1

Supporting information

Spray drying of zeolitic imidazolate frameworks Investigation of crystal formation and properties Somboon Chaemchuenab Kui Zhouac Bibimaryam Mousavia Marzieh Ghadamyaria Philippe M Heynderickxd Serge Zhuiykovd Mekhman S Yusubovb Francis Verpoortabd

a Laboratory of Organometallics Catalysis and Ordered Materials State Key Laboratory of Advanced Technology for Materials Synthesis and Processing Center for Chemical and Material Engineering Wuhan University of Technology Wuhan 430070 PR China b National Research Tomsk Polytechnic University Lenin Avenue 30 634050 Tomsk Russian Federation c School of Materials Science and Engineering Wuhan University of Technology Wuhan 430070 PR China d Ghent University Global Campus Songdo 119 Songdomunhwa-Ro Yeonsu-Gu Incheon Korea

1) Synthesis and characterization

11 Experimental

All sample were synthesized via spray drying technique The metal salt and ligand were dissolved in up-water (25 mL) followed by addition of the adequate amount The amount of metal salt and ligand are provided in Table S1 The mixture obtained from the two solutions (metal and ligand solution) was fed to the spray drying instrument with a feed rate of 400 mLh a flow rate of 160 m3h and an inlet temperature of 180 degC The solid powders (as-synthesized) were collected in the collecting bottle of the instrument and immersed in solvent (200 mL) followed by drying to obtain the final product

Table S1 Mole and massvolume of reagent used to synthesize ZIF-8 ZIF-67 and dual metal ZnCo-ZIF

Sample Metal salt Ligand Total solvent

Zn(OAc)22H2O Co(OAc)24H2O 2-IMI Water

ZIF-8 6 mmol 132 g - 8 mmol 066g 50 mL ZIF-67 - 6 mmol 149g 8 mmol 066g 50 mL

ZnCo-ZIF 3 mmol 066 g 3 mmol 0745g 8 mmol 066g 50 mL

Electronic Supplementary Material (ESI) for CrystEngCommThis journal is copy The Royal Society of Chemistry 2018

2

12 General description of the spray drying process

A complete diagram of the spray drying apparatus is illustrated in Scheme S1 In a typical experiment the drying gas enters the apparatus from the top and is heated up to the pre-set inlet temperature then flows through the drying chamber and is filtered before finally leaving the instrument to remove the fine particles The inlet temperature is measured just after the heating and the outlet temperature just before the cyclone The feed solution is introduced to the spray head by a peristaltic pump and is then atomized in a nozzle with a standard diameter of 08 mm in order to disperse the solution into the drying chamber as fine droplets

Scheme S1 Schematic illustration of the laboratory spray dryer (AF-8000)

13 Characterization instruments

The powder X-ray diffraction spectra (XRD) were collected using an Empyrean instrument Bruker D8 applying a monochromatic Cu Kα radiation at ambient conditions Data were collected in 2θ range from 3 to 30o with a scanning rate of 5omin All gas adsorption measurements were analyzed using ASAP 2020 (Micromeritics) apparatus The BET and Langmuir surface areas were calculated at PPo = 001-005 from the nitrogen isotherm The data of pore volume and pore size were estimated using the H-K equation at the relative pressure of PPo = 05 The sample pretreatment (degas) at 200degC for 3h before analyzed samples The morphology studies were conducted on a Scanning Electron Microscope (SEM) from JEOL (JSM-5610LV 05ndash35 kV) Elemental analysis was performed using ICP-AES (Optima4300DV)

3

2) Characterization of materials

5 10 15 20 25 30

8 8

6 8

5 8

4 8Inten

sity

(au

)

2θ

Simulation

Figure S1 XRD analysis effect of ML mmol ratio (M= mole of zinc acetate L= mole of 2-methylimidazole) in 50 mL water with 2-methylimidazole (8 mmol) kept constant

