Synthesis · Development of a UiO-Type Thin Film Electrocatalysis Platform with Redox-Active Linkers

4 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Other

main p.8 · Experimental Section: dcphOH-NDI

Linker precursors4-amino-3-hydroxybenzoic acid; naphthalene-1,4,5,8-tetracarboxylic dianhydride

SolventsDMF; precipitation into ice-cooled water; washes with ethanol, water, ether

Additives1 M HCl added before precipitation

AtmosphereAr

Temperaturereflux; exact temperature not stated

Timeovernight

Work-upCool to room temperature; add 5 mL 1 M HCl; precipitate into 250 mL ice-cooled water; centrifuge; wash with ethanol, water, and ether, 25 mL each; dry under vacuum.

Scalability contextReported yield 1.15 g (71%).

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4-amino-3-hydroxybenzoic acid	1.01 g, 6.6 mmol	main p.8 · Experimental Section: dcphOH-NDI
Linker	naphthalene-1,4,5,8-tetracarboxylic dianhydride	0.804 g, 3 mmol	main p.8 · Experimental Section: dcphOH-NDI
Solvent	DMF	20 mL	main p.8 · Experimental Section: dcphOH-NDI
Acid	HCl	5 mL · 1 M	main p.8 · Experimental Section: dcphOH-NDI

Complete recipeSource: Main

Route 2: Other

main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis

Linker precursorsdcphOH-NDI

SolventsDMF

AtmosphereNot specified

Temperatureroom temperature implied

Timeovernight / 18 h

Substrate orientationFTO slides

Work-upFTO slides cut to 2 x 1 cm2 and cleaned by sequential sonication in Alconox, ethanol, and acetone before immersion in linker solution.

Scalability contextSingle-slide preparation used as seed/monolayer for film growth.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	dcphOH-NDI	1 mM	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis
Solvent	DMF	Not specified	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis
Other	FTO slide	2 x 1 cm2 · 7 ohm/sq substrate	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis

Complete recipeSource: Main

Route 3: Solvothermal

main p.8 · Zr(dcphOH-NDI) MOF Bulk Synthesis

Metal precursorsZrCl4

Linker precursorsdcphOH-NDI

SolventsDMF; solvent exchange to MeOH

Additivesglacial acetic acid modulator

AtmosphereNot specified for MOF synthesis

Temperature120

Time72

Work-upSonicate reagents for 10 min; heat in preheated oven; cool to room temperature; collect pale-yellow precipitate by centrifugation; wash three times with DMF; incubate in DMF 24 h; exchange solvent for MeOH by washing three times and incubating in MeOH.

ActivationDegas bulk microcrystalline powder under vacuum at 85 deg C for 12 h.

Scalability context20 mL scintillation vial scale.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	82 mg, 0.35 mmol	main p.8 · Zr(dcphOH-NDI) MOF Bulk Synthesis
Linker	dcphOH-NDI	177.3 mg, 0.35 mmol	main p.8 · Zr(dcphOH-NDI) MOF Bulk Synthesis
Additive	glacial acetic acid	0.602 mL, 10.5 mmol	main p.8 · Zr(dcphOH-NDI) MOF Bulk Synthesis
Solvent	DMF	4 mL	main p.8 · Zr(dcphOH-NDI) MOF Bulk Synthesis

Complete recipeSource: Main

Route 4: Solvothermal

main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis

Metal precursorsZrCl4

Linker precursorsdcphOH-NDI on SAM-modified FTO plus dcphOH-NDI in growth solution

SolventsDMF; washes with DMF and ethanol

Additivesglacial acetic acid modulator

AtmosphereNot specified

Temperature120

Time72

Substrate orientationSingle SAM-modified FTO slide inserted into 20 mL scintillation vial

Work-upSonicate growth solution 10 min; insert SAM-modified FTO; heat; cool to room temperature; wash films with DMF and ethanol; soak in DMF until further use.

ActivationNo separate activation reported for electrochemical thin films.

Scalability contextSingle FTO slide per 20 mL vial; film thickness ca. 1 um.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ZrCl4	23.3 mg, 0.10 mmol	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis
Linker	dcphOH-NDI	53.8 mg, 0.10 mmol	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis
Additive	glacial acetic acid	171 uL, 3 mmol	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis
Solvent	DMF	8 mL	main p.8 · Zr(dcphOH-NDI)@FTO MOF Thin Film Synthesis