铀酰/矿物表面复合结构的ATR-FTIR法原位研究

项目名称： 铀酰/矿物表面复合结构的ATR-FTIR法原位研究

项目编号： No.21507118

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 化学工业

项目作者： 任一鸣

作者单位： 中国工程物理研究院

项目金额： 22万元

中文摘要： 铀是军事和能源领域最重要的核材料，由于放射性和化学毒性的存在，铀在自然界中的迁移规律日益引起社会各界的关注，掌握铀的迁移规律对于估算铀矿冶中水污染情况和评价核废物长期贮存的安全性十分重要。本项目拟采用衰减全反射红外光谱（ATR-FTIR）/第一性原理计算（DFT）相结合的方法，对铀酰在矿物表面形成的各种复合结构进行原位研究。由于铀酰反对称伸缩振动对配位环境极为灵敏，因而可通过红外光谱对各种条件下铀酰/矿物复合结构进行区分和识别。同时，采用DFT方法对红外结果进行验证和预测，尤其有助于对较复杂体系中复合结构的计算。两种方法相结合可实现对铀酰/矿物复合结构的精确解析。项目的成果不仅能够从微观尺度上阐述铀酰在矿物表面的作用过程和机制，对铀的迁移行为进行推测和估算；而且可从红外光谱角度进一步加深对铀酰与材料表面的非共价作用和络合行为等基础化学问题的认识，进而推动包括铀化学在内的锕系化学学科的发展。

中文关键词： 放射性核素迁移；铀酰；衰减全反射红外光谱；矿物；第一性原理

英文摘要： Uranium is an important material in both military and energy industry. The migration of uranium in the natural world has attracted lots of concerns due to its radioactivity and chemical toxicity. It is of great significance to comprehend uranium migration rule for not only assessing situation of water waste in uranium mining, but also evaluating the security of radioactive waste long-term treatments. The current proposal plans to combine attenuated total reflection - Fourier transform infrared spectroscopy (ATR-FTIR) and Density Function Theory (DFT) to study various uranyl/mineral surface complexes in situ. Due to the sensitivity of anti-symmetric stretching vibration of uranyl ion to the coordination environment, infrared spectroscopy is an excellent approach to differentiate and identify uranyl/mineral complexes in different circumstances. Meanwhile, we use DFT to validate infrared results and predict unknown structures. The concise resolution will be realized through the combination of the two methods above. The results of this proposal will illustrate the process and mechanisms of uranyl/mineral interactions and make an assessment of uranium migration behavior in the environment. Also, the results could help us to comprehend the non-covalent and coordination interactions between uranium and surfaces from the angle of infrared spectroscopy, and finally improve the developments of actinide chemistry including uranium chemistry.

英文关键词： radionuclide migration;uranyl;ATR-FTIR;mineral;DFT