4

Figure S2 The morphologies of obtained products by variation of zinc acetate concentration in the feed solution (50 mL water 066 g or 8 mmol 2-MIM) a) 4 mmol or 088 g b) 5 mmol or 110 g c) 6 mmol or 132 g and d) 8 mmol or 176 g

a) b)

c) d)

5

Table S2 Influence of the feed concentration on product yield and porosity (surface area)

Items Zn (mmol) 2-MIM (mmol) Immersed Yield of product (g) BET (m2g)

1 4 8 3h 011155 1569

21 4 8 1day 013255 1614

22 4 8 1day 013625 1630

23 4 8 1day 01392 1652

3 5 8 3h 017925 1517

41 5 8 1day 02225 1695

42 5 8 1day 02095 1703

43 5 8 1day 01825 1616

5 6 8 3h 02025 1600

61 6 8 1day 02025 1755

62 6 8 1day 02148 1728

63 6 8 1day 02313 1717

7 334 6 1day 01743 1728

8 566 10 1 day 022885 1732

9 8 8 3h 01816 1273

101 8 8 1Day 018435 1328

102 8 8 1Day 016915 1433

103 8 8 1Day 019445 1431 Note Total volume of mixture (feed solution) is 50 mL and water as solvent The synthesis

repeatability was investigate such as 21 22 22 etc

6

5 10 15 20 25 30

ZIF-8

Feed solidMeOHTEA

Feed solidMeOH

Feed solid

Inten

sity

(au

)

2θ

Figure S3 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-8 as reference

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZIF-67

Figure S4 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-67 as reference

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

2

12 General description of the spray drying process

A complete diagram of the spray drying apparatus is illustrated in Scheme S1 In a typical experiment the drying gas enters the apparatus from the top and is heated up to the pre-set inlet temperature then flows through the drying chamber and is filtered before finally leaving the instrument to remove the fine particles The inlet temperature is measured just after the heating and the outlet temperature just before the cyclone The feed solution is introduced to the spray head by a peristaltic pump and is then atomized in a nozzle with a standard diameter of 08 mm in order to disperse the solution into the drying chamber as fine droplets

Scheme S1 Schematic illustration of the laboratory spray dryer (AF-8000)

13 Characterization instruments

The powder X-ray diffraction spectra (XRD) were collected using an Empyrean instrument Bruker D8 applying a monochromatic Cu Kα radiation at ambient conditions Data were collected in 2θ range from 3 to 30o with a scanning rate of 5omin All gas adsorption measurements were analyzed using ASAP 2020 (Micromeritics) apparatus The BET and Langmuir surface areas were calculated at PPo = 001-005 from the nitrogen isotherm The data of pore volume and pore size were estimated using the H-K equation at the relative pressure of PPo = 05 The sample pretreatment (degas) at 200degC for 3h before analyzed samples The morphology studies were conducted on a Scanning Electron Microscope (SEM) from JEOL (JSM-5610LV 05ndash35 kV) Elemental analysis was performed using ICP-AES (Optima4300DV)

3

2) Characterization of materials

5 10 15 20 25 30

8 8

6 8

5 8

4 8Inten

sity

(au

)

2θ

Simulation

Figure S1 XRD analysis effect of ML mmol ratio (M= mole of zinc acetate L= mole of 2-methylimidazole) in 50 mL water with 2-methylimidazole (8 mmol) kept constant

4

Figure S2 The morphologies of obtained products by variation of zinc acetate concentration in the feed solution (50 mL water 066 g or 8 mmol 2-MIM) a) 4 mmol or 088 g b) 5 mmol or 110 g c) 6 mmol or 132 g and d) 8 mmol or 176 g

a) b)

c) d)

5

Table S2 Influence of the feed concentration on product yield and porosity (surface area)

Items Zn (mmol) 2-MIM (mmol) Immersed Yield of product (g) BET (m2g)

