Bi4B2O9晶体及其熔体结构的高温原位拉曼光谱研究

doi:10.7503/cjcu20190260

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (10): 2143.doi: 10.7503/cjcu20190260

Bi₄B₂O₉晶体及其熔体结构的高温原位拉曼光谱研究

徐琰东,尤静林(),王建,龚晓晔,丁雅妮,曹培明,郑少波,吴永全,余仲达

省部共建高品质特殊钢冶金与制备国家重点实验室, 上海市钢铁冶金新技术开发与应用重点实验室, 上海大学材料科学与工程学院, 上海 200444

收稿日期:2019-05-07 出版日期:2019-09-12 发布日期:2019-09-12
通讯作者: 尤静林 E-mail:jlyou@staff.shu.edu.cn
基金资助:
国家自然科学基金(No.21773152);上海市科学技术委员会项目(No.12520709200);111引智项目(No.D17002);省部共建高品质特殊钢冶金与制备国家重点实验室开放课题(Nos.SKLASS2015-01);省部共建高品质特殊钢冶金与制备国家重点实验室开放课题(Nos.SKLASS2017-02);科技部中央引导上海市科学技术委员会专项基金(No.YDZX20173100001316)

High-temperature in situ Raman Spectroscopic Study on the Micro-structure of Bi₄B₂O₉ Crystal and Melt ^†

XU Yandong,YOU Jinglin(),WANG Jian,GONG Xiaoye,DING Yani,CAO Peiming,ZHENG Shaobo,WU Yongquan,YU Zhongda

State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferrometallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China

Received:2019-05-07 Online:2019-09-12 Published:2019-09-12
Contact: YOU Jinglin E-mail:jlyou@staff.shu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21773152);the Shanghai Committee of Science and Technology Fund, China(No.12520709200);the National 111 Project, China(No.D17002);the Open and Independent Project of State Key Laboratory of Advanced Special Steel, China(Nos.SKLASS2015-01);the Open and Independent Project of State Key Laboratory of Advanced Special Steel, China(Nos.SKLASS2017-02);the Special Fund Project of Shanghai Municipality for Science and Technology Development, China(No.YDZX20173100001316)

摘要/Abstract

摘要：

利用密度泛函理论计算了Bi₄B₂O₉晶体的常温拉曼光谱, 并通过与实验拉曼光谱对比, 对其振动模式进行了归属. 利用高温原位拉曼光谱研究了Bi₄B₂O₉从常温到750 ℃升温过程中微结构的变化. 随着温度的升高, 晶体的平均键长变长, 键角分布变宽, 熔化后晶体中的BiO₄和BiO₅多面体解体, BO₃构型则保持三配位不变. 运用量子化学从头算法模拟了Bi₄B₂O₉的熔体结构并与实验拉曼光谱进行了对比分析, 发现在Bi₄B₂O₉熔体中B原子团簇为孤立的BO₃构型, Bi ³⁺游离于BO₃之间, 并结合未参与形成BO₃的O原子起到平衡电荷的作用.

关键词: Bi₄B₂O₉晶体, 高温原位拉曼光谱, 熔体微结构, 从头算法

Abstract:

Raman spectrum of Bi₄B₂O₉ crystal at ambient temperature was measured and calculated via density functional theory and vibration modes of all the peaks were assigned. Then high temperature in situ Raman spectroscopic technique was utilized to measure Raman spectra of Bi₄B₂O₉ crystal from room temperature to 750 ℃(above the melting point) to investigate its micro-structure’s evolution. With the temperature increasing, the lattice lengthens in bond length and broadens in bond angle. After melting, BiO₄ and BiO₅ polyhedron in crystal tends to convert, while BO₃ triangle stays constant. Ab initio method was used to simulate the microstructure of Bi₄B₂O₉ melt cluster, calculate and analyze its Raman spectra. It is found that B atoms in Bi₄B₂O₉ melt form isolated BO₃ triangle structure and Bi ³⁺ cation among BO₃, connecting O atoms out of BO₃, functions as charge balancer.

