三斜水钠锰矿层间阳离子交换作用的拉曼谱学

段鉴书; 李艳; 许晓明; 丁竑瑞; 刘菲菲; 鲁安怀

doi:10.3799/dqkx.2018.416

三斜水钠锰矿层间阳离子交换作用的拉曼谱学

doi: 10.3799/dqkx.2018.416

段鉴书^1,2,3,,
李艳^1,2,3, ,,
许晓明^1,2,3,
丁竑瑞^1,2,3,
刘菲菲^1,2,3,
鲁安怀^1,2,3

1.
北京大学造山带与地壳演化教育部重点实验室, 北京 100871
2.
北京大学矿物环境功能北京市重点实验室, 北京 100871
3.
北京大学地球与空间科学学院, 北京 100871

基金项目:

国家自然科学基金优青项目 41522201

国家自然科学基金重点项目 41230103

国家重点基础研究发展计划（973计划）项目 2014CB846001

详细信息

作者简介:
段鉴书(1996-), 男, 本科生, 主要从事环境矿物学研究

通讯作者:
李艳

中图分类号: P575
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- 被引次数: 0
出版历程
- 收稿日期: 2017-09-07
- 刊出日期: 2018-05-15

Raman Spectroscopy of Ion Exchange in Interlayer of Triclinic Birnessite

Duan Jianshu^{1,2,3
,},
Li Yan^{1,2,3
, ,},
Xu Xiaoming^1,2,3,
Ding Hongrui^1,2,3,
Liu Feifei^1,2,3,
Lu Anhuai^1,2,3

1.
Key Laboratory of Orogenic Belts and Crustal Evolution, Ministry of Education, Peking University, Beijing 100871, China
2.
Beijing Key Laboratory of Mineral Environmental Function, Peking University, Beijing 100871, China
3.
School of Earth and Space Sciences, Peking University, Beijing 100871, China

摘要

摘要: 水钠锰矿为自然界中常见的锰氧化物矿物，其离子交换作用及结构转变理解尚不深刻，矿物表征手段较为局限.为探究水钠锰矿的离子交换特性以及结构转变在拉曼光谱上的反映，利用MnSO₄和NaOH合成了三斜晶系的Na型水钠锰矿，进行了NH₄⁺、K⁺、Mg²⁺、Ca²⁺、Ba²⁺、Co²⁺、Zn²⁺的离子交换实验，使用ICP-OES、XRD、拉曼光谱等手段对离子交换水钠锰矿进行表征.拉曼光谱分析表明，570~585 cm^-1与640~655 cm^-1两个锰氧八面体伸缩振动模式的相对强度及570~585 cm^-1附近拉曼峰峰位指示水钠锰矿的结构对称型；570~585 cm^-1拉曼峰强度大、振动频率高指示三斜对称型.280 cm^-1与500 cm^-1附近的拉曼峰是层间离子种类的识别标志.水钠锰矿层间若为Na⁺、K⁺、Mg²⁺、Ca²⁺、Ba²⁺等碱金属、碱土金属离子，则在280 cm^-1附近存在1个峰值，500 cm^-1存在2个分立的峰值；其他种类的层间离子仅500 cm^-1处有1个孤峰，指示层间离子排列无序.
- 水钠锰矿 /
- 离子交换 /
- 拉曼光谱 /
- 结构对称型 /
- 层间距 /
- 矿物学
Abstract: Birnessite is a group of manganese oxide minerals widely found in nature. However, its ion exchange behavior and structural transformation have not been fully understood, and the characterization techniques are limited. To study the ion exchange behavior of birnessite and the reflection of structural transformation in Raman spectroscopy, triclinic Na-birnessite was synthesized using MnSO₄ and NaOH, and ion exchange experiments on NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺, Co²⁺, and Zn²⁺ were carried out. Ion exchange birnessite samples were characterized using ICP-OES, XRD, and Raman spectroscopy. Raman study shows the relative strength of two stretching vibration modes in[MnO₆] octahedra around 570-585 cm^-1 and 640-655 cm^-1 and the band location of the mode around 570-585 cm^-1 are indicators of the symmetry of birnessite. High strength and frequency of the mode around 570-585 cm^-1 are signs of triclinic symmetry. Raman bands around 280 cm^-1 and 500 cm^-1 are indicators of interlayer cations. If alkalis and alkaline-earth metals (i.e., Na⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺, etc.) are in the interlayer of birnessite, a band around 280 cm^-1 and two separate bands around 500 cm^-1 will appear; whereas other interlayer cations only give rise to one single band at 500 cm^-1, indicating disorder in the interlayer.
- birnessite /
- ion exchange /
- Raman spectroscopy /
- structural symmetry /
- interlayer distance /
- mineralogy

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图 1 三斜水钠锰矿的晶体结构

据Lanson et al.(2002)确定的晶体结构重绘.三斜水钠锰矿中层内Mn为+3或+4价，结构八面体(图中蓝色八面体)配体为氧原子(图中橙色原子)；层间含大半径阳离子(如Na⁺等，图中以灰色原子表示)与水分子(图中以氧原子表示)

