Re-H<sub>2</sub>O体系高温高压化学反应的拉曼证据

赵慧芳; 谭大勇; 姜峰; 谢亚飞; 姜昌国; 罗兴丽; 肖万生

doi:10.11858/gywlxb.20200518

Re-H₂O体系高温高压化学反应的拉曼证据

doi: 10.11858/gywlxb.20200518

赵慧芳^{1, 2, 3,},
谭大勇^{1, 2,*, ,},
姜峰^{1, 2, 3},
谢亚飞^{1, 2, 3},
姜昌国^{1, 2, 3},
罗兴丽^{1, 2, 3},
肖万生^{1, 2}

1.
中国科学院广州地球化学研究所矿物学与成矿学重点实验室，广东广州　510640
2.
广东省矿物物理与材料研究开发重点实验室，广东广州　510640
3.
中国科学院大学，北京　100049

基金项目: 国家自然科学基金（41372047，41572030）；中国科学院战略性先导科技专项B类（XDB18000000）

详细信息

作者简介:
赵慧芳（1993－），女，博士研究生，主要从事高压矿物学研究. E-mail：zhaohuifang@gig.ac.cn

通讯作者:
谭大勇（1975－），男，博士，副研究员，主要从事高压矿物学研究. E-mail：dytan04@gig.ac.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2020-03-02
- 修回日期: 2020-03-10

Raman Evidences of Chemical Reaction of Re-H₂O System at High Pressure and High Temperature

ZHAO Huifang^{1, 2, 3
,},
TAN Dayong^{1, 2,*
, ,},
JIANG Feng^{1, 2, 3},
XIE Yafei^{1, 2, 3},
JIANG Changguo^{1, 2, 3},
LUO Xingli^{1, 2, 3},
XIAO Wansheng^{1, 2}

1.
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
2.
Key Lab of Guangdong Province for Mineral Physics and Materials, Guangzhou 510640, Guangdong,China
3.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 铼片是金刚石对顶砧超高压装置实验中常用的封垫材料，深部水是地球深部物质循环与能量交换的纽带，Re-H₂O体系高温高压化学反应研究具有重要的科学和技术意义。比较高温高压与常温常压条件的显微观察和拉曼测试结果表明：Re-H₂O体系在高压、高温环境（如40.5 GPa，（1 800 ± 200） K）发生氧化还原反应（${2{{\rm{H}}_2}{\rm{O}} + {\rm{Re}}\;\;\;\begin{matrix}{40.5\;{\rm{GPa}}} \\\hline \hline{1\;800\;{\rm{K}}}\\\end{matrix}\;\;\;{\rm{Re}}{{\rm{O}}_2} + 4{\rm{H}}}$）生成4价态的铼氧化物（β-ReO₂）和零价态的氢（H）。氧化产物β-ReO₂的14个特征拉曼峰随着压力卸载向低波数方向连续不等性移动，未观察到还原产物氢原子在高压下与水分子、金属铼及其反应产物β-ReO₂和H发生明显相互作用，直到压力卸载至常压时，氢原子发生聚合生成氢分子。Re-H₂O体系高温高压化学反应揭示了地球深部的温度、压力以及还原性物质环境中水（羟基）裂解为氢原子，该发现为地幔和核幔边界的深部水裂解反应提供了新的实验证据，为探讨地球深部水的可能地球化学行为提供了重要依据。
- Re-H₂O体系 /
- 深部水 /
- 水裂解 /
- 金刚石对顶砧 /
- 拉曼光谱
Abstract: Rhenium tablet is a frequently used gasket material at the ultra-high pressures in Diamond anvil cell (DAC) experiment. Water in deep Earth is the link between material exchange and energy circulation in the Earth’s interior. It is greatly scientific and technical significance on the study of chemical reaction of Re-H₂O system at high pressures and temperatures. Microscopic observations and Raman measurements show that the Re-H₂O system takes place the redox reaction ${2{{\rm{H}}_2}{\rm{O}} + {\rm{Re}}\;\;\;\begin{matrix}{40.5\;{\rm{GPa}}} \\\hline \hline{1\;800\;{\rm{K}}}\\\end{matrix}\;\;\;{\rm{Re}}{{\rm{O}}_2} + 4{\rm{H}}}$ under the conditions of high pressures and high temperatures, and produce rhenium oxide (β-ReO₂) with Re⁴⁺ and atomic hydrogen (H). Observed fourteen characteristic Raman peaks of oxidation product ReO₂ have a continuous unequal shift to lower Raman frequencies with the release of pressure. Reduction product H does not further take place interreaction with the water molecules, rhenium metals and their reaction products β-ReO₂ and atomic H under high pressures. But the hydrogen molecules are formed when the pressure is released to near atmospheric pressure. The chemical reaction of Re-H₂O system under the conditions of high-pressure and temperature reveals that water (hydroxyl) can decompose to produce atomic hydrogen in the Earth’s interior with the high pressure, high temperature and reductive material. This discovery not only provides a new experimental evidence for the conversion of water to hydrogen in deep Earth, but also gives important basis for exploring the possible geochemical behaviors of water in the Earth’s interior.
- Re-H₂O system /
- water in deep Earth /
- water splitting /
- DAC /
- Raman spectra

