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金属氧化物在特定任务离子液体中的溶解

Dissolution of metal oxides in task-specific ionic liquid.

作者信息

Richter Janine, Ruck Michael

机构信息

Faculty of Chemistry and Food Chemistry, Technische Universität Dresden 01062 Dresden Germany

Max Planck Institute for Chemical Physics of Solids 01187 Dresden Germany.

出版信息

RSC Adv. 2019 Sep 19;9(51):29699-29710. doi: 10.1039/c9ra06423k. eCollection 2019 Sep 18.

Abstract

Due to their typically low reactivity, the activation of metal oxides, as found in ores, earths and minerals, is in general performed by high temperature reactions, which consume much energy. Owing to the prevalence of fossil fuels, this is accompagnied by the generation of large amounts of CO. Alternatively, ionic liquids (ILs) can be used as solvents for metal oxide dissolution and downstream chemistry at much lower temperatures. The dissolution ability of the dry ionic liquid betainium bis(trifluoromethylsulfonyl)imide, [Hbet][NTf], was investigated for 30 metal oxides at 175 °C and compared to chloride containing IL [Hbet][NTf]Cl. A general dissolution-promoting effect of chloride anions was found, regarding reaction time as well as the variety of dissolved metal oxides. Up to now, the dissolution in [Hbet][NTf]Cl is limited to basic or amphoteric metal oxides and assumed to be influenced by multiple factors, such as reaction conditions and the lattice energy of the metal oxide as well as its crystal structure. Comprehensive investigations were performed for the dissolution of CuO, which led to the discovery of the water-free complex compound [Cu(bet)(NTf)][NTf]. Proceeding from this compound, a complete exchange of the O-coordination sphere by other ligands was demonstrated, opening up promising possibilities for downstream chemistry.

摘要

由于金属氧化物通常具有较低的反应活性,存在于矿石、泥土和矿物中的金属氧化物的活化一般通过高温反应来进行,而高温反应会消耗大量能量。由于化石燃料的广泛使用,这会伴随着大量一氧化碳的产生。另外,离子液体(ILs)可以用作金属氧化物溶解及下游化学过程的溶剂,且反应温度要低得多。研究了干燥的离子液体甜菜碱双(三氟甲基磺酰)亚胺([Hbet][NTf])在175℃下对30种金属氧化物的溶解能力,并与含氯的离子液体[Hbet][NTf]Cl进行了比较。发现氯离子对反应时间以及溶解的金属氧化物种类都有普遍的促进溶解作用。到目前为止,在[Hbet][NTf]Cl中的溶解仅限于碱性或两性金属氧化物,并且被认为受多种因素影响,如反应条件、金属氧化物的晶格能及其晶体结构。对氧化铜的溶解进行了全面研究,发现了无水配合物[Cu(bet)(NTf)][NTf]。从该化合物出发,证明了其O配位球可以被其他配体完全取代,这为下游化学过程开辟了广阔前景。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1015/9071953/7f71b4f62e6a/c9ra06423k-f1.jpg

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