Chem. J. Chinese Universities ›› 2019, Vol. 40 ›› Issue (1): 108.doi: 10.7503/cjcu20180558
• Physical Chemistry • Previous Articles Next Articles
WU Zhidong, YOU Jinglin*(), WANG Jian, WANG Min, HE Yingxia, YANG Yejin
Received:
2018-08-06
Online:
2019-01-10
Published:
2018-12-19
Contact:
YOU Jinglin
E-mail:jlyou@staff.shu.edu.cn
Supported by:
CLC Number:
TrendMD:
WU Zhidong,YOU Jinglin,WANG Jian,WANG Min,HE Yingxia,YANG Yejin. NMR Spectroscopic Study on Binary Sodium Silicate Glass Based on the Fine Structure†[J]. Chem. J. Chinese Universities, 2019, 40(1): 108.
Chemical formula | Chemical shift, δ | |||
---|---|---|---|---|
6-311G(2df,2pd) | 6-311G++(3df,2pd) | |||
Na4SiO4(a) | Q0 | Q0 | -36.9 | -36.1 |
Na2Si7O6(b) | 2Q1 | 2Q1 | -66.2 | -64.0 |
Na12Si18O6(c) | -89.8 | -87.3 | ||
Na8Si12O4(d) | -86.4 | -84.2 | ||
Na6Si9O3(e) | -80.3 | -78.4 | ||
Na12Si30O12(f) | -98.2 | -95.0 | ||
Na8Si20O8(g) | -96.2 | -93.2 | ||
Na8Si28O12(h) | -96.1, -103.3 | -93.6, -101.2 | ||
Na6Si18O12(i) | -87.1 | -84.7 | ||
Na6Si21O9(j) | -87.7, -95.5 | -85.3, -92.1 | ||
Na4Si10O4(k) | -83.0 | -81.3 | ||
Na6Si19O8(l) | -85.5, -81.8 | -83.6, -80.2 | ||
Na6Si27O12(m) | -88.8, -89.3 | -87.0, -87.4 | ||
Na4Si34O16(n) | -91.2, -87.6 | -89.2, -85.6 |
Table 1 Structural characteristics of fine structure in binary sodium silicate and chemical shift
Chemical formula | Chemical shift, δ | |||
---|---|---|---|---|
6-311G(2df,2pd) | 6-311G++(3df,2pd) | |||
Na4SiO4(a) | Q0 | Q0 | -36.9 | -36.1 |
Na2Si7O6(b) | 2Q1 | 2Q1 | -66.2 | -64.0 |
Na12Si18O6(c) | -89.8 | -87.3 | ||
Na8Si12O4(d) | -86.4 | -84.2 | ||
Na6Si9O3(e) | -80.3 | -78.4 | ||
Na12Si30O12(f) | -98.2 | -95.0 | ||
Na8Si20O8(g) | -96.2 | -93.2 | ||
Na8Si28O12(h) | -96.1, -103.3 | -93.6, -101.2 | ||
Na6Si18O12(i) | -87.1 | -84.7 | ||
Na6Si21O9(j) | -87.7, -95.5 | -85.3, -92.1 | ||
Na4Si10O4(k) | -83.0 | -81.3 | ||
Na6Si19O8(l) | -85.5, -81.8 | -83.6, -80.2 | ||
Na6Si27O12(m) | -88.8, -89.3 | -87.0, -87.4 | ||
Na4Si34O16(n) | -91.2, -87.6 | -89.2, -85.6 |
Type of Si—Ob | Length of Si—Ob/nm | Bond angle of Si—Ob/(°) | Type of Si—Ob | Length of Si—Ob/nm | Bond angle of Si—Ob/(°) | ||
---|---|---|---|---|---|---|---|
Q2—O—Q2 | 0.166 | 168.7 | Q3—O—Q3 | 0.163 | 161.5 | ||
Q2—O—Q2 | 0.165 | 151.1 | Q3—O—Q3 | 0.165 | 134.1 | ||
Q2—O—Q2 | 0.166 | 134.5 | Q3—O—Q3 | 0.166 | 121.9 | ||
Q3—O—Q3 | 0.163 | 166.1 | Q4—O—Q4 | 0.165 | 160.7 | ||
Q3—O—Q3 | 0.163 | 161.1 | Q4—O—Q4 | 0.164 | 134.4 | ||
Q3—O—Q3 | 0.165 | 134.2 | Q4—O—Q4 | 0.163 | 118.2 | ||
Q3—O—Q3 | 0.166 | 120.4 |
Table 2 Bridging oxygen bond angles and length in fine structure models of binary sodium silicate optimized by 6-311G++(3df,2pd) of ab initio method
Type of Si—Ob | Length of Si—Ob/nm | Bond angle of Si—Ob/(°) | Type of Si—Ob | Length of Si—Ob/nm | Bond angle of Si—Ob/(°) | ||
---|---|---|---|---|---|---|---|
Q2—O—Q2 | 0.166 | 168.7 | Q3—O—Q3 | 0.163 | 161.5 | ||
Q2—O—Q2 | 0.165 | 151.1 | Q3—O—Q3 | 0.165 | 134.1 | ||
Q2—O—Q2 | 0.166 | 134.5 | Q3—O—Q3 | 0.166 | 121.9 | ||
Q3—O—Q3 | 0.163 | 166.1 | Q4—O—Q4 | 0.165 | 160.7 | ||
Q3—O—Q3 | 0.163 | 161.1 | Q4—O—Q4 | 0.164 | 134.4 | ||
Q3—O—Q3 | 0.165 | 134.2 | Q4—O—Q4 | 0.163 | 118.2 | ||
Q3—O—Q3 | 0.166 | 120.4 |
Fig.3 29Si NMR spectra of binary sodium silicate glassMolar fraction of Na2O(%): a. 20; b. 25; c. 28.6; d. 33.3; e. 36.4; f. 40; g. 42.8; h. 44.4; i. 50; j. 55.6.
