Synthesis · Creating Dual Active Sites in Conductive Metal-Organic Frameworks for Efficient Water Splitting

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: Solvothermal

S2-S3 · Experimental section - Synthesis of Co-CAT/CC

Metal precursorsCo(OAc)2.4H2O (40 mg)

Linker precursorsHHTP (28 mg)

Solvents6 mL deionized water; 660 uL NMP

AdditivesNMP; carbon cloth pretreated in 10 wt% potassium permanganate, water and ethanol

Atmospherenot reported

Temperature85

Time12

Substrate orientationclean carbon cloth (1 x 3 cm2) immersed in glass vial reaction solution

Oxidant / reductant10 wt% potassium permanganate used only for carbon-cloth pretreatment; HHTP partially oxidized during reaction

Work-upcooled to room temperature within 30 min; washed with deionized water (3 x 3 mL), then acetone (6 x 3 mL)

Activationsonicated 30 min before NMP addition; no post-synthetic activation reported

Scalability contextMass loading on CC about 1.5 mg cm^-2 for 4 h, 12 h and 20 h samples.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-Hexahydroxytriphenylene (HHTP, 99%)	28 mg	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Metal Source	Cobalt acetate tetrahydrate (Co(OAc)2.4H2O, 99%)	40 mg	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Solvent	deionized water	6 mL	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Solvent	1-Methylpyrrolidone (NMP, 98%)	660 uL	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Oxidant	potassium permanganate pretreatment solution	not reported · 10 wt%	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Other	carbon cloth	1 x 3 cm2	S2-S3 · Experimental section - Synthesis of Co-CAT/CC

Complete recipeSource: SI

Route 2: Solvothermal

S2-S3 · Experimental section - Synthesis of Co-CAT/CC

Metal precursorsCo(OAc)2.4H2O (40 mg)

Linker precursorsHHTP (28 mg)

Solvents6 mL deionized water; 660 uL NMP

AdditivesNMP; carbon cloth pretreated in 10 wt% potassium permanganate, water and ethanol

Atmospherenot reported

Temperature85

Time20

Substrate orientationclean carbon cloth (1 x 3 cm2) immersed in glass vial reaction solution

Oxidant / reductant10 wt% potassium permanganate used only for carbon-cloth pretreatment; HHTP partially oxidized during reaction

Work-upcooled to room temperature within 30 min; washed with deionized water (3 x 3 mL), then acetone (6 x 3 mL)

Activationsonicated 30 min before NMP addition; no post-synthetic activation reported

Scalability contextMass loading on CC about 1.5 mg cm^-2 for 4 h, 12 h and 20 h samples.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-Hexahydroxytriphenylene (HHTP, 99%)	28 mg	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Metal Source	Cobalt acetate tetrahydrate (Co(OAc)2.4H2O, 99%)	40 mg	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Solvent	deionized water	6 mL	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Solvent	1-Methylpyrrolidone (NMP, 98%)	660 uL	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Oxidant	potassium permanganate pretreatment solution	not reported · 10 wt%	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Other	carbon cloth	1 x 3 cm2	S2-S3 · Experimental section - Synthesis of Co-CAT/CC

Complete recipeSource: SI

Route 3: Solvothermal

S2-S3 · Experimental section - Synthesis of Co-CAT/CC

Metal precursorsCo(OAc)2.4H2O (40 mg)

Linker precursorsHHTP (28 mg)

Solvents6 mL deionized water; 660 uL NMP

AdditivesNMP; carbon cloth pretreated in 10 wt% potassium permanganate, water and ethanol

Atmospherenot reported

Temperature85

Time4

Substrate orientationclean carbon cloth (1 x 3 cm2) immersed in glass vial reaction solution

Oxidant / reductant10 wt% potassium permanganate used only for carbon-cloth pretreatment; HHTP partially oxidized during reaction

Work-upcooled to room temperature within 30 min; washed with deionized water (3 x 3 mL), then acetone (6 x 3 mL)

Activationsonicated 30 min before NMP addition; no post-synthetic activation reported

Scalability contextMass loading on CC about 1.5 mg cm^-2 for 4 h, 12 h and 20 h samples.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-Hexahydroxytriphenylene (HHTP, 99%)	28 mg	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Metal Source	Cobalt acetate tetrahydrate (Co(OAc)2.4H2O, 99%)	40 mg	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Solvent	deionized water	6 mL	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Solvent	1-Methylpyrrolidone (NMP, 98%)	660 uL	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Oxidant	potassium permanganate pretreatment solution	not reported · 10 wt%	S2-S3 · Experimental section - Synthesis of Co-CAT/CC
Other	carbon cloth	1 x 3 cm2	S2-S3 · Experimental section - Synthesis of Co-CAT/CC

Complete recipeSource: SI

Route 4: Solvothermal

S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC

Metal precursorsCo(OAc)2.4H2O (40 mg); IrCl3 (5 mg)

Linker precursorsHHTP (28 mg)

Solvents6 mL deionized water; 660 uL NMP

AdditivesNMP; carbon cloth pretreated in 10 wt% potassium permanganate, water and ethanol

Atmospherenot reported

Temperature85

Time12

Substrate orientationclean carbon cloth (1 x 3 cm2) immersed in glass vial reaction solution

Oxidant / reductant10 wt% potassium permanganate used only for carbon-cloth pretreatment; HHTP partially oxidized during reaction

Work-upwashed with deionized water; RuCo-CAT used directly without drying. For Co-CAT recipe: cooled to room temperature within 30 min and washed with water/acetone; Ir/Rh workup otherwise same as RuCo-CAT.

