Spasovski Martin, Avdeev Maxim, Söhnel Tilo
School of Chemical Sciences & Centre for Green Chemical Science, University of Auckland, Private Bag 92019, Auckland, 1142, New Zealand.
MacDiarmid Institute of Advanced Materials and Nanotechnology, Victoria University of Wellington, PO Box 600, Wellington, New Zealand.
Chem Asian J. 2019 Apr 15;14(8):1286-1292. doi: 10.1002/asia.201801835. Epub 2019 Feb 12.
The ternary copper antimony oxide Cu Sb O (x=0.23) has been synthesized under 0.8-1.3 MPa pO at 1022-1082 °C. Rietveld refinements of X-ray and neutron powder diffraction patterns concluded that the oxide adopts a bixbyite type structure, crystallising in the cubic space group Ia-3 with the unit cell parameter a=9.61164(4) Å at room temperature from powder neutron diffraction data. The cationic 8b and 24d sites were found to be occupationally disordered where both Cu and Sb could be found on both sites. This is supported by X-ray absorption spectroscopy experiments showing more than one possible Cu environment. There was a significant net deficiency of oxygen in the compound which was first inferred from observations of a thermochromic-like phenomena and also seen from in situ high temperature neutron diffraction experiments. Magnetic susceptibility and magnetization measurements show paramagnetic behaviour with spin-glass like transition below 6 K.
三元铜锑氧化物CuSbO（x = 0.23）是在1022 - 1082°C、0.8 - 1.3 MPa的氧气压力下合成的。对X射线和中子粉末衍射图谱进行的Rietveld精修得出结论，该氧化物具有方铁锰矿型结构，从粉末中子衍射数据可知，在室温下其在立方空间群Ia-3中结晶，晶胞参数a = 9.61164(4) Å。发现阳离子8b和24d位点存在占位无序，在这两个位点上都能找到Cu和Sb。X射线吸收光谱实验支持了这一点，该实验表明存在不止一种可能的Cu环境。该化合物中存在明显的净氧缺陷，这首先是从类似热致变色现象的观察中推断出来的，并且在原位高温中子衍射实验中也能看到。磁化率和磁化测量表明，该化合物具有顺磁性行为，在6 K以下有类似自旋玻璃的转变。