1 4 8 3h 011155 1569

21 4 8 1day 013255 1614

22 4 8 1day 013625 1630

23 4 8 1day 01392 1652

3 5 8 3h 017925 1517

41 5 8 1day 02225 1695

42 5 8 1day 02095 1703

43 5 8 1day 01825 1616

5 6 8 3h 02025 1600

61 6 8 1day 02025 1755

62 6 8 1day 02148 1728

63 6 8 1day 02313 1717

7 334 6 1day 01743 1728

8 566 10 1 day 022885 1732

9 8 8 3h 01816 1273

101 8 8 1Day 018435 1328

102 8 8 1Day 016915 1433

103 8 8 1Day 019445 1431 Note Total volume of mixture (feed solution) is 50 mL and water as solvent The synthesis

repeatability was investigate such as 21 22 22 etc

6

5 10 15 20 25 30

ZIF-8

Feed solidMeOHTEA

Feed solidMeOH

Feed solid

Inten

sity

(au

)

2θ

Figure S3 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-8 as reference

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZIF-67

Figure S4 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-67 as reference

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

3

2) Characterization of materials

5 10 15 20 25 30

8 8

6 8

5 8

4 8Inten

sity

(au

)

2θ

Simulation

Figure S1 XRD analysis effect of ML mmol ratio (M= mole of zinc acetate L= mole of 2-methylimidazole) in 50 mL water with 2-methylimidazole (8 mmol) kept constant

4

Figure S2 The morphologies of obtained products by variation of zinc acetate concentration in the feed solution (50 mL water 066 g or 8 mmol 2-MIM) a) 4 mmol or 088 g b) 5 mmol or 110 g c) 6 mmol or 132 g and d) 8 mmol or 176 g

a) b)

c) d)

5

Table S2 Influence of the feed concentration on product yield and porosity (surface area)

Items Zn (mmol) 2-MIM (mmol) Immersed Yield of product (g) BET (m2g)

1 4 8 3h 011155 1569

21 4 8 1day 013255 1614

22 4 8 1day 013625 1630

23 4 8 1day 01392 1652

3 5 8 3h 017925 1517

41 5 8 1day 02225 1695

42 5 8 1day 02095 1703

43 5 8 1day 01825 1616

5 6 8 3h 02025 1600

61 6 8 1day 02025 1755

62 6 8 1day 02148 1728

63 6 8 1day 02313 1717

7 334 6 1day 01743 1728

8 566 10 1 day 022885 1732

9 8 8 3h 01816 1273

101 8 8 1Day 018435 1328

102 8 8 1Day 016915 1433

103 8 8 1Day 019445 1431 Note Total volume of mixture (feed solution) is 50 mL and water as solvent The synthesis

repeatability was investigate such as 21 22 22 etc

6

5 10 15 20 25 30

ZIF-8

Feed solidMeOHTEA

Feed solidMeOH

Feed solid

Inten

sity

(au

)

2θ

Figure S3 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-8 as reference

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZIF-67

Figure S4 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-67 as reference

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

4

Figure S2 The morphologies of obtained products by variation of zinc acetate concentration in the feed solution (50 mL water 066 g or 8 mmol 2-MIM) a) 4 mmol or 088 g b) 5 mmol or 110 g c) 6 mmol or 132 g and d) 8 mmol or 176 g

a) b)

c) d)

5

Table S2 Influence of the feed concentration on product yield and porosity (surface area)

Items Zn (mmol) 2-MIM (mmol) Immersed Yield of product (g) BET (m2g)

