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一种磷灰石族碳酸镨氟羟硅铈矿：水热合成、晶体结构及其对天然和合成硅铈矿的启示

An Apatite-Group Praseodymium Carbonate Fluoroxybritholite: Hydrothermal Synthesis, Crystal Structure, and Implications for Natural and Synthetic Britholites.

作者信息

Anenburg Michael, Panikorovskii Taras L, Jennings Eleanor S, Shendrik Roman Yu, Antonov Andrey A, Gavrilenko Veronika

机构信息

Research School of Earth Sciences, Australian National University, Canberra 2600, Australia.

Laboratory of Nature-Inspired Technologies and Environmental Safety of the Arctic, Kola Science Centre, Russian Academy of Sciences, Apatity 184200, Russia.

出版信息

Inorg Chem. 2024 Jun 24;63(25):11788-11801. doi: 10.1021/acs.inorgchem.4c01490. Epub 2024 Jun 13.

DOI:10.1021/acs.inorgchem.4c01490
PMID:38867694
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11200260/
Abstract

Britholites are the lanthanide-silica-rich end-members of the apatite group, commonly studied for their optical properties. Here, we show ∼50-100 μm single crystals synthesized hydrothermally at 650-500 °C and 500-300 MPa composed of a solid solution between CaPr(SiO)F-fluorbritholite and CaPr(SiO)O-oxybritholite, with a significant carbonate component substitution, via C replacing Si. Single-crystal X-ray diffraction and density functional theory computations show that a planar carbonate group occupies the face of a now-vacant silica tetrahedron. This modifies Pr-O bond lengths, diversifying lanthanide optical emission wavelengths. Our britholite was synthesized in geologically reasonable conditions and compositions, suggesting that carbonated oxybritholites could exist as yet-unrecognized natural minerals.

摘要

氟硅铈矿是磷灰石族中富含镧系元素和硅的端元矿物，通常因其光学性质而被研究。在此，我们展示了通过水热法在650 - 500 °C和500 - 300 MPa条件下合成的约50 - 100 μm的单晶，其由CaPr(SiO)F - 氟硅铈矿和CaPr(SiO)O - 氧硅铈矿之间的固溶体组成，通过C取代Si存在显著的碳酸盐成分替代。单晶X射线衍射和密度泛函理论计算表明，一个平面碳酸根基团占据了现在空缺的硅四面体的面。这改变了Pr - O键长，使镧系元素的光发射波长多样化。我们的氟硅铈矿是在地质合理的条件和成分下合成的，这表明碳酸化氧硅铈矿可能作为尚未被识别的天然矿物存在。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/5867cbf61031/ic4c01490_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/0ab482d7c394/ic4c01490_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/7169a4dde4ca/ic4c01490_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/015c1cac0814/ic4c01490_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/2d53eba73811/ic4c01490_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/f3b957f71f97/ic4c01490_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/22fd43ec7471/ic4c01490_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/bb6b51f17fcc/ic4c01490_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/d47d90c69736/ic4c01490_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/41965e721680/ic4c01490_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/90ca71c74ada/ic4c01490_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/5867cbf61031/ic4c01490_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/0ab482d7c394/ic4c01490_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/7169a4dde4ca/ic4c01490_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/015c1cac0814/ic4c01490_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/2d53eba73811/ic4c01490_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/f3b957f71f97/ic4c01490_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/22fd43ec7471/ic4c01490_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/bb6b51f17fcc/ic4c01490_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/d47d90c69736/ic4c01490_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/41965e721680/ic4c01490_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/90ca71c74ada/ic4c01490_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81ed/11200260/5867cbf61031/ic4c01490_0011.jpg

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