cMOF Evidence Base

Synthesis evidence

Tarnishing Silver Metal into Mithrene

Trang B., Yeung M., Popple D.C. et al. · Journal of the American Chemical Society · 2018 · 13892-13903

9 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Other

13897 · Substitution of Silver(0) with Silver(I) Oxide · Table 1

Metal precursorsSilver(I) oxide
Linker precursorsDiphenyl diselenide (DPSe)
SolventsNone stated
Oxidant / reductantBoth reagents are described as most-oxidised common forms; no reaction
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcesilver(I) oxideNot specified13897 · Substitution of Silver(0) with Silver(I) Oxide · Table 1
Linkerdiphenyl diselenide (DPSe)Not specified13897 · Substitution of Silver(0) with Silver(I) Oxide · Table 1
Complete recipeSource: Main

Route 2: Other

13899 · Materials and Methods

Metal precursorsSilver(I) oxide, 50 mg
Linker precursorsNeat benzeneselenol, 100 uL
SolventsNeat PhSeH during reaction; ethanol and isopropyl alcohol for workup
AtmosphereDram vial with chemically inert lid, sealed within secondary container
Temperature80
Time0.333
Oxidant / reductantAcid-base reaction between Ag2O and PhSeH; not Ag(0)/DPSe redox
Work-upRemove from oven; add 1.5 mL ethanol and stir with disposable spatula; rest 1-3 days; decant; suspend in fresh isopropyl alcohol; repeat resuspension/centrifugation/decanting three times
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceAg2O50 mg13899 · Materials and Methods
Linkerneat benzeneselenol100 uL13899 · Materials and Methods
Solventethanol1.5 mL13899 · Materials and Methods
Solventisopropyl alcoholNot specified13899 · Materials and Methods
Complete recipeSource: Main

Route 3: Solvothermal

13899 · Materials and Methods

Metal precursorsSilver nitrate, 1.4 g, 0.008 mol
Linker precursorsDPSe, 1.3 g, 0.004 mol; triphenylphosphine, 4.4 g, 0.017 mol
SolventsDry THF (250 mL plus 80 mL DPSe solution); diethyl ether 75 mL; isopropyl alcohol workup
AdditivesTriphenylphosphine
AtmosphereNitrogen for initial 16 h stirring
Temperature-50 to ambient
Time16 h initial stirring plus warm-to-room-temperature reaction; later purification/drying
Oxidant / reductantSolution reaction of AgNO3/PPh3 with DPSe
Work-upLayer with diethyl ether and stir rapidly until crystals precipitate; decant solvent; purify by isopropyl alcohol addition, sonication, centrifugation; dry under vacuum
ActivationVacuum drying
Scalability contextReported as gram-scale; 2.3 g isolated canary-yellow fine powder.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcesilver nitrate1.4 g, 0.008 mol13899 · Materials and Methods
Additivetriphenylphosphine4.4 g, 0.017 mol13899 · Materials and Methods
Solventdry tetrahydrofuran250 mL plus 80 mL13899 · Materials and Methods
LinkerDPSe1.3 g, 0.004 mol13899 · Materials and Methods
Solventdiethyl ether75 mL13899 · Materials and Methods
Solventisopropyl alcoholNot specified13899 · Materials and Methods
Complete recipeSource: Main

Route 4: Other

13896 · Thin Films on Glass Substrates for Optical Characterization · Figure 7

Metal precursors1, 2, 3, 5, and 10 nm silver films deposited on glass coverslips
Linker precursorsDPSe vapour
SolventsNone
AtmosphereSealed glass jar, standard gas-phase tarnishing setup
Temperature80
Time72
Substrate orientationGlass coverslips; Ag thickness controls final [AgSePh]inf layer count
Oxidant / reductantAg(0)/DPSe redox tarnishing
Work-upAnalysed by UV-vis transmission, photoluminescence, and GIWAXS
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcesilver film on glass coverslips1-10 nm Ag13896 · Thin Films on Glass Substrates for Optical Characterization · Figure 7
Linkerdiphenyl diselenide (DPSe)Not specified13896 · Thin Films on Glass Substrates for Optical Characterization · Figure 7
Complete recipeSource: Main

