Strutures nd Retion Mehnisms of Glyerol Dehydrtion over H ZSM 5 Zeolite: A Density Funtionl Theory Study Knokwn Kongptpnih,,,d, Tnin Nnok,,,d, Bundet Boekf,,d, Mihel Prost e nd Jumrs Limtrkul *,,,d Lortory for Computtionl nd Applied Chemistry, Deprtment of Chemistry, Fulty of Siene, Ksetsrt University, Bngkok 10900, Thilnd Center for Advned Studies in Nnotehnology nd Its Applitions in Chemil, Food nd Agriulturl Industries, Ksetsrt University, Bngkok 10900, Thilnd Center of Nnotehnology, Ksetsrt University Reserh nd Development Institute, Ksetsrt University, Bngkok 10900, Thilnd d NANOTEC Center of Nnotehnology, Ntionl Nnotehnology Center, Ksetsrt University, Bngkok 10900, Thilnd e Institute of Ion Physis nd Applied Physis, University of Innsruk, A 6020 Innsruk, Austri Supporting Informtion Sheme S1 The retion pthwy of glyerol dehydrtion: the rolein formtion pthwy.
Sheme S2 Proposed retion mehnism of glyerol dehydrtion to rolein in the stepwise mehnism (1) First Dehydrtion (2) Keto enol Tutomeriztion nd (3) Seond Dehydrtion.
Sheme S3 The retion pthwy of glyerol dehydrtion: the etol formtion pthwy. Sheme S4 Proposed retion mehnism of glyerol dehydrtion to etol in the onerted mehnism (1) Dehydrtion nd (2) Keto enol Tutomeriztion.
Tle S1 Reltive energies of of ll strutures involved in the first dehydrtion nd the keto enol tutomeriztion of the rolein formtion pthwy. Stepwise ds_2 ts_dehyd_1 lk_1 + H 2 O lk_1 ts_lk_1 hyd_enol_1 ts_tuto_1 keto_co 12T M06 2X/6 31G(d,p) 36.55 8.04 13.67 2.68 33.29 2.28 13.39 13.31 12T MP2/6 31G(d,p) 32.71 10.43 10.66 3.81 35.01 0.28 11.68 15.94 12T M06 2X/6 311+G(2df,2p) 27.66 13.02 7.09 4.23 31.53 0.36 13.45 12.70 128T M062X/6 31G(d,p) + SCREEP 42.46 0.02 14.72 1.64 21.37 6.31 2.67 17.10 Conerted ds_2 ts_dehyd_1 hyd_enol_1 + H2O hyd_enol_1 12T M06 2X/6 31G(d,p) 36.55 24.87 15.09 0.12 12T MP2/6 31G(d,p) 32.71 27.65 16.37 0.28 12T M06 2X/6 311+G(2df,2p) 27.66 29.20 11.56 0.36 128T M062X/6 31G(d,p) + SCREEP 42.46 29.54 20.63 6.31 12T MP2/6 31G(d,p)//12T M06 2X/6 31G(d,p) 12T M06 2X/6 311+G(2df,2p)//12T M06 2X/6 31G(d,p) 128T M06 2X/6 31G(d,p) + SCREEP// 12T M06 2X/6 31G(d,p) Tle S2 Reltive energies of ll strutures involved in the seond dehydrtion of the rolein formtion pthwy. Stepwise keto_oh ts_lk_2 lk_2 + H2O lk_2 ts_rolein prod 12T M06 2X/6 31G(d,p) 11.34 31.47 8.62 20.26 50.13 7.78 12T MP2/6 31G(d,p) 16.11 25.97 3.41 13.66 43.73 0.12 12T M06 2X/6 311+G(2df,2p) 10.05 31.37 8.20 15.26 45.08 1.87 128T M062X/6 31G(d,p) + SCREEP 14.40 21.42 8.42 21.05 45.10 1.45 Conerted keto_oh ts_dehyd_2 rolein + H2O prod 12T M06 2X/6 31G(d,p) 11.34 25.61 5.46 7.78 12T MP2/6 31G(d,p) 16.11 24.58 11.67 0.12 12T M06 2X/6 311+G(2df,2p) 10.05 25.53 8.20 1.87 128T M062X/6 31G(d,p) + SCREEP 14.40 24.93 9.47 1.45 12T MP2/6 31G(d,p)//12T M06 2X/6 31G(d,p) 12T M06 2X/6 311+G(2df,2p)//12T M06 2X/6 31G(d,p) 128T M06 2X/6 31G(d,p) + SCREEP// 12T M06 2X/6 31G(d,p)
