Supplementary information

Mechanochemical defect engineering of HKUST-1 and impact of the resulting

defects on carbon dioxide sorption and catalytic cyclopropanation

Timothy Steenhaut,* Nicolas Grégoire, Gabriella Barozzino-Consiglio, Yaroslav Filinchuk* and Sophie

Hermans*

Université catholique de Louvain, Institute of Condensed Matter and Nanosciences, Place Louis Pasteur 1/L4.01.03,

1348 Louvain-la-Neuve, Belgium

E-mail: timothy.steenhaut@uclouvain.be; yaroslav.filinchuk@uclouvain.be; sophie.hermans@uclouvain.be

A. Optical microscopy morphological and size characterization of the reactants used for the syntheses and

KHUST-1 single crystals

Fig. S1. PXRD of HKUST-1 materials

Fig. S2. FTIR spectra of reactants and obtained materials

Fig. S3. NH3 TPD experiments

Fig. S4. TGA characterization of the HKUST-1 materials

Fig. S5. XPS characterization of the HKUST-1 materials

Table S1. CO2 uptakes for various porous materials

Fig. S6. GC kinetic follow-up of cyclopropanation reaction

Table S2. Results of catalytic cyclopropanation

B. Details of the corrections applied on the raw data of the gravimetric CO2 sorption results

C. Measurement and calculation of T1 for styrene

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2020

- A -

A. Optical microscopy morphological and size characterization of the reactants used for the

mechanochemical syntheses and of the HKUST-1 single crystals.

Sodium chloride

Trimesic acid

Copper (II) acetate monohydrate

HKUST-1 single crystals

- Fig. S1 -

Fig. S1. X-ray powder patterns of the HKUST-1 materials obtained through the different synthesis

pathways.

0 5 10 15 20 25

Norm

aliz

ed i

nte

nsi

ty

2θ (degrees)

SAG EtOH 20 min

SAG EtOH 10 min

SAG EtOH 5 min

SAG MeOH 20 min

SAG MeOH 10 min

SAG MeOH 5 min

LAG

Single crystals

Simulation

- Fig. S2 -

Fig. S2. A. FTIR spectra of copper (II) acetate monohydrate and trimesic acid.

Fig. S2. B. FTIR spectra of as synthesized and activated (150°C, vacuum) samples of HKUST-1 synthesized

by LAG. The 𝜈 C–O bands of ethanol (arrow) disappear upon activation.

05001000150020002500300035004000

Ab

sorb

ance

(a.

u.)

Wavenumber (cm-1)

Trimesic acid

Copper (II) acetate monohydrate

05001000150020002500300035004000

Abso

rban

ce (

a.u

.)

Wavenumber (cm-1)

LAG activated

LAG as synthesized↓

- Fig. S2 -

Fig. S2. C. FTIR spectra of activated (150°C, vacuum) HKUST-1 materials.

05001000150020002500300035004000

Wavenumber (cm-1)

SAG EtOH 20 min

SAG EtOH 10 min

SAG EtOH 5 min

SAG MeOH 20 min

SAG MeOH 10 min

SAG MeOH 5 min

LAG

Single crystals

- Fig. S3 -

Fig. S3. NH3 temperature-programmed desorption on HKUST materials prepared by SAG and treated with

ethanol in comparison with the sample prepared by LAG.

0 50 100 150 200 250 300 350 400

Norm

aliz

ed T

CD

sig

nal

Temperature (°C)

20 min

10 min

5 min

LAG

- Fig. S4 -

Fig. S4. A1. TGA analyses (under air) of HKUST-1 single crystals (as synthesized and powdered).

Fig. S4. A2. TGA analysis (under air) of HKUST-1 obtained by LAG.

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

gh

t (%

)

Temperature (°C)

Single crystals

Single crystals,

powdered

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

ght

(%)

Temperature (°C)

- Fig. S4 -

Fig. S4. A3. TGA analysis (under air) of HKUST-1 obtained by SAG (5 min) and treated with MeOH.

Fig. S4. A4. TGA analysis (under air) of HKUST-1 obtained by SAG (10 min) and treated with MeOH.

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

gh

t (%

)

Temperature (°C)

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

ght

(%)

Temperature (°C)

- Fig. S4 -

Fig. S4. A5. TGA analysis (under air) of HKUST-1 obtained by SAG (20 min) and treated with MeOH.

Fig. S4. A6. TGA analysis (under air) of HKUST-1 obtained by SAG (5 min) and treated with EtOH.

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

gh

t (%

)

Temperature (°C)

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

ght

(%)

Temperature (°C)

- Fig. S4 -

Fig. S4. A7. TGA analysis (under air) of HKUST-1 obtained by SAG (10 min) and treated with EtOH.

Fig. S4. A8. TGA analysis (under air) of HKUST-1 obtained by SAG (20 min) and treated with EtOH.

