Supporting Information Wiley-VCH 27 69451 Weinheim, Germany
Supplementary Figure 1. Synthetic results as detected by XRD (Cu-Kα). Simulation pattern of MCM-68 Relative Intensity / a.u. YNU-2P Conventional MCM-68 2 1 2 3 4 5 2 theta / degree Relative Intensity / a.u. After direct calcination of YNU-2P at 4ºC for 3 h YNU-2P 2 1 2 3 4 5 2 theta / degree YNU-2 (after calcination of silylated YNU-2P at 45ºC) Relative Intensity / a.u. YNU-2P-silylated 2 1 2 3 4 5 2 theta / degree YNU-2P
Supplementary Figure 2. Structural drawing of (a)ynu-2p and (b)ynu-2 along [1] direction. In the Figure 2(a), pale yellow and pale red (pink) mean defective silicon and oxygen atoms, respectively. (a) TEBOP Na (b) H 2 O
Supplementary Figure 3. 1 H MAS NMR spectra of YNU-2. Blue and red curves were drawn with Y-offset of 25. 5 YNU-2P modified YNU-2P after post-synthetic silylation siliceous zeolite YNU-2 after calcination of modified YNU-2P 4 Arbitrary intensity 3 2 Š15.8ppm 1 25 2 15 1 5-5 -1-15 Chemical shift / ppm
Supplementary Figure 4. TG-DTA curves of YNU-2P. 8 6-2 -4 7 4-6 -8 6 Weight loss / wt% 2-1 -12-14 -16 T / µv 5 4 3 Temperature / C -18-2 2-22 -24 1 2 4 6 8 1 12 Time / min 14 16 18 2-26 22
Supplementary Figure 5. N 2 adsorption-desorption isotherms of YNU-2 and MCM-68. 25 adsorption Adsorped amount / cm 3 g -1 (STP) 2 15 1 5 desorption YNU-2 S BET = 573 m 3 g -1 Pore volume (t-plot) =.29 cm 3 g -1.5 1 Relative pressure (P/P ) 6 Adsorped amount / cm 3 g -1 (STP) 5 4 3 2 adsorption desorption MCM-68 S BET = 628 m 3 g -1 Pore volume (t-plot) =.24 cm 3 g -1 1.5 1 Relative pressure (P/P )
Title: A New Multi-Dimensional Microporous Silicate Isomorphous to Zeolite MCM-68 Supplementary Figure 6. SEM images of YNU-2P, YNU-2, and MCM-68. YNU-2P YNU-2 MCM-68
Supplementary Table 1. Structural parameters g, x, y, z and B of YNU-2P obtained by the Rietveld refinement. Estimated standard deviations (ESDs) are given as uncertainties in the last reported decimal digit. Site M g x y z B(Å 2 ) Si1 16k.844(5).1296(3).7492(3).1134(3) 2.17(4) Si2 16k 1..1293(3).7515(3).273(3) = B(Si1) Si3 16k.92(5).34(3).2157(3).764(3) = B(Si1) Si4 16k 1..1348(2).2569(3).1913(4) = B(Si1) Si5 16k 1..348(2).219(3).3139(3) = B(Si1) Si6 8j.395(8).593(7) = x.123(1) = B(Si1) Si7 8j.4(9).64(7) = x.2765(9) = B(Si1) Si8 16k 1..1364(3).2537(3).4244(2) = B(Si1) O1 16k 1..1187(3).741(3).1927(5) 2.97(6) O2 16k.873 I).464(5).752(5).817(4) = B(O1) O3 16k 1..1727(5).6751(5).874(4) = B(O1) O4 16k 1..467(4).7563(4).323(5) = B(O1) O5 16k 1..1713(4).6837(4).31(5) = B(O1) O6 16k 