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Supplementary information for:
Kinetic analysis of the thermal processing of
silica and organosilica
Emiel J. Kappert, Henny J.M. Bouwmeester, Nieck E. Benes*, Arian Nijmeijer
1 Overview of all recorded MS-data
These figures give the full overview of the MS-data, of which a selection is given in the main article figures 1-4. In the main article, the following m/z-ratios were assigned to specific compounds (where ‘sim’ indicates ‘recorded simultaneous with’ and [O2] and [N2] implies that signal may be masked by O2 or N2 from atmosphere): 2 to hydrogen, 16 to oxygen (sim 32, [O2]), 17 to water (sim 18, 19), 26 to acetylene (sim 25), 30 to NOx (or, when sim 46 for NO2), 31 to ethanol (sim 45, 46), 41 to unknown, 42 to C2H4O, 43 to acetaldehyde (when sim 29 and 44), 44 to C2H4O (when sim with 41, 42, 43, acetylene and/or 29 [N2]) or to carbon dioxide (when sim with 12 or 28 [N2]).
S2 Figure S1: Overview of all recorded MS-signals for silica under nitrogen, the numbers in the legend denote the m/z-signal.
0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 17 19 18 2 Ion cur rent ( a. u. ) 0 250 500 750 1000 1E-12 1E-11 12 44 0 250 500 750 1000 5E-12 1E-11 15 0 250 500 750 1000 1E-12 1E-11 1E-10 30 31 43 45 46 Ion cur rent ( a. u. ) Temperature (°C) 0 500 1000 5E-13 1E-12 1.5E-12 2E-12 25 26 42 Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 16 32 Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 1E-8 14 28 29 40 Ion cur rent ( a. u. ) Temperature (°C) 0 250 500 750 1000 1E-12 13 41 Temperature (°C) Temperature (°C) Temperature (°C) Temperature (°C)
S3 Figure S2: Overview of all recorded MS-signals for silica under air, the numbers in the legend denote the m/z-signal.
0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 2 17 18 19 Ion cur rent ( a. u. ) 0 250 500 750 1000 1E-12 1E-11 12 44 0 250 500 750 1000 1E-12 1E-11 1E-10 13 15 0 250 500 750 1000 1E-12 26 31 43 45 Ion cur rent ( a. u. ) Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 30 46 Temperature (°C) 0 250 500 750 1000 1E-9 32 16 Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 1E-8 14 28 29 40 Ion cur rent ( a. u. ) Temperature (°C) 0 250 500 750 1000 1E-12 25 41 42 Temperature (°C) Temperature (°C) Temperature (°C) Temperature (°C)
S4 Figure S3: Overview of all recorded MS-signals for BTESE under nitrogen, the numbers in the legend denote the m/z-signal.
0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 17 18 19 32 Ion cur rent ( ar b. uni t.) 0 250 500 750 1000 1E-12 1E-11 44 0 250 500 750 1000 1E-12 1E-11 1E-10 2 12 13 15 16 0 250 500 750 1000 1E-12 1E-11 25 26 42 Ion cur rent ( ar b. uni t.) Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 30 44 46 Temperature (°C) 0 250 500 750 1000 1E-13 1E-12 31 41 43 45 Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 1E-8 14 28 29 40 Ion cur rent ( ar b. uni t.) Temperature (°C) Temperature (°C) Temperature (°C) Temperature (°C)
S5 Figure S4: Overview of all recorded MS-signals for BTESE under air, the numbers in the legend denote the m/z-signal.
0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 17 18 19 Ion cur rent ( a. u. ) 0 250 500 750 1000 1E-12 1E-11 1E-10 12 44 45 0 250 500 750 1000 1E-12 1E-11 2 13 15 0 250 500 750 1000 1E-12 1E-11 25 26 Ion cur rent ( a. u. ) Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 30 46 Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 31 41 42 43 Temperature (°C) 0 250 500 750 1000 1E-10 1.5E-10 2E-10 29 Ion cur rent ( a. u. ) Temperature (°C) 0 250 500 750 1000 1E-12 1E-11 1E-10 1E-9 1E-8 14 16 28 32 40 Temperature (°C) Temperature (°C) Temperature (°C) Temperature (°C)
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2 Mass loss data
These figures give the mass loss data and the corresponding conversion curves for silica and organosilica under N2 and air for all heating rates.
Figure S5: TGA-graphs for the thermal treatment of silica under N2 at heating rates β of 5, 10, 15, and 20 °C min-1. 0 250 500 750 1000 80 90 100 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1 R e la tive ma ss (% ) Temperature (°C)
S7 Figure S6: Conversion of the mass loss of silica under N2 at heating rates β of 5, 10, 15, and 20 °C min-1. 0 250 500 750 1000 0.0 0.5 1.0 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1
C
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Temperature (°C)
S8 Figure S7: TGA-graphs for the thermal treatment of silica under air at heating rates β of 5, 10, 15, and 20 °C min-1. 0 250 500 750 1000 80 90 100 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1
R
e
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tive
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Temperature (°C)
S9 Figure S8: Conversion of the mass loss of silica under air at heating rates β of 5, 10, 15, and 20 °C min-1. 0 250 500 750 1000 0.0 0.5 1.0 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1
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Temperature (°C)
S10 Figure S9: TGA-graphs for the thermal treatment of organosilica under N2 at heating rates β of 5, 10, 15, and 20 °C min-1.
0 250 500 750 1000 90 100 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1
R
e
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tive
ma
ss
(%
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Temperature (°C)
S11 Figure S10: Conversion of the mass loss of organosilica under N2 at heating rates β of 5, 10, 15, and 20 °C min-1. 0 250 500 750 1000 0.0 0.5 1.0 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1
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Temperature (°C)
S12 Figure S11: TGA-graphs for the thermal treatment of organosilica under air at heating rates β of 5, 10, 15, and 20 °C min-1.
0 250 500 750 1000 80 90 100 = 5 °C min-1 = 10 °C min-1 = 15 °C min-1 = 20 °C min-1
Relative
ma
ss (%)
Temperature (°C)
S13 Figure S12: Conversion of the mass loss of organosilica under air at heating rates β of 5, 10, 15, and 20 °C min-1. 0 250 500 750 1000 0.0 0.5 1.0
= 5 °C min
-1 = 10 °C min
-1 = 15 °C min
-1 = 20 °C min
-1Conve
rsion
(-)
Temperature (°C)
unexpected accelerationS14
3 Activation energy from isoconversional analysis
This figure shows the full data of figure 5b in the manuscript (see the explanation in the manuscript).
Figure S13: Apparent activation energy for calcination of silica (a) and organosilica (b) under nitrogen (●) and air (□). See Figure 5 in the paper.
