cMOF Evidence Base

Synthesis evidence

Electrically conductive Pt-MOFs for acidic oxygen reduction: Optimized performance via altering conjugated ligands

Iqbal R., Ali S., Saleem A. et al. · Chemical Engineering Journal · 2023 · 140799

6 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

p. 15-16 · Pt3(C12N6O6)2 MOF-modified MEA in fuel cell · Figure S16

Solventsdeionized water; Nafion 520 PFSA in isopropyl alcohol
AdditivesNafion 520 PFSA ionomer
AtmosphereN2 drying step at 90 C for 3 min; fuel-cell test in H2/air or H2/O2 environment
Temperature130 transfer; 60 drying; 90 drying
Time30 min ultrasonic; 1 h homogenizer; 10 min at 60 C; 3 min at 90 C
Substrate orientationNafion 211 membrane, PTFE thin film decal, GDL Toray TGP-H-060
Work-upcatalyst slurry transferred onto membrane at 130 C and 5 MPa using decal technique; catalyst slurry sprayed onto PTFE thin film
Activationcell activated to steady value before polarization curves
Scalability contextCatalyst loading: 0.8 mg cm^-2 total Pt3(C12N6O6)2 MOF in cathode; 0.15 mg cm^-2 Pt as Pt/C anode.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
OtherPt3(C12N6O6)2 MOF catalyst0.1 gp. 15-16 · Pt3(C12N6O6)2 MOF-modified MEA in fuel cell · Figure S16
Solventdeionized water1.0 mLp. 15-16 · Pt3(C12N6O6)2 MOF-modified MEA in fuel cell · Figure S16
AdditiveNafion 520 PFSA7.5 mL · 5 wt% in isopropyl alcoholp. 15-16 · Pt3(C12N6O6)2 MOF-modified MEA in fuel cell · Figure S16
OtherNafion 211 membraneNot specifiedp. 15-16 · Pt3(C12N6O6)2 MOF-modified MEA in fuel cell · Figure S16
OtherPt/C anode catalyst0.15 mg cm^-2 Pt · 20 wt% Pt/Cp. 15-16 · Pt3(C12N6O6)2 MOF-modified MEA in fuel cell · Figure S16
Partial recipeSource: Main

Route 2: Solvothermal

p. 3 · 2.3 · Fig. 1

Metal precursorsplatinum chloride hexahydrate, 15 mg
Linker precursorsdipyrazino quinoxaline-2,3,6,7,10,11-hexamine, 10 mg; hexaketo cyclohexane, 23.5 mg
Solventsn-methyl pyridone, 80 mL; 2 M H2SO4, 15 mL
Additivesconcentrated NH4OH, 3 mL
Atmospherenot reported
Temperature80
Time6
Work-upcentrifuged; washed twice each with tetrahydrofuran, water, ethanol and acetone
Activationvacuum dried overnight at 120 C
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourceplatinium chloride hexahydrate15 mgp. 3 · 2.3 · Fig. 1
Linkerdipyrazino quinoxaline-2,3,6,7,10,11-hexamine10 mgp. 3 · 2.3 · Fig. 1
Linkerhexaketo cyclohexane23.5 mgp. 3 · 2.3 · Fig. 1
Solventn-methyl pyridone80 mLp. 3 · 2.3 · Fig. 1
AcidH2SO415 mL · 2 Mp. 3 · 2.3 · Fig. 1
Baseconcentrated NH4OH3 mLp. 3 · 2.3 · Fig. 1
Partial recipeSource: Main

Route 3: Solvothermal

p. 3 · 2.2 · Fig. 1

Metal precursorsplatinum chloride hexahydrate, 12 mg
Linker precursorsdipyrazino quinoxaline-2,3,6,7,10,11-hexamine, 9 mg
Solventsn-methyl pyridone, 30 mL; 2 M H2SO4, 15 mL
Additivesconcentrated NH4OH, 3 mL
Atmospherenot reported
Temperature80
Time6
Work-upcentrifuged; washed twice each with tetrahydrofuran, water, ethanol and acetone
Activationvacuum dried overnight at 120 C
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourceplatinium chloride hexahydrate12 mgp. 3 · 2.2 · Fig. 1
Linkerdipyrazino quinoxaline-2,3,6,7,10,11-hexamine9 mgp. 3 · 2.2 · Fig. 1
Solventn-methyl pyridone30 mLp. 3 · 2.2 · Fig. 1
AcidH2SO415 mL · 2 Mp. 3 · 2.2 · Fig. 1
Baseconcentrated NH4OH3 mLp. 3 · 2.2 · Fig. 1
Complete recipeSource: SI

