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Photo- and radiation-induced preparation of nanocrystalline copper and cuprous oxide catalysts

机译:光和辐射诱导的纳米晶铜和氧化亚铜催化剂的制备

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Spherical copper nanoparticles have been prepared by photo- or radiation-induced reduction of aqueous solutions containing 10−3 mol.dm−3 copper sulphate or formate, 1.3 mol.dm−3 propan-2-ol and polyvinyl alcohol as a stabilizer. Increase of initial copper concentration to 10−2 mol.dm−3 resulted in formation of different reaction product—octahedral cuprous oxide nanoparticles. Solutions were irradiated by means of electron beam, 60Co γ rays (dose rate 70 Gy.h−1) or by 400 W medium-pressure mercury lamp and were characterised by UV-Vis spectrophotometry, X-Ray Powder Diffraction, TEM and SEM. Pink to violet colour of colloidal copper solutions corresponded to measured copper surface plasmon band at circa 580 nm and has been found to be very sensitive to oxygen, which causes dissolution of particles. Therefore, the influence of purging by nitrogen gas prior to irradiation was thoroughly examined and has been found to only hinder, not alter irradiation effects. Moreover, the evolution of absorption spectrum of colloidal copper solution in contact with air has been measured, revealing interesting non-monotonous dependence on the air exposure time, probably caused by formation of protective oxide layer. Catalytic activity of prepared cuprous oxide has been measured by catalytic decomposition of hydrogen peroxide and has been found to be higher or comparable to commercial cuprous oxide.
机译:球形铜纳米粒子是通过光或辐射诱导的含有10 mol dm -3 mol.dm -3 硫酸铜或甲酸的水溶液的还原而制得的sup> -3 丙-2-醇和聚乙烯醇作为稳定剂。初始铜浓度增加到10 −2 mol.dm −3 导致形成了不同的反应产物八面体氧化亚铜纳米颗粒。用电子束, 60 Coγ射线(剂量率70 Gy.h -1 )或400 W中压汞灯辐照溶液,并对其进行表征。紫外可见分光光度法,X射线粉末衍射,TEM和SEM。胶态铜溶液的粉红色至紫色对应于约580 nm处测得的铜表面等离激元带,并且发现对氧非常敏感,这会导致颗粒溶解。因此,彻底检查了在辐照之前用氮气吹扫的影响,发现仅阻碍而不改变辐照效果。此外,已经测量了胶体铜溶液与空气接触时吸收光谱的演变,揭示了有趣的非单调依赖于空气暴露时间的情况,这很可能是由保护性氧化层的形成引起的。制备的氧化亚铜的催化活性已经通过过氧化氢的催化分解来测量,并且发现其与市售的氧化亚铜相比更高或相当。

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