cMOF Evidence Base

Synthesis evidence

Ag Nanoparticles-Induced Metallic Conductivity in Thin Films of 2D Metal-Organic Framework Cu3(HHTP)2

Saha S., Ananthram K.S., Hassan N. et al. · Nano Letters · 2023 · 9326-9332

9 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

S2 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O; 1 mM ethanolic AgOAc
Linker precursors0.1 mM ethanolic HHTP
SolventsEthanol
AdditivesAgOAc dipping time varied
AtmosphereN2 drying; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and HHTP; 24.9 C (298 K) for AgOAc
Time10 min AgOAc step variant; other steps as AgNPs@Cu3(HHTP)2 route; 20 cycles
Substrate orientationFunctionalised substrate; no orientation specified
Oxidant / reductantAg(I) to Ag(0) reduction during LbL growth
Work-upEthanol washing and N2 drying after dipping steps
ActivationNo separate activation reported
Scalability contextAg content threshold series prepared by varying AgOAc dipping time to 5, 10, or 20 min.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS2 · Methods
Metal SourceAgOAc1 mM ethanolic solutionS2 · Methods
LinkerHHTP0.1 mM ethanolic solutionS2 · Methods
SolventethanolNot specifiedS2 · Methods
Complete recipeSource: SI

Route 2: Other

S2 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O; 1 mM ethanolic AgOAc
Linker precursors0.1 mM ethanolic HHTP
SolventsEthanol
AdditivesAgOAc dipping time varied
AtmosphereN2 drying; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and HHTP; 24.9 C (298 K) for AgOAc
Time20 min AgOAc step variant; other steps as AgNPs@Cu3(HHTP)2 route; 20 cycles
Substrate orientationFunctionalised substrate; no orientation specified
Oxidant / reductantAg(I) to Ag(0) reduction during LbL growth
Work-upEthanol washing and N2 drying after dipping steps
ActivationNo separate activation reported
Scalability contextAg content threshold series prepared by varying AgOAc dipping time to 5, 10, or 20 min.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS2 · Methods
Metal SourceAgOAc1 mM ethanolic solutionS2 · Methods
LinkerHHTP0.1 mM ethanolic solutionS2 · Methods
SolventethanolNot specifiedS2 · Methods
Complete recipeSource: Both

Route 3: Other

S2 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O; 1 mM ethanolic AgOAc
Linker precursors0.1 mM ethanolic HHTP
SolventsEthanol; substrate functionalisation solvents as in pristine route
AdditivesAgOAc inserted between Cu and HHTP dipping steps; MUDA or FTO functionalisation chemistry for substrates
AtmosphereDried under N2 flow/stream of N2 gas; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and HHTP steps; 24.9 C (298 K) for AgOAc step
Time15 min Cu step + 15 min AgOAc step + 15 min HHTP step per cycle; 20 cycles
Substrate orientationFunctionalised Au-coated Si wafer or FTO coated glass; no crystallographic orientation specified
Oxidant / reductantAg(I) reduced to Ag(0); main text proposes Cu(I) to Cu(II) oxidation within Cu3(HHTP)2 facilitates Ag(I) to Ag(0) conversion
Work-upAfter each step, wash with ethanol and dry under N2 gas flow
ActivationNo separate activation reported
Scalability context20-cycle LbL sequence forms approximately 750 nm film; Ag content tuneable by AgOAc dipping time.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS2 · Methods
Metal SourceAgOAc1 mM ethanolic solutionS2 · Methods
LinkerHHTP0.1 mM ethanolic solutionS2 · Methods
SolventethanolNot specifiedS2 · Methods
Complete recipeSource: SI

Route 4: Other

S2 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O; 1 mM ethanolic AgOAc
Linker precursors0.1 mM ethanolic HHTP
SolventsEthanol
AdditivesAgOAc dipping time varied
AtmosphereN2 drying; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and HHTP; 24.9 C (298 K) for AgOAc
Time5 min AgOAc step variant; other steps as AgNPs@Cu3(HHTP)2 route; 20 cycles
Substrate orientationFunctionalised substrate; no orientation specified
Oxidant / reductantAg(I) to Ag(0) reduction during LbL growth
Work-upEthanol washing and N2 drying after dipping steps
ActivationNo separate activation reported
Scalability contextAg content threshold series prepared by varying AgOAc dipping time to 5, 10, or 20 min.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS2 · Methods
Metal SourceAgOAc1 mM ethanolic solutionS2 · Methods
LinkerHHTP0.1 mM ethanolic solutionS2 · Methods
SolventethanolNot specifiedS2 · Methods
Complete recipeSource: SI

