Synthesis · Rational Design of Conductive MOF-Based Diatomic Electrocatalysts for Selective Ammonia Synthesis

7 structured synthesis routes

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

Partial recipeSource: SI

Route 1: Solvothermal

3 · Synthesis of Cu95M5-DBCO catalysts

Metal precursorsCu(OAc)2.H2O plus corresponding M(OAc)2.H2O salts, M = Co, Fe, Rh, Pd, Ru

Linker precursorsH8DBCO

Solventssame as Cu95Ni5-DBCO generic Cu-rich route

Atmospherenot specified

Temperature85

Time12

Work-upsame as Cu95Ni5-DBCO / Cu-rich route

Activationoven drying; no separate activation reported

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2.H2O	not specified	3 · Synthesis of Cu95M5-DBCO catalysts
Metal Source	M(OAc)2.H2O salts (M = Co, Fe, Rh, Pd, Ru)	not specified	3 · Synthesis of Cu95M5-DBCO catalysts
Linker	H8DBCO	not specified for M series	3 · Synthesis of Cu95M5-DBCO catalysts

Partial recipeSource: Both

Route 2: Solvothermal

7 · Rational Design · Figure 5a

Metal precursorsCu(OAc)2.H2O and Ni(OAc)2.H2O adjusted to Cu/Ni = 98.5/1.5

Linker precursorsH8DBCO

SolventsDMF and deionized water

Atmospherenot specified

Temperature85

Time12

Work-upsame as Cu-rich CuxNiy-DBCO route

Activationoven drying; no separate activation reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H8DBCO	not composition-specific; generic route uses 57 mg	7 · Rational Design · Figure 5a
Metal Source	Cu(OAc)2.H2O	stoichiometric amount for Cu98.5Ni1.5	7 · Rational Design · Figure 5a
Metal Source	Ni(OAc)2.H2O	stoichiometric amount for Cu98.5Ni1.5	7 · Rational Design · Figure 5a
Solvent	DMF/deionized water	generic Cu-rich route volumes	7 · Rational Design · Figure 5a

Complete recipeSource: SI

Route 3: Solvothermal

2 · Synthesis of Cu-DBCO catalysts

Metal precursorsCu(OAc)2.H2O (199 mg, 1 mmol)

Linker precursorsH8DBCO (228 mg, 0.5 mmol)

Solventsdeionized water (30.4 mL) and DMF (9.6 mL)

Atmospherenot specified

Temperature85

Time12

Work-upcool naturally; centrifuge; wash three times each with DMF and methanol; dry overnight at 60 C

Activationoven drying at 60 C overnight; no separate activation reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H8DBCO	228 mg, 0.5 mmol	2 · Synthesis of Cu-DBCO catalysts
Metal Source	Cu(OAc)2.H2O	199 mg, 1 mmol	2 · Synthesis of Cu-DBCO catalysts
Solvent	deionized water	30.4 mL	2 · Synthesis of Cu-DBCO catalysts
Solvent	N,N Dimethylformamide (DMF)	9.6 mL	2 · Synthesis of Cu-DBCO catalysts

Complete recipeSource: SI

Route 4: Solvothermal

2 · Synthesis of CuxNiy-DBCO catalysts (y<70)

Metal precursorsCu(OAc)2.H2O and Ni(OAc)2.H2O in desired stoichiometric amounts; Ni introduced first, then Cu

Linker precursorsH8DBCO (57 mg)

SolventsDMF (2.4 mL) plus deionized water to total solvent volume 10 mL

Atmospherenot specified

Temperature85

Time12

Work-upsame procedure as Cu-DBCO: natural cooling, centrifugation, DMF/methanol washing, overnight drying at 60 C