1 4 8 3h 011155 1569

21 4 8 1day 013255 1614

22 4 8 1day 013625 1630

23 4 8 1day 01392 1652

3 5 8 3h 017925 1517

41 5 8 1day 02225 1695

42 5 8 1day 02095 1703

43 5 8 1day 01825 1616

5 6 8 3h 02025 1600

61 6 8 1day 02025 1755

62 6 8 1day 02148 1728

63 6 8 1day 02313 1717

7 334 6 1day 01743 1728

8 566 10 1 day 022885 1732

9 8 8 3h 01816 1273

101 8 8 1Day 018435 1328

102 8 8 1Day 016915 1433

103 8 8 1Day 019445 1431 Note Total volume of mixture (feed solution) is 50 mL and water as solvent The synthesis

repeatability was investigate such as 21 22 22 etc

6

5 10 15 20 25 30

ZIF-8

Feed solidMeOHTEA

Feed solidMeOH

Feed solid

Inten

sity

(au

)

2θ

Figure S3 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-8 as reference

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZIF-67

Figure S4 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-67 as reference

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

5

Table S2 Influence of the feed concentration on product yield and porosity (surface area)

Items Zn (mmol) 2-MIM (mmol) Immersed Yield of product (g) BET (m2g)

1 4 8 3h 011155 1569

21 4 8 1day 013255 1614

22 4 8 1day 013625 1630

23 4 8 1day 01392 1652

3 5 8 3h 017925 1517

41 5 8 1day 02225 1695

42 5 8 1day 02095 1703

43 5 8 1day 01825 1616

5 6 8 3h 02025 1600

61 6 8 1day 02025 1755

62 6 8 1day 02148 1728

63 6 8 1day 02313 1717

7 334 6 1day 01743 1728

8 566 10 1 day 022885 1732

9 8 8 3h 01816 1273

101 8 8 1Day 018435 1328

102 8 8 1Day 016915 1433

103 8 8 1Day 019445 1431 Note Total volume of mixture (feed solution) is 50 mL and water as solvent The synthesis

repeatability was investigate such as 21 22 22 etc

6

5 10 15 20 25 30

ZIF-8

Feed solidMeOHTEA

Feed solidMeOH

Feed solid

Inten

sity

(au

)

2θ

Figure S3 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-8 as reference

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZIF-67

Figure S4 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-67 as reference

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

6

5 10 15 20 25 30

ZIF-8

Feed solidMeOHTEA

Feed solidMeOH

Feed solid

Inten

sity

(au

)

2θ

Figure S3 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-8 as reference

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZIF-67

Figure S4 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZIF-67 as reference

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

7

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

Feed solid

Feed solidMeOH

ZnCo-ZIF

Figure S5 The XRD analysis of precipitated solid from the feed solution and after treatment at different conditions and XRD of ZnCo ZIF as reference

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

8

Table S3 Elemental analysis and theoretical calculated element analysis

Compound Structure Element content () Element ratio Zn N C H NZn CZn HZn

Zn-1La

4463 1912 3279 344 0429 0735 0077

Zn-2La

2873 2462 4222 443 0857 1470 0154

Zn-3La

2118 2722 4669 490 1285 2205 0231

Zn-4La

1677 2875 4930 517 1714 2940 0308

ZIF-8a

2873 2461 4222 442 0857 1469 0154

ZIF-8b

3150 2305 4083 349 0732 1296 0111

3150 2293 4078 403 0728 1295 0128

P 1b

2743 1447 3478 4679 0528 1268 0170

2743 1447 3443 458 0528 1255 0167

Note a Calculation based on theoretical structure b Calculation based on the analysis result Zn-1L theoretical elemental analysis Zn 4463 N 1912 C 3279 H 344 Zn-2L theoretical elemental analysis Zn 2872 N 2462 C 4222 H 443 Zn-3L theoretical elemental analysis Zn 2118 N 2722 C 4669 H 489 Zn-4L theoretical elemental analysis Zn 1677 N 2875 C 4930 H 517 ZIF-8 theoretical elemental analysis Zn 2873 N 2461 C 4222 H 442

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

9

5 10 15 20 25 30

2-methylimidazole

Zinc acetate

2θ

Inte

nsity

(au

)

