Synthesis evidence

Microfluidic Printing-Induced Dynamic Splitting of Conductive MOF to Expose High-Density Active Sites for Boosted CO2 Electroreduction

Yue J.-N., Wang Y., Meng J. et al. · Small · 2026 · e00018

11 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

6 · Section S2 Supplementary figures and tables · Table S1

Metal precursorsSolution A: Cu(OAc)2.H2O in methanol
Linker precursorsSolution B: HHTP in methanol
Solventsmethanol; silicone oil segmented phase; petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.0833
Substrate orientationPTFE reaction tube, 2 mm i.d. and 3 mm o.d.; flow programme from SI Table S1
Work-upFiltration, washing with organic solvent, Soxhlet extraction with petroleum ether, drying at 60 deg C for 12 h.
ActivationSoxhlet extraction using petroleum ether; dry at 60 deg C for 12 h.
Scalability contextTable S1: injection volume 14 mL; tube volume tied to Qt 0.64 mL min^-1; residence time 5 min; actual time 132 min; yield 0.268 g h^-1; STY 460 kg m^-3 day^-1.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g per 40 mL methanol stock solution6 · Section S2 Supplementary figures and tables · Table S1
LinkerHHTP0.140 g per 40 mL methanol stock solution6 · Section S2 Supplementary figures and tables · Table S1
Additivesilicone oilQoil = 0.533 mL min^-1; Qm+Qo = 0.1067 mL min^-1; Qm = 0.0533 mL min^-1; Qo = 0.0533 mL min^-1 · 500 cs viscosity6 · Section S2 Supplementary figures and tables · Table S1
Complete recipeSource: Both

Route 2: Other

6-7 · Section S2 Supplementary figures and tables · Table S2

Metal precursorsSolution A: 0.200 g Cu(OAc)2.H2O in 40 mL methanol
Linker precursorsSolution B: 0.140 g HHTP in 40 mL methanol
Solventsmethanol; dimethyl silicone oil/silicone oil (PMX-200, 500 cs); petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.1667
Substrate orientationPTFE tubing; Table S2 tube volume 12566 mm^3; residence time 10 min at Qt 1.28 mL min^-1
Work-upCool to room temperature; filtration; wash with organic solvent; collect black powder.
ActivationSoxhlet extraction using petroleum ether as eluent, then dry at 60 deg C for 12 h.
Scalability contextTable S2: injection volume 14 mL; Qt 1.28 mL min^-1; Qoil 1.067 mL min^-1; Qm = Qo = 0.1067 mL min^-1; actual time 66 min; quantity 24 mg; yield 0.146 g h^-1; STY 251 kg m^-3 day^-1.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g in 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
LinkerHHTP0.140 g in 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
Solventmethanol40 mL for solution A; 40 mL for solution B6-7 · Section S2 Supplementary figures and tables · Table S2
Additivedimethyl silicone oil / silicone oil PMX-200Qoil = 1.067 mL min^-1; Qm+Qo = 0.2133 mL min^-1; Qm = Qo = 0.1067 mL min^-1 · 500 cs viscosity6-7 · Section S2 Supplementary figures and tables · Table S2
Solventpetroleum etherSoxhlet eluent6-7 · Section S2 Supplementary figures and tables · Table S2
Complete recipeSource: Both

Route 3: Other

6-7 · Section S2 Supplementary figures and tables · Table S2

Metal precursorsSolution A: 0.200 g Cu(OAc)2.H2O in 40 mL methanol
Linker precursorsSolution B: 0.140 g HHTP in 40 mL methanol
Solventsmethanol; dimethyl silicone oil/silicone oil (PMX-200, 500 cs); petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.3333
Substrate orientationPTFE tubing; Table S2 tube volume 25132 mm^3; residence time 20 min at Qt 1.28 mL min^-1
Work-upCool to room temperature; filtration; wash with organic solvent; collect black powder.
ActivationSoxhlet extraction using petroleum ether as eluent, then dry at 60 deg C for 12 h.
Scalability contextTable S2: injection volume 14 mL; Qt 1.28 mL min^-1; Qoil 1.067 mL min^-1; Qm = Qo = 0.1067 mL min^-1; actual time 66 min; quantity 29 mg; yield 0.088 g h^-1; STY 151 kg m^-3 day^-1.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g in 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
LinkerHHTP0.140 g in 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
Solventmethanol40 mL for solution A; 40 mL for solution B6-7 · Section S2 Supplementary figures and tables · Table S2
Additivedimethyl silicone oil / silicone oil PMX-200Qoil = 1.067 mL min^-1; Qm+Qo = 0.2133 mL min^-1; Qm = Qo = 0.1067 mL min^-1 · 500 cs viscosity6-7 · Section S2 Supplementary figures and tables · Table S2
Solventpetroleum etherSoxhlet eluent6-7 · Section S2 Supplementary figures and tables · Table S2
Complete recipeSource: Both

