NMR Spectroscopic Study on Binary Sodium Silicate Glass Based on the Fine Structure†

doi:10.7503/cjcu20180558

Abstract

Abstract:

A series of fine structure denotations( $Q i jklm$ ) was applied to analysis NMR spectra of binary sodium silicate glasse, and a variety of clusters was simulated by quantum chemistry ab initio. The results shows that the ²⁹Si chemical shift of the fine structure with the same Q_i is linearly related to the bridging oxygen bond angle. The chemical shifts of the experimental $Q i jklm$ structure does not fluctuate with the glass’ composition, and the Gaussian peak of the $Q i jklm$ structure is narrower. It is indicated that the fine structure characterization is a representation of the basic characteristic structure of the binary sodium silicate glass. It is found that there is a certain gap between theoretical values and experimental values. The results shows that there are multiple configurations of $Q i jklm$ structures coexisting in the glass, and the interaction between neighboring structures was characterized by NMR. However, the $Q i jklm$ structural characterization can describe the configuration of various silicate-oxygen tetrahedron more precisely.

Key words: Solid-state nuclear magnetic resonance spectroscopy, Fine structure, ab initio Calculation, Binary sodium silicate glass, Chemical shift

CLC Number:

O641
O655-4

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.

Figures/Tables 11

Table 1 Structural characteristics of fine structure in binary sodium silicate and chemical shift

Chemical formula	$Q i (n 1 h, n 2 q, n 3 t) jklm$	$Q i jklm$	Chemical shift, δ
Chemical formula	$Q i (n 1 h, n 2 q, n 3 t) jklm$	$Q i jklm$	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)	$Q 2 (h) 22$	$Q 222$	-89.8	-87.3
Na₈Si₁₂O₄(d)	$Q 2 (q) 22$	$Q 222$	-86.4	-84.2
Na₆Si₉O₃(e)	$Q 2 (t) 22$	$Q 222$	-80.3	-78.4
Na₁₂Si₃₀O₁₂(f)	$Q 3 (2 q, h) 333$	$Q 3333$	-98.2	-95.0
Na₈Si₂₀O₈(g)	$Q 3 (3 q) 333$	$Q 3333$	-96.2	-93.2
Na₈Si₂₈O₁₂(h)	$Q 3 (3 q) 334$ , $Q 4 (5 q) 3344$	$Q 3334$ , $Q 43344$	-96.1, -103.3	-93.6, -101.2
Na₆Si₁₈O₁₂(i)	$Q 3 (t, 2 q) 333$	$Q 3333$	-87.1	-84.7
Na₆Si₂₁O₉(j)	$Q 3 (t, 2 q) 334$ , $Q 4 (4 q, t) 3344$	$Q 3334$ , $Q 43344$	-87.7, -95.5	-85.3, -92.1
Na₄Si₁₀O₄(k)	$Q 3 (3 t) 333$	$Q 3333$	-83.0	-81.3
Na₆Si₁₉O₈(l)	$Q 3 (3 t) 334$ , $Q 4 (3 t) 3334$	$Q 3334$ , $Q 43334$	-85.5, -81.8	-83.6, -80.2
Na₆Si₂₇O₁₂(m)	$Q 3 (3 t) 344$ , $Q 4 (3 t, h) 3344$	$Q 3344$ , $Q 43344$	-88.8, -89.3	-87.0, -87.4
Na₄Si₃₄O₁₆(n)	$Q 3 (3 t) 444$ , $Q 4 (3 t, 2 h) 3444$	$Q 3444$ , $Q 43444$	-91.2, -87.6	-89.2, -85.6

Table 1 Structural characteristics of fine structure in binary sodium silicate and chemical shift

