The crystal structure of non-metamict Ti- and Fe2+-rich chevkinite-(Ce) has been redetermined with the single -crystal sample collected from Bayan Obo, Inner Mongolia, China. The chemical formula of the sample is Ce4F...The crystal structure of non-metamict Ti- and Fe2+-rich chevkinite-(Ce) has been redetermined with the single -crystal sample collected from Bayan Obo, Inner Mongolia, China. The chemical formula of the sample is Ce4Fe2Ti3Si4O22. The crystals are monoclinic with the unit cell parameters a = 13.4656(15) ?, b = 5.7356(6) ?, c = 11.0977(12) ?, β= 100.636(2)o, V = 842.39 (16) ?3 and Z = 2. The structures of Ti- and Fe2+-rich chevkinite-(Ce) were refined with space groups P21/a and C2/m. Least-squares refinement results show that both structural models of Ti- and Fe2+-rich chevkinite-(Ce) are very good, R[F2>2σ(F2)] =0.027 with P21/a and R[F2>2σ(F2)] =0.021 with C2/m. In order to illustrate the relationship between the two space groups P21/a and C2/m, the distribution of diffraction intensities was inspected. Pseudo extinction was found, i.e., reflections with h+k=2n are systematically strong, while those with h+k=2n+1 are weak. By neglecting the systematically weak (h+k=2n+1) reflections the space group becomes C2/m. There is a mirror plane in the C2/m perpendicular to the b axis. However, oxygen atoms in the P21/a model are of a symmetrical relationship with the corresponding pseudo mirror plane. It is concluded that the crystal structure of non-metamict Ti- and Fe2+-rich chevkinite-(Ce) is a superstructure with the space group of P21/a, which is of pseudo symmetry corresponding to the space group C2/m.展开更多
层状无机材料的弱层间耦合和大面积表面为构建低导热性无机固体材料提供了基本框架.合成具有足够散射和非谐波性的稳定层状材料,从而降低热导率,仍是一项挑战.本文在层状无机FeOCl材料体系中,通过一步氧化还原反应成功获得了一种结构稳...层状无机材料的弱层间耦合和大面积表面为构建低导热性无机固体材料提供了基本框架.合成具有足够散射和非谐波性的稳定层状材料,从而降低热导率,仍是一项挑战.本文在层状无机FeOCl材料体系中,通过一步氧化还原反应成功获得了一种结构稳定的富含Fe^(2+)的层状材料,实现了表面和界面的同步改性,并实现了超低的热导率.具体而言,系统的X射线吸收精细结构(XAFS)分析和电子能量损失光谱(EELS)分析表明,碱金属原子的层间插层和表面缺陷的引入诱导了大量Fe^(2+)的存在,从而增强了其非谐波性和声子散射.此外,声子态密度(PDOS)分布也提供了确凿的证据,证明了散射概率的提高和声子模式整体的软化.所制得的层状无机材料Fe(III)_(1−n)Fe(II)_(n)O_(1−x)Cl[K^(+)]_(m)不仅结构稳定,而且在298 K时的热导率比原始FeOCl降低了近60%,低至0.29 W m^(−1) K^(−1),这在层状无机材料中是极低的.这项研究为低导热层状材料的设计提供了新的视角.展开更多
基金supported by the National Natural Science Foundation of China(Grant 40472030)
文摘The crystal structure of non-metamict Ti- and Fe2+-rich chevkinite-(Ce) has been redetermined with the single -crystal sample collected from Bayan Obo, Inner Mongolia, China. The chemical formula of the sample is Ce4Fe2Ti3Si4O22. The crystals are monoclinic with the unit cell parameters a = 13.4656(15) ?, b = 5.7356(6) ?, c = 11.0977(12) ?, β= 100.636(2)o, V = 842.39 (16) ?3 and Z = 2. The structures of Ti- and Fe2+-rich chevkinite-(Ce) were refined with space groups P21/a and C2/m. Least-squares refinement results show that both structural models of Ti- and Fe2+-rich chevkinite-(Ce) are very good, R[F2>2σ(F2)] =0.027 with P21/a and R[F2>2σ(F2)] =0.021 with C2/m. In order to illustrate the relationship between the two space groups P21/a and C2/m, the distribution of diffraction intensities was inspected. Pseudo extinction was found, i.e., reflections with h+k=2n are systematically strong, while those with h+k=2n+1 are weak. By neglecting the systematically weak (h+k=2n+1) reflections the space group becomes C2/m. There is a mirror plane in the C2/m perpendicular to the b axis. However, oxygen atoms in the P21/a model are of a symmetrical relationship with the corresponding pseudo mirror plane. It is concluded that the crystal structure of non-metamict Ti- and Fe2+-rich chevkinite-(Ce) is a superstructure with the space group of P21/a, which is of pseudo symmetry corresponding to the space group C2/m.
基金supported by the Chinese Academy of Sciences(CAS)Project for Young Scientists in Basic Research(YSBR-070)the National Natural Science Foundation of China(21925110,22321001 and 12147105)+5 种基金the USTC Research Funds of the Double FirstClass Initiative(YD2060002004)the National Key Research and Development Program of China(2022YFA1203600)the Anhui Provincial Key Research and Development Project(202004a050200760)the Key R&D Program of Shandong Province(2021CXGC010302)the Fellowship of China Postdoctoral Science Foundation(2022M710141)the Open Foundation of the Key Lab(Center)of Engineering Research Center of Building Energy Efficiency Control and Evaluation,Ministry of Education(AHJZNX-2023-04).
文摘层状无机材料的弱层间耦合和大面积表面为构建低导热性无机固体材料提供了基本框架.合成具有足够散射和非谐波性的稳定层状材料,从而降低热导率,仍是一项挑战.本文在层状无机FeOCl材料体系中,通过一步氧化还原反应成功获得了一种结构稳定的富含Fe^(2+)的层状材料,实现了表面和界面的同步改性,并实现了超低的热导率.具体而言,系统的X射线吸收精细结构(XAFS)分析和电子能量损失光谱(EELS)分析表明,碱金属原子的层间插层和表面缺陷的引入诱导了大量Fe^(2+)的存在,从而增强了其非谐波性和声子散射.此外,声子态密度(PDOS)分布也提供了确凿的证据,证明了散射概率的提高和声子模式整体的软化.所制得的层状无机材料Fe(III)_(1−n)Fe(II)_(n)O_(1−x)Cl[K^(+)]_(m)不仅结构稳定,而且在298 K时的热导率比原始FeOCl降低了近60%,低至0.29 W m^(−1) K^(−1),这在层状无机材料中是极低的.这项研究为低导热层状材料的设计提供了新的视角.