Route 4: Other

6-7 · Section S2 Supplementary figures and tables · Table S2

Metal precursorsSolution A: 0.200 g Cu(OAc)2.H2O in 40 mL methanol
Linker precursorsSolution B: 0.140 g HHTP in 40 mL methanol
Solventsmethanol; dimethyl silicone oil/silicone oil (PMX-200, 500 cs); petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.0417
Substrate orientationPTFE tubing; Table S2 tube volume 3141 mm^3; residence time 2.5 min at Qt 1.28 mL min^-1
Work-upCool to room temperature; filtration; wash with organic solvent; collect black powder.
ActivationSoxhlet extraction using petroleum ether as eluent, then dry at 60 deg C for 12 h.
Scalability contextTable S2: injection volume 14 mL; Qt 1.28 mL min^-1; Qoil 1.067 mL min^-1; Qm = Qo = 0.1067 mL min^-1; actual time 66 min; quantity 25 mg; yield 0.611 g h^-1; STY 1047 kg m^-3 day^-1.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g in 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
LinkerHHTP0.140 g in 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
Solventmethanol40 mL for solution A; 40 mL for solution B6-7 · Section S2 Supplementary figures and tables · Table S2
Additivedimethyl silicone oil / silicone oil PMX-200Qoil = 1.067 mL min^-1; Qm+Qo = 0.2133 mL min^-1; Qm = Qo = 0.1067 mL min^-1 · 500 cs viscosity6-7 · Section S2 Supplementary figures and tables · Table S2
Solventpetroleum etherSoxhlet eluent6-7 · Section S2 Supplementary figures and tables · Table S2
Complete recipeSource: Both

Route 5: Other

6 · Section S2 Supplementary figures and tables · Table S1

Metal precursorsSolution A: 0.200 g Cu(OAc)2.H2O in 40 mL methanol
Linker precursorsSolution B: 0.140 g HHTP in 40 mL methanol
Solventsmethanol; dimethyl silicone oil/silicone oil (PMX-200, 500 cs) as segmented phase; petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.0833
Substrate orientationPTFE reaction tube, 2 mm i.d. and 3 mm o.d.; flow programme from SI Table S1
Work-upCool to room temperature; filtration; wash with organic solvent; collect black powder.
ActivationSoxhlet extraction using petroleum ether as eluent, then dry at 60 deg C for 12 h.
Scalability contextTable S1: injection volume 14 mL; tube volume tied to Qt 1.28 mL min^-1; residence time 5 min; actual time 66 min; yield 0.293 g h^-1; STY 502 kg m^-3 day^-1.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g in 40 mL methanol6 · Section S2 Supplementary figures and tables · Table S1
LinkerHHTP0.140 g in 40 mL methanol6 · Section S2 Supplementary figures and tables · Table S1
Solventmethanol40 mL for solution A; 40 mL for solution B6 · Section S2 Supplementary figures and tables · Table S1
Additivedimethyl silicone oil / silicone oil PMX-200, 500 csQoil = 1.067 mL min^-1; Qm+Qo = 0.2133 mL min^-1; Qm = 0.1067 mL min^-1; Qo = 0.1067 mL min^-16 · Section S2 Supplementary figures and tables · Table S1
Solventpetroleum etherSoxhlet eluent6 · Section S2 Supplementary figures and tables · Table S1
Complete recipeSource: Both

Route 6: Other

6-7 · Section S2 Supplementary figures and tables · Table S2

Metal precursorsSolution A: Cu(OAc)2.H2O in methanol
Linker precursorsSolution B: HHTP in methanol
Solventsmethanol; silicone oil segmented phase; petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.0417-0.333
Substrate orientationPTFE tubing length adjusted to control residence time
Work-upFiltration, washing with organic solvent, Soxhlet extraction with petroleum ether, drying at 60 deg C for 12 h.
ActivationSoxhlet extraction using petroleum ether; dry at 60 deg C for 12 h.
Scalability contextTotal flow rate fixed at 1.28 mL min^-1; residence times 2.5, 5, 10, and 20 min.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g per 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
LinkerHHTP0.140 g per 40 mL methanol stock solution6-7 · Section S2 Supplementary figures and tables · Table S2
Additivesilicone oilpump rate not recovered for all ty variants · 500 cs viscosity6-7 · Section S2 Supplementary figures and tables · Table S2
Complete recipeSource: Both

Route 7: Other

6 · Section S2 Supplementary figures and tables · Table S1

Metal precursorsSolution A: Cu(OAc)2.H2O in methanol
Linker precursorsSolution B: HHTP in methanol
Solventsmethanol; silicone oil segmented phase; petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.0833
Substrate orientationPTFE reaction tube, 2 mm i.d. and 3 mm o.d.; flow programme from SI Table S1
Work-upFiltration, washing with organic solvent, Soxhlet extraction with petroleum ether, drying at 60 deg C for 12 h.
ActivationSoxhlet extraction using petroleum ether; dry at 60 deg C for 12 h.
Scalability contextTable S1: injection volume 14 mL; tube volume tied to Qt 2.56 mL min^-1; residence time 5 min; actual time 33 min; yield 0.305 g h^-1; STY 523 kg m^-3 day^-1.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g per 40 mL methanol stock solution6 · Section S2 Supplementary figures and tables · Table S1
LinkerHHTP0.140 g per 40 mL methanol stock solution6 · Section S2 Supplementary figures and tables · Table S1
Additivesilicone oilQoil = 2.133 mL min^-1; Qm+Qo = 0.4267 mL min^-1; Qm = 0.2133 mL min^-1; Qo = 0.2133 mL min^-1 · 500 cs viscosity6 · Section S2 Supplementary figures and tables · Table S1
Complete recipeSource: Both

