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氧化铜/聚乙烯吡咯烷酮球晶的生长机制与微观结构

Growth mechanism and microstructures of CuO/PVP spherulites.

作者信息

Sun Weihao, Zhou Wuzong

机构信息

School of Chemistry, University of St Andrews St Andrews, Fife KY16 9ST UK

出版信息

RSC Adv. 2022 Jul 11;12(31):20022-20028. doi: 10.1039/d2ra03302j. eCollection 2022 Jul 6.

Abstract

CuO spherulites are solvothermaly fabricated by using Cu(NO) as the starting material and polyvinylpyrrolidone (PVP) as a multifunctional growth agent. The specimens at different growth stages are investigated by using X-ray diffraction, electron microscopy, energy dispersive X-ray spectroscopy, soft X-ray emission spectroscopy and infrared spectroscopy. The formation mechanism of CuO spherulites is proposed accordingly. Hierarchically, the spherulites are composed of needle-like submicron-rods lying along the radial orientations. The submicron-rods are constructed by piling up of small CuO/PVP spheres. The embedded CuO nanocrystallites can generate a dipolar field in each along the [100] direction. They deposit at the surface of a negatively charged PVP-containing spherical core, and self-oriented along the radial directions. Therefore, all the CuO nanocrystallites would have their positively charged (100) facet facing to the core and their negatively charged (1̄00) facet turning towards to the spherulite surface, leading to a negatively charged surface of spherulites. Unlike randomly oriented nanocrystallites embedded in polymer microspheres, the spherulites would not undergo surface recrystallisation into a single crystal shell due to the restricted potential of local shift and rotation of the nanocrystallites by the Coulomb force from the core. This work provides new perspective towards the formation of spherulites and their structural properties.

摘要

以硝酸铜为原料、聚乙烯吡咯烷酮(PVP)为多功能生长剂,通过溶剂热法制备了氧化铜球晶。利用X射线衍射、电子显微镜、能量色散X射线光谱、软X射线发射光谱和红外光谱对不同生长阶段的样品进行了研究,并据此提出了氧化铜球晶的形成机制。从层次结构来看,球晶由沿径向排列的针状亚微米棒组成。亚微米棒由小的氧化铜/PVP球体堆积而成。嵌入的氧化铜纳米微晶在每个微晶中沿[100]方向产生偶极场。它们沉积在带负电的含PVP球形核的表面,并沿径向自取向。因此,所有的氧化铜纳米微晶都将其带正电的(100)面朝向核,带负电的(1̄00)面转向球晶表面,导致球晶表面带负电。与嵌入聚合物微球中的随机取向纳米微晶不同,由于核心库仑力对纳米微晶局部位移和旋转的限制,球晶不会发生表面重结晶形成单晶壳。这项工作为球晶的形成及其结构性质提供了新的视角。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e487/9272154/43f3b043d4a2/d2ra03302j-f1.jpg

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