This Communication describes the synthesis of highly monodispersed 12 nm nickel nanocubes. The cubic shape was achieved by using trioctylphosphine and hexadecylamine surfactants under a reducing hydrogen atmosphere to favor thermodynamic growth and the stabilization of {100} facets. Varying the metal precursor to trioctylphosphine ratio was found to alter the nanoparticle size and shape from 5 nm spherical nanoparticles to 12 nm nanocubes. High-resolution transmission electron microscopy showed that the nanocubes are protected from further oxidation by a 1 nm NiO shell. Synchrotron-based X-ray diffraction techniques showed the nickel nanocubes order into [100] aligned arrays. Magnetic studies showed the nickel nanocubes have over 4 times enhancement in magnetic saturation compared to spherical superparamagnetic nickel nanoparticles.
Understanding the oxidation and reduction mechanisms of catalytically active transition metal nanoparticles is important to improve their application in a variety of chemical processes. In nanocatalysis the nanoparticles can undergo oxidation or reduction in situ, and thus the redox species are not what are observed before and after reactions. We have used the novel environmental scanning transmission electron microscope (ESTEM) with 0.1 nm resolution in systematic studies of complex dynamic oxidation and reduction mechanisms of copper nanoparticles. The oxidation of copper has previously been reported to be dependent on its crystallography and its interaction with the substrate. By following the dynamic oxidation process in situ in real time with high-angle annular dark-field imaging in the ESTEM, we use conditions ideal to track the oxidation front as it progresses across a copper nanoparticle by following the changes in the atomic number (Z) contrast with time. The oxidation occurs via the nucleation of the oxide phase (CuO) from one area of the nanoparticle which then progresses unidirectionally across the particle, with the Cu-to-CuO interface having a relationship of Cu{111}//CuO{111}. The oxidation kinetics are related to the temperature and oxygen pressure. When the process is reversed in hydrogen, the reduction process is observed to be similar to the oxidation, with the same crystallographic relationship between the two phases. The dynamic observations provide unique insights into redox mechanisms which are important to understanding and controlling the oxidation and reduction of copper-based nanoparticles.
Branched metal nanostructures are of great technological importance because of their unique size- and shape-dependent properties. A kinetically controlled synthesis that uses polymorphism to produce branched nickel nanoparticles is presented. These nanoparticles consist of a face-centred cubic (fcc) core and extended arms of alternating fcc and hexagonal close-packed (hcp) nickel phases.
Quantum dot (QD) solar cells have emerged as promising low-cost alternatives to existing photovoltaic technologies. Here, we investigate charge transfer and separation at PbS QDs and phenyl-C61-butyric acid methyl ester (PCBM) interfaces using a combination of femtosecond broadband transient absorption (TA) spectroscopy and steady-state photoluminescence quenching measurements. We analyzed ultrafast electron injection and charge separation at PbS QD/PCBM interfaces for four different QD sizes and as a function of PCBM concentration. The results reveal that the energy band alignment, tuned by the quantum size effect, is the key element for efficient electron injection and charge separation processes. More specifically, the steady-state and time-resolved data demonstrate that only small-sized PbS QDs with a bandgap larger than 1 eV can transfer electrons to PCBM upon light absorption. We show that these trends result from the formation of a type-II interface band alignment, as a consequence of the size distribution of the QDs. Transient absorption data indicate that electron injection from photoexcited PbS QDs to PCBM occurs within our temporal resolution of 120 fs for QDs with bandgaps that achieve type-II alignment, while virtually all signals observed in smaller bandgap QD samples result from large bandgap outliers in the size distribution. Taken together, our results clearly demonstrate that charge transfer rates at QD interfaces can be tuned by several orders of magnitude by engineering the QD size distribution. The work presented here will advance both the design and the understanding of QD interfaces for solar energy conversion.
The formation mechanism of iron oxide nanoparticles reveals an initial segregation into ferrihydrite seeds and a Fe2+ rich growth reservoir.
