Synthesis · Tuning the dxy Orbital Energy Level in 2D Cobalt-Organic-Framework via in-Plane Conjugated Phthalocyanine for Self-Powered Sensing

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

2 · Synthesis of 2D MOF

Metal precursorsCo(NO3)2.6H2O (0.250 g)

Linker precursorsp-phthalic acid (PTA, 0.0714 g)

Solvents20 mL deionised water for cobalt salt; 40 mL DMF/ethanol (1:1 v/v) for PTA

Additivestriethylamine (0.8 mL)

Atmosphereair/ambient, not otherwise specified

Temperatureroom temperature

Time1

Work-upWashed with deionised water and ethanol several times; air dried naturally.

Activationnone reported

Scalability contextRoom-temperature ultrasound route; no yield or batch scaling reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	0.250 g	2 · Synthesis of 2D MOF
Linker	p-phthalic acid (PTA)	0.0714 g · 99%	2 · Synthesis of 2D MOF
Solvent	deionized water	20 mL	2 · Synthesis of 2D MOF
Solvent	DMF/C2H5OH	40 mL · 1:1 v/v	2 · Synthesis of 2D MOF
Base	triethylamine	0.8 mL	2 · Synthesis of 2D MOF

Complete recipeSource: SI

Route 2: Other

2 · Synthesize of 2D MOF@Pc · Figure S1

Metal precursorsCo(NO3)2.6H2O (0.250 g), inherited from 2D MOF route

Linker precursorsPTA (0.0714 g) plus phthalocyanine (Pc, 0.0416 g)

Solventswater and DMF/ethanol as in 2D MOF route

Additivestriethylamine; Pc

Atmosphereair/ambient, not otherwise specified

Temperatureroom temperature

Time1 h ultrasound plus 1 h stirring with Pc

Work-upSame as 2D MOF route; obtained product denoted 2D MOF@Pc.

Activationnone reported

Scalability contextNo yield or scale-up data reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	0.250 g	2 · Synthesize of 2D MOF@Pc · Figure S1
Linker	p-phthalic acid (PTA)	0.0714 g · 99%	2 · Synthesize of 2D MOF@Pc · Figure S1
Additive	Pc	0.0416 g	2 · Synthesize of 2D MOF@Pc · Figure S1
Base	triethylamine	0.8 mL	2 · Synthesize of 2D MOF@Pc · Figure S1
Solvent	DMF/C2H5OH and water	40 mL plus 20 mL · DMF/C2H5OH 1:1 v/v	2 · Synthesize of 2D MOF@Pc · Figure S1

Complete recipeSource: SI

Route 3: Other

3 · Synthesis of composite DNH · Figure S2

Metal precursors2D MOF@Pc nanofiller

Linker precursorsCMC and PVA polymer matrix; EG additive

Solventsdeionised water

Additivesethylene glycol (1 mL)

Atmosphereair/ambient, not otherwise specified

Temperature60 C for CMC solution; 90 C for PVA solution; -20 C freeze; room temperature thaw

Time2 h CMC stirring; 2 h PVA stirring; 1 h mixing; 12 h freeze; 2 h thaw; three freeze-thaw cycles

Substrate orientationTeflon mould

Work-upMixture poured into Teflon mould, frozen and thawed for three cycles.

Activationnone reported

Scalability contextBatch used 50 mL filler/CMC dispersion and 50 mL PVA solution; no production scale data.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	CMC powder	1 g · 2 wt% solution in 49 mL water	3 · Synthesis of composite DNH · Figure S2
Additive	2D MOF@Pc	1 g; 50 mL of dispersion used · ~20 mg/mL in CMC solution	3 · Synthesis of composite DNH · Figure S2
Additive	PVA powder	10 g · 10 wt% solution in 90 mL water	3 · Synthesis of composite DNH · Figure S2
Additive	ethylene glycol (EG)	1 mL	3 · Synthesis of composite DNH · Figure S2
Solvent	deionized water	49 mL plus 90 mL	3 · Synthesis of composite DNH · Figure S2

Partial recipeSource: SI

Route 4: Other

2-3 · Synthesis of 3D MOF and 3D MOF@Pc

Metal precursorsCo(NO3)2.6H2O, as in 2D MOF route

Linker precursorsPTA, as in 2D MOF route

Solventswater and DMF/ethanol as in 2D MOF route

Additivestriethylamine

Atmosphereair/ambient, not otherwise specified

Temperatureroom temperature

Timenot fully specified for non-ultrasonic variant

Work-upNot separately specified; presumed as 2D MOF route.

Activationnone reported

Scalability contextNo yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	same as 2D MOF route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc
Linker	PTA	same as 2D MOF route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc
Base	triethylamine	same as 2D MOF route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc

Partial recipeSource: SI

Route 5: Other

2-3 · Synthesis of 3D MOF and 3D MOF@Pc

Metal precursorsCo(NO3)2.6H2O, as in 2D MOF@Pc route

Linker precursorsPTA plus Pc, as in 2D MOF@Pc route

Solventswater and DMF/ethanol as in 2D MOF@Pc route

Additivestriethylamine; Pc

Atmosphereair/ambient, not otherwise specified

Temperatureroom temperature

Timenot fully specified for non-ultrasonic variant

Work-upNot separately specified; presumed as 2D MOF@Pc route.

