Synthesis · Conductive Metal–Organic Frameworks with Extra Metallic Sites as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction

10 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsCobalt chloride, 159 mg

Linker precursorsHAHATN, 100 mg by similar method

SolventsEthanol, 30 mL by similar method

AdditivesHydrochloric acid to adjust pH to 4 by similar method

AtmosphereNot specified

Time4 by similar method

Work-upRecrystallise in ethanol by similar method.

Scalability contextYield reported as 102 mg.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	cobalt chloride	159 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	HAHATN	100 mg by similar method	main p.8, article p.2000012-8 · Experimental Section
Solvent	ethanol	30 mL by similar method	main p.8, article p.2000012-8 · Experimental Section
Acid	hydrochloric acid	pH adjusted to 4 by similar method	main p.8, article p.2000012-8 · Experimental Section

Partial recipeSource: Main

Route 2: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsCupric chloride, 53 mg

Linker precursorsCu3.HAHATN ligand, 100 mg by similar method

SolventsDeionized water, 42 mL by similar method

AdditivesAmmonium hydroxide, 2.5 mL by similar method

AtmosphereAir by similar method

Temperature65 by similar method

Time2 after ligand addition by similar method

Work-upWash with ethanol and deionized water by similar method.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	cupric chloride	53 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	Cu3.HAHATN ligand	100 mg by similar method	main p.8, article p.2000012-8 · Experimental Section
Solvent	deionized water	42 mL by similar method	main p.8, article p.2000012-8 · Experimental Section
Base	ammonium hydroxide	2.5 mL by similar method	main p.8, article p.2000012-8 · Experimental Section

Partial recipeSource: Main

Route 3: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsCupric chloride, 164 mg

Linker precursorsHAHATN, 100 mg by similar method

SolventsEthanol, 30 mL by similar method

AdditivesHydrochloric acid to adjust pH to 4 by similar method

AtmosphereNot specified

Time4 by similar method

Work-upRecrystallise in ethanol by similar method.

Scalability contextYield line states 95 mg but names Co3.HAHATN, likely a source typo.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	cupric chloride	164 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	HAHATN	100 mg by similar method	main p.8, article p.2000012-8 · Experimental Section
Solvent	ethanol	30 mL by similar method	main p.8, article p.2000012-8 · Experimental Section
Acid	hydrochloric acid	pH adjusted to 4 by similar method	main p.8, article p.2000012-8 · Experimental Section

Complete recipeSource: Main

Route 4: Other

main p.7-8, article p.2000012-7 to 8 · Experimental Section

Metal precursorsNone

Linker precursors1,2,4,5-benzenetetramine tetrahydrochloride, 702 mg, 2.47 mmol; hexaketocyclohexane octahydrate, 224 mg, 0.718 mmol

SolventsEthanol, 10 mL

AdditivesConcentrated hydrochloric acid, 38%, 2 mL

AtmosphereNot specified

Temperature160

Time0.75

Work-upFilter to remove black byproduct; concentrate under vacuum to dryness; recrystallise in ethanol; wash twice with ether.

Scalability contextMicrowave reaction vessel; reported product 225 mg, 45% yield.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	1,2,4,5-benzenetetramine tetrahydrochloride	702 mg; 2.47 mmol	main p.7-8, article p.2000012-7 to 8 · Experimental Section
Linker	hexaketocyclohexane octahydrate	224 mg; 0.718 mmol	main p.7-8, article p.2000012-7 to 8 · Experimental Section
Solvent	ethanol	10 mL	main p.7-8, article p.2000012-7 to 8 · Experimental Section
Acid	concentrated hydrochloric acid	2 mL · 38%	main p.7-8, article p.2000012-7 to 8 · Experimental Section