Activationsonicated 30 min before NMP addition; no drying for RuCo-CAT; no separate activation reported

Scalability contextMass loading on CC about 1.5 mg cm^-2 for RuCo-CAT; same loading implied for MCo-CAT/CC electrodes.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-Hexahydroxytriphenylene (HHTP, 99%)	28 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Metal Source	Cobalt acetate tetrahydrate (Co(OAc)2.4H2O, 99%)	40 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Metal Source	IrCl3	5 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Solvent	deionized water	6 mL	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Solvent	1-Methylpyrrolidone (NMP, 98%)	660 uL	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Oxidant	potassium permanganate pretreatment solution	not reported · 10 wt%	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Other	carbon cloth	1 x 3 cm2	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC

Complete recipeSource: SI

Route 5: Drop Cast

S3 · Experimental section - Synthesis of the Pt/C/CC

Metal precursorscommercial Pt/C (20% Pt on Vulcan XC-72R), 1.5 mg

Linker precursorsnot_applicable

Solvents450 uL ethanol

Additives50 uL of 5 wt% Nafion solution

Atmospherenot reported

Substrate orientationink coated onto carbon cloth

Oxidant / reductantnot_applicable

Work-upultrasound for at least 30 min to form homogeneous ink; coated onto CC

Activationnone reported

Scalability contextPt/C loading 1.5 mg cm^-2 on CC.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	commercial Pt/C (20% Pt on Vulcan XC-72R)	1.5 mg	S3 · Experimental section - Synthesis of the Pt/C/CC
Solvent	ethanol	450 uL	S3 · Experimental section - Synthesis of the Pt/C/CC
Additive	Nafion solution	50 uL · 5 wt%	S3 · Experimental section - Synthesis of the Pt/C/CC
Other	carbon cloth	not reported · loading 1.5 mg cm^-2	S3 · Experimental section - Synthesis of the Pt/C/CC

Complete recipeSource: SI

Route 6: Solvothermal

S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC

Metal precursorsCo(OAc)2.4H2O (40 mg); RhCl3 xH2O (5 mg)

Linker precursorsHHTP (28 mg)

Solvents6 mL deionized water; 660 uL NMP

AdditivesNMP; carbon cloth pretreated in 10 wt% potassium permanganate, water and ethanol

Atmospherenot reported

Temperature85

Time12

Substrate orientationclean carbon cloth (1 x 3 cm2) immersed in glass vial reaction solution

Oxidant / reductant10 wt% potassium permanganate used only for carbon-cloth pretreatment; HHTP partially oxidized during reaction

Activationsonicated 30 min before NMP addition; no drying for RuCo-CAT; no separate activation reported

Scalability contextMass loading on CC about 1.5 mg cm^-2 for RuCo-CAT; same loading implied for MCo-CAT/CC electrodes.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-Hexahydroxytriphenylene (HHTP, 99%)	28 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Metal Source	Cobalt acetate tetrahydrate (Co(OAc)2.4H2O, 99%)	40 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Metal Source	RhCl3 xH2O	5 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Solvent	deionized water	6 mL	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Solvent	1-Methylpyrrolidone (NMP, 98%)	660 uL	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Oxidant	potassium permanganate pretreatment solution	not reported · 10 wt%	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Other	carbon cloth	1 x 3 cm2	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC

Complete recipeSource: SI

Route 7: Solvothermal

S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC

Metal precursorsCo(OAc)2.4H2O (40 mg); RuCl3.xH2O (5 mg)

Linker precursorsHHTP (28 mg)

Solvents6 mL deionized water; 660 uL NMP

AdditivesNMP; carbon cloth pretreated in 10 wt% potassium permanganate, water and ethanol

Atmospherenot reported

Temperature85

Time12

Substrate orientationclean carbon cloth (1 x 3 cm2) immersed in glass vial reaction solution

Oxidant / reductant10 wt% potassium permanganate used only for carbon-cloth pretreatment; HHTP partially oxidized during reaction

Activationsonicated 30 min before NMP addition; no drying for RuCo-CAT; no separate activation reported

Scalability contextMass loading on CC about 1.5 mg cm^-2 for RuCo-CAT; same loading implied for MCo-CAT/CC electrodes.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	2,3,6,7,10,11-Hexahydroxytriphenylene (HHTP, 99%)	28 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Metal Source	Cobalt acetate tetrahydrate (Co(OAc)2.4H2O, 99%)	40 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Metal Source	RuCl3.xH2O	5 mg	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Solvent	deionized water	6 mL	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Solvent	1-Methylpyrrolidone (NMP, 98%)	660 uL	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Oxidant	potassium permanganate pretreatment solution	not reported · 10 wt%	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC
Other	carbon cloth	1 x 3 cm2	S3 · Experimental section - Synthesis of RuCo-CAT/CC; Synthesis of Ir and Rh-doped Co-CAT/CC

Complete recipeSource: SI

Route 8: Drop Cast

S3-S4 · Experimental section - Synthesis of the RuO2/CC

Metal precursorscommercial RuO2/C, 1.5 mg

Linker precursorsnot_applicable

Solvents450 uL ethanol

Additives50 uL of 5 wt% Nafion solution

Atmospherenot reported

Substrate orientationink coated onto carbon cloth

Oxidant / reductantnot_applicable

Work-upultrasound for at least 30 min to form homogeneous ink; coated onto CC

Activationnone reported

Scalability contextRuO2 loading 1.5 mg cm^-2 on CC.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	commercial RuO2/C	1.5 mg	S3-S4 · Experimental section - Synthesis of the RuO2/CC
Solvent	ethanol	450 uL	S3-S4 · Experimental section - Synthesis of the RuO2/CC
Additive	Nafion solution	50 uL · 5 wt%	S3-S4 · Experimental section - Synthesis of the RuO2/CC
Other	carbon cloth	not reported · loading 1.5 mg cm^-2	S3-S4 · Experimental section - Synthesis of the RuO2/CC