de Alwis Chathura, Leftwich Timothy R, Mukherjee Pinaki, Denofre Alex, Perrine Kathryn A
Department of Chemistry, Michigan Technological University Houghton MI 49931 USA
Department of Material Science & Engineering, Michigan Technological University Houghton MI 49931 USA.
Nanoscale Adv. 2019 Oct 2;1(12):4729-4744. doi: 10.1039/c9na00472f. eCollection 2019 Dec 3.
Iron oxide nanomaterials participate in redox processes that give them ideal properties for their use as earth-abundant catalysts. Fabricating nanocatalysts for such applications requires detailed knowledge of the deposition and growth. We report the spontaneous deposition of iron oxide nanoparticles on HOPG in defect areas and on step edges from a metal precursor solution. To study the nucleation and growth of iron oxide nanoparticles, tailored defects were created on the surface of HOPG using various ion sources that serve as the target sites for iron oxide nucleation. After solution deposition and annealing, the iron oxide nanoparticles were found to nucleate and coalesce at 400 °C. AFM revealed that the particles on the sp carbon sites enabled the nanoparticles to aggregate into larger particles. The iron oxide nanoparticles were characterized as having an Fe oxidation state and two different oxygen species, Fe-O and Fe-OH/Fe-OOH, as determined by XPS. STEM imaging and EDS mapping confirmed that the majority of the nanoparticles grown were converted to hematite after annealing at 400 °C. A mechanism of spontaneous and selective deposition on the HOPG surface and transformation of the iron oxide nanoparticles is proposed. These results suggest a simple method for growing nanoparticles as a model catalyst.
氧化铁纳米材料参与氧化还原过程,这使其具有作为储量丰富的地球催化剂的理想特性。制造用于此类应用的纳米催化剂需要详细了解沉积和生长过程。我们报告了氧化铁纳米颗粒在HOPG的缺陷区域和来自金属前驱体溶液的台阶边缘上的自发沉积。为了研究氧化铁纳米颗粒的成核和生长,使用各种离子源在HOPG表面制造了定制缺陷,这些离子源作为氧化铁成核的目标位点。经过溶液沉积和退火后,发现氧化铁纳米颗粒在400°C时成核并聚结。原子力显微镜显示,sp碳位点上的颗粒使纳米颗粒聚集成更大的颗粒。通过XPS确定,氧化铁纳米颗粒的特征是具有Fe氧化态以及两种不同的氧物种,即Fe-O和Fe-OH/Fe-OOH。扫描透射电子显微镜成像和能谱映射证实,在400°C退火后,生长的大多数纳米颗粒转化为赤铁矿。提出了一种在HOPG表面自发和选择性沉积以及氧化铁纳米颗粒转化的机制。这些结果表明了一种作为模型催化剂生长纳米颗粒的简单方法。