Activationoven drying at 60 C overnight; no separate activation reported

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H8DBCO	57 mg	2 · Synthesis of CuxNiy-DBCO catalysts (y<70)
Metal Source	Ni(OAc)2.H2O	desired stoichiometric amount	2 · Synthesis of CuxNiy-DBCO catalysts (y<70)
Metal Source	Cu(OAc)2.H2O	desired stoichiometric amount	2 · Synthesis of CuxNiy-DBCO catalysts (y<70)
Solvent	DMF	2.4 mL	2 · Synthesis of CuxNiy-DBCO catalysts (y<70)
Solvent	deionized water	added to total solvent volume 10 mL	2 · Synthesis of CuxNiy-DBCO catalysts (y<70)

Partial recipeSource: SI

Route 5: Solvothermal

3 · Synthesis of CuxNiy-DBCO catalysts (y>70)

Metal precursorsCu(OAc)2.H2O (4.4 mg, 0.022 mmol) and Ni(OAc)2.4H2O (49.5 mg, 0.198 mmol) for Cu10Ni90-DBCO; Ni(OAc)2.4H2O (55 mg, 0.2 mmol) for Ni-DBCO

Linker precursorsH8DBCO (50 mg, 0.11 mmol)

SolventsNMP (3 mL) and deionized water (3 mL)

AdditivesKOH (100 uL, 1 M)

Atmospherenot specified

Temperature100

Time48

Work-upnot specified after heating in the high-Ni route

Activationnot specified

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	H8DBCO	50 mg, 0.11 mmol	3 · Synthesis of CuxNiy-DBCO catalysts (y>70)
Solvent	NMP	3 mL	3 · Synthesis of CuxNiy-DBCO catalysts (y>70)
Base	KOH	100 uL · 1 M	3 · Synthesis of CuxNiy-DBCO catalysts (y>70)
Metal Source	Cu(OAc)2.H2O	4.4 mg, 0.022 mmol for Cu10Ni90	3 · Synthesis of CuxNiy-DBCO catalysts (y>70)
Metal Source	Ni(OAc)2.4H2O	49.5 mg, 0.198 mmol for Cu10Ni90; 55 mg, 0.2 mmol for Ni-DBCO	3 · Synthesis of CuxNiy-DBCO catalysts (y>70)
Solvent	deionized water	3 mL	3 · Synthesis of CuxNiy-DBCO catalysts (y>70)

Partial recipeSource: SI

Route 6: Drop Cast

5 · Electrochemical measurements

Solventscatalyst ink solvent not specified for carbon cloth coating

AtmosphereAr purged electrolyte during testing

Temperatureambient

Substrate orientationcarbon cloth working electrode, area 0.5 x 1 cm2; carbon paper/graphene paper for some spectroscopies

Work-upcatalyst-coated carbon cloth used directly as working electrode

Activationelectrolyte purged with high-purity Ar for 30 min before NO3RR

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CuxNiy-DBCO catalyst	0.3 mg cm-2 loading	5 · Electrochemical measurements
Other	carbon cloth	0.5 x 1 cm2	5 · Electrochemical measurements
Electrolyte	KHCO3 + KNO3	0.1 M KHCO3 + 0.05 M KNO3	5 · Electrochemical measurements

Complete recipeSource: SI

Route 7: Other

7 · Assembly of the Zn-NO3 battery

Metal precursorsZn plate anode; Cu98.5Ni1.5-DBCO catalyst cathode

Solventsaqueous KOH/KNO3 electrolytes

Atmospherenot specified

Temperatureroom temperature

Substrate orientationH-type cell with bipolar membrane

Oxidant / reductantNO3- cathodic reduction; Zn anodic oxidation

Work-upbattery assembled and discharged/polarised electrochemically

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	carbon cloth-supported Cu98.5Ni1.5-DBCO catalyst	Not specified	7 · Assembly of the Zn-NO3 battery
Other	Zn plate	Not specified	7 · Assembly of the Zn-NO3 battery
Electrolyte	cathode electrolyte	30 mL · 1.0 M KOH + 0.1 M KNO3	7 · Assembly of the Zn-NO3 battery
Electrolyte	anode electrolyte	30 mL · 1 M KOH	7 · Assembly of the Zn-NO3 battery
Other	bipolar membrane	Not specified	7 · Assembly of the Zn-NO3 battery