Synthesis · Photocatalytic Hydrogen Peroxide Production through Functionalized Semiconductive Metal-Organic Frameworks

8 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Hydrothermal

SI p.S7 · Base stoichiometry effect · Figure S4

Metal precursorsCu(NO3)2.2.5H2O (26.6 mg)

Linker precursorsTHQ (15 mg) and DPT (21 mg)

Solvents15 mL H2O plus 15 mL DMF

AdditivesEthylenediamine varied from 4 equiv to 2, 1, 0.5, and 0.25 equiv corresponding to THQ

AtmosphereN2 atmosphere

Temperatureroom temperature

Time1

Work-upCentrifuged at 6000 rpm for seven minutes; washed with water twice, DMF twice, methanol twice, and acetone twice.

ActivationDried in vacuum oven at 60 C for 1 h.

Scalability context100 mL round-bottom flask optimisation screen.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Base	ethylenediamine	4, 2, 1, 0.5, or 0.25 equiv corresponding to THQ	SI p.S7 · Base stoichiometry effect · Figure S4

Complete recipeSource: Both

Route 2: Hydrothermal

main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF

Metal precursorsCu(NO3)2.2.5H2O (26.6 mg, 0.1145 mmol)

Linker precursorsTetrahydroxy-1,4-benzoquinone hydrate (THQ, 15 mg, 0.087 mmol); DPT (21 mg, 0.087 mmol)

Solvents15 mL H2O plus 15 mL DMF

AdditivesEthylenediamine, 0.5 equiv corresponding to THQ

AtmosphereInert atmosphere

Temperature50

Time1

Work-upCooled to room temperature; centrifuged; washed with H2O twice, DMF twice, methanol once, and acetone once.

ActivationDried in vacuum oven at 20 mTorr and 70 C for 1 h.

Scalability contextFlask-scale powder synthesis; 50 mL round-bottom flask in main final recipe.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	26.6 mg, 0.1145 mmol	main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF
Linker	tetrahydroxy-1,4-benzoquinone (THQ)	15 mg, 0.087 mmol	main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF
Linker	3,6-di(4-pyridyl)-1,2,4,5-tetrazine (DPT)	21 mg, 0.087 mmol	main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF
Base	ethylenediamine	0.5 equiv corresponding to THQ	main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF
Solvent	H2O	15 mL	main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF
Solvent	DMF	15 mL	main p.7, article p.11325 · Experimental Section - Synthesis of DPT-MOF

Complete recipeSource: SI

Route 3: Hydrothermal

SI p.S5 · Solvent composition effect · Figure S2

Metal precursorsCu(NO3)2.2.5H2O (26.6 mg)

Linker precursorsTHQ (15 mg) and DPT (21 mg)

Solvents15 mL H2O initially; 15 mL second solvent varied among H2O, DMF, DMSO, DMA

AdditivesEthylenediamine, 2 equiv to THQ

AtmosphereN2 atmosphere

Temperatureroom temperature

Time1

Work-upCentrifuged at 6000 rpm for seven minutes; washed with water twice, DMF twice, methanol twice, and acetone twice.

ActivationDried in vacuum oven at 60 C for 1 h.

Scalability context100 mL round-bottom flask optimisation screen.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	26.6 mg	SI p.S5 · Solvent composition effect · Figure S2
Base	ethylenediamine	2 equiv. to THQ	SI p.S5 · Solvent composition effect · Figure S2
Linker	tetrahydroxy-1,4-benzoquinone hydrate (THQ)	15 mg	SI p.S5 · Solvent composition effect · Figure S2
Linker	DPT	21 mg	SI p.S5 · Solvent composition effect · Figure S2

Complete recipeSource: SI

Route 4: Hydrothermal

SI p.S8 · Temperature effect · Figure S5

Metal precursorsCu(NO3)2.2.5H2O (26.6 mg)

Linker precursorsTHQ (15 mg) and DPT (21 mg)

Solvents15 mL H2O plus 15 mL DMF

AdditivesEthylenediamine, 0.5 equiv corresponding to THQ

AtmosphereN2 atmosphere

Temperature25, 50, or 75

Time1

Work-upCentrifuged at 6000 rpm for seven minutes; washed with water twice, DMF twice, methanol twice, and acetone twice.

