Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2017
Supporting Information
for
Standard and Rapid-Scan Infrared Spectroscopic Studies of o-Xylene Transformations in Terms of Pore Arrangement of 10-ring zeolites - 2D COS Analysis Kinga Gołąbek, Karolina A. Tarach*, and Kinga Góra-Marek* Faculty of Chemistry, Jagiellonian University in Kraków, 3 Ingardena St., 30-060 Kraków, Poland, phone: +48 12 663 2081, fax: +48 12 634 0515
Corresponding Author *Karolina A. Tarach, Faculty of Chemistry, Jagiellonian University in Kraków, 3 Ingarden St., 30-060 Kraków, Poland, phone +48 (12) 663-20-81, fax. +48 (12) 634-05-15 E-mail address:
[email protected] *Kinga Góra-Marek, Faculty of Chemistry, Jagiellonian University in Kraków, 3 Ingarden St., 30-060 Kraków, Poland, phone +48 (12) 663-20-81, fax. +48 (12) 634-05-15 E-mail address:
[email protected]
TNU-10 ZSM-22 ZSM-5
TNU-9
IM-5 10
15
20
25
30
2
35
40
B
200
N2 ads./cm3 STP g-1
ZSM-5_hs
0,6
160
Al-OH
C
Si-OH 3745
0,4
D
Si(OH)Al 3591
0,2
0,0
ZSM-5_hs 0,6 2
4
6
8
10
absorbance
240
dV/d log D
A
D/nm
120 80
3597
TNU-10
3606
0,3
ZSM-22
3613
ZSM-5 3614
TNU-9
40
3610
IM-5
0,0
0 0,0
0,3
0,6
p/p0
0,9
3800
3600
3400
/cm
3200
-1
Figure 1_SI. XRD patterns (A) and N2 adsorption (full symbols) and desorption (empty symbols) isotherms (B), pore size distribution (C) as well as the IR spectra of the zeolites studied in the region of the O-H groups vibrations (D).
A o-xylene
A = 0.02 1650
1600
1550
1500
1450
1400
m-xylene
1650
1600
1550
1500
1450
1400
p-xylene
1650
1600
1550
1500
1450
1400
cm-1
1,3,5-TMB
A = 0.02
1650
1600
1550
1500
1450
1400
1,2,4-TMB
1650
1600
1550
1500
1450
1400
toluene 1650
1600
1550
1500
1450
1400
cm-1
B
A = 0.01
b a 1650
1575
1500
1425
/cm-1 Figure 2_SI. A: The coloured curves represent all the bands found for individual reagent upon deconvolution procedure. The shaded curve represents the diagnostic band used in quantitative studies. The black dashed curve is the sum of the spectrum of the already considered product and the spectra of the products presented above. B: a – the IR spectrum reconstructed from the spectra of reactants, b - the spectrum recorded upon contact with o-xylene with zeolite ZSM-5 at o 250 C in 15 min.
ZSM-5 1 min. A=0.01
15 min.
1650
1600
1550
1350
1500
1450
1350 /cm-1
1350
5,540E-05 4,438E-05
1400
1400
5,750E-07 4,312E-07
1400
3,335E-05
2,875E-07
1450
1450
1,438E-07
1500
1,130E-05 2,750E-07
1550
cm-1
cm-1
2,233E-05
1500
0,000 -1,438E-07
1550 -2,875E-07
-1,075E-05
1600
1600
1650 1650
-4,313E-07
-2,177E-05 -3,280E-05
1600
1550
1500
1450
1400
1350
1650 1650
-5,750E-07
1600
1550
1500
1450
1400
1350
cm-1
cm-1
Synchronous
Asynchronous −1
−1
(+) (m-xylene) 1605 cm ~ 1515 cm (p-xylene) −1 −1 −1 −1 (-) (p-xylene) 1515 cm ~ 1465 cm (o-xylene) (-) (p-xylene) 1515 cm ~ 1465 cm (o-xylene) −1 −1 −1 −1 (-) (m-xylene) 1605 cm ~ 1465 cm (o-xylene) (-) (m-xylene) 1605 cm ~ 1465 cm (o-xylene) −1 −1 −1 −1 (-) (1,3,5-TMB) 1610 cm ~ 1465 cm (o-xylene) (-) (1,3,5-TMB) 1610 cm ~ 1465 cm (o-xylene) −1 −1 −1 −1 (+) (1,3,5-TMB) 1610 cm ~ 1605 cm (m-xylene) (+) (1,3,5-TMB) 1610 cm ~ 1605 cm (m-xylene) −1 −1 −1 −1 (+) (1,3,5-TMB) 1610 cm ~ 1515 cm (p-xylene) (+) (1,3,5-TMB) 1610 cm ~ 1515 cm (p-xylene) −1 −1 −1 −1 (-) (p-xylene) 1515 cm ~ 1495 cm (toluene) (-) (p-xylene) 1515 cm ~ 1495 cm (toluene) −1 −1 −1 −1 (-) (m-xylene) 1605 cm ~ 1495 cm (toluene) (-) (m-xylene) 1605 cm ~ 1495 cm (toluene) o Figure 3_SI. The 2D synchronous and asynchronous correlation maps of ortho-xylene isomerization reaction at 250 C for zeolite ZSM-5 in 15 min. of the reaction. The IR spectra subjected the correlation procedure are presented in the upper part. The correlations are listed in the table.