Fig. 1. Crystal structure of triclinic birnessite

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图 2 离子交换前后水钠锰矿的XRD图谱

黑色三角形表示水黑锰矿杂质产生的衍射峰，在所有样品中都可见

Fig. 2. XRD patterns of birnessite before and after ion exchange

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图 3 15.5°~33°范围内NaBi、KBi、NH₄Bi、CoBi、ZnBi的XRD图谱

a.15.5°~17.5°范围内5种水钠锰矿的衍射图，三斜水钠锰矿的(200)、(111)衍射峰在NaBi中标出；KBi、NH₄Bi、CoBi、ZnBi中指示三斜对称型的衍射峰消失，后3种水钠锰矿中还可见六方水钠锰矿的(100)和(101)衍射峰.b.18°~33°范围内5种水钠锰矿的衍射图，在KBi、NH₄Bi、CoBi和ZnBi中均出现了d值约为2.03 ×10^-10 m、1.71 ×10^-10 m左右的指示六方对称型的(102)、(103)特征衍射峰，并且观察到了六方水钠锰矿的(104)、(110)、(111)与(112)衍射峰.图中三角形指示水黑锰矿杂质的衍射峰

Fig. 3. XRD patterns of NaBi, KBi, NH₄Bi, CoBi and ZnBi in the range of 15.5°-33°

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图 4 8种离子交换水钠锰矿样品在100~800 cm^-1范围内的拉曼光谱

Fig. 4. Raman spectra of eight kinds of ion exchange birnessite in the range of 100-800 cm^-1

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图 5 水钠锰矿中[MnO₆]八面体两种伸缩振动模式峰位关系

三斜水钠锰矿NaBi、MgBi、CaBi和BaBi用三角形表示；六方水钠锰矿KBi、NH₄Bi、CoBi和ZnBi用六边形表示

Fig. 5. Relationship between two stretching vibration modes of [MnO₆] octahedra in different kinds of birnessite

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图 6 4种离子交换水钠锰矿阳离子半径与500 cm^-1两峰值波数之差关系

Fig. 6. Relationship between positive ionic radii and difference of wavenumbers of two Raman bands around 500 cm^-1 in four kinds of ion exchange birnessite

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图 7 7×10^-10 m水钠锰矿层间距与v₂，v₄振动模式波数差Δv_{2, 4}关系

Fig. 7. Relationship between difference of wavenumbers of v₂ and v₄ model (Δv_{2, 4}) and interlayer distance of 7×10^-10 m birnessite

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表 1 不同种类水钠锰矿阳离子半径、离子水合能、化学组成及层间距

Table 1. Ionic radii, hydration energies, chemical compositions, and interlayer distances of different kinds of birnessite

阳离子	有效离子半径(10^-10 m)^a	离子水合能(kcal/g)^b	Na/Mn摩尔比(%)	交换离子/Mn摩尔比(%)	总阳离子含量(%)^d	层间距(10^-10 m)
Na⁺	1.02	98.2	19.77	-	19.77	7.088
NH₄⁺	1.40^b	-	0.19	-^c		7.162
K⁺	1.38	80.6	0.19	12.32	12.51	7.136
Mg²⁺	0.72	455.5	0.25	12.81	25.87	9.590
Ca²⁺	1.00	380.8	0.20	17.29	34.78	7.126、9.895
Ba²⁺	1.35	315.1	1.89	13.33	28.55	6.953
Co²⁺	0.65	479.5	0.95	10.94	22.83~33.77^e	7.149、9.423
Zn²⁺	0.74	484.6	2.58	34.74	72.06	7.125
注：a.所有离子半径均选择六配位状态的，过渡金属离子半径选择低自旋条件下的(Shannon，1976)；b.数据引用自Rosseinsky(1965)；c.该测试手段无法测定NH₄⁺含量；d.按照阳离子含量×阳离子电荷计算；e.CoBi中Co可能为+2或+3两种价态，按照两端元情况计算得到含量范围.

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表 2 8种离子交换水钠锰矿样品拉曼峰位统计

Table 2. Summary table of Raman bands in eight kinds of ion exchange birnessite

模式	NaBi	MgBi	NH₄Bi	KBi	CaBi	CoBi	ZnBi	BaBi
v₁							692(sh)
v₂	651(m)	643(m)	650(s)	645(s)	650(m)	653(s)	655(s)	644(m)
v₃			608(vw)			609(vw)	612(w)
v₄	583(s)	584(s)	577(s)	575(s)	586(s)	570(s)	573(s)	581(s)
v₅	511(m)	511(m)	498(m)	509(w)	515(m)	496(m)	497(m)	508(m)
v₆	480(sh)	483(sh)		484(sh)	480(sh)			472(sh)
v₇	406(m)	407(m)	387(w)	393(vw)	407(m)	386(w)	403(w)	397(w)
v₈	283(w)	278(m)		280(w)	278(m)			282(w)
v₉	199(w)	198(vw)	201(vw)		198(w)	199(vw)	214(vw)	204(vw)
v₁₀	150(vw)	140(vw)	142(m)	165(w)	140(vw)	142(m)	145(m)	163(w)
注：振动频率单位均为cm^-1.vs.很强；s.强；m.中等；w.弱；vw.很弱；sh.肩峰.在NH₄Bi、CoBi、ZnBi中，v₅与v₆振动简并为一个拉曼峰.

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表 3 离子交换水钠锰矿[MnO₆]两种伸缩振动模式强度之比

Table 3. Relative strength of two [MnO₆] stretching vibration modes in different kinds of ion exchange birnessite

样品	NaBi	MgBi	CaBi	BaBi	NH₄Bi	KBi	CoBi	ZnBi
v₄/v₂强度	4.32±1.37	2.97±0.76	2.70±0.35	1.39±0.42	0.43±0.03	0.66±0.12	0.56±0.01	0.77±0.15
对称型	三斜	三斜	三斜	三斜	六方	六方	六方	六方
注：每个样品按照两个峰强的积分面积进行比较，取3个及以上数据进行统计，正负号之后为样本标准差.

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