Atomically Dispersed Pd-O Species on CeO2(111) as Highly Active Sites for Low-Temperature CO Oxidation.

Ceria-supported Pd is a promising heterogeneous catalyst for CO oxidation relevant to environmental cleanup reactions. Pd loaded onto a nanorod form of ceria exposing predominantly (111) facets is already active at 50 °C. Here we report a combination of CO-FTIR spectroscopy and theoretical calculations that allows assigning different forms of Pd on the CeO2(111) surface during reaction conditions. Single Pd atoms stabilized in the form of PdO and PdO2 in a CO/O2 atmosphere participate in a catalytic cycle involving very low activation barriers for CO oxidation. The presence of single Pd atoms on the Pd/CeO2-nanorod, corroborated by aberration-corrected TEM and CO-FTIR spectroscopy, is considered pivotal to its high CO oxidation activity.

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping.

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoring the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.

Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina.

Catalysis by single isolated atoms of precious metals has attracted much recent interest, as it promises the ultimate in atom efficiency. Most previous reports are on reducible oxide supports. Here we show that isolated palladium atoms can be catalytically active on industrially relevant γ-alumina supports. The addition of lanthanum oxide to the alumina, long known for its ability to improve alumina stability, is found to also help in the stabilization of isolated palladium atoms. Aberration-corrected scanning transmission electron microscopy and operando X-ray absorption spectroscopy confirm the presence of intermingled palladium and lanthanum on the γ-alumina surface. Carbon monoxide oxidation reactivity measurements show onset of catalytic activity at 40 °C. The catalyst activity can be regenerated by oxidation at 700 °C in air. The high-temperature stability and regenerability of these ionic palladium species make this catalyst system of potential interest for low-temperature exhaust treatment catalysts.

Sintering of catalytic nanoparticles: particle migration or Ostwald ripening?

Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental understanding of catalyst sintering is very important for achieving clean energy and a clean environment, and for efficient chemical conversion processes with atom selectivity. Scientists have proposed two mechanisms for sintering of nanoparticles: particle migration and coalescence (PMC) and Ostwald ripening (OR). PMC involves the mobility of particles in a Brownian-like motion on the support surface, with subsequent coalescence leading to nanoparticle growth. In contrast, OR involves the migration of adatoms or mobile molecular species, driven by differences in free energy and local adatom concentrations on the support surface. In this Account, we divide the process of sintering into three phases. Phase I involves rapid loss in catalyst activity (or surface area), phase II is where sintering slows down, and phase III is where the catalyst may reach a stable performance. Much of the previous work is based on inferences from catalysts that were observed before and after long term treatments. While the general phenomena can be captured correctly, the mechanisms cannot be determined. Advancements in the techniques of in situ TEM allow us to observe catalysts at elevated temperatures under working conditions. We review recent evidence obtained via in situ methods to determine the relative importance of PMC and OR in each of these phases of catalyst sintering. The evidence suggests that, in phase I, OR is responsible for the rapid loss of activity that occurs when particles are very small. Surprisingly, very little PMC is observed in this phase. Instead, the rapid loss of activity is caused by the disappearance of the smallest particles. These findings are in good agreement with representative atomistic simulations of sintering. In phase II, sintering slows down since the smallest particles have disappeared. We now see a combination of PMC and OR, but do not fully understand the relative contribution of each of these processes to the overall rates of sintering. In phase III, the particles have grown large and other parasitic phenomena, such as support restructuring, can become important, especially at high temperatures. Examining the evolution of particle size and surface area with time, we do not see a stable or equilibrium state, especially for catalysts operating at elevated temperatures. In conclusion, the recent literature, especially on in situ studies, shows that OR is the dominant process causing the growth of nanoparