Chun Dong Hyun, Park Ji Chan, Rhim Geun Bae, Lee Ho-Tae, Yang Jung-Il, Jung Heon
J Nanosci Nanotechnol. 2016 Feb;16(2):1660-4. doi: 10.1166/jnn.2016.11933.
Temperature-programmed reduction using H2 (H2-TPR) and CO (CO-TPR) was carried out to investigate the reduction and carburization behavior of nanocrystalline ferrihydrite-based Fe/Cu/K/SiO2 catalysts for use in Fischer-Tropsch synthesis (FTS). Unlike pure ferrihydrite, the ferrihydrite-based catalysts did not pass through the intermediate decomposition step of ferrihydrite (Fe9O2(OH)23) into hematite (a-Fe2O3) as they were reduced into magnetite (Fe3O4). This is attributed to the enhanced thermal stability induced by SiO2. For the ferrihydrite-based catalysts, the reduction of ferrihydrite into magnetite occurred in two stages because the reduction promoter, Cu, is not homogeneously distributed on the catalyst surfaces. The Cu-rich sites are likely to be reduced in the first stage, and the Cu-lean sites may be reduced in the second stage. After the ferrihydrite is reduced to magnetite, the reduction process of magnetite was similar to that for conventional hematite-based FTS catalysts: 'magnetite --> metallic iron' and 'magnetite --> wüstite (FeO) or fayalite (Fe2SiO4) --> metallic iron' in the H2 atmosphere; 'magnetite --> iron carbides' in the CO atmosphere.
采用氢气程序升温还原(H2-TPR)和一氧化碳程序升温还原(CO-TPR)来研究用于费托合成(FTS)的纳米晶水铁矿基Fe/Cu/K/SiO2催化剂的还原和渗碳行为。与纯水铁矿不同,水铁矿基催化剂在还原成磁铁矿(Fe3O4)时,并未经历水铁矿(Fe9O2(OH)23)分解为赤铁矿(α-Fe2O3)的中间步骤。这归因于SiO2所诱导的热稳定性增强。对于水铁矿基催化剂,水铁矿还原成磁铁矿的过程分两个阶段进行,这是因为还原促进剂Cu并非均匀分布在催化剂表面。富铜位点可能在第一阶段被还原,贫铜位点可能在第二阶段被还原。水铁矿还原成磁铁矿后,磁铁矿的还原过程与传统赤铁矿基FTS催化剂类似:在氢气气氛中为“磁铁矿→金属铁”和“磁铁矿→浮氏体(FeO)或铁橄榄石(Fe2SiO4)→金属铁”;在一氧化碳气氛中为“磁铁矿→碳化铁”。