Activationnone reported

Scalability contextNo yield reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Co(NO3)2.6H2O	same as 2D MOF@Pc route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc
Linker	PTA	same as 2D MOF@Pc route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc
Additive	Pc	same as 2D MOF@Pc route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc
Base	triethylamine	same as 2D MOF@Pc route	2-3 · Synthesis of 3D MOF and 3D MOF@Pc

Partial recipeSource: SI

Route 6: Other

3 · Synthesis of composite DNH

Metal precursors3D MOF, 3D MOF@Pc, 2D MOF or 2D MOF@Pc fillers

Linker precursorsCMC/PVA/EG hydrogel matrix

Solventsdeionised water

Additivesethylene glycol

Atmosphereair/ambient, not otherwise specified

Temperature60 C; 90 C; -20 C freeze; room temperature thaw

Timesame freeze-thaw strategy as target 2D MOF@Pc/DNH

Substrate orientationTeflon mould

Work-upFreeze-thawing strategy with little modifications.

Activationnone reported

Scalability contextControls use the same strategy but detailed filler substitutions are not separately quantified.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	MOF filler	not separately specified for each variant	3 · Synthesis of composite DNH
Additive	CMC	1 g for target recipe · 2 wt%	3 · Synthesis of composite DNH
Additive	PVA	10 g for target recipe · 10 wt%	3 · Synthesis of composite DNH
Additive	EG	1 mL for target recipe	3 · Synthesis of composite DNH

Complete recipeSource: SI

Route 7: Other

3 · Assembling of 2D MOF@Pc/DNH sensor

Metal precursors2D MOF@Pc/DNH strip

AdditivesAg conductive tape; copper wires; VHB tape

Atmosphereair/ambient

Temperatureroom temperature

Substrate orientationattached to human body positions with VHB tape

Work-upRectangular strip connected to Ag tape and copper wires.

Activationnone reported

Scalability contextDevice geometry reported; no fabrication yield reported.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2D MOF@Pc/DNH strip	8 cm x 1 cm x 0.3 cm	3 · Assembling of 2D MOF@Pc/DNH sensor
Other	Ag conductive tape	two pieces, 10 cm x 1 cm	3 · Assembling of 2D MOF@Pc/DNH sensor
Other	copper wires	Phi = 2 mm	3 · Assembling of 2D MOF@Pc/DNH sensor

Complete recipeSource: SI

Route 8: Other

4 · Fabrication of 2D MOF@Pc/DNH supercapacitor · Figure S15

Metal precursors2D MOF@Pc/DNH strip

SolventsH2SO4 electrolyte solution

Additivesactive carbon films; nickel foam

Atmosphereair/ambient

Temperatureroom temperature

Time2 h H2SO4 soak

Substrate orientationsandwiched between AC films and encapsulated with nickel foam

Work-upWiped with filter paper to remove residual electrolyte.

Activation2 mol L-1 H2SO4 soaking for 2 h

Scalability contextDevice geometry reported; no production scale data.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2D MOF@Pc/DNH strip	4 cm x 2 cm x 0.2 cm	4 · Fabrication of 2D MOF@Pc/DNH supercapacitor · Figure S15
Electrolyte	H2SO4 solution	soak for 2 h · 2 mol L-1	4 · Fabrication of 2D MOF@Pc/DNH supercapacitor · Figure S15
Other	active carbon films	sandwich layers	4 · Fabrication of 2D MOF@Pc/DNH supercapacitor · Figure S15
Other	nickel foam	encapsulation	4 · Fabrication of 2D MOF@Pc/DNH supercapacitor · Figure S15

Complete recipeSource: SI

Route 9: Other

4 · Construction of 2D MOF@Pc/DNH TENG

Metal precursors2D MOF@Pc/DNH hydrogel

AdditivesVHB elastomer; PVDF; Ag electrodes

Atmosphereair/ambient

Temperature~25 C test temperature

Substrate orientationsingle-electrode vertical contact-separation mode; effective area 4 x 4 cm2

Work-upHydrogel sealed by VHB elastomer; paired with PVDF tribonegative layer.

Activationnone reported

Scalability contextDevice area reported; no manufacturing scale data.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	2D MOF@Pc/DNH hydrogel	4 cm x 4 cm x 0.2 cm	4 · Construction of 2D MOF@Pc/DNH TENG
Other	PVDF	tribonegative layer	4 · Construction of 2D MOF@Pc/DNH TENG
Other	Ag	electrode layers	4 · Construction of 2D MOF@Pc/DNH TENG
Other	VHB elastomer	sealant	4 · Construction of 2D MOF@Pc/DNH TENG