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图 1 常温常压和常温高压下Re-H₂O体系的代表性拉曼光谱

Figure 1. Representative Raman spectra of Re-H₂O system at ambient and high pressure and room temperature

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图 2 常温常压和常温高压下黑色样品中心β-ReO₂的代表性拉曼光谱

Figure 2. Representative Raman spectra of β-ReO₂ locating in the center of the black sample at ambient and high pressure and room temperature

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图 3 加压(黑色曲线)和卸压(红色曲线)过程100～1 000 cm⁻¹范围黑色样品边缘水的代表性拉曼光谱

Figure 3. Representative Raman spectra of water locating on the edge of black sample in the range of 100−1 000 cm⁻¹ under loading (black curves) and unloading (red curves)

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图 4 加压(黑色曲线)和卸压(红色曲线)过程2 000～4 500 cm⁻¹范围黑色样品边缘水的代表性拉曼光谱（星形标注峰为金刚石特征拉曼峰，插图为卸压（红色外框）和加压过程腔体的显微图像）

Figure 4. Representative Raman spectra of water locating on the edge of black sample in the range of 2 000−4 500 cm⁻¹ under loading (black curves) and unloading (red curves) (Characteristic Raman peaks of diamond are marked with the stars, and the microscopic images of loading and unloading (with red borders) were inserted.)

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图 5 常压和高压下H₂-H₂O混合物的代表性拉曼光谱

Figure 5. Representative Raman spectra of H₂-H₂O mixtures at atmospheric pressure and high pressure

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表 1 β-ReO₂的拉曼频率及其与压力的关系

Table 1. Raman frequencies and their pressure dependence dω/dP of the β-ReO₂

No.	ω/cm⁻¹					(dω/dp)/(cm⁻¹·GPa⁻¹)
No.	0.1 MPa	10.5 GPa	20.2 GPa	30.7 GPa	40.8 GPa	(dω/dp)/(cm⁻¹·GPa⁻¹)
1	166	177	182	189	194	0.7
2	170	181	190	199	201	0.8
3	199	214	223	231	237	0.9
4	240	249	255	261	265	0.6
5	287	315	342	361	372	2.2
6	359	372	385	390	401	1.1
7	373	388	404	416	424	1.3
8	437	454	470	482	488	1.3
9	513	548	578	596	607	2.4
10	561	586				2.6
11	577	602	625	640	650	1.8
12	688	747	807	841	869	4.4
13	722	784	850	891	917	4.9
14	751	809	864	904	929	4.4

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