cMOF Evidence Base

Synthesis evidence

Electrochemical Synthesis of Large Area Two-Dimensional Metal–Organic Framework Films on Copper Anodes

Liu Y., Wei Y., Liu M. et al. · Angewandte Chemie - International Edition · 2021 · 2887-2891

6 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Electrochemical

SI p.S2 · Preparation of 2D MOF films

Metal precursorsCu foil anode releasing Cu2+.
Linker precursorsMTCP ligand, 0.25 mmol/L.
SolventsSame EC solution protocol as Cu3(HHTP)2, except ligand substitution.
AdditivesAmmonia/base conditions analogous to HHTP route; exact per-ligand additive volume not separately restated.
AtmosphereCu foil annealed in H2 before growth by the general procedure; EC atmosphere not stated.
TemperatureCu anneal 1030 deg C; EC growth temperature not stated.
TimeNot separately stated; procedure similar to Cu3(HHTP)2.
Substrate orientationCu foil anode, analogous to Cu3(HHTP)2 route.
Oxidant / reductantAnodic dissolution of Cu releases Cu2+.
Work-upNot separately stated; analogous to Cu3(HHTP)2 film procedure.
ActivationNone reported.
Scalability contextReported to confirm universality of the EC method.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu foil anodeNot specifiedSI p.S2 · Preparation of 2D MOF films
LinkerMTCP0.25 mmol/LSI p.S2 · Preparation of 2D MOF films
Complete recipeSource: Both

Route 2: Electrochemical

SI p.S2 · Preparation of 2D MOF films

Metal precursorsCu foil anode, pretreated and annealed; Cu2+ released electrochemically.
Linker precursors8.107 mg HHTP powder in 100 mL deionized water/ethanol (1:1 v/v).
SolventsDeionized water and ethanol, 1:1 v/v, 100 mL total.
Additives30 uL ammonia to dissolve/ionize HHTP; hydrochloric acid, deionized water and isopropyl alcohol for Cu pretreatment.
AtmosphereCu foil annealed in hydrogen atmosphere at 60 sccm before EC growth; EC growth atmosphere not stated.
TemperatureCu anneal 1030 deg C; EC growth temperature not stated.
TimeCu anneal 2 h; EC growth time varied/controlled, not a single fixed recipe time.
Substrate orientationSingle-crystal Cu(100) foil, sizes 2 x 2 cm, 10 x 10 cm, and 5 x 100 cm; anode-cathode distance about 3 cm; cylindrical vessel diameter 10 cm.
Oxidant / reductantAnodic oxidation of Cu releases Cu2+; Ag/AgCl reference electrode used.
Work-upCu foils washed with 10% HCl, deionized water and isopropyl alcohol before anneal; post-growth workup for as-grown film not separately stated.
ActivationNone reported for MOF film; annealing is Cu-substrate pretreatment.
Scalability contextLarge-area films prepared on 4-inch Cu foil and on 5 x 100 cm Cu foil; method proposed for industrial-scale production.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
LinkerHHTP8.107 mgSI p.S2 · Preparation of 2D MOF films
Solventdeionized water and ethanol100 ml · volume ratio = 1:1SI p.S2 · Preparation of 2D MOF films
Baseammonia30 uLSI p.S2 · Preparation of 2D MOF films
Metal Sourceannealed Cu foil anode2 x 2 cm, 10 x 10 cm, or 5 x 100 cmSI p.S2 · Preparation of 2D MOF films
Acidhydrochloric acidwash · 10%SI p.S2 · Preparation of 2D MOF films
Solventisopropyl alcoholwashSI p.S2 · Preparation of 2D MOF films
Complete recipeSource: SI

Route 3: Other

SI p.S2 · Preparation of Cu3(HHTP)2 powder

Metal precursors0.3 mmol CuSO4.5H2O.
Linker precursors0.2 mmol HHTP powder.
Solvents10 mL deionized water; ethanol and deionized water washes.
Additives4 uL ammonia.
AtmosphereNot stated.
Temperature80 deg C drying.
TimeUltrasonication 15 min; stirring 5 h; drying 10 h.
Substrate orientationNo substrate; 20 mL beaker powder synthesis.
Oxidant / reductantNone stated.
Work-upCollected, washed by ethanol and deionized water, dried at 80 deg C for 10 h.
ActivationDrying at 80 deg C for 10 h.
Scalability contextPowder control only, not the large-area film route.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCuSO4.5H2O0.3 mmolSI p.S2 · Preparation of Cu3(HHTP)2 powder
LinkerHHTP powder0.2 mmolSI p.S2 · Preparation of Cu3(HHTP)2 powder
Solventdeionized water10 mLSI p.S2 · Preparation of Cu3(HHTP)2 powder
Baseammonia4 uLSI p.S2 · Preparation of Cu3(HHTP)2 powder
Solventethanol and deionized waterwashSI p.S2 · Preparation of Cu3(HHTP)2 powder
Complete recipeSource: SI