1..911(4).2542(5).1223(5) = B(O1) O7 16k.649 II).337(7).1324(9).947(6) = B(O1) O8 16k 1..796(4).2521(5).2551(5) = B(O1) O9 16k 1..383(3).1331(5).396(5) = B(O1) O1 16k 1..659(5).2487(5).3816(4) = B(O1) O11 4e = g(si6)..98(2) = B(O1) O12 4e = g(si7)..297(2) = B(O1) O13 8j 1..1861(3) = x.1948(7) = B(O1) O14 8j.397 III).649(1) = x.199(2) = B(O1) O15 8j 1..1877(4) = x.435(5) = B(O1) O16 8j = g(si1).172(6) = x.917(6) = B(O1) O17 8j 1..1765(4) = x.2816(5) = B(O1) O18 8i = g(si3).689(6).226(6) = B(O1) O19 8i 1..1147(5).2473(6) 1/2 = B(O1) N 4f 1..132 = x 1/2 4.6(8) C1 8j.5.26 = x.56 = B(N1) C2 4g 1..5 = x 1/2 = B(N1) C3 16k.5.7.1.47 = B(N1) C4 8i 1..134.5 1/2 = B(N1) C5 8j 1..171 = x.557 = B(N1) C6 8j.5.134 = x.615 = B(N1) C7 16k.25.745.161.557 = B(N1) N1b 16k.25.489.13.327 48.1(8) C1b 16k.125.53.76.497 = B(N1b) C2b 16k.125.457.69.51 = B(N1b) C3b 16k.25.57.5.496 = B(N1b) C4b 16k.25.466.47.564 = B(N1b) C5b 16k.25.542.41.436 = B(N1b) C6b 16k.25.522.75.717 = B(N1b) C7b 16k.5.575.1.624 = B(N1b) C8b 16k.125.458.87.764 = B(N1b) C9b 16k.25.51.61.719 = B(N1b) C1b 16k.125.559.83.238 = B(N1b) C11b 16k.25.497.132.682 = B(N1b) WO1 8i.714(5).7529(13).6113(8) 16.(6) WO2 8j =1-g(WO1).57(14) = x.44(2) = B(WO1) WO3 8i.46(2).941(2).477(2) = B(WO1) WO4 16k.341(11).964(2).565(2).83(2) = B(WO1) WO5 16k.468(12).9431(1).519(13).179(11) = B(WO1) Na1 8j.77(2).555(7) = x.7759(9) 21.4(2) Na2 4g.7(2).494(13) = x = B(Na1) Na3 16k.26(12).12(3).5(3).9(3) = B(Na1) Note: Scattering amplitude of carbons were modified in consideration of protons. All parameters of C and N sites were fixed except B parameters. WO1 and WO3 are OH, and WO3, WO4 and WO5 are water molecules in consideration of protons. Linear constrains were imposed for occupancies of oxygen sites as follows: I) g(o2) =.5 (g(si1) + g(si3)), II) g(o7) =.5 (g(si3) + g(si6)), III) g(o14) =.5 (g(si6) + g(si7)).
Supplementary Table 2: Bond lengths, l, and bond angles, φ, in YNU-2P calculated from refined lattice and structural parameters. l (Å) φ ( º) φ ( º) Si1 O1 1.613(1) O1 Si1 O2 15.5 (5) O8 Si5 O1 19.3 (5) Si1 O2 1.648(1) O1 Si1 O3 16.6 (5) O8 Si5 O4 15.9 (5) Si1 O3 1.649(1) O1 Si1 O16 113.5 (6) O8 Si5 O9 18.9 (5) Si1 O16 1.691(8) O2 Si1 O3 19.1 (6) O1 Si5 O4 111.9 (6) Si2 O5 1.575(8) O2 Si1 O16 18.3 (7) O1 Si5 O9 112.2 (6) Si2 O1 1.584(9) O3 Si1 O16 113.5 (6) O4 Si5 O9 18.4 (5) Si2 O17 1.589(5) O5 Si2 O1 19.3 (5) O7 Si6 O7 114 (2) Si2 O4 1.643(8) O5 Si2 O17 19.4 (5) O7 Si6 O14 19.5 (11) Si3 O6 1.559(1) O5 Si2 O4 11. (5) O7 Si6 O11 15.5 (13) Si3 O7 1.566(14) O1 Si2 O17 18.4 (5) O7 Si6 O14 19.5 (11) Si3 