Synthesis · Single-Atom Catalysts in Conductive Metal-Organic Frameworks: Enabling Reversible Gas Sensing at Room Temperature

6 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Electrochemical

rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9

Metal precursorsAgNO3, 0.1 mM in deionised water

Linker precursorspreformed Cu3(HITP)2

Solventsanhydrous ethanol for cMOF dispersion; deionised water electrolyte for Ag deposition

Atmospherenot specified

Temperatureroom temperature

Timenot specified

Substrate orientationcMOF drop-coated on graphite working electrode, 40 x 20 x 1 mm

Oxidant / reductantCathodic linear-sweep voltammetry; potential swept from 0.513 to 0.013 V vs Ag/AgCl at 5 mV/s; 10 cycles

Work-upAfter deposition, electrode washed twice with deionised water and once with methanol; powder after centrifugation dried in vacuum oven overnight at room temperature.

ActivationVacuum drying overnight at room temperature.

Scalability contextSame route described as a versatile method for M1-cMOFs.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HITP)2 cMOF	15 mg in 1.5 mL ethanol for electrode coating	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9
Metal Source	AgNO3	0.1 mM in deionised water	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9
Solvent	deionised water	Not specified	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9
Solvent	methanol	wash solvent	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9

Complete recipeSource: Main

Route 2: Other

rendered page 7 / article p.26072 · Experimental Section - Synthesis of cMOF

Metal precursorsCuSO4.5H2O, 17.5 mg

Linker precursorsHITP.6HCl, 25 mg

SolventsDMA, 7.5 mL; deionised water, 7.5 mL; NaOAc aqueous solution, 10 mL

AdditivesNaOAc aqueous solution, 164 mg/mL, 10 mL

Atmosphereopen glass vial; atmosphere not otherwise specified

Temperature65

Time3.5

Work-upPowder washed twice with water and twice with MeOH using centrifugation.

ActivationDried in a vacuum oven overnight at room temperature.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuSO4.5H2O	17.5 mg	rendered page 7 / article p.26072 · Experimental Section - Synthesis of cMOF
Linker	HITP.6HCl	25 mg	rendered page 7 / article p.26072 · Experimental Section - Synthesis of cMOF
Solvent	N,N-dimethylacetamide (DMA)	7.5 mL	rendered page 7 / article p.26072 · Experimental Section - Synthesis of cMOF
Solvent	deionised water	7.5 mL	rendered page 7 / article p.26072 · Experimental Section - Synthesis of cMOF
Additive	sodium acetate (NaOAc) aqueous solution	10 mL · 164 mg/mL	rendered page 7 / article p.26072 · Experimental Section - Synthesis of cMOF

Complete recipeSource: Main

Route 3: Electrochemical

rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9

Metal precursorsIrCl3.xH2O, 0.1 mM in DMF

Linker precursorspreformed Cu3(HITP)2

Solventsanhydrous ethanol for cMOF dispersion; DMF electrolyte for Ir deposition

Atmospherenot specified

Temperatureroom temperature

Timenot specified

Substrate orientationcMOF drop-coated on graphite working electrode, 40 x 20 x 1 mm

Oxidant / reductantCathodic linear-sweep voltammetry; potential swept from 0.513 to 0.013 V vs Ag/AgCl at 5 mV/s; 10 cycles

Work-upAfter deposition, electrode washed twice with DMF and once with methanol; powder after centrifugation dried in vacuum oven overnight at room temperature.

ActivationVacuum drying overnight at room temperature.

Scalability contextSame route described as a versatile method for M1-cMOFs.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HITP)2 cMOF	15 mg in 1.5 mL ethanol for electrode coating	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9
Metal Source	IrCl3.xH2O	0.1 mM in DMF	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9
Solvent	N,N-dimethylformamide (DMF)	Not specified	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9
Solvent	methanol	wash solvent	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figures S7-S9

Complete recipeSource: Main

Route 4: Electrochemical

rendered pages 3 and 7 / article pp.26068 and 26072 · Functionalization; Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figure 1b

Metal precursorsPd(NH3)4(NO3)2, 0.1 mM in DMF for standard Pd SACs

Linker precursorspreformed Cu3(HITP)2

Solventsanhydrous ethanol for cMOF dispersion; DMF electrolyte for Pd deposition

Atmospherenot specified

Temperatureroom temperature

Timenot specified

Substrate orientationcMOF drop-coated on graphite working electrode, 40 x 20 x 1 mm

Oxidant / reductantCathodic linear-sweep voltammetry; potential swept from 0.513 to 0.013 V vs Ag/AgCl at 5 mV/s; 10 cycles

Work-upAfter deposition, electrode washed twice with DMF and once with methanol; resulting powder after centrifugation dried in vacuum oven overnight at room temperature.