Route 8: Other

6 · Section S2 Supplementary figures and tables · Table S1

Metal precursorsSolution A: Cu(OAc)2.H2O in methanol
Linker precursorsSolution B: HHTP in methanol
Solventsmethanol; silicone oil segmented phase; petroleum ether Soxhlet eluent
Additivessilicone oil segmented phase
Atmospherenot stated
Temperature65
Time0.0833
Substrate orientationPTFE reaction tube, 2 mm i.d. and 3 mm o.d.; flow programme from SI Table S1
Work-upFiltration, washing with organic solvent, Soxhlet extraction with petroleum ether, drying at 60 deg C for 12 h.
ActivationSoxhlet extraction using petroleum ether; dry at 60 deg C for 12 h.
Scalability contextTable S1: injection volume 14 mL; tube volume tied to Qt 5.12 mL min^-1; residence time 5 min; actual time 7 min; yield 0.146 g h^-1; STY 251 kg m^-3 day^-1.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(OAc)2.H2O0.200 g per 40 mL methanol stock solution6 · Section S2 Supplementary figures and tables · Table S1
LinkerHHTP0.140 g per 40 mL methanol stock solution6 · Section S2 Supplementary figures and tables · Table S1
Additivesilicone oilQoil = 3.143 mL min^-1; Qm+Qo = 1.977 mL min^-1; Qm = 0.9885 mL min^-1; Qo = 0.9885 mL min^-1 · 500 cs viscosity6 · Section S2 Supplementary figures and tables · Table S1
Complete recipeSource: SI

Route 9: Drop Cast

3-4 · Section S1 Electrochemical measurements, H-cell

Solvents900 uL isopropanol
Additives100 uL NafionD521 dispersion solution (5 wt%)
Atmosphereroom temperature, not otherwise stated
Temperature298.15 K room temperature
Time0.5 h sonication
Substrate orientation5 mm diameter glassy carbon electrode; 10 uL ink drop-cast
Work-upUltrasound sonication for 30 min to form ink; 10 uL dispensed onto GCE.
Activationnone stated
Scalability contextApplication electrode preparation, not framework synthesis.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherMF-cMOFQx/ty catalyst10 mg catalyst in ink preparation; 10 uL ink contains approximately 0.1 mg catalyst3-4 · Section S1 Electrochemical measurements, H-cell
Solventisopropanol900 uL3-4 · Section S1 Electrochemical measurements, H-cell
AdditiveNafionD521 dispersion solution100 uL · 5 wt %3-4 · Section S1 Electrochemical measurements, H-cell
Complete recipeSource: SI

Route 10: Drop Cast

3-4 · Section S1 Electrochemical measurements, H-cell

Solvents900 uL isopropanol
Additives100 uL NafionD521 dispersion solution (5 wt%)
Atmosphereroom temperature, not otherwise stated
Temperature298.15 K room temperature
Time0.5 h sonication
Substrate orientation5 mm diameter glassy carbon electrode; 10 uL ink drop-cast
Work-upUltrasound sonication for 30 min to form ink; 10 uL dispensed onto GCE.
Activationnone stated
Scalability contextApplication electrode preparation, not framework synthesis.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherST-cMOF catalyst10 mg catalyst in ink preparation; 10 uL ink contains approximately 0.1 mg catalyst3-4 · Section S1 Electrochemical measurements, H-cell
Solventisopropanol900 uL3-4 · Section S1 Electrochemical measurements, H-cell
AdditiveNafionD521 dispersion solution100 uL · 5 wt %3-4 · Section S1 Electrochemical measurements, H-cell
Complete recipeSource: Both

Route 11: Solvothermal

Section S1 Experimental section, Synthesis

Metal precursors10 mg copper(II) acetate monohydrate, Cu(OAc)2.H2O
Linker precursors7 mg HHTP
Solvents4 mL methanol
Atmospherenot stated
Temperature65
Time24
Work-upCool to room temperature; centrifuge; wash with DI water and ethanol several times; vacuum dry at 60 deg C for 12 h.
ActivationVacuum drying at 60 deg C for 12 h; no separate solvent activation reported for ST-cMOF.
Scalability contextConventional control; reported STY 1.78 kg m^-3 day^-1 and 24 h synthesis.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal Sourcecopper (II) acetate monohydrate (Cu(OAc)2.H2O)10 mgSection S1 Experimental section, Synthesis
Linker2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)7 mgSection S1 Experimental section, Synthesis
Solventmethanol4 mLSection S1 Experimental section, Synthesis