TNU-9 1 min. A=0.01
15 min.
1650
1600
1550
1350
1500
1450
1350 /cm-1
1350
4,320E-05 3,310E-05
1400
1400
7,550E-07 5,662E-07
1400
3,775E-07
2,300E-05
1450
1450
1,887E-07
1500
2,800E-06 -7,300E-06
1550
2/cm-1
cm-1
1,290E-05
1500
0,000 -1,887E-07
1550 -3,775E-07
-1,740E-05
1600
1600
1650 1650
-5,662E-07
-2,750E-05 -3,760E-05
1600
1550
1500
1450
1400
1350
1650 1650
-7,550E-07
1600
1550
1500
1450
1400
1350
1/cm-1
cm-1
Synchronous
Asynchronous −1
−1
−1
−1
(+) (m-xylene) 1605 cm ~ 1515 cm (p-xylene) (+) (m-xylene) 1605 cm ~ 1515 cm (p-xylene) −1 −1 −1 −1 (-) (p-xylene) 1515 cm ~ 1465 cm (o-xylene) (-) (p-xylene) 1515 cm ~ 1465 cm (o-xylene) −1 −1 −1 −1 (-) (m-xylene) 1605 cm ~ 1465 cm (o-xylene) (-) (m-xylene) 1605 cm ~ 1465 cm (o-xylene) −1 −1 (-) (p-xylene) 1515 cm ~ 1495 cm (toluene) −1 −1 (-) (m-xylene) 1605 cm ~ 1495 cm (toluene) −1 −1 −1 −1 (+) (toluene) 1495 cm ~ 1465 cm (o-xylene) (-) (toluene) 1495 cm ~ 1465 cm (o-xylene) o Figure 4_SI. The 2D synchronous and asynchronous correlation maps of ortho-xylene isomerization reaction at 250 C for zeolite TNU-9 in 15 min. of the reaction. The IR spectra subjected the correlation procedure are presented in the upper part. The synchronous and asynchronous correlations are listed in the table.
IM-5 1 min. A=0.005
15 min.
1650
1600
1550
1500
1350
1450
1350 /cm-1
1350
0,004320 0,003778
1400
1400
4,700E-05 3,525E-05
1400
2,350E-05
0,003235
1450
1450
1,175E-05
1500
0,002150 0,001608
1550
/cm-1
2/cm-1
0,002693
1500
0,000 -1,175E-05
1550 -2,350E-05
0,001065
1600
1600
1650 1650
-3,525E-05
5,225E-04 -2,000E-05
1600
1550
1500
1450
1400
1350
1650 1650
-4,700E-05
1600
1550
1500
1450
1400
1350
1/cm-1
/cm-1
Synchronous
Asynchronous −1
−1
(+) (m-xylene) 1605 cm ~ 1515 cm (p-xylene) −1 −1 (+) (m-xylene) 1605 cm ~ 1495 cm (toluene) −1 −1 −1 −1 (+) (p-xylene) 1515 cm ~ 1495 cm (toluene) (+) (p-xylene) 1515 cm ~ 1495 cm (toluene) −1 −1 −1 −1 (+) (p-xylene) 1515 cm ~ 1485 cm (intermediate) (-) (p-xylene) 1515 cm ~ 1485 cm (intermediate) −1 −1 −1 −1 (+) (m-xylene) 1605 cm ~ 1485 cm (intermediate) (-) (m-xylene) 1605 cm ~ 1485 cm (intermediate) o Figure 5_SI. The 2D synchronous and asynchronous correlation maps of ortho-xylene isomerization reaction at 250 C for zeolite IM-5 in 15 min. of the reaction. The IR spectra subjected the correlation procedure are presented in the upper part. The synchronous and asynchronous correlations are listed in the table.
TNU-10 1 min.
A=0.01
15 min.