O2 1.599(1) O1 Si2 O4 16.2 (5) O7 Si6 O11 15.5 (13) Si3 O18 1.662(6) O17 Si2 O4 113.5 (6) O14 Si6 O11 114 (2) Si4 O5 1.595(7) O6 Si3 O7 17.6 (7) O9 Si7 O9 15.6 (12) Si4 O6 1.599(11) O6 Si3 O2 113.5 (6) O9 Si7 O14 113.5 (1) Si4 O13 1.599(5) O6 Si3 O18 15.4 (6) O9 Si7 O12 17.4 (13) Si4 O8 1.632(1) O7 Si3 O2 111.1 (8) O9 Si7 O14 113.5 (1) Si5 O1 1.56(1) O7 Si3 O18 15.5 (7) O9 Si7 O12 17.4 (13) Si5 O4 1.57(7) O2 Si3 O18 113.2 (6) O14 Si7 O12 19 (2) Si5 O9 1.572(8) O5 Si4 O6 113.5 (6) O3 Si8 O1 11.4 (6) Si5 O1 1.573(9) O5 Si4 O13 19.4 (4) O3 Si8 O19 19.2 (6) Si6 O7(x2) 1.53(14) O5 Si4 O8 17.8 (6) O3 Si8 O15 11.6 (6) Si6 O14 1.542(11) O6 Si4 O13 17.8 (7) O1 Si8 O19 18.7 (6) Si6 O11 1.612(14) O6 Si4 O8 111.7 (4) O1 Si8 O15 17.5 (6) Si7 O9(x2) 1.539(11) O13 Si4 O8 16.5 (7) O19 Si8 O15 11.3 (6) Si7 O14 1.55(16) Si7 O12 1.615(16) Average φ 19.5 Si8 O3 1.538(1) Si8 O1 1.549(9) Si8 O19 1.573(5) Si8 O15 1.584(6) Average l(si O) 1.59 Na1 O12 2.5(4) Na1 O14(x2) 2.26(2) Na2 O11(x2) 2.34(4) Na3 O2 2.37(5) Na3 O7 1.56(5)
Supplementary Table 3. Structural parameters g, x, y, z and B of YNU-2 obtained by the Rietveld refinement. Estimated standard deviations (ESDs) are given as uncertainties in the last reported decimal digit. Site M g x y z B(Å 2 ) Si1 16k 1..1293(4).7489(4).118(4) 1.7(5) Si2 16k 1..1296(4).7544(4).2741(3) = B(Si1) Si3 16k 1..292(4).2187(4).741(3) = B(Si1) Si4 16k 1..133(3).2576(3).1893(4) = B(Si1) Si5 16k 1..322(3).2213(4).3112(4) = B(Si1) Si6 8j.97(9).594(4) = x.1178(6) = B(Si1) Si7 8j.98(8).587(3) = x.2783(5) = B(Si1) Si8 16k 1..1377(4).2573(4).4232(3) = B(Si1) O1 16k 1..122(4).7414(4).1953(6) 1.98(8) O2 16k 1..527(6).752(6).884(5) = B(O1) O3 16k 1..1666(6).6774(5).916(5) = B(O1) O4 16k 1..495(5).7568(5).388(7) = B(O1) O5 16k 1..1739(5).6863(5).347(8) = B(O1) O6 16k 1..85(5).2658(5).122(5) = B(O1) O7 16k 1..359(5).1347(7).883(5) = B(O1) O8 16k 1..765(6).256(7).2516(7) = B(O1) O9 16k 1..361(4).1353(5).349(7) = B(O1) O1 16k 1..637(6).2483(7).3798(5) = B(O1) O11 4e 1..98(1) = B(O1) O12 4e 1..295(1) = B(O1) O13 8j 1..188(4) = x.1861(8) = B(O1) O14 8j 1..646(4) = x.198(1) = B(O1) O15 8j 1..1943(4) = x.471(6) = B(O1) O16 8j 1..1775(6) = x.986(7) = B(O1) O17 8j 1..1695(5) = x.291(8) = B(O1) O18 8i 1..517(8).2315(8) = B(O1) O19 8i 1..1156(7).25 1/2 = B(O1) WO1 16k.64(1).488(1).747(9).14(1) 22.6(3) WO2 8j.4(1).19(3).745(3) 1/2 = B(WO1) WO3 8i.34(1).54(4).22(3) = B(WO1) WO4 8i.367(8).2(3).69(4) 1/2 = B(WO1) WO5 16k.23(1).7(3).625(4).83(4) = B(WO1) All WO are water molecules in consideration of scattering amplitude of protons.