Chemical formula	$Q i (n 1 h, n 2 q, n 3 t) jklm$	$Q i jklm$	Chemical shift, δ
Chemical formula	$Q i (n 1 h, n 2 q, n 3 t) jklm$	$Q i jklm$	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)	$Q 2 (h) 22$	$Q 222$	-89.8	-87.3
Na₈Si₁₂O₄(d)	$Q 2 (q) 22$	$Q 222$	-86.4	-84.2
Na₆Si₉O₃(e)	$Q 2 (t) 22$	$Q 222$	-80.3	-78.4
Na₁₂Si₃₀O₁₂(f)	$Q 3 (2 q, h) 333$	$Q 3333$	-98.2	-95.0
Na₈Si₂₀O₈(g)	$Q 3 (3 q) 333$	$Q 3333$	-96.2	-93.2
Na₈Si₂₈O₁₂(h)	$Q 3 (3 q) 334$ , $Q 4 (5 q) 3344$	$Q 3334$ , $Q 43344$	-96.1, -103.3	-93.6, -101.2
Na₆Si₁₈O₁₂(i)	$Q 3 (t, 2 q) 333$	$Q 3333$	-87.1	-84.7
Na₆Si₂₁O₉(j)	$Q 3 (t, 2 q) 334$ , $Q 4 (4 q, t) 3344$	$Q 3334$ , $Q 43344$	-87.7, -95.5	-85.3, -92.1
Na₄Si₁₀O₄(k)	$Q 3 (3 t) 333$	$Q 3333$	-83.0	-81.3
Na₆Si₁₉O₈(l)	$Q 3 (3 t) 334$ , $Q 4 (3 t) 3334$	$Q 3334$ , $Q 43334$	-85.5, -81.8	-83.6, -80.2
Na₆Si₂₇O₁₂(m)	$Q 3 (3 t) 344$ , $Q 4 (3 t, h) 3344$	$Q 3344$ , $Q 43344$	-88.8, -89.3	-87.0, -87.4
Na₄Si₃₄O₁₆(n)	$Q 3 (3 t) 444$ , $Q 4 (3 t, 2 h) 3444$	$Q 3444$ , $Q 43444$	-91.2, -87.6	-89.2, -85.6

Fig.1 Fine structure models for ab initio calculation

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

$Q i (n 1 h, n 2 q, n 3 t) jklm$	Type of Si—O_b	Length of Si—O_b/nm	Bond angle of Si—O_b/(°)	$Q i (n 1 h, n 2 q, n 3 t) jklm$	Type of Si—O_b	Length of Si—O_b/nm	Bond angle of Si—O_b/(°)
$Q 2 (h) 22$ (c)	Q₂—O—Q₂	0.166	168.7	$Q 3 (3 q) 334$ (h)	Q₃—O—Q₃	0.163	161.5
$Q 2 (q) 22$ (d)	Q₂—O—Q₂	0.165	151.1	$Q 3 (t, 2 q) 334$ (j)	Q₃—O—Q₃	0.165	134.1
$Q 2 (t) 22$ (e)	Q₂—O—Q₂	0.166	134.5	$Q 3 (3 t) 334$ (l)	Q₃—O—Q₃	0.166	121.9
$Q 3 (2 q, h) 333$ (f)	Q₃—O—Q₃	0.163	166.1	$Q 4 (5 q) 3344$ (h)	Q₄—O—Q₄	0.165	160.7
$Q 3 (3 q) 333$ (g)	Q₃—O—Q₃	0.163	161.1	$Q 4 (4 q, t) 3344$ (j)	Q₄—O—Q₄	0.164	134.4
$Q 3 (t, 2 q) 333$ (i)	Q₃—O—Q₃	0.165	134.2	$Q 4 (3 t, h) 3344$ (m)	Q₄—O—Q₄	0.163	118.2
$Q 3 (3 t) 333$ (k)	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

