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High entropy alloys (HEAs) are an important new material class with significant application potential in catalysis and electrocatalysis. The entropy-driven formation of HEA materials requires high temperatures and controlled cooling rates. However, catalysts in general also require highly dispersed materials, i.e., nanoparticles. Only then a favorable utilization of the expensive raw materials can be achieved. Several recently reported HEA nanoparticle synthesis strategies, therefore, avoid the high-temperature regime to prevent particle growth. In our work, we investigate a system of five noble metal single-source precursors with superior catalytic activity for the oxygen reduction reaction. Combining in situ X-ray powder diffraction with multi-edge X-ray absorption spectroscopy, we address the fundamental question of how single-phase HEA nanoparticles can form at low temperatures. It is demonstrated that the formation of HEA nanoparticles is governed by stochastic principles and the inhibition of precursor mobility during the formation process favors the formation of a single phase. The proposed formation principle is supported by simulations of the nanoparticle formation in a randomized process, rationalizing the experimentally found differences between two-element and multi-element metal precursor mixtures.

Surface intermediate species and oxygen vacancy-assisted mechanism over CeO2 catalyst in the direct dimethyl carbonate (DMC) synthesis from carbon dioxide and methanol are suggested by means of transient spectroscopic methodologies in conjunction with multivariate spectral analysis. How the two reactants, i.e. CO2 and methanol, interact with the CeO2 surface and how they form decisive surface intermediates leading to DMC are unraveled by DFT-based molecular dynamics simulation by precise statistical sampling of various configurations of surface states and intermediates. The atomistic simulations and uncovered stability of different intermediate states perfectly explain the unique DMC formation profile experimentally observed upon transient operations, strongly supporting the proposed oxygen vacancy-assisted reaction mechanism., ChemE/Catalysis Engineering

High entropy alloys (HEAs) are an important new material class with significant application potential incatalysis and electrocatalysis. The entropy-driven formation of HEA materials requires high temperaturesand controlled cooling rates. However, catalysts in general also require highly dispersed materials, i.e.,nanoparticles. Only then a favorable utilization of the expensive raw materials can be achieved. Severalrecently reported HEA nanoparticle synthesis strategies, therefore, avoid the high-temperature regime toprevent particle growth. In our work, we investigate a system of five noble metal single-source precursorswith superior catalytic activity for the oxygen reduction reaction. Combining in situ X-ray powderdiffraction with multi-edge X-ray absorption spectroscopy, we address the fundamental question of howsingle-phase HEA nanoparticles can form at low temperatures. It is demonstrated that the formation ofHEA nanoparticles is governed by stochastic principles and the inhibition of precursor mobility during theformation process favors the formation of a single phase. The proposed formation principle is supported bysimulations of the nanoparticle formation in a randomized process, rationalizing the experimentally founddifferences between two-element and multi-element metal precursor mixtures.

Understanding and utilizing structure-performance relationships in catalytic nanomaterials is the epitome of catalysis science. Knowledge at the atomic level can potentially allow rational design of more selective and energy-efficient catalytic materials. Fischer-Tropsch synthesis on cobalt is an example of a complicated system that operates in a narrow process regime, and the nature of the reaction product is governed by numerous parameters. On an industrial model catalyst, we have simplified the structure of the active, metallic nanoparticles into a predominantly hexagonal close-packed structure via the use of a Co2C precursor. By varying the final reduction temperature, we could mildly modify catalyst microstructural properties at the nanoparticle (NP) level. Catalytic materials, although with minimal structural differences, showed significantly different performance. Evidently there is a narrow window for complete utilization of the hexagonal close-packed Co crystallites that lies between removal of lattice carbon, that remains from the Co2C precursor, and the initiation of stacking disorder, because of a transition to the face-centered cubic Co structure. Fischer-Tropsch synthesis performance indicators show that Co NPs with minimum number of crystal defects outperform catalysts with lattice defects, because of the existence of either lattice carbon or stacking faults. Therefore, catalyst preparation and activation procedures probably should be designed targeting defect-free Co crystallites., QC 20190129