Molar fraction of Na2O(%) | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|
20 | 25 | 28.6 | 33.3 | 36.4 | 40 | 42.8 | 44.4 | 50 | 55.6 | |
Q0 | -59.9 | -59.0 | ||||||||
Q1 | -67.1 | -67.1 | -67.0 | -66.8 | ||||||
-72.6 | -72.6 | -72.6 | -72.6 | -72.6 | -72.6 | |||||
-74.7 | -74.7 | -74.7 | -74.7 | -74.7 | -74.7 | -74.7 | ||||
-76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | |
-79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | |
-82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | |
-85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | |
-88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | |
-91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | ||
-93.2 | -93.2 | -93.2 | -93.2 | -93.2 | -93.2 | -93.2 | -93.2 | |||
-95.8 | -95.8 | -95.8 | -95.8 | -95.8 | -95.4 | -95.4 | -95.3 | |||
-98.8 | -98.8 | -98.8 | -98.8 | -98.8 | -98.8 | -98.8 | -98.8 | |||
-101.4 | -101.4 | -101.4 | -101.4 | -101.4 | ||||||
-104.0 | -104.0 | -104.0 | -104.0 | -104.0 | ||||||
-107.2 | -107.2 | -107.2 | -107.2 | -107.2 | ||||||
-110.6 | -110.6 | -109.8 | ||||||||
-113.3 |
Table 3 Chemical shifts of Qijklm by fitting spectra of binary sodium silicate glass
Molar fraction of Na2O(%) | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|
20 | 25 | 28.6 | 33.3 | 36.4 | 40 | 42.8 | 44.4 | 50 | 55.6 | |
Q0 | -59.9 | -59.0 | ||||||||
Q1 | -67.1 | -67.1 | -67.0 | -66.8 | ||||||
-72.6 | -72.6 | -72.6 | -72.6 | -72.6 | -72.6 | |||||
-74.7 | -74.7 | -74.7 | -74.7 | -74.7 | -74.7 | -74.7 | ||||
-76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | -76.7 | |
-79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | -79.2 | |
-82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | -82.6 | |
-85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | -85.9 | |
-88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | -88.1 | |
-91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | -91.2 | ||
-93.2 | -93.2 | -93.2 | -93.2 | -93.2 | -93.2 | -93.2 | -93.2 | |||
-95.8 | -95.8 | -95.8 | -95.8 | -95.8 | -95.4 | -95.4 | -95.3 | |||
-98.8 | -98.8 | -98.8 | -98.8 | -98.8 | -98.8 | -98.8 | -98.8 | |||
-101.4 | -101.4 | -101.4 | -101.4 | -101.4 | ||||||
-104.0 | -104.0 | -104.0 | -104.0 | -104.0 | ||||||
-107.2 | -107.2 | -107.2 | -107.2 | -107.2 | ||||||
-110.6 | -110.6 | -109.8 | ||||||||
-113.3 |
Method | ||||||
---|---|---|---|---|---|---|
1Q0 | 4Q0 | 8Q0 | 1Q1 | 4Q1 | 8Q1 | |
Calculated | -36 | -57 | -58.2 | -64.0 | -66.8 | -67.9 |
Experimental | -59 | -69 |
Table 4 δisoSivalues of Q0 and Q1 species in binary sodium silicate model clusters with polymolecular structure calculated by different basis sets in ab initio method
Method | ||||||
---|---|---|---|---|---|---|
1Q0 | 4Q0 | 8Q0 | 1Q1 | 4Q1 | 8Q1 | |
Calculated | -36 | -57 | -58.2 | -64.0 | -66.8 | -67.9 |
Experimental | -59 | -69 |
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