Supplementary Table 4: Bond lengths, l, and bond angles, φ, in YNU-2 calculated from refined lattice and structural parameters. l (Å) φ ( º) φ ( º) Si1 O2 1.518 (11) O2 Si1 O3 17.4 (7) O4 Si5 O1 17.5 (8) Si1 O3 1.561 (11) O2 Si1 O1 18.2 (7) O4 Si5 O9 17.5 (6) Si1 O1 1.562 (12) O2 Si1 O16 111.5 (8) O4 Si5 O8 111.5 (8) Si1 O16 1.649 (7) O3 Si1 O1 17.4 (7) O1 Si5 O9 111.5 (8) Si2 O17 1.597 (8) O3 Si1 O16 111.6 (7) O1 Si5 O8 11.5 (6) Si2 O5 1.62 (11) O1 Si1 O16 11.5 (8) O9 Si5 O8 18.4 (8) Si2 O1 1.63 (12) O17 Si2 O5 111.5 (8) O7 Si6 O7 11. (11) Si2 O4 1.617 (1) O17 Si2 O1 111.4 (8) O7 Si6 O11 18.5 (8) Si3 O18 1.558 (8) O17 Si2 O4 17.6 (8) O7 Si6 O14 11.1 (7) Si3 O7 1.562 (12) O5 Si2 O1 17.7 (7) O7 Si6 O11 18.5 (8) Si3 O2 1.612 (1) O5 Si2 O4 18.1 (7) O7 Si6 O14 11.1 (7) Si3 O6 1.62 (1) O1 Si2 O4 11.5 (7) O11 Si6 O14 19.5 (11) Si4 O8 1.588 (12) O18 Si3 O7 17.5 (8) O12 Si7 O9 111.5 (8) Si4 O5 1.618 (9) O18 Si3 O2 111.3 (9) O12 Si7 O9 111.5 (8) Si4 O6 1.618 (12) O18 Si3 O6 17.4 (7) O12 Si7 O14 17.6 (13) Si4 O13 1.676 (6) O7 Si3 O2 111.4 (7) O9 Si7 O9 111.1 (1) Si5 O4 1.542 (9) O7 Si3 O6 111.5 (7) O9 Si7 O14 17.5 (7) Si5 O1 1.569 (12) O2 Si3 O6 17.7 (7) O9 Si7 O14 17.5 (7) Si5 O9 1.574 (9) O8 Si4 O5 11.1 (8) O15 Si8 O3 17.5 (7) Si5 O8 1.575 (13) O8 Si4 O6 111.1 (6) O15 Si8 O19 17.5 (8) Si6 O7(x2) 1.553 (12) O8 Si4 O13 11.8 (9) O15 Si8 O1 111.3 (8) Si6 O11 1.553 (12) O5 Si4 O6 18.3 (8) O3 Si8 O19 111.5 (6) Si6 O14 1.583 (13) O5 Si4 O13 17.5 (5) O3 Si8 O1 111.6 (8) Si7 O12 1.612 (17) O6 Si4 O13 19. (8) O19 Si8 O1 17.4 (7) Si7 O9(x2) 1.548 (11) Si7 O14 1.549 (1) Average φ 19.5 Si8 O15 1.549 (1) Si8 O3 1.62 (2) Si8 O19 1.576 (7) Si8 O15 1.592 (11) Average l 1.59