$Q i (n 1 h, n 2 q, n 3 t) jklm$	Type of Si—O_b	Length of Si—O_b/nm	Bond angle of Si—O_b/(°)	$Q i (n 1 h, n 2 q, n 3 t) jklm$	Type of Si—O_b	Length of Si—O_b/nm	Bond angle of Si—O_b/(°)
$Q 2 (h) 22$ (c)	Q₂—O—Q₂	0.166	168.7	$Q 3 (3 q) 334$ (h)	Q₃—O—Q₃	0.163	161.5
$Q 2 (q) 22$ (d)	Q₂—O—Q₂	0.165	151.1	$Q 3 (t, 2 q) 334$ (j)	Q₃—O—Q₃	0.165	134.1
$Q 2 (t) 22$ (e)	Q₂—O—Q₂	0.166	134.5	$Q 3 (3 t) 334$ (l)	Q₃—O—Q₃	0.166	121.9
$Q 3 (2 q, h) 333$ (f)	Q₃—O—Q₃	0.163	166.1	$Q 4 (5 q) 3344$ (h)	Q₄—O—Q₄	0.165	160.7
$Q 3 (3 q) 333$ (g)	Q₃—O—Q₃	0.163	161.1	$Q 4 (4 q, t) 3344$ (j)	Q₄—O—Q₄	0.164	134.4
$Q 3 (t, 2 q) 333$ (i)	Q₃—O—Q₃	0.165	134.2	$Q 4 (3 t, h) 3344$ (m)	Q₄—O—Q₄	0.163	118.2
$Q 3 (3 t) 333$ (k)	Q₃—O—Q₃	0.166	120.4

Fig.2 Correlation between 29Si chemical shifts δisoSi and bond angles of bridge oxygen incrystals and 6-311G++(3df,2pd) basis set of ab initio method

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.　　

Fig.4 Deconvolution of 29Si NMR spectrum of Na2O (25%, molar fraction) glass based on Qi

Fig.5 Deconvolution of 29Si NMR spectrum of Na2O (25%, molar fraction) glass based on Qijklm

Fig.6 Chemical shifts for fitting spectra by Qi

Fig.7 Chemical shifts for fitting spectra by Qijklm

Table 3 Chemical shifts of Qijklm by fitting spectra of binary sodium silicate glass

$Q i jklm$	Molar fraction of Na₂O(%)
$Q i jklm$	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
$Q 211$					-72.6	-72.6	-72.6	-72.6	-72.6	-72.6
$Q 221$				-74.7	-74.7	-74.7	-74.7	-74.7	-74.7	-74.7
$Q 222$	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7
$Q 223$	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2
$Q 233$	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6
$Q 3223$	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9
$Q 3233$	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1
$Q 3333$	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2
$Q 3334$	-93.2	-93.2	-93.2	-93.2	-93.2	-93.2	-93.2	-93.2
$Q 3344$	-95.8	-95.8	-95.8	-95.8	-95.8	-95.4	-95.4	-95.3
$Q 3444$	-98.8	-98.8	-98.8	-98.8	-98.8	-98.8	-98.8	-98.8
$Q 43333$	-101.4	-101.4	-101.4	-101.4	-101.4
$Q 43334$	-104.0	-104.0	-104.0	-104.0	-104.0
$Q 43344$	-107.2	-107.2	-107.2	-107.2	-107.2
$Q 43444$	-110.6	-110.6	-109.8
$Q 44444$	-113.3

Table 3 Chemical shifts of Qijklm by fitting spectra of binary sodium silicate glass

$Q i jklm$	Molar fraction of Na₂O(%)
$Q i jklm$	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
$Q 211$					-72.6	-72.6	-72.6	-72.6	-72.6	-72.6
$Q 221$				-74.7	-74.7	-74.7	-74.7	-74.7	-74.7	-74.7
$Q 222$	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7	-76.7
$Q 223$	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2	-79.2
$Q 233$	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6	-82.6
$Q 3223$	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9	-85.9
$Q 3233$	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1	-88.1
$Q 3333$	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2	-91.2
$Q 3334$	-93.2	-93.2	-93.2	-93.2	-93.2	-93.2	-93.2	-93.2
$Q 3344$	-95.8	-95.8	-95.8	-95.8	-95.8	-95.4	-95.4	-95.3
$Q 3444$	-98.8	-98.8	-98.8	-98.8	-98.8	-98.8	-98.8	-98.8
$Q 43333$	-101.4	-101.4	-101.4	-101.4	-101.4
$Q 43334$	-104.0	-104.0	-104.0	-104.0	-104.0
$Q 43344$	-107.2	-107.2	-107.2	-107.2	-107.2
$Q 43444$	-110.6	-110.6	-109.8
$Q 44444$	-113.3

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	$δ iso Si$
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	$δ iso Si$
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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