The oriented attachment of molecular clusters and nanoparticles in solution is now recognized as an important mechanism of crystal growth in many materials, yet the alignment process and attachment mechanism have not been established. We performed high-resolution transmission electron microscopy using a fluid cell to directly observe oriented attachment of iron oxyhydroxide nanoparticles. The particles undergo continuous rotation and interaction until they find a perfect lattice match. A sudden jump to contact then occurs over less than 1 nanometer, followed by lateral atom-by-atom addition initiated at the contact point. Interface elimination proceeds at a rate consistent with the curvature dependence of the Gibbs free energy. Measured translational and rotational accelerations show that strong, highly direction-specific interactions drive crystal growth via oriented attachment.

SummaryWe present a short overview of the influence of inter-particle interactions on the properties of magnetic nanoparticles. Strong magnetic dipole interactions between ferromagnetic or ferrimagnetic particles, that would be superparamagnetic if isolated, can result in a collective state of nanoparticles. This collective state has many similarities to spin-glasses. In samples of aggregated magnetic nanoparticles, exchange interactions are often important and this can also lead to a strong suppression of superparamagnetic relaxation. The temperature dependence of the order parameter in samples of strongly interacting hematite nanoparticles or goethite grains is well described by a simple mean field model. Exchange interactions between nanoparticles with different orientations of the easy axes can also result in a rotation of the sub-lattice magnetization directions.

Electrification of conventionally fired chemical reactors has the potential to reduce CO2 emissions and provide flexible and compact heat generation. Here, we describe a disruptive approach to a fundamental process by integrating an electrically heated catalytic structure directly into a steam-methane–reforming (SMR) reactor for hydrogen production. Intimate contact between the electric heat source and the reaction site drives the reaction close to thermal equilibrium, increases catalyst utilization, and limits unwanted byproduct formation. The integrated design with small characteristic length scales allows compact reactor designs, potentially 100 times smaller than current reformer platforms. Electrification of SMR offers a strong platform for new reactor design, scale, and implementation opportunities. Implemented on a global scale, this could correspond to a reduction of nearly 1% of all CO2 emissions.

The magnetic properties of nanoparticles of antiferromagnetic materials are reviewed. The magnetic structure is often similar to the bulk structure, but there are several examples of size-dependent magnetic structures. Owing to the small magnetic moments of antiferromagnetic nanoparticles, the commonly used analysis of magnetization curves above the superparamagnetic blocking temperature may give erroneous results, because the distribution in magnetic moments and the magnetic anisotropy are not taken into account. We discuss how the magnetic dynamics can be studied by use of magnetization measurements, Mössbauer spectroscopy and neutron scattering. Below the blocking temperature, the magnetic dynamics in nanoparticles is dominated by thermal excitations of the uniform mode. In antiferromagnetic nanoparticles, the frequency of this mode is much higher than in ferromagnetic and ferrimagnetic nanoparticles, but it depends crucially on the size of the uncompensated moment. Excitation of the uniform mode results in a socalled thermoinduced moment, because the two sublattices are not strictly antiparallel when this mode is excited. The magnetic dipole interaction between antiferromagnetic nanoparticles is usually negligible, and therefore such particles present a unique possibility to study exchange interactions between magnetic particles. The interactions can have a significant influence on both the magnetic dynamics and the magnetic structure. Nanoparticles can be attached with a common crystallographic orientation such that both the crystallographic and the magnetic order continue across the interfaces.

Iron Hopping Iron oxide minerals shuttle electrons around in a wide range of biogeochemical processes. Katz et al. (p. 1200 ) used time-resolved x-ray absorption spectroscopy to take a closer look at how this happens. By using photoionized surface dyes to inject electrons into three different solid oxide phases, they found that electrons hop among iron centers at rates that depend more on structure in their immediate vicinity than on the extended ordering of the crystal lattice. These observations bolster the prevailing small polaron model in which charge carriers associate closely with individual metal sites.

Chemical and photochemical processes at semiconductor surfaces are highly influenced by the size of the band gap, and ability to control the band gap by particle size in nanomaterials is part of their promise. The combination of soft x-ray absorption and emission spectroscopies provides band-gap determination in bulk and nanoscale itinerant electron semiconductors such as CdS and ZnO, but this approach has not been established for materials such as iron oxides that possess band-edge electronic structure dominated by electron correlations. We performed soft x-ray spectroscopy at the oxygen K-edge to reveal band-edge electronic structure of bulk and nanoscale hematite. Good agreement is found between the hematite band gap derived from optical spectroscopy and the energy separation of the first inflection points in the x-ray absorption and emission onset regions. By applying this method to two sizes of phase-pure hematite nanoparticles, we find that there is no evidence for size-driven change in the band gap of hematite nanoparticles down to around 8 nm.

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Recent ex situ observations of crystallization in both natural and synthetic systems indicate that the classical models of nucleation and growth are inaccurate. However, in situ observations that can provide direct evidence for alternative models have been lacking due to the limited temporal and spatial resolution of experimental techniques that can observe dynamic processes in a bulk solution. Here we report results from liquid cell transmission electron microscopy studies of nucleation and growth of Au, CaCO3, and iron oxide nanoparticles. We show how these in situ data can be used to obtain direct evidence for the mechanisms underlying nanoparticle crystallization as well as dynamic information that provide constraints on important energetic parameters not available through ex situ methods.