Route 4: Other

p. 2-3 · Synthesis route · Figure S2

Linker precursorshexahydrodipyrazino triquinoxalinylene intermediate from hexaketocyclohexane and o-ethane-1,2-diamine
SolventsAcOH/ethanol 1:1, 25 mL; 30 wt% HNO3; chloroform/trifluoroacetic acid for single crystals; benzene; water/CH3CN; CH2Cl2; AcOEt/hexane chromatography eluent
AdditivesFe/Cr powder; chloride metal salt catalysis mentioned
AtmosphereAr flush 15 min for 3Q synthesis; later oxidation with O2-catalysed chloride metal salts
Temperaturereflux; 140; 50
Time24; 3; 17
Oxidant / reductant30 wt% HNO3; Fe/Cr powder/O2 oxidation system
Work-upfiltered; washed with hot acetic acid, acetone, water, ethanol; column chromatography on silica gel with AcOEt/hexane (1:4)
Activationdried in vacuum
Scalability contextSI reports hexaol yield 178 mg, 79%; 3Q yield about 350 mg, 57%.
Show 7 structured reagent records
RoleReagentAmount / concentrationSource
Linkerhexaketocyclohexane0.499 g, 1.6 mmolp. 2-3 · Synthesis route · Figure S2
Linkero-ethane-1,2-diamine0.53 g, 4.8 mmolp. 2-3 · Synthesis route · Figure S2
Solventacetic acid/ethanol25 mL · 1:1 vol/volp. 2-3 · Synthesis route · Figure S2
OxidantHNO350 mL · 30 wt%p. 2-3 · Synthesis route · Figure S2
OtherFe/Cr powder1:10 by moles with respect to 3Qp. 2-3 · Synthesis route · Figure S2
Solventbenzene1 mL · 11.3 mmolp. 2-3 · Synthesis route · Figure S2
Solventwater/CH3CN/3Q two-phase system4.5:4.5:1 mLp. 2-3 · Synthesis route · Figure S2
Complete recipeSource: Both

Route 5: Solvothermal

p. 3 · 2.4 · Fig. 1

Metal precursorsplatinum chloride hexahydrate, 15 mg
Linker precursorsdipyrazino quinoxaline-2,3,6,7,10,11-hexaol, 10 mg; hexaketo cyclohexane, 23.5 mg
Solventsn-methyl pyridone, 80 mL; 2 M H2SO4, 15 mL
Additivesconcentrated NH4OH, 3 mL
Atmospherenot reported for MOF step; hexaol precursor route used Ar flushing and O2 oxidation chemistry
Temperature80
Time6
Oxidant / reductanthexaol precursor route: Fe/Cr powder and O2/chloride-metal-salt oxidation system
Work-upcentrifuged; washed twice each with tetrahydrofuran, water, ethanol and acetone
Activationvacuum dried overnight at 120 C
Show 8 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourceplatinium chloride hexahydrate15 mgp. 3 · 2.4 · Fig. 1
Linkerdipyrazino quinoxaline-2,3,6,7,10,11-hexaol10 mgp. 3 · 2.4 · Fig. 1
Linkerhexaketo cyclohexane23.5 mgp. 3 · 2.4 · Fig. 1
Solventn-methyl pyridone80 mLp. 3 · 2.4 · Fig. 1
AcidH2SO415 mL · 2 Mp. 3 · 2.4 · Fig. 1
Baseconcentrated NH4OH3 mLp. 3 · 2.4 · Fig. 1
Otherhexaol precursor: hexahydrodipyrazino triquinoxalinylene with Fe/Cr powder200 mg 3Q; Fe/Cr 1:10 molar ratiop. 3 · 2.4 · Fig. 1
Solventhexaol precursor: benzene; water/CH3CN/two-phase systembenzene 1 mL; water/CH3CN/3Q = 4.5:4.5:1 mLp. 3 · 2.4 · Fig. 1
Complete recipeSource: Main

Route 6: Drop Cast

p. 3 · 2.6-2.7

Solvents70% isopropanol solution, 1980 microL
Additives5 wt% Nafion ionomer, 20 microL
Atmosphereink dried slowly in air for RRDE
Temperatureroom temperature
Time1 h sonication
Substrate orientationglassy carbon RRDE area 0.1256 cm2
Work-upsonication; 5 microL ink drop-cast on RRDE; drying adjusted until uniform distribution
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherPt3(C12N6O6)2 MOF catalyst2 mgp. 3 · 2.6-2.7
Solvent70% isopropanol solution1,980 microL · 70%p. 3 · 2.6-2.7
AdditiveNafion ionomers20 microL · 5 wt%p. 3 · 2.6-2.7