Selective suppression of {112} anatase facets by fluorination for enhanced TiO particle size and phase stability at elevated temperatures.

Generally, anatase is the most desirable TiO polymorphic phase for photovoltaic and photocatalytic applications due to its higher photoconductivity and lower recombination rates compared to the rutile phase. However, in applications where temperatures above 500 °C are required, growing pure anatase phase nanoparticles is still a challenge, as above this temperature TiO crystallite sizes are larger than 35 nm which thermodynamically favors the growth of rutile crystallites. In this work, we show strong evidence, for the first time, that achieving a specific fraction (50%) of the {112} facets on the TiO surface is the key limiting step for anatase-to-rutile phase transition, rather than the crystallite size.

Blurring the boundary between homogenous and heterogeneous catalysis using palladium nanoclusters with dynamic surfaces.

Using a magnetron sputtering approach that allows size-controlled formation of nanoclusters, we have created palladium nanoclusters that combine the features of both heterogeneous and homogeneous catalysts. Here we report the atomic structures and electronic environments of a series of metal nanoclusters in ionic liquids at different stages of formation, leading to the discovery of Pd nanoclusters with a core of ca. 2 nm surrounded by a diffuse dynamic shell of atoms in [CCIm][NTf].

Imaging and analysis of covalent organic framework crystallites on a carbon surface: a nanocrystalline scaly COF/nanotube hybrid.

Synthesis of covalent organic frameworks (COFs) is well-advanced but understanding their nanoscale structure and interaction with other materials remains a significant challenge. Here, we have developed a methodology for the detailed imaging and analysis of COF crystallites using carbon nanotube substrates for COF characterisation. Detailed investigation using powder X-ray diffraction, infrared spectroscopy, mass spectrometry and scanning electron microscopy in conjunction with a local probe method, transmission electron microscopy (TEM), revealed details of COF growth and nucleation at the nanoscale.

An integrated approach to determine interactive genotoxic and global gene expression effects of multiwalled carbon nanotubes (MWCNTs) and benzo[a]pyrene (BaP) on marine mussels: evidence of reverse 'Trojan Horse' effects.

The interactions between carbon-based engineered nanoparticles (ENPs) and organic pollutants might enhance the uptake of contaminants into biota. The present integrated study aimed to assess this potential 'Trojan Horse', probing the interactive effects of purpose-made multi-walled carbon nanotubes (MWCNTs), a representative ENP, and benzo[]pyrene (BaP), a ubiquitous polycyclic aromatic hydrocarbon (PAH) pollutant, on the marine mussel Mussels were exposed to MWCNTs and BaP either alone or in various combinations. The co-exposure of BaP with MWCNTs revealed that the presence of MWCNTs enhanced the aqueous concentrations of BaP, thereby reducing the uptake of this pollutant by mussels as evidenced by lowering BaP concentrations in the tissues.

Host-Guest Hybrid Redox Materials Self-Assembled from Polyoxometalates and Single-Walled Carbon Nanotubes.

The development of next-generation molecular-electronic, electrocatalytic, and energy-storage systems depends on the availability of robust materials in which molecular charge-storage sites and conductive hosts are in intimate contact. It is shown here that electron transfer from single-walled carbon nanotubes (SWNTs) to polyoxometalate (POM) clusters results in the spontaneous formation of host-guest POM@SWNT redox-active hybrid materials. The SWNTs can conduct charge to and from the encapsulated guest molecules, allowing electrical access to >90% of the encapsulated redox species.

Core-Shell NaHoF@TiO NPs: A Labeling Method to Trace Engineered Nanomaterials of Ubiquitous Elements in the Environment.

Understanding the fate and behavior of nanoparticles (NPs) in the natural environment is important to assess their potential risk. Single particle inductively coupled plasma mass spectrometry (spICP-MS) allows for the detection of NPs at extremely low concentrations, but the high natural background of the constituents of many of the most widely utilized nanoscale materials makes accurate quantification of engineered particles challenging. Chemical doping, with a less naturally abundant element, is one approach to address this; however, certain materials with high natural abundance, such as TiO NPs, are notoriously difficult to label and differentiate from natural NPs.

Movement of palladium nanoparticles in hollow graphitised nanofibres: the role of migration and coalescence in nanocatalyst sintering during the Suzuki-Miyaura reaction.

The evolution of individual palladium nanoparticle (PdNP) catalysts in graphitised nanofibres (GNF) in the liquid-phase Suzuki-Miyaura (SM) reaction has been appraised. The combination of identical location-transmission electron microscopy (IL-TEM) and a nano test tube approach allowed spatiotemporally continuous observations at the single nanoparticle level, revealing that migration and coalescence is the most significant pathway to coarsening of the nanocatalyst, rather than Ostwald ripening. IL-TEM gave unprecedented levels of detail regarding the movement of PdNP on carbon surfaces at the nanoscale, including size-dependent migration and directional movement, opening horizons for the optimisation of future catalysts through surface morphology design.