Supplementary informationSupplementary information Mechanochemical defect engineering of HKUST-1 and...
Transcript of Supplementary informationSupplementary information Mechanochemical defect engineering of HKUST-1 and...
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: [email protected]; [email protected]; [email protected]
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).