Co-precipitation is by far the most common synthesis for magnetic iron oxide nanoparticles (IONPs), as cheap and environmentally friendly precursors and simple experimental procedures facilitate IONP production in many labs. Optimising co-precipitation syntheses remains challenging however, as particle formation mechanisms are not well understood. This is partly due to the rapid particle formation (within seconds) providing insufficient time to characterise initial precipitates. To overcome this limitation, a flow chemistry approach has been developed using steady-state operation to "freeze" transient reaction states locally. This allowed for the first time a comprehensive analysis of the early stages of co-precipitation syntheses via in-situ Small Angle X-ray Scattering and in-situ synchrotron X-Ray Diffraction. These studies revealed that after mixing the ferrous/ferric chloride precursor with the NaOH base solution, the most magnetic iron oxide phase forms within 5 s, the particle size changes only marginally afterwards, and co-precipitation and agglomeration occur simultaneously. As these agglomerates were too large to achieve colloidal stability via subsequent stabiliser addition, co-precipitated IONPs had to be de-agglomerated. This was achieved by adding the appropriate quantity of a citric acid solution which yielded within minutes colloidally stable IONP solutions around a neutral pH value. The new insights into the particle formation and the novel stabilisation procedure (not requiring any ultra-sonication or washing step) allowed to design a multistage flow reactor to synthesise and stabilise IONPs continuously with a residence time of less than 5 min. This reactor was robust against fouling and produced stable IONP solutions (of ~ 1.5 mg particles per ml) reproducibly via fast mixing (< 50 ms) and accurate temperature control at large scale (> 500 ml/h) for low materials cost.
The effect of trioctylphosphine (TOP) concentration on the growth of nickel nanoparticles is studied using in situ synchrotron small-angle X-ray scattering. The growth kinetics are fitted using a two-step nucleation and autocatalytic growth model. TOP acts as a nucleating agent and then acts as an inhibitor against rapid particle growth. Increasing the TOP concentration results in smaller nanoparticles. Once there is a critical concentration of nickel particles above a certain size, they start to aggregate. This results in a broadening of the particle size distribution at later times due to particles on the outside of the aggregates continuing to grow, while those on the inside cease to grow as the nickel precursor is locally depleted.
Metrics & MoreArticle Recommendations CONSPECTUS: Many heterogeneous chemical reactions involve gases catalyzed over solid surfaces at elevated temperatures and play a critical role in the production of energy, healthcare, pollution control, industrial products, and food. These catalytic reactions take place at the atomic level, with active structures forming under reaction conditions. A fundamental understanding of catalysis at the single atom resolution is therefore a major advance in a rational framework upon which future catalytic processes can be built. Visualization and analysis of gas-catalyst chemical reactions at the atomic level under controlled reaction conditions are key to understanding the catalyst structural evolution and atomic scale reaction mechanisms crucial to the performance and the development of improved catalysts and chemical processes. Increasingly, dynamic single atoms and atom clusters are believed to lead to enhanced catalyst performance, but despite considerable efforts, reaction mechanisms at the single atom level under reaction conditions of gas and temperature are not well understood. The development of the atomic lattice resolution environmental transmission electron microscope (ETEM) by the authors is widely used to visualize gas−solid catalyst reactions at this atomic level. It has recently been advanced to the environmental scanning TEM (ESTEM) with single atom resolution and full analytical capabilities. The ESTEM employs high-angle annular dark-field imaging where intensity is approximately proportional to the square of the atomic number (Z). In this Account, we highlight the ESTEM development also introduced by the authors for real time in situ studies to reliably discern metal atoms on lighter supports in gas and high temperature environments, evolving oxide/metal interfaces, and atomic level reaction mechanisms in heterogeneous catalysts more generally and informatively, with utilizing the wider body of literature. The highlights include platinum/carbon systems of interest in fuel cells to meet energy demands and reduce environmental pollution, in reduction/oxidation (redox) mechanisms of copper and nickel nanoparticles extensively employed in catalysis, electronics, and sensors, and in the activation of supported cobalt catalysts in Fischer−Tropsch (FT) synthesis to produce fuels. By following the dynamic reduction process at operating temperature, we investigate Pt atom migrations from irregular nanoparticles in a carbon supported platinum catalyst and the resulting faceting. We outline the factors that govern the mechanism involved, with the discovery of single atom interactions which indicate that a primary role of the nanoparticles is to act as reservoirs of low coordination atoms and clusters. This has important implications in supported nanoparticle catalysis and nanoparticle science. In copper and nickel systems, we track the oxidation front at the atomic level as it proceeds across a nanoparticle, by directly monitoring Z-contrast changes with time and temperature...
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