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

gh

t (%

)

Temperature (°C)

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

ght

(%)

Temperature (°C)

- Fig. S4 -

Fig. S4. A9. TGA analysis (under air) of trimesic acid.

Fig. S4. A10. TGA analysis (under air) of copper (II) acetate.

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

gh

t (%

)

Temperature (°C)

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900

Wei

ght

(%)

Temperature (°C)

- Fig. S4 -

Fig. S4. B. Weight losses during decomposition of the HKUST-1 materials and calculated value for a perfect

Cu3BTC2 structure. Error bars of 1% are shown, corresponding to the typical error for TGA measurements.

Fig. S4. C. Decomposition temperatures of the HKUST-1 materials determined by TGA under air.

55

60

65

70

Calculated Single

crystals

LAG 5 MeOH 10 MeOH 20 MeOH 5 EtOH 10 EtOH 20 EtOH

Wei

ght

loss

du

ring d

eco

mpo

siti

on (

%)

280

300

320

340

360

380

400

Dec

om

posi

tion t

emper

ature

(°C

)

- Fig. S5 -

Fig. S5. A. CuI/CuII surface ratios determined by XPS for the HKUST-1 materials (the single crystal samples

were ground before analysis, the resulting data is thus not representative of the external surface composition

whereas it is for all the other samples that were analyzed as such).

Fig. S5. B. Cu/O and Cu/C atomic ratios determined by XPS for the HKUST-1 materials.

0

1

2

3

4

Single

crystals

LAG MeOH

5 min

MeOH

10 min

MeOH

20 min

EtOH

5 min

EtOH

10 min

EtOH

20 min

Cu(I

)/C

u(I

I) s

urf

ace

com

po

siti

on

(X

PS

)

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

Cu/O

0

0.05

0.1

0.15

0.2

0.25

0.3

Cu/C

- Fig. S5 -

Fig. S5. C. Cu2p region of the XPS spectra of the HKUST-1 materials.

Attribution of deconvolution peaks:

Red: Cu(I) 2p3/2 Blue: Cu(II) 2p3/2

Green: Cu(II) 2p sat. Yellow: Cu(II) 2p sat.

LAG

SAG 5 min MeOH

SAG 10 min MeOH

SAG 20 min MeOH

925930935940945950

Inte

nsi

ty (

a.u

.)

Binding energy (eV)

925930935940945950

Inte

nsi

ty (

a.u

.)

Binding energy (eV)

925930935940945950

Inte

nsi

ty (

a.u.)

Binding energy (eV)

925930935940945950

Inte

nsi

ty (

a.u.)

Binding energy (eV)

- Fig. S5 -

Attribution of deconvolution peaks:

Red: Cu(I) 2p3/2 Blue: Cu(II) 2p3/2

Green: Cu(II) 2p sat. Yellow: Cu(II) 2p sat.

SAG 5 min EtOH SAG 10 min EtOH

SAG 20 min EtOH

925930935940945950

Inte

nsi

ty (

a.u

.)

Binding energy (eV)

925930935940945950

Inte

nsi

ty (

a.u

.)

Binding energy (eV)

925930935940945950

Inte

nsi

ty (

a.u.)

Binding energy (eV)

- Table S1 -

Table S1. CO2 uptakes for illustrative porous materials.

Type of material Material Uptake T P Reference

(mmol/g) (weight %) (K)

MOF HKUST-1 SAG EtOH washed samples 0.5† 2.0 300 1 bar This study

HKUST-1 single crystals 3.9† 17.0 300 1 bar This study

HKUST-1 1.8† 8.1 300 1 bar 1

MIL-96 3.7 16.3† 303 3.5 bar* 2

ZIF-100 1.0 4.2† 298 850 torr 2

MIL-102 3.4 15.0† 304 3 MPa* 2

MIL-53 7.5 33.0† 304 20 bar* 2

MIL-53 10.0 44.0† 304 30 bar* 2

Mg-MOF-74 6.8† 30.1 298 1 bar 2

Ni-MOF-74 4.4† 19.4 298 1 bar 2

MIL-100(Cr) 2.2† 9.5 298 1 bar 2

HKUST-1 2.9† 12.8 313 1 bar 2

MOF and corresponding

post-synthetic modified

derivatives

MIL-101 0.3 1.5† 298 0.15 bar 2

MIL-101-PEI (polyethyleneimine) 4.2 18.5† 298 0.15 bar 2

Mg-MOF-74 5.3† 23.4 298 760 torr 2

Mg-MOF-74-TEPA (tetraethylenepentamine) 6.1† 26.9 298 760 torr 2

MOF composite materials HKUST-1 6.9 30.1† 273‡ 1 bar 2

GO@HKUST-1 9.0 39.7† 273‡ 1 bar 2

ZIF-8 2.2 9.6† 273‡ 1 bar 2

ZIF-8/CNT 2.2 9.7† 273‡ 1 bar 2

Activated carbon from African palm shell 4.4 19.4† 298 n.a. 3

from almond shell 2.1 9.2† 298 n.a. 3

from rice husk 1.3 5.7† 298 n.a. 3

from cotton stalk treated with NH3 at 900°C 1.8 7.9† 298 n.a. 3

Filtrasorb 400 11.1 48.9† 318 16 MPa* 4

Filtrasorb 400 8.0 35.2† 318 5 MPa* 4

Fibers (ACF A10) 4.4† 19.5† 273‡ 100 kPa 5

† Converted values. * Pressures well above 1 bar and should thus not be directly compared to the results of this study. ‡ Temperatures well below 300 K and should thus not be directly compared to the

results of our study. n.a. = non available.

