Understanding bottom-up continuous hydrothermal synthesis of nanoparticles using empirical measurement and computational simulation

Continuous hydrothermal synthesis was highlighted in a recent review as an enabling technology for the production of nanoparticles. In recent years, it has been shown to be a suitable reaction medium for the synthesis of a wide range of nanomaterials. Many single and complex nanomaterials such as metals, metal oxides, doped oxides, carbonates, sulfides, hydroxides, phosphates, and metal organic frameworks can be formed using continuous hydrothermal synthesis techniques. This work presents a methodology to characterize continuous hydrothermal flow systems both experimentally and numerically, and to determine the scalability of a counter current supercritical water reactor for the large scale production (>1,000 T·year–1) of nanomaterials. Experiments were performed using a purpose-built continuous flow rig, featuring an injection loop on a metal salt feed line, which allowed the injection of a chromophoric tracer. At the system outlet, the tracer was detected using UV/Vis absorption, which could be used to measure the residence time distribution within the reactor volume. Computational fluid dynamics (CFD) calculations were also conducted using a modeled geometry to represent the experimental apparatus. The performance of the CFD model was tested against experimental data, verifying that the CFD model accurately predicted the nucleation and growth of the nanomaterials inside the reactor

Self-assembly of Fe nanocluster arrays on templated surfaces

The growth of Fe nanoclusters on the Ge(001) and MoO2/Mo(110) surfaces has been studied using low-temperature scanning tunneling microscopy (STM) and X-ray magnetic circular dichroism (XMCD). STM results indicate that at low coverage Fe atoms self-assemble on both surfaces into well-separated nanoclusters, which nucleate at equivalent surface sites. Their size, shape, and the observed spatial separation are dictated by the substrate and depend on preparation conditions. Annealing the Fe nanoclusters on Ge(001) at 420K leads to the formation of linear nanocluster arrays, which follow the Ge dimer rows of the substrate, due to cluster mobility at such temperature. In turn, linear Fe nanocluster arrays are formed on the MoO2/Mo(110) surface at room temperature at a surface coverage greater than 0.5 monolayer. This is due to the more pronounced row pattern of the MoO2/Mo(110) surface compared to Ge(001). These nanocluster arrays follow the direction of the oxide rows of the strained MoO2/Mo(110) surface. The Fe nanoclusters formed on both surfaces show a superparamagnetic behavior as measured by XMCD

High resolution STM imaging with oriented single crystalline tips

Precise knowledge of the atomic and electronic structure of scanning tunneling microscopy (STM) tips is crucial for a correct interpretation of atomically resolved STM data and an improvement of the spatial resolution. Here we demonstrate that tungsten probes with controllable electronic structure can be fabricated using oriented single crystalline tips. High quality of the [0 0 1]-oriented W tips sharpened in ultra high vacuum was proved by electron microscopy. Distance dependent STM studies carried out on a graphite (0 0 0 1) surface demonstrate that application of crystallographically oriented single crystalline tips allows one to control the tip electron orbitals responsible for high resolution imaging under specific tunneling conditions. (C) 2012 Elsevier B. V. All rights reserved

Fe Nanoclusters on the Ge(001) Surface Studied by Scanning Tunneling Microscopy, Density Functional Theory Calculations and X-Ray Magnetic Circular Dichroism

The growth of Fe nanoclusters on the Ge(001) surface has been studied using low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM results indicate that Fe nucleates on the Ge(001) surface, forming well-ordered nanoclusters of uniform size. Depending on the preparation conditions, two types of nanoclusters were observed having either four or sixteen Fe atoms within a nanocluster. The results were confirmed by DFT calculations. Annealing the nanoclusters at 420 K leads to the formation of nanorow structures, due to cluster mobility at such temperature. The Fe nanoclusters and nanorow structures formed on the Ge(001) surface show a superparamagnetic behaviour as measured by X-ray magnetic circular dichroism