Route 5: Other

13894 · Water's Role in Silver Tarnishing by Diphenyl Diselenide · Figure 4

Metal precursors100 nm Ag thermally evaporated on silicon wafer
Linker precursorsDPSe vapour
SolventsNone
AdditivesDry: calcium sulfate desiccant (Drierite); humid: 0.5 mL water in small vial; ambient-air control; no-DPSe control
AtmosphereDry, ambient room air, or water-saturated sealed vessel
Temperature80
Time72
Substrate orientationSilver-coated silicon substrate; in dry experiment substrate placed on Drierite
Oxidant / reductantWater-enabled corrosion/tarnishing; DPSe as reducible diselenide
Work-upSamples removed after heating and analysed by diffuse reflectance
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcesilicon wafers with 100 nm of silver metal100 nm Ag13894 · Water's Role in Silver Tarnishing by Diphenyl Diselenide · Figure 4
Linkerdiphenyl diselenide (DPSe)Not specified13894 · Water's Role in Silver Tarnishing by Diphenyl Diselenide · Figure 4
Additivewater0.5 mL for humid condition13894 · Water's Role in Silver Tarnishing by Diphenyl Diselenide · Figure 4
AdditiveDrieriteNot specified13894 · Water's Role in Silver Tarnishing by Diphenyl Diselenide · Figure 4
Partial recipeSource: Both

Route 6: Other

S-2 · Figure S1 caption · Figure S1a,b

Metal precursorsSilver metal film/wafer
Linker precursorsBenzeneselenol (PhSeH), gas phase or condensed in jar
SolventsNone stated for gas-phase attempt
AdditivesOxygen and water varied; no controlled MOCHA formation
AtmosphereOxygen-free conditions and oxygen-containing conditions discussed
Temperature80
Substrate orientationSilver on silicon substrate
Oxidant / reductantPhSeH weak acid; may oxidise in air to DPSe; silver heavily corroded/delaminated
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcesilver metalNot specifiedS-2 · Figure S1 caption · Figure S1a,b
Linkerbenzeneselenol (PhSeH)Not specifiedS-2 · Figure S1 caption · Figure S1a,b
Complete recipeSource: Main

Route 7: Other

13895 · Progression of the Tarnishing Reaction · Figure 5; Figure 6

Metal precursors200 nm thermally evaporated silver metal films
Linker precursorsDPSe vapour
SolventsNone
AtmosphereSealed glass jar, standard tarnishing setup
Temperature80
Time24-192
Substrate orientationThermally evaporated silver film; cross-sections examined after growth
Oxidant / reductantAg(0)/DPSe redox tarnishing
Work-upSamples removed at time points for SEM/GIWAXS
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcethermally evaporated silver metal200 nm thick films13895 · Progression of the Tarnishing Reaction · Figure 5; Figure 6
Linkerdiphenyl diselenide (DPSe)Not specified13895 · Progression of the Tarnishing Reaction · Figure 5; Figure 6
Partial recipeSource: SI

Route 8: Other

S-3 · Figure S2 caption · Figure S2

Metal precursorsSilver films on silicon wafer, 100 nm Ag or 5 nm Ag in SI examples
Linker precursorsDPSe in toluene
SolventsToluene
Temperatureambient
Time72
Substrate orientationAg film immersed in DPSe/toluene solution
Oxidant / reductantSolution exposure of Ag to DPSe; produces low-yield [AgSePh]inf and fibrous byproduct
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceAg film on silicon wafer100 nm Ag or 5 nm AgS-3 · Figure S2 caption · Figure S2
LinkerDPSeNot specifiedS-3 · Figure S2 caption · Figure S2
SolventtolueneNot specifiedS-3 · Figure S2 caption · Figure S2
Complete recipeSource: Both

Route 9: Other

13898 · Materials and Methods

Metal precursorsThermally evaporated Ag films on substrates; Ti adhesion layer 5-7 nm used prior to Ag when needed
Linker precursorsDiphenyl diselenide (DPSe; PhSeSePh), ca. 50 mg in 2 mL glass dram vial
SolventsNone during tarnishing; solvent-free gas-phase reaction
AdditivesOptional water vial for humidity; optional Drierite for dry-atmosphere controls
AtmosphereSealed glass jar; reactions in dark oven; room-air humidity unless modified; no high/low pressure or special atmosphere required for standard route
Temperature80
Time24-192
Substrate orientationSilver-coated substrates placed on floor of glass jar; avoid blocking sample surface to prevent shadowing
Oxidant / reductantAg(0) oxidised and DPSe reduced in proposed tarnishing redox reaction
Work-upJars removed from oven; samples removed; tarnished samples stored in drawer/shielded from light; jar and precursor can be reused
Scalability contextLarge-area films greater than 6 cm2 and wafer-scale/mild-temperature processing are reported.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcesilver-coated substrate / thermally evaporated Ag filmdesired thickness; examples 1-10 nm, 100 nm, 200 nm Ag13898 · Materials and Methods
Linkerdiphenyl diselenide (DPSe)approximately 50 mg13898 · Materials and Methods
Additivedeionized water, optional humidity experimentapproximately 0.5 mL · 18.2 Mohm deionized water13898 · Materials and Methods
AdditiveDrierite, optional dry experiment4 g13898 · Materials and Methods