Tle S3 Reltive energies of ll strutures involved in the seond dehydrtion of the etol formtion pthwy. By produt ds_1 TS1 ALK + H 2 O ALK TS2 ENOL TS3 etol 12T M06 2X/6 31G(d,p) 29.20 13.87 8.90 3.36 48.43 1.51 5.83 21.26 12T MP2/6 31G(d,p) 28.20 13.93 7.70 3.50 48.25 1.92 5.57 24.76 12T M06 2X/6 311+G(2df,2p) 23.39 20.52 3.11 4.13 46.67 3.48 6.60 20.61 128T M062X/6 31G(d,p) + SCREEP 39.45 2.86 10.05 3.33 30.13 12.97 1.70 27.20 12T MP2/6 31G(d,p)//12T M06 2X/6 31G(d,p) 12T M06 2X/6 311+G(2df,2p)//12T M06 2X/6 31G(d,p) 128T M06 2X/6 31G(d,p) + SCREEP// 12T M06 2X/6 31G(d,p) Tle S4 Comprision of tivtion energy in eh step of rolein nd etol formtion pthwys. Ativtion Energy (kl/mol) Model Method Alkoxide formtion Proton k dontion Tutomeriztion Arolein By produt Arolein By produt Arolein By produt 12T M06 2X/6 31G(d,p) 44.59 43.06 30.62 45.07 11.11 7.34 12T MP2/6 31G(d,p) 43.15 42.13 31.20 44.75 11.96 7.49 12T M06 2X/6 311+G(2df,2p) 40.67 43.91 27.03 42.54 13.09 10.08 128T M062X/6 31G(d,p) + SCREEP d 42.44 42.31 19.73 26.80 3.64 11.27 12T MP2/6 31G(d,p)//12T M06 2X/6 31G(d,p) 12T M06 2X/6 311+G(2df,2p)//12T M06 2X/6 31G(d,p) 128T M06 2X/6 31G(d,p) + SCREEP// 12T M06 2X/6 31G(d,p) Tle S5 Computed imginry frequenies of ll trnsition sttes lulted t the M06 2X/6 31G(d,p). Struture Imginry Frequeny (m 1 ) Arolein Formtion Pthwy ts_dehyd_1 209.86 ts_lk_2 203.35 ts_tuto_1 891.30 ts_lk_2 392.63 ts_rolein 871.23 ts_dehyd_1 1144.91 ts_enol_1 287.49 Aetol Formtion Pthwy TS1 507.81 TS2 415.78 TS3 1049.85
Tle S6 Clulted enthlpies nd free energies (in kl/mol) t different tempertures. T ( o C) T (K) ΔH forwrd ΔG forwrd ΔH reverse ΔG reverse 200 473 43.00 39.75 19.02 18.08 250 523 43.08 39.40 19.01 17.98 300 573 43.15 39.05 18.99 17.88 350 623 43.19 38.69 18.97 17.79 400 673 43.22 38.33 18.94 17.70 450 723 43.23 37.96 18.91 17.60 500 773 43.22 37.60 18.87 17.52 550 823 43.20 37.24 18.82 17.43 600 873 43.17 36.87 18.77 17.35 650 923 43.13 36.51 18.72 17.27 700 973 43.08 36.16 18.67 17.19 Tle S7 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of re H ZSM 5 zeolite luster (12T), isolted glyerol, glyerol dsorption using the primry OH group (ds_1) nd the seondry OH group (ds_2) over H ZSM 5 zeolite lulted with the M06 2X/6 31G(d,p) method. Prmeters Bre luster H ZSM 5 C 3 O 3 H 8 C 3 O 3 H 8 /H ZSM 5 (ds_1) C 3 O 3 H 8 /H ZSM 5 (ds_2) O1 Si1 1.672 1.648 1.656 Al O1 1.830 1.790 1.784 O2 Al 1.686 1.693 1.689 O2 Si2 1.595 1.588 1.587 O1 Hz 0.969 1.069 1.060 Hz O(glyerol) 0.965* 1.407 1.403 O(glyerol) C 1.413* 1.436 1.432 C1 C2 1.517* 1.513 1.517 O1 Hz O(glyerol) 171.49 177.26 Si1 O1 Al 130.78 128.67 128.52 Si2 O2 Al 135.05 135.90 138.40 *verge onds Tle S8 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of ll strutures involved in the first dehydrtion (stepwise mehnism) of the rolein formtion pthwy lulted with the M06 2X/6 31G(d,p). Prmeters ds_2 ts_dehyd_1 lk_1 + H 2 O lk_1 ts_lk_1 hyd_enol_1 O1 Si1 1.656 1.597 1.599 1.598 1.601 1.597 Al O1 1.784 1.714 1.687 1.684 1.711 1.679 O2 Al 1.689 1.743 1.831 1.828 1.701 1.676 O2 Si2 1.587 1.612 1.691 1.690 1.589 1.581 Hz O4 1.060 O4 C2 1.432 2.401 3.009 O2 C2 3.645 2.277 1.510 1.505 3.346 3.465 C2 C3 1.516 1.470 1.535 1.538 1.406 1.323 C3 H(C3) 1.098 1.099 1.089 1.099 1.201 2.390 H(C3) O3 2.664 3.474 3.473 1.560 1.021 Si1 O1 Al 128.52 131.92 131.76 131.70 130.89 133.37 Si2 O2 Al 138.41 131.10 125.73 126.58 139.87 141.77