1 Y. Chen, X. Mu, E. Lester and T. Wu, Prog. Nat. Sci. Mater. Int., 2018, 28, 584–589.

2 T. Ghanbari, F. Abnisa and W. M. A. Wan Daud, Sci. Total Environ., 2020, 707, 135090.

3 A. Mukherjee, J. A. Okolie, A. Abdelrasoul, C. Niu and A. K. Dalai, J. Environ. Sci. (China), 2019, 83, 46–63.

4 Y. Gensterblum, P. van Hemert, P. Billemont, A. Busch, D. Charriére, D. Li, B. M. Krooss, G. de Weireld, D. Prinz and K. H. A. A. Wolf, Carbon N. Y., 2009, 47, 2958–2969.

5 Y. Nakahigashi, H. Kanoh, T. Ohba, M. Baba, Y. Hattori, N. Inoue and M. Morimoto, Adsorpt. Sci. Technol., 2012, 30, 621–626.

- Fig. S6 -

Fig. S6. GC kinetic follow-up of the concentration of styrene, cis and trans cyclopropane and diethyl

maleate and fumarate during the catalytic cyclopropanation of styrene with EDA using the LAG synthesized

HKUST-1 material as catalyst.

The plot was obtained by using the following equation:

𝑁𝐶 =𝐼𝑋

𝐼𝑆𝑡𝑦𝑟𝑒𝑛𝑒 + 𝐼𝑡𝑟𝑎𝑛𝑠−𝑐𝑦𝑐𝑙𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 + 𝐼𝑐𝑖𝑠−𝑐𝑦𝑐𝑙𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒

In which 𝑁𝐶 is the normalized concentration of the species 𝑋, 𝐼𝑋 is the measured intensity of the GC signal

of compound 𝑋, and 𝐼𝑆𝑡𝑦𝑟𝑒𝑛𝑒, 𝐼𝑡𝑟𝑎𝑛𝑠−𝑐𝑦𝑐𝑙𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 and 𝐼𝑐𝑖𝑠−𝑐𝑦𝑐𝑙𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 are the intensities of the peaks

observed for styrene, trans-cyclopropane and cis-cyclopropane respectively.

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.5 1 1.5 2 2.5

Norm

aliz

ed c

once

ntr

atio

n (

a.u.)

Time (hours)

Styrene

Diethyl fumarate

Diethyl maleate

Trans-cyclopropane

Cis-cyclopropane

- Table S2 -

Table S2. Conversions and selectivity of the reaction of styrene with EDA obtained with the different tested

catalysts.

Material Conversion (%) Selectivity (%)

EDA Diethylfumarate Diethylmaleate Cis-cyclopropane Trans-cyclopropane

None 0 - - - -

Single crystals 92.6 36.1 19.8 13.0 31.1

LAG 100 26.0 10.8 20.4 42.9

5 min MeOH 7.2 49.0 30.2 6.3 14.6

10 min MeOH 15.2 38.7 28.6 13.4 19.3

20 min MeOH 100 25.7 12.9 20.6 40.8

5 min EtOH 1.9 * * * *

10 min EtOH 0 - - - -

20 min EtOH 0 - - - -

* The conversion obtained for the 5 min EtOH sample is too low to calculate the selectivity with acceptable accuracy.

- B -

B. Corrections applied on the raw data of the gravimetric CO2 sorption and reproducibility test.

Blank measurement (automatically corrected by TGA software)

Raw data with automatic blank correction from TGA software for the 5 min EtOH sample and indication

of the applied corrections

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0.0

0 5000 10000 15000 20000 25000

Wei

ght

(mg)

Time (s)

Isotherm starts here

85

90

95

100

0 5000 10000 15000 20000 25000

Wei

ght

(%)

Time (s)

Set at 100%

Linear deviation that was corrected

Time required

for stabilization

- B -

Reproducibility test, showing two measurements of HKUST-1 LAG sample (red and blue curves) with the

applied corrections, the grey zone around the curves are error bars set at 1%, which is the typical value for

error in TGA measurement.

75

100

125

150

0 5000 10000 15000 20000 25000

Wei

ght

(%)

Time (s)

- C -

C. Measurement and calculation of T1 for styrene (measured on a Bruker AVANCE 500MHz spectrometer).