Route 5: Other

S3 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O; 1 mM ethanolic AgOAc
Linker precursors0.1 mM ethanolic TCPP
SolventsEthanol
AdditivesAgOAc inserted between Cu and TCPP dipping steps
AtmosphereDried under N2 flow/stream of N2 gas; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and TCPP steps; 24.9 C (298 K) for AgOAc step
Time15 min Cu step + 30 min AgOAc step + 15 min TCPP step per LbL cycle; 20 cycles
Substrate orientationFunctionalised Au substrate
Oxidant / reductantAg(I) to Ag(0) reduction during LbL growth inferred from AgNP formation
Work-upWash with ethanol after Cu and Ag steps; dry under N2 flow/gas flow
ActivationNo separate activation reported
Scalability context20-cycle AgNP-decorated Cu-TCPP control-film fabrication.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS3 · Methods
Metal SourceAgOAc1 mM ethanolic solutionS3 · Methods
LinkerTCPP0.1 mM ethanolic solutionS3 · Methods
SolventethanolNot specifiedS3 · Methods
Complete recipeSource: Both

Route 6: Other

S3 · Methods

Metal precursorsPre-fabricated CuTCNQ thin film; 1 mM ethanolic AgNO3
Linker precursors1 mM ethanolic TCNQ
SolventsEthanol
AdditivesNone reported
AtmosphereDried under N2 flow; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for AgNO3 and TCNQ steps
Time30 min AgNO3 step + 30 min TCNQ step per cycle; two cycles
Substrate orientationPre-fabricated CuTCNQ thin film on functionalised substrate
Oxidant / reductantCuTCNQ acts as sacrificial reducing agent for Ag(I) to Ag(0) conversion according to main text
Work-upWash with ethanol to remove uncoordinated species; dry under N2 flow
ActivationNo separate activation reported
Scalability contextPostsynthetic two-cycle LbL modification of pre-formed CuTCNQ film.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceAgNO31 mM ethanolic solutionS3 · Methods
LinkerTCNQ1 mM ethanolic solutionS3 · Methods
SolventethanolNot specifiedS3 · Methods
Complete recipeSource: SI

Route 7: Other

S2 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O
Linker precursors0.1 mM ethanolic HHTP
SolventsEthanol; ethanol/acetic acid 9:1 for MUDA functionalisation; Milli-Q water; piranha solution for Au cleaning; acetone/ethanol/water and KOH/H2O2 for FTO cleaning/functionalisation
AdditivesMUDA SAM for Au substrate; KOH/H2O2 treatment for FTO substrate
AtmosphereDried under N2 flow/stream of N2 gas; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and HHTP dipping; room temperature for cleaning unless specified; FTO functionalisation 80 C
Time30 min Cu step + 30 min HHTP step per LbL cycle; 20 cycles; Au MUDA functionalisation 48 h
Substrate orientationAu-coated Si wafer (100 nm Au) and FTO coated glass substrate; no crystallographic orientation specified
Oxidant / reductantNone reported
Work-upWash with ethanol to remove uncoordinated species after each dipping step; dry under N2 flow
ActivationNo separate activation reported
Scalability contextLayer-by-layer thin-film process; 20 repeated cycles used for uniform films.
Show 7 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS2 · Methods
LinkerHHTP0.1 mM ethanolic solutionS2 · Methods
SolventethanolNot specifiedS2 · Methods
AdditiveMUDA1 mM in ethanol/acetic acid (v/v 9:1)S2 · Methods
OxidantH2O230% in piranha and FTO treatmentS2 · Methods
AcidH2SO495-98%, piranha H2SO4/H2O2 3:1S2 · Methods
BaseKOH2 mmol · concentrated aqueous solution for FTO treatmentS2 · Methods
Complete recipeSource: SI

Route 8: Other

S3 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O
Linker precursors0.1 mM ethanolic TCPP
SolventsEthanol
AdditivesNone reported for film growth
AtmosphereDried under N2 flow; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and TCPP steps
Time30 min Cu step + 30 min TCPP step per LbL cycle; 20 cycles
Substrate orientationFunctionalised Au substrate
Oxidant / reductantNone reported
Work-upWash with ethanol; dry under N2 flow
ActivationNo separate activation reported
Scalability context20-cycle LbL fabrication of thin film.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS3 · Methods
LinkerTCPP0.1 mM ethanolic solutionS3 · Methods
SolventethanolNot specifiedS3 · Methods
Complete recipeSource: SI

Route 9: Other

S2-S3 · Methods

Metal precursors1 mM ethanolic Cu(OAc)2.H2O
Linker precursors1 mM ethanolic TCNQ
SolventsEthanol; substrate cleaning/functionalisaton solvents as applicable
AdditivesNone reported for film growth
AtmosphereDried under N2 flow; reaction atmosphere otherwise not stated
Temperature56.9 C (330 K) for Cu and TCNQ steps
Time30 min Cu step + 30 min TCNQ step per LbL cycle; 20 cycles
Substrate orientationFunctionalised substrate; no orientation specified
Oxidant / reductantNone reported for pristine CuTCNQ growth
Work-upEthanol washing to remove uncoordinated species; dry under N2 flow
ActivationNo separate activation reported
Scalability context20-cycle LbL thin-film fabrication.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O1 mM ethanolic solutionS2-S3 · Methods
LinkerTCNQ1 mM ethanolic solutionS2-S3 · Methods
SolventethanolNot specifiedS2-S3 · Methods