Key words: Bi₄B₂O₉ crystal, High temperature in situ Raman spectroscopy, Melt micro-structure, Ab initio calculation method

中图分类号:

O641
O657.37

TrendMD:

徐琰东,尤静林,王建,龚晓晔,丁雅妮,曹培明,郑少波,吴永全,余仲达. Bi₄B₂O₉晶体及其熔体结构的高温原位拉曼光谱研究. 高等学校化学学报, 2019, 40(10): 2143.

XU Yandong,YOU Jinglin,WANG Jian,GONG Xiaoye,DING Yani,CAO Peiming,ZHENG Shaobo,WU Yongquan,YU Zhongda. High-temperature in situ Raman Spectroscopic Study on the Micro-structure of Bi₄B₂O₉ Crystal and Melt ^†. Chem. J. Chinese Universities, 2019, 40(10): 2143.

图/表 7

Fig.1 Crystal structure of Bi4B2O9

Fig.2 Calculated(a) and experimental(b) Raman spectra of Bi4B2O9 crystal

Table 1 Vibration modes assignments of Bi4B2O9 crystal

$ν ˙ expt.$ /cm^-1	$ν ˙ calcd.$ /cm^-1	Assignment of vibration mode
148	148	External lattice vibration
173	188	External lattice vibration
198	216	External lattice vibration
355	340	Bending vibration of BO₃
389	378	Asymmetrical stretching vibration of BiO₄
432	448	Stretching vibration of Bi—O bond in BiO₄
529	514	Stretching vibration of Bi—O bond in BiO₅
572	557	Bending vibration of BO₃
620	627	Bending vibration of BO₃
915	903	Symmetric stretching vibration of BO₃
1184	1164	Stretching vibration of BO₃
1238	1237	Stretching vibration of BO₃
1298	1281	Stretching vibration of BO₃
1324	1308	Stretching vibration of BO₃

Table 1 Vibration modes assignments of Bi4B2O9 crystal

$ν ˙ expt.$ /cm^-1	$ν ˙ calcd.$ /cm^-1	Assignment of vibration mode
148	148	External lattice vibration
173	188	External lattice vibration
198	216	External lattice vibration
355	340	Bending vibration of BO₃
389	378	Asymmetrical stretching vibration of BiO₄
432	448	Stretching vibration of Bi—O bond in BiO₄
529	514	Stretching vibration of Bi—O bond in BiO₅
572	557	Bending vibration of BO₃
620	627	Bending vibration of BO₃
915	903	Symmetric stretching vibration of BO₃
1184	1164	Stretching vibration of BO₃
1238	1237	Stretching vibration of BO₃
1298	1281	Stretching vibration of BO₃
1324	1308	Stretching vibration of BO₃

Fig.3 Temperature dependent Raman spectra of Bi4B2O9 crystal and its melt ν ˙ /cm-1: (A) 200—1800; (B) 800—1800. Temperature/℃: a. r. t.; b. 200; c. 400; d. 600; e. 700; f. 750.

Fig.4 Simulated cluster model of Bi4B2O9 melt

Fig.5 Raman spectra of the melt and simulated cluster a. Experimental; b. calculated.

Table 2 Vibration modes assignments of the simulated cluster

$ν ˙$ /cm^-1	Assignment of vibration mode	$ν ˙$ /cm^-1	Assignment of vibration mode
208	External bending vibration	650	Stretching vibration of Bi—O bond
303	Bending vibration of Bi—O—Bi bond	870	Symmetric stretching vibration of BO₃
482	Bending vibration of BO₃	1110	Asymmetric stretching vibration of BO₃
548	Bending vibration of BO₃	1231	Asymmetric stretching vibration of BO₃

Table 2 Vibration modes assignments of the simulated cluster

$ν ˙$ /cm^-1	Assignment of vibration mode	$ν ˙$ /cm^-1	Assignment of vibration mode
208	External bending vibration	650	Stretching vibration of Bi—O bond
303	Bending vibration of Bi—O—Bi bond	870	Symmetric stretching vibration of BO₃
482	Bending vibration of BO₃	1110	Asymmetric stretching vibration of BO₃
548	Bending vibration of BO₃	1231	Asymmetric stretching vibration of BO₃

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Bi₄B₂O₉晶体及其熔体结构的高温原位拉曼光谱研究

High-temperature in situ Raman Spectroscopic Study on the Micro-structure of Bi₄B₂O₉ Crystal and Melt ^†

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