As-synthesized

Figure S6 XRD analysis of metal salt ligand precursor and product as-synthesized

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

10

Figure S7 FTIR analysis ZIF-8 ZIF-67 ZnCo-ZIF and spray dried product (as-synthesis)

3500 3000 2500 1500 1000 500

2-MIM

Tran

sittan

ce (a

u)

Wave number (cm-1)

ZIF-8

3500 3000 2500 1500 1000 500

ZIF-8

As-synthesisZIF-8

Wave number (cm-1)

Tran

smitt

ance

(au

)

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

ZnCo-ZIF

As-synthesisZnCo-ZIF

3500 3000 2500 1500 1000 500

Tran

smitt

ance

(au

)

Wave number (cm-1)

As-synthesisZIF-67

ZIF-67

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

11

100 200 300 400 500 600 700 800 900

20

40

60

80

100

w

eight

chan

ge

Temp (C)

ZIF-8-SP AF-SP ZIF-8-SV

bp of 2-MIM=270 C

ZIF-8 to ZnO

Decoordination Znamp2-MIM

(Maybe) 2-MIM defect

370 C 610 C 740 C

Figure S8 Thermal analysis of as-synthesized (AF-SP) solvothermal (ZIF-8-SV) and spray dried product (ZIF-8-SP)

5 10 15 20 25 30

Inte

nsity

(au

)

2θ

DMF

WaterChloroform

Acetonitrile

Iso-propanol

2-butanol

Ethanol

Methanol

Simulation

Figure S9 XRD analysis of spray dry samples after immersion in different solvents

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

12

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

Iso propanol

Quan

tity

Adso

rbed

(cm

3 g S

TP)

Relative Pressure (PPo)

Methanol

Ethanol

Solvent immersed

BET (m2g)

Langmuir (m2g)

P vol (cm3g

)

P size (nm)

Methanol 1634 1720 06053 128Ethanol 1545 1611 05447 127Iso-propanol 1400 1487 05056 128

Figure S10 Nitrogen isotherm and porosity properties of spray dried product after immersion in different solvents

0 20 40 60 80 1000

5

10

15

20

25

30

35

40

uant

ity A

dsor

bed

(cm

3 g S

TP)

Absolute Pressure (kPa)

ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

a

0 20 40 60 80 100

0

2

4

6

8

10

12

Relative Pressure (PPo)

Qu

antit

y Ad

sorb

ed (c

m3 g

STP

) ZIF-8 adsorption ZIF-8 desorption ZnCo-ZIF adsorption ZnCo-ZIF desorption ZIF-67 adsorption ZIF-67 desorption

b

Figure S11 The gas adsorption capacity of CO2 (a) and CH4 (b) at 273K of ZIFs synthesized via spray drying technique

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

13

Figure S12 CO2 conversion to chloropropene carbonate using NMR spectroscopy The reaction progression was identified using 1H-NMR in CDCl3 500 MHz

Epichlorohydrin δ 357-363 (m 2H) 323 (m 1H) 268 (m 1H) 288 (m 1H)

Chloropropene carbonate 1H NMR (500 MHz CDCl3) δ 490-502 (m 1H) 461 (t J = 86 Hz 1H) 445 (dd J = 89 57 Hz 1H) 368-378 (m 1H) 13C NMR (100 MHz CDCl3) δ 1545 745 670 441

1st run

2nd run

3rd run

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF

14

The catalytic performance was calculated using the peak ratio (323 (m 1H) of epichlorohydrin to 490-502 (m 1H) of chloropropene carbonate)

5 10 15 20 25 30

Spend ZnCo-ZIF

Fresh ZnCo-ZIF

2θ

In

tens

ity (a

u)

Figure S13 XRD analysis of fresh and spend (after 3rd cycle) ZnCo ZIF for the CO2 addition to epoxide

Figure S14 SEM-EDX metals mapping of ZnCo-ZIF