ActivationVacuum drying overnight at room temperature.

Scalability contextPd loading tunable from 0.11 to 0.51 wt % by changing precursor concentration.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HITP)2 cMOF	15 mg in 1.5 mL ethanol for electrode coating	rendered pages 3 and 7 / article pp.26068 and 26072 · Functionalization; Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figure 1b
Solvent	anhydrous ethanol	1.5 mL	rendered pages 3 and 7 / article pp.26068 and 26072 · Functionalization; Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figure 1b
Metal Source	Pd(NH3)4(NO3)2	0.1 mM in DMF for standard Pd SAC sample	rendered pages 3 and 7 / article pp.26068 and 26072 · Functionalization; Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figure 1b
Solvent	N,N-dimethylformamide (DMF)	Not specified	rendered pages 3 and 7 / article pp.26068 and 26072 · Functionalization; Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figure 1b
Other	graphite plate working electrode	40 x 20 x 1 mm	rendered pages 3 and 7 / article pp.26068 and 26072 · Functionalization; Experimental Section - Synthesis of Single-Atom-Stabilized cMOF · Figure 1b

Complete recipeSource: Main

Route 5: Other

rendered page 7 / article p.26072 · Experimental Section - Synthesis of Pd-NP@cMOF · Figure S10

Metal precursorsPd(NH3)4(NO3)2 aqueous solution diluted from 10 wt % stock

Linker precursorspreformed Cu3(HITP)2

Solventsdeionised water

AdditivesNaBH4 reducing agent, 1 mg/mL aqueous solution

Atmospherenot specified

Temperatureroom temperature

Time1

Oxidant / reductantNaBH4 reduction to form Pd nanoparticles in cMOF pores

Work-upResulting powder washed with water three times.

ActivationDried under vacuum.

Scalability contextPd-NP loading controlled by precursor concentration; adjusted to match Pd1-cMOF for comparison.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cu3(HITP)2 cMOF	20 mg	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Pd-NP@cMOF · Figure S10
Solvent	deionised water	1 mL for cMOF dispersion	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Pd-NP@cMOF · Figure S10
Metal Source	Pd(NH3)4(NO3)2 aqueous solution	0.5 mL · diluted from 10 wt % stock to predetermined concentration	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Pd-NP@cMOF · Figure S10
Reductant	NaBH4 aqueous solution	0.5 mL · 1 mg/mL	rendered page 7 / article p.26072 · Experimental Section - Synthesis of Pd-NP@cMOF · Figure S10

Complete recipeSource: Main

Route 6: Drop Cast

rendered page 8 / article p.26073 · Experimental Section - Gas Sensing Measurement · Figure 4

Metal precursorsPd1-cMOF, Pd-NP@cMOF, or pristine cMOF sensing material

Linker precursorsHITP-containing cMOF powder

Solventsethanol, 300 mL per 6 mg sensing material

Atmospheresensing in sealed chamber at room temperature after stabilisation in dry air for 3 h

Temperatureroom temperature

Time0.1667 ultrasonication; 3 h dry-air stabilisation before sensing

Substrate orientationAl2O3 substrate, 2.5 x 2.5 x 0.2 mm, with two interdigitated Au electrodes spaced 75 um apart

Work-up5 uL suspension drop-coated three times to ensure uniform coverage.

ActivationDry-air stabilisation for 3 h before each sensing measurement.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	sensing material	6 mg	rendered page 8 / article p.26073 · Experimental Section - Gas Sensing Measurement · Figure 4
Solvent	ethanol	300 mL	rendered page 8 / article p.26073 · Experimental Section - Gas Sensing Measurement · Figure 4
Other	Al2O3 substrate with interdigitated Au electrodes	2.5 x 2.5 x 0.2 mm; Au electrodes spaced 75 um	rendered page 8 / article p.26073 · Experimental Section - Gas Sensing Measurement · Figure 4