Tle S9 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of ll strutures involved in the first dehydrtion (onerted mehnism) of the rolein formtion pthwy lulted with the M06 2X/6 31G(d,p). Prmeters ds_2 ts_dehyd_1 hyd_enol_1 + H 2 O hyd_enol_1 O1 Si1 1.656 1.599 1.596 1.597 Al O1 1.784 1.694 1.680 1.679 O2 Al 1.689 1.695 1.675 1.676 O2 Si2 1.587 1.583 1.579 1.581 Hz O4 1.060 0.982 O4 C2 1.432 2.204 3.018 O2 C2 3.645 3.784 3.621 3.465 C2 C3 1.516 1.388 1.323 1.323 C3 H(C3) 1.098 1.348 2.266 2.390 H(C3) O3 2.664 1.295 1.017 1.021 Si1 O1 Al 128.52 133.30 132.76 133.37 Si2 O2 Al 138.41 138.61 142.75 141.77 Tle S10 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of ll strutures involved in the keto enol tutomeriztion of the rolein formtion pthwy lulted with the M06 2X/6 31G(d,p). Prmeters hyd_enol_1 ts_tuto_1 keto_co keto_oh O1 Si1 1.597 1.618 1.652 1.648 Al O1 1.679 1.726 1.796 1.798 O3 Al 1.827 1.753 1.681 1.685 O3 Si3 1.685 1.646 1.617 1.617 O3 Hz 1.021 1.350 Hz C2 2.390 1.297 1.100 1.092 C2 C3 1.322 1.399 1.489 1.518 C3 O6 1.410 1.277 1.222 1.207 O6 H6 0.965 1.048 1.450 H6 O1 2.008 1.494 1.043 1.053 O5 H6 1.432 Si1 O1 Al 133.37 128.78 129.53 128.91 Si2 O3 Al 131.52 134.99 132.92 133.42 Tle S11 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of ll strutures involved in the seond dehydrtion (stepwise mehnism) of the rolein formtion pthwy lulted with the M06 2X/6 31G(d,p). Prmeters keto_oh ts_lk_2 lk_2 + H 2 O lk_2 ts_rolein prod O1 Si1 1.648 1.584 1.580 1.585 1.628 1.652 Al O1 1.798 1.706 1.674 1.672 1.733 1.791 O2 Al 1.689 1.745 1.842 1.849 1.754 1.693 O2 Si2 1.589 1.610 1.683 1.688 1.628 1.589 O1 H6 1.053 H6 O5 1.432 0.973 0.963 O5 C1 1.438 2.112 2.954 C1 O2 3.387 2.247 1.500 1.494 2.026 C2 H(C2) 1.096 1.090 1.098 1.096 1.264 H(C2) O1 3.248 3.821 2.621 2.820 1.382 O6 Hz 1.416 Hz O1 1.058 Si1 O1 Al 128.91 132.88 137.67 137.00 130.63 129.41 Si2 O2 Al 136.19 132.08 125.41 124.94 131.18 136.58
Tle S12 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of ll strutures involved in the seond dehydrtion (onerted mehnism) of the rolein formtion pthwy lulted with the M06 2X/6 31G(d,p). Prmeters keto_oh ts_dehyd_2 rolein + H 2 O prod O1 Si1 1.648 1.611 1.588 1.652 Al O1 1.798 1.715 1.681 1.791 O2 Al 1.689 1.678 1.688 1.693 O2 Si2 1.589 1.589 1.587 1.589 O1 H5 1.053 1.497 2.260 H5 O5 1.433 1.031 0.966 O5 C1 1.438 1.676 3.056 C1 C2 1.529 1.433 1.338 1.33569 C2 Hz 1.092 1.714 2.888 Hz O3 3.904 1.045 1.064 O6 Hz 1.416 Hz O1 1.058 Si1 O1 Al 128.91 131.00 135.17 129.41 Si2 O2 Al 136.19 140.74 139.19 136.58 Tle S13 The optimized geometri prmeters (distnes in pm nd ngles in degrees) of ll strutures involved in the first dehydrtion (stepwise mehnism) of the etol formtion pthwy lulted with the M06 2X/6 31G(d,p). Prmeters ds_1 TS1 ALK + H 2 O ALK TS2 ENOL O1 Si1 1.648 1.582 1.586 1.588 1.594 1.590 Al O1 1.790 1.695 1.675 1.678 1.685 1.694 O2 Al 1.693 1.765 1.845 1.848 1.732 1.663 O2 Si2 1.588 1.620 1.680 1.681 1.602 1.576 O1 Hz 1.069 Hz O5 1.407 0.972 0.964 O5 C1 1.436 2.101 3.050 O2 C1 3.109 2.044 1.487 1.485 2.246 C1 C2 1.513 1.520 1.532 1.530 1.411 1.331 C2 H(C2) 1.102 1.099 1.101 1.095 1.228 1.458 H(C2) O3 3.100 2.331 3.046 1.482 1.042 Si1 O1 Al 128.67 135.29 135.69 135.02 131.98 133.02 Si2 O2 Al 135.90 130.58 127.25 127.40 136.01 144.88