Kappen Jincymol, John S Abraham
Centre for Nanoscience and Nanotechnology, Department of Chemistry, The Gandhigram Rural Institute-Deemed to be University, Gandhigram, 624 302 Dindigul, Tamilnadu, India.
Inorg Chem. 2021 Jun 7;60(11):7834-7843. doi: 10.1021/acs.inorgchem.1c00324. Epub 2021 May 19.
Unlike other metals, Hg forms droplets at ambient conditions when a Hg(II) salt interacts with hydroxyl-enriched graphene quantum dots (HEGQDs). The hydroxylation of GQD surface is evident from FT-IR, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) techniques. The scanning electron microscopy images of Hg(II)-HEGQDs incubated for 0, 1, 24, and 168 h show Hg droplets with the size of 0.1, 0.3, 0.8, and 2 μm, respectively. The XPS studies confirm the presence of Hg(0) and also reveal a noticeable decline in the composition percentage of C-O, whereas a marked increase is observed in the C═O composition percentage. The pathway for the formation of droplets induces immediate reduction of Hg(II) to Hg(0) by both hydroxyl groups and π electron cloud present on the surface of HEGQDs, followed by coalescence. The formed Hg(0) is then strongly adsorbed on the hollow sites of graphene and acts as a nucleation site for the growth of droplets. The kinetics of the reaction obeys LaMer Burst nucleation followed by coalescent growth in addition to autocatalytic reduction and finally follows the Oswald ripening mechanism. The internal pressure of Hg droplets gradually decreases as the radius of the drop increases over the incubation time and liquid-rhombohedral transformation is likely to take place at a radius of 0.8 nm.
与其他金属不同,当汞(II)盐与富含羟基的石墨烯量子点(HEGQDs)相互作用时,汞在环境条件下会形成液滴。从傅里叶变换红外光谱(FT-IR)、拉曼光谱和X射线光电子能谱(XPS)技术可以明显看出GQD表面的羟基化。汞(II)-HEGQDs在0、1、24和168小时孵育后的扫描电子显微镜图像显示,汞液滴的大小分别为0.1、0.3、0.8和2μm。XPS研究证实了Hg(0)的存在,还揭示了C-O组成百分比的显著下降,而C═O组成百分比则显著增加。液滴形成的途径是,HEGQDs表面存在的羟基和π电子云将Hg(II)立即还原为Hg(0),随后发生聚结。然后,形成的Hg(0)强烈吸附在石墨烯的中空位点上,并作为液滴生长的成核位点。该反应的动力学遵循LaMer爆发成核,随后是聚结生长,此外还有自催化还原,最终遵循奥斯特瓦尔德熟化机制。随着孵育时间的延长,汞液滴的半径增加,其内部压力逐渐降低,在半径为0.8nm时可能会发生液-菱面体转变。