recipeSource: SI

Route 6: Hydrothermal

4 · Hydrothermal synthesis of Co-ZIF-62

Metal precursorsCo(OAc)2.4H2O, 4.1 mmol

Linker precursorsimidazole, 11.6 mmol; benzimidazole, 1.66 mmol

SolventsDMF, 90 mL

Atmospheresealed autoclave

Temperature130

Time168

Work-uprinsed with deionized water and methanol three times

Activationdried in vacuum oven at 70 C for 24 h

Scalability contextComparison route only.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(OAc)2.4H2O	4.1 mmol	4 · Hydrothermal synthesis of Co-ZIF-62
Linker	imidazole	11.6 mmol	4 · Hydrothermal synthesis of Co-ZIF-62
Linker	benzimidazole	1.66 mmol	4 · Hydrothermal synthesis of Co-ZIF-62
Solvent	DMF	90 mL	4 · Hydrothermal synthesis of Co-ZIF-62

Complete recipeSource: SI

Route 7: Other

3 · Mechanochemical synthesis of Co-ZIF-62

Metal precursorsZnO and Co(OAc)2.4H2O; total metal oxide/acetate amount 3 mmol

Linker precursorsimidazole (5.25 mmol); benzimidazole (0.75 mmol)

SolventsN,N-dimethylformamide (DMF, 200 uL)

Additivesagate balls (25 g)

AtmosphereN2 atmosphere; sealed in glove box

Time4

Work-upwashed with deionized water and methanol

Activationdried in vacuum oven at 70 C for 24 h

Scalability contextMechanochemical planetary ball-mill route; percentages controlled by Co(OAc)2.4H2O proportion.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Imidazole (Im)	5.25 mmol	3 · Mechanochemical synthesis of Co-ZIF-62
Linker	benzimidazole (bIm)	0.75 mmol	3 · Mechanochemical synthesis of Co-ZIF-62
Solvent	N,N-dimethylformamide (DMF)	200 uL	3 · Mechanochemical synthesis of Co-ZIF-62
Metal Source	ZnO	part of total 3 mmol ZnO + Co(OAc)2.4H2O	3 · Mechanochemical synthesis of Co-ZIF-62
Metal Source	Co(OAc)2.4H2O	proportion varied; part of total 3 mmol ZnO + Co(OAc)2.4H2O	3 · Mechanochemical synthesis of Co-ZIF-62
Other	agate balls	25 g	3 · Mechanochemical synthesis of Co-ZIF-62

Partial recipeSource: Both

Route 8: Other

3 · Results and Discussion · Figure 1d,e

Metal precursors10% Co-ZIF-62 crystal

Linker precursorsIm and bIm retained from Co-ZIF-62

AtmosphereN2 for DSC characterisation; Ar protection for photoanode melt-quench recipe

Temperature400-450 for photoanode melt-quench; Co-ZIF-62 melting signal 369.3 C

Time0.0167 for photoanode hold; bulk powder hold time not separately specified

Work-upmelt-quenched/cooled to room temperature naturally for photoanode samples

Scalability contextMain text describes glass made by melting glass-forming Co-ZIF-62; SI gives detailed melt-quench conditions for supported photoanodes.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	10% Co-ZIF-62 crystal	Not specified	3 · Results and Discussion · Figure 1d,e

Partial recipeSource: SI

Route 9: Electrochemical

3 · Preparation of NiO/BiVO4 array

Metal precursorsNiSO4.6H2O electrolyte; BiVO4 electrode prepared by previous reported method

Solventsaqueous electrolyte

Additives2 M NaOH to adjust pH to 7

Atmospherecell purged with N2 for 30 min; annealing under Ar flow

Temperature300

Time0.5 annealing

Substrate orientationfabricated BiVO4 electrode as working electrode

Work-upelectrodeposition at 1.16 V vs SCE with continuous stirring, total charge 0.2-0.6 C/cm2

Activationannealed at 300 C for 30 min with 10 C min-1 heating rate under Ar flow

Scalability contextBiVO4 synthesis itself is cited to a previous report rather than reproduced.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	NiSO4.6H2O solution	0.025 M	3 · Preparation of NiO/BiVO4 array
Base	NaOH solution	2 M	3 · Preparation of NiO/BiVO4 array