1650
1600
1550
1500
1350
1450
1350 /cm-1
1350
8,350E-05 6,387E-05
1400
1400
3,940E-06 2,955E-06
1400
1,970E-06
4,425E-05
1450
1450
9,850E-07
1500
5,000E-06 -1,463E-05
1550
2/cm-1
/cm-1
2,463E-05
1500
0,000 -9,850E-07
1550 -1,970E-06
-3,425E-05
1600
1600
1650 1650
-2,955E-06
-5,387E-05 -7,350E-05
1600
1550
1500
1450
1400
1350
1650 1650
-3,940E-06
1600
1550
1450
1400
1350
1/cm-1
/cm-1
Synchronous
1500
Asynchronous −1
−1
−1
−1
(-) (p-xylene) 1515 cm ~ 1465 cm (o-xylene) (+) (p-xylene) 1515 cm ~ 1465 cm (o-xylene) −1 −1 −1 −1 (-) (p-xylene) 1515 cm ~ 1495 cm (toluene) (+) (p-xylene) 1515 cm ~ 1495 cm (toluene) −1 −1 −1 −1 (-) (p-xylene) 1515 cm ~ 1474 cm (benzene) (+) (p-xylene) 1515 cm ~ 1474 cm (benzene) −1 −1 (+) (toluene) 1495 cm ~ 1474 cm (benzene) −1 −1 (+) (toluene) 1495 cm ~ 1465 cm (o-xylene) −1 −1 (+) (benzene) 1474 cm ~ 1465 cm (o-xylene) o Figure 6_SI. The 2D synchronous and asynchronous correlation maps of ortho-xylene isomerization reaction at 250 C for zeolite TNU-10 in 15 min. of the reaction. The IR spectra subjected the correlation procedure are presented in the upper part. The synchronous and asynchronous correlations are listed in the table.
ZSM-22 1 min.
A=0.01
15 min. 1650
1600
1550
1500
1350
1450
1350 /cm-1
1350
2,430E-06 2,087E-06
1400
1400
3,460E-08 2,595E-08
1400
1,730E-08
1,745E-06
1450
1450
1500
1,060E-06 7,175E-07
1550
8,650E-09
2/cm-1
/cm-1
1,403E-06
1500
0,000 -8,650E-09
1550 -1,730E-08
3,750E-07
1600
1600
1650 1650
-2,595E-08
3,250E-08 -3,100E-07
1600
1550
1500
1450
1400
1650 1650
-3,460E-08
1600
1550
1500
1350
1400
1350
/cm-1
1/cm-1
Synchronous
1450
Asynchronous −1
−1
(+) (toluene) 1495 cm ~ 1465 cm (o-xylene) −1 −1 (+) (benzene) 1474 cm ~ 1465 cm (o-xylene) −1 −1 (+) (1,2,4-TMB) 1505 cm ~ 1465 cm (o-xylene) −1 −1 (+) (1,2,4,-TMB) 1505 cm ~ 1495 cm (toluene) −1 −1 (+) (m-xylene) 1605 cm ~ 1495 cm (toluene) −1 −1 (+) (m-xylene) 1605 cm ~ 1465 cm (o-xylene) −1 −1 (+) (m-xylene) 1605 cm ~ 1505 cm (1,2,4-TMB) −1 −1 (+) (toluene) 1495 cm ~ 1474 cm (benzene) -1 -1 (-) (aromatic deposit) 1640-1530 cm ~ 1465 cm (o-xylene)
(-) (benzene) 1474 cm
−1
~
−1
−1
1465 cm (o-xylene)
−1
(+) (m-xylene) 1605 cm ~ 1495 cm (toluene) −1 −1 (+) (m-xylene) 1605 cm ~ 1465 cm (o-xylene) −1
−1
(-) (toluene) 1495 cm ~ 1474 cm (benzene) -1 -1 (+) (aromatic deposit) 1640-1530 cm ~ 1465 cm (oxylene) -1 -1 -1 -1 (-) (aromatic deposit) 1640-1530 cm ~ 1505 cm (1,2,4- (+) (aromatic deposit) 1640-1530 cm ~ 1505 cm (1,2,4TMB) TMB) -1 -1 -1 -1 (-) (aromatic deposit) 1640-1530 cm ~ 1495 cm (toluene) (+) (aromatic deposit) 1640-1530 cm ~ 1495 cm (toluene) -1 -1 -1 -1 (-) (aromatic deposit) 1640-1530 cm ~ 1474 cm (benzene) (+) (aromatic deposit) 1640-1530 cm ~ 1474 cm (benzene) o Figure 7_SI. The 2D synchronous and asynchronous correlation maps of ortho-xylene isomerization reaction at 250 C for zeolite ZSM-22 in 15 min. the reaction. The IR spectra subjected the correlation procedure are presented in the upper part. The synchronous and asynchronous correlations are listed in the table.
IM-5 A=0.01
1650
1600
1550
1500
1450
1400
1350 /cm-1
ZSM-5 A=0.01
1650
1600
1550
1500
1450
1400
1350
/cm-1
TNU-9 A=0.01
1650
1600
1550
1500
1450
1400
1350
/cm-1
TNU-10 A=0.01
1650
1600
1550
1500
1450
1400
1350 /cm-1 o
Figure 8_SI. The IR spectra collected during Rapid Scan measurements of ortho-xylene isomerization at 250 C all the zeolites studied in 4 min. the reaction. These spectra were subjected the correlation procedure.