Partial recipeSource: Main

Route 5: Drop Cast

main p.8, article p.2000012-8 · Experimental Section

SolventsMixed solvent Vwater:VDMF = 1:1, total 2 mL

AdditivesNafion ethanol solution, 5 uL

AtmosphereVacuum drying after drop casting

TimeUltrasonicated 10 min before drop casting

Substrate orientation3 mm glassy carbon rotating disk electrode, pre-polished

Work-upDrop 10 uL ink onto pre-treated RDE and dry in vacuum; add 5 uL Nafion ethanol solution.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	M23(M13.HAHATN)2 catalyst sample	8 mg	main p.8, article p.2000012-8 · Experimental Section
Solvent	water/DMF	2 mL · Vwater:VDMF = 1:1	main p.8, article p.2000012-8 · Experimental Section
Additive	Nafion ethanol solution	5 uL	main p.8, article p.2000012-8 · Experimental Section

Complete recipeSource: Main

Route 6: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsNickel chloride, 51 mg

Linker precursorsCo3.HAHATN ligand, 100 mg

SolventsDeionized water, 42 mL

AdditivesAmmonium hydroxide, 2.5 mL

AtmosphereAir

Temperature65

Time2 after ligand addition

Work-upWash with ethanol and deionized water.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride	51 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	Co3.HAHATN ligand	100 mg	main p.8, article p.2000012-8 · Experimental Section
Solvent	deionized water	42 mL	main p.8, article p.2000012-8 · Experimental Section
Base	ammonium hydroxide	2.5 mL	main p.8, article p.2000012-8 · Experimental Section

Complete recipeSource: Main

Route 7: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsNickel chloride, 51 mg

Linker precursorsCu3.HAHATN ligand, 100 mg

SolventsDeionized water, 42 mL

AdditivesAmmonium hydroxide, 2.5 mL

AtmosphereAir

Temperature65

Time2 after ligand addition

Work-upWash with ethanol and deionized water.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride	51 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	Cu3.HAHATN ligand	100 mg	main p.8, article p.2000012-8 · Experimental Section
Solvent	deionized water	42 mL	main p.8, article p.2000012-8 · Experimental Section
Base	ammonium hydroxide	2.5 mL	main p.8, article p.2000012-8 · Experimental Section

Partial recipeSource: Main

Route 8: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsNickel chloride, 162 mg

Linker precursorsHAHATN, 100 mg

SolventsEthanol, 30 mL

AdditivesHydrochloric acid to adjust pH to 4

AtmosphereNot specified

Time4

Work-upRecrystallise in ethanol to remove unreacted nickel chloride.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride	162 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	HAHATN	100 mg	main p.8, article p.2000012-8 · Experimental Section
Solvent	ethanol	30 mL	main p.8, article p.2000012-8 · Experimental Section
Acid	hydrochloric acid	pH adjusted to 4	main p.8, article p.2000012-8 · Experimental Section

Complete recipeSource: Main

Route 9: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsNickel chloride, 6.6 mg

Linker precursorsHITP solution, 10 mg HITP in 5 mL water

SolventsWater, 5 mL for metal solution plus 5 mL for HITP solution

AdditivesConcentrated aqueous ammonia, 0.3 mL

AtmosphereNot specified

Temperature65

Time3

Work-upCentrifuged, filtered, washed by ethanol and deionized water.

ActivationDried under vacuum at 150 C.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride	6.6 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	HITP	10 mg in 5 mL water	main p.8, article p.2000012-8 · Experimental Section
Solvent	water	5 mL metal solution; 5 mL HITP solution	main p.8, article p.2000012-8 · Experimental Section
Base	concentrated aqueous ammonia	0.3 mL	main p.8, article p.2000012-8 · Experimental Section

Complete recipeSource: Main

Route 10: Other

main p.8, article p.2000012-8 · Experimental Section

Metal precursorsNickel chloride, 51 mg

Linker precursorsNi3.HAHATN ligand, 100 mg

SolventsDeionized water, 42 mL

AdditivesAmmonium hydroxide, 2.5 mL

AtmosphereAir

Temperature65

Time2 after ligand addition

Work-upWash with ethanol and deionized water.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	nickel chloride	51 mg	main p.8, article p.2000012-8 · Experimental Section
Linker	Ni3.HAHATN ligand	100 mg	main p.8, article p.2000012-8 · Experimental Section
Solvent	deionized water	42 mL	main p.8, article p.2000012-8 · Experimental Section
Base	ammonium hydroxide	2.5 mL	main p.8, article p.2000012-8 · Experimental Section