Route 4: Other

SI p.S2-S3 · Transfer of 2D MOF film · Figure S1

Metal precursorsPreformed Cu3(HHTP)2 film on Cu foil.
Linker precursorsPreformed Cu3(HHTP)2 film.
Solvents1 M FeCl3 solution, deionized water, acetone.
AdditivesPMMA protective layer.
AtmosphereNot stated for transfer; FET measurement later in N2.
Temperature60 deg C acetone treatment.
Time120 min acetone treatment.
Substrate orientationSiO2/Si substrate.
Oxidant / reductantFeCl3 etches/dissolves Cu foil.
Work-upSpin-coat PMMA, float on FeCl3 to remove Cu, rinse on deionized-water surface multiple times, scoop onto SiO2/Si, immerse in acetone at 60 deg C for 120 min to remove PMMA.
ActivationNo activation beyond PMMA removal.
Scalability contextTransfer applicable to arbitrary substrates and PEN using similar procedure.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
AdditivePMMAprotective layerSI p.S2-S3 · Transfer of 2D MOF film · Figure S1
OxidantFeCl3 solutionliquid surface · 1 MSI p.S2-S3 · Transfer of 2D MOF film · Figure S1
Solventdeionized watermultiple rinse transfersSI p.S2-S3 · Transfer of 2D MOF film · Figure S1
Solventacetoneimmersion · 60 deg C for 120 minSI p.S2-S3 · Transfer of 2D MOF film · Figure S1
Partial recipeSource: Both

Route 5: Electrochemical

SI p.S31 · Section 25 · Figure S31

Metal precursorsCu foil anode releasing Cu2+.
Linker precursorsTBTC/TPTC ligand, 0.5 mmol/L as reported in SI Methods for TPTC and SI figures for TBTC.
SolventsSame EC solution protocol as Cu3(HHTP)2, except ligand substitution.
AdditivesAmmonia/base conditions analogous to HHTP route; exact per-ligand additive volume not separately restated.
AtmosphereCu foil annealed in H2 before growth by the general procedure; EC atmosphere not stated.
TemperatureCu anneal 1030 deg C; EC growth temperature not stated.
TimeNot separately stated; procedure similar to Cu3(HHTP)2.
Substrate orientationCu foil anode, analogous to Cu3(HHTP)2 route.
Oxidant / reductantAnodic dissolution of Cu releases Cu2+.
Work-upNot separately stated; analogous to Cu3(HHTP)2 film procedure.
ActivationNone reported.
Scalability contextReported to confirm universality of the EC method.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu foil anodeNot specifiedSI p.S31 · Section 25 · Figure S31
LinkerTBTC/TPTC0.5 mmol/LSI p.S31 · Section 25 · Figure S31
Partial recipeSource: Both

Route 6: Electrochemical

SI p.S2 · Preparation of 2D MOF films

Metal precursorsCu foil anode releasing Cu2+.
Linker precursorsBTPA ligand, 0.5 mmol/L.
SolventsSame EC solution protocol as Cu3(HHTP)2, except ligand substitution; exact solvent inherited from main HHTP route.
AdditivesAmmonia/base conditions analogous to HHTP route; exact per-ligand additive volume not separately restated.
AtmosphereCu foil annealed in H2 before growth by the general procedure; EC atmosphere not stated.
TemperatureCu anneal 1030 deg C; EC growth temperature not stated.
TimeNot separately stated; procedure similar to Cu3(HHTP)2.
Substrate orientationCu foil anode, analogous to Cu3(HHTP)2 route.
Oxidant / reductantAnodic dissolution of Cu releases Cu2+.
Work-upNot separately stated; analogous to Cu3(HHTP)2 film procedure.
ActivationNone reported.
Scalability contextReported to confirm universality of the EC method.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu foil anodeNot specifiedSI p.S2 · Preparation of 2D MOF films
LinkerBTPA0.5 mmol/LSI p.S2 · Preparation of 2D MOF films