Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum–rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

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Psychopsidae (silky lacewings) is a species-poor ingroup of Neuroptera. Silky lacewings show a distinct relic distribution, indicating that the group was more speciesrich and diverse in the past. Silky lacewings have distinct larvae that resemble antlion larvae but differ from these in lacking teeth on their mouth parts, and in having a projecting labrum, which makes them "long-nosed antlion larvae". These larvae are well known from Myanmar amber (about 100 mya) and Baltic amber (mostly 34-38 mya, possibly 23-48 mya), as well as from the extant fauna. We report and figure numerous additional specimens from both amber types and from ca. 100 mya old French Charentese amber, expanding the known record of well-illustrated extant and fossil specimens from 26 to 52 specimens. We compare the diversity of head shape among these larvae through time by outline analysis. Results indicate that morphological diversity was pronouncedly higher in the Cretaceous, even after sample size correction. Eocene representatives are more diverse than modern representatives, but less diverse than Cretaceous ones, in one shape aspect that explains most of the overall variation (55.7%). Eocene representatives are less diverse in another shape aspect that explains the second-most variation (26.9%), but this might reflect a lack of first larval stage specimens. There seems to be no strong correlation between size and shape. This type of analysis enables a test for the loss of diversity over time, based on morphological diversity as a proxy, without the requirement of identifying fossil larvae down to a narrow taxonomical range.

BackgroundAdult mantis lacewings, neuropteran holometabolan insects of the group Mantispidae, possess anterior walking legs transformed into prey-catching grasping appendages reminiscent of those of praying mantises. While adult mantis lacewings are hence active “wait-and-catch” predators, the larvae of many mantis lacewings have a quite different biology: first-stage larvae seek out female spiders, mount them, and either wait until the spider has produced an egg sac or, in some cases, choose a female already bearing an egg sac. The larva then enters the egg sac and feeds on the eggs. While first stage larvae are highly mobile with comparably long legs and a certain degree of dorso-ventral flattening (“campodeiform”), larval stages two and three are almost immobile, grub-like, and simply remain within the egg sac. Fossils of mantis lacewings are relatively rare, fossils of larval mantis lacewings are even rarer; only a single larva sitting on a juvenile spider has been described from ca. 50 million year old Baltic amber.ResultsHere we describe a second occurrence of a larval mantis lacewing from significantly older Burmese amber, about 100 million years old. The specimen is preserved in a position right at the leg of a spider, similar to modern-day larvae that are about to mount their prospective host. The claws of the larva can be seen to grab around the leg of the spider.ConclusionsWe discuss how reliable these fossils are as indicators of palaeo-parasitism, and in which aspects the behaviour of mantis lacewing larvae in general indeed represents parasitism. While the specimen appears to be about to board the spider, it may not necessarily represent a parasite in the strict sense. Evaluating the actual ecological role of a fossil heavily depends on comparison to modern forms, and not all modern-day larvae of Mantispidae are parasites. We therefore provide a closer look into the known feeding habits of modern mantis lacewing larvae.

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High-energy surface-sensitive x-ray diffraction (HESXRD) is a powerful high-energy photon technique (E > 70 keV) that has in recent years proven to allow a fast data acquisition for the 3D structure determination of surfaces and nanoparticles under in situ and operando conditions. The use of a large-area detector facilitates the direct collection of nearly distortion-free diffraction patterns over a wide q range, including crystal truncation rods perpendicular to the surface and large-area reciprocal space maps from epitaxial nanoparticles, which is not possible in the conventional low-photon energy approach (E = 10−20 keV). Here, we present a comprehensive mathematical approach, explaining the working principle of HESXRD for both single-crystal surfaces and epitaxial nanostructures on single-crystal supports. The angular calculations used in conventional crystal truncation rod measurements at low-photon energies are adopted for the high-photon-energy regime, illustrating why and to which extent large reciprocal-space areas can be probed in stationary geometry with fixed sample rotation. We discuss how imperfections such as mosaicity and finite domain size aid in sampling a substantial part of reciprocal space without the need of rotating the sample. An exact account is given of the area probed in reciprocal space using such a stationary mode, which is essential for in situ or operando time-resolved experiments on surfaces and nanostructures.

Alloy nanoparticles on oxide supports are widely used as heterogeneous catalysts in reactions involving oxygen. Here we discuss the oxidation behavior of Pd-Rh alloy nanoparticles on MgAl2O4(001) supports with a particle diameter from 6-11 nm. As an In situ tool, we employed high energy grazing incidence X-ray diffraction at a photon energy of 85 keV. We find that physical vapor deposited Pd-Rh nanoparticles grow epitaxially on MgAl2O4(001) with a truncated octahedral shape over the whole concentration range. During our systematic oxidation experiments performed at 670 K in the pressure range from 10(-3) to 0.1 mbar, we observe for Rh containing nanoparticles the formation of two different Rh oxide phases, namely RhO2 and a spinel-like Rh3O4 phase. PdO formation is only observed for pure Pd nanoparticles. This oxidation induced segregation behavior is also reflected in the oxidation induced enlargement of the average nanoparticle lattice parameter towards to value for pure Pd. Our results have ramifications for the phase separation behavior of alloy nanocatalysts under varying reducing and oxidizing environments.

Background Biological diversity is a hot topic in current research, especially its observed decrease in modern times. Investigations of past ecosystems offer additional insights to help better understand the processes underlying biodiversity. The Cretaceous period is of special interest in this context, especially with respect to arthropods. During that period, representatives of many modern lineages appeared for the first time, while representatives of more ancient groups also co-occurred. At the same time, side branches of radiating groups with ‘experimental morphologies’ emerged that seemed to go extinct shortly afterwards. However, larval forms, with their morphological diversity, are largely neglected in such studies, but may provide important insights into morphological and ecological diversity and its changes in the past. Results We present here a new fossil insectan larva, a larval lacewing, in Cretaceous amber, exhibiting a rather unusual, ‘experimental’ morphology. The specimen possesses extremely large (in relation to body size) mandibulo-maxillary piercing stylets. Additionally, the labial palps are very long and are subdivided into numerous elements, overall appearing antenniform. In other aspects, the larva resembles many other neuropteran-type larvae. Conclusions We provide a comparison that includes quantitative aspects of different types of neuropteran larvae to emphasise the exceptionality of the new larva, and discuss its possible relationships to known lineages of Neuroptera; possible interpretations are closer relationships to Dilaridae or Osmylidae. In any case, several of the observed characters must have evolved convergently. With this new find, we expand the known morphological diversity of neuropterans in the Cretaceous fauna.