Synthesis · A Computation-Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-Dimensional Conductive Metal–Organic Framework for Efficient H2O2 Electrosynthesis

8 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Hydrothermal

S5 · Experimental section

Metal precursorsCo(NO3)2·6H2O plus Co(NO3)2·6H2O replacing Ni(NO3)2·6H2O

Linker precursorsTCPP

SolventsDMF; ethanol

AdditivesPVP mentioned in main text but not quantified

AtmosphereAr for first step inferred unchanged

Temperature170 then 80

Time3 then 24

Work-uphigh-speed centrifuging; washed many times with DMF and EtOH (unchanged from Ni-TCPP(Co))

Activationnot stated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O replacing Ni(NO3)2·6H2O	corresponding metal salt; amount not explicitly stated	S5 · Experimental section
Linker	TCPP	7.9 mg, 10 umol inferred unchanged	S5 · Experimental section
Solvent	DMF; EtOH	5 mL DMF; 1.5 mL EtOH inferred unchanged	S5 · Experimental section

Partial recipeSource: SI

Route 2: Hydrothermal

S5 · Experimental section

Metal precursorsCo(NO3)2·6H2O plus copper nitrate trihydrate (Cu(NO3)2·3H2O) replacing Ni(NO3)2·6H2O

Linker precursorsTCPP

SolventsDMF; ethanol

AdditivesPVP mentioned in main text but not quantified

AtmosphereAr for first step inferred unchanged

Temperature170 then 80

Time3 then 24

Work-uphigh-speed centrifuging; washed many times with DMF and EtOH (unchanged from Ni-TCPP(Co))

Activationnot stated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper nitrate trihydrate (Cu(NO3)2·3H2O) replacing Ni(NO3)2·6H2O	corresponding metal salt; amount not explicitly stated	S5 · Experimental section
Linker	TCPP	7.9 mg, 10 umol inferred unchanged	S5 · Experimental section
Solvent	DMF; EtOH	5 mL DMF; 1.5 mL EtOH inferred unchanged	S5 · Experimental section

Partial recipeSource: SI

Route 3: Hydrothermal

S5 · Experimental section

Metal precursorsCo(NO3)2·6H2O plus ferrous sulfate (FeSO4·7H2O) replacing Ni(NO3)2·6H2O

Linker precursorsTCPP

SolventsDMF; ethanol

AdditivesPVP mentioned in main text but not quantified

AtmosphereAr for first step inferred unchanged

Temperature170 then 80

Time3 then 24

Work-uphigh-speed centrifuging; washed many times with DMF and EtOH (unchanged from Ni-TCPP(Co))

Activationnot stated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	ferrous sulfate (FeSO4·7H2O) replacing Ni(NO3)2·6H2O	corresponding metal salt; amount not explicitly stated	S5 · Experimental section
Linker	TCPP	7.9 mg, 10 umol inferred unchanged	S5 · Experimental section
Solvent	DMF; EtOH	5 mL DMF; 1.5 mL EtOH inferred unchanged	S5 · Experimental section

Complete recipeSource: SI

Route 4: Other

S7 · Electrochemical tests in flow-cell

Solvents700 uL deionized water; 250 uL isopropanol

Additives0.5 mg CNT; 50 uL Nafion solution; GDL SGL-39BB

Atmosphereroom temperature ink preparation; O2 purged during tests

Temperature~25

Work-upcatalyst coated homogeneously on gas-diffusion layer with 100 ug loading

ActivationNafion membrane pretreated for flow-cell

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-TCPP(Co) sample	4.5 mg in 5 mg/mL catalyst ink; 100 ug catalyst loading on GDL · 5 mg/mL	S7 · Electrochemical tests in flow-cell
Additive	CNT	0.5 mg	S7 · Electrochemical tests in flow-cell
Additive	Nafion solution	50 uL	S7 · Electrochemical tests in flow-cell
Other	gas-diffusion layer (GDL, SGL-39BB)	1x1 cm active area	S7 · Electrochemical tests in flow-cell

Partial recipeSource: SI

Route 5: Hydrothermal

S5 · Experimental section

Metal precursorsCo(NO3)2·6H2O plus manganese acetate tetrahydrate ((CH3COO)2Mn·4H2O) replacing Ni(NO3)2·6H2O

Linker precursorsTCPP

SolventsDMF; ethanol

AdditivesPVP mentioned in main text but not quantified

AtmosphereAr for first step inferred unchanged

Temperature170 then 80

Time3 then 24

Work-uphigh-speed centrifuging; washed many times with DMF and EtOH (unchanged from Ni-TCPP(Co))

Activationnot stated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	manganese acetate tetrahydrate ((CH3COO)2Mn·4H2O) replacing Ni(NO3)2·6H2O	corresponding metal salt; amount not explicitly stated	S5 · Experimental section
Linker	TCPP	7.9 mg, 10 umol inferred unchanged	S5 · Experimental section
Solvent	DMF; EtOH	5 mL DMF; 1.5 mL EtOH inferred unchanged	S5 · Experimental section

Partial recipeSource: Both

Route 6: Hydrothermal

S5 · Experimental section

Metal precursorsCo(NO3)2·6H2O then Ni(NO3)2·6H2O

Linker precursorsTCPP

SolventsDMF; ethanol

AdditivesPVP mentioned in main text but not quantified in SI recipe

AtmosphereAr for first 170 C step

Temperature170 then 80

Time3 then 24

Work-uphigh-speed centrifuging; washed many times with DMF and EtOH

Activationnot stated

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2·6H2O	2.9 mg, 10 umol	S5 · Experimental section
Linker	TCPP	7.9 mg, 10 umol	S5 · Experimental section
Solvent	DMF	5 mL	S5 · Experimental section
Metal Source	Ni(NO3)2·6H2O	5.9 mg, 20 umol	S5 · Experimental section
Solvent	EtOH	1.5 mL	S5 · Experimental section
Additive	polyvinylpyrrolidone (PVP)	not stated	S5 · Experimental section

Partial recipeSource: SI

Route 7: Hydrothermal

S5 · Experimental section

Metal precursorsNi(NO3)2·6H2O plus Mn or Cu salt replacing Co(NO3)2·6H2O

Linker precursorsTCPP

SolventsDMF; ethanol

AdditivesPVP mentioned in main text but not quantified

AtmosphereAr for first step inferred unchanged

Temperature170 then 80

Time3 then 24

Work-uphigh-speed centrifuging; washed many times with DMF and EtOH inferred unchanged

Activationnot stated

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Mn or Cu corresponding metal salt replacing Co(NO3)2·6H2O	not explicitly stated	S5 · Experimental section
Metal Source	Ni(NO3)2·6H2O	5.9 mg, 20 umol inferred unchanged	S5 · Experimental section
Linker	TCPP	7.9 mg, 10 umol inferred unchanged	S5 · Experimental section

Complete recipeSource: SI

Route 8: Drop Cast

S6 · Electrochemical Measurements

Solvents700 uL deionized water; 250 uL isopropanol

Additives0.5 mg CNT; 50 uL Nafion solution

Atmosphereroom temperature; electrochemical tests O2- or Ar-saturated as specified

Temperature~25

Work-up10 uL ink dropped to RRDE to form uniform catalyst layer

Activationnot stated

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-TCPP(Co) sample	4.5 mg	S6 · Electrochemical Measurements
Additive	CNT	0.5 mg	S6 · Electrochemical Measurements
Solvent	deionized water	700 uL	S6 · Electrochemical Measurements
Solvent	isopropanol	250 uL	S6 · Electrochemical Measurements
Additive	Nafion solution	50 uL	S6 · Electrochemical Measurements