ActivationDried in vacuum oven at 60 C for 1 h.

Scalability context100 mL round-bottom flask optimisation screen.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Base	ethylenediamine	0.5 equiv. corresponding to THQ	SI p.S8 · Temperature effect · Figure S5

Complete recipeSource: SI

Route 5: Hydrothermal

SI p.S6 · Reaction time effect · Figure S3

Metal precursorsCu(NO3)2.2.5H2O (26.6 mg)

Linker precursorsTHQ (15 mg) and DPT (21 mg)

Solvents15 mL H2O plus 15 mL DMF

AdditivesEthylenediamine, 2 equiv corresponding to THQ

AtmosphereN2 atmosphere

Temperatureroom temperature

Time1, 2, or 4

Work-upCentrifuged at 6000 rpm for seven minutes; washed with water twice, DMF twice, methanol twice, and acetone twice.

ActivationDried in vacuum oven at 60 C for 1 h.

Scalability context100 mL round-bottom flask optimisation screen.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2.2.5H2O	26.6 mg	SI p.S6 · Reaction time effect · Figure S3
Linker	THQ	15 mg	SI p.S6 · Reaction time effect · Figure S3
Linker	DPT	21 mg	SI p.S6 · Reaction time effect · Figure S3
Solvent	DMF	15 mL	SI p.S6 · Reaction time effect · Figure S3

Complete recipeSource: Both

Route 6: Other

main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a

Metal precursorsDPT-MOF precursor framework containing Cu nodes

Linker precursorsDPT-MOF tetrazine pillar; 1-ethynyl-4-fluorobenzene (EFB)

Solvents2 mL methanol

AdditivesEFB, 20 equiv to DPT

Temperature75

Time72

Work-upProducts isolated by centrifugation and washed with methanol twice and acetone twice.

ActivationDried in vacuum oven at 20 mTorr and 70 C for 1 h.

Scalability context4 mL vial; 10 mg DPT-MOF scale.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	DPT-MOF	10 mg, 8.09 x 10^-6 mol	main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a
Linker	1-ethynyl-4-fluorobenzene (EFB)	20 equiv to DPT	main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a
Solvent	methanol	2 mL	main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a

Complete recipeSource: SI

Route 7: Drop Cast

SI p.S3 · Photoelectrochemical and Electrochemical Measurements

SolventsEthanol, 30 uL per 1 mg of MOF

AdditivesPTFE binder solution, 20 wt% of ink solids

Temperature65

Time0.5

Substrate orientationITO glass for photocurrent; Pt disc for OCVD

Work-upSuspension ground to homogeneous slurry, drop-cast on working electrode.

ActivationDried for 30 min in 65 C oven.

Scalability contextElectrode preparation method applies to DPT-MOF, PA-MOF, and EFB-MOF electrochemical samples.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MOF powder	80 wt%	SI p.S3 · Photoelectrochemical and Electrochemical Measurements
Additive	PTFE binder solution	20 wt% · 60 wt% in H2O	SI p.S3 · Photoelectrochemical and Electrochemical Measurements
Solvent	ethanol	30 uL per 1 mg MOF	SI p.S3 · Photoelectrochemical and Electrochemical Measurements

Complete recipeSource: Both

Route 8: Other

main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a

Metal precursorsDPT-MOF precursor framework containing Cu nodes

Linker precursorsDPT-MOF tetrazine pillar; phenylacetylene (PA)

Solvents2 mL methanol

AdditivesPA, 20 equiv to DPT

Temperature75

Time72

Work-upProducts isolated by centrifugation and washed with methanol twice and acetone twice.

ActivationDried in vacuum oven at 20 mTorr and 70 C for 1 h.

Scalability context4 mL vial; 10 mg DPT-MOF scale.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	DPT-MOF	10 mg, 8.09 x 10^-6 mol	main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a
Linker	phenylacetylene (PA)	20 equiv to DPT	main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a
Solvent	methanol	2 mL	main p.7, article p.11325 · Experimental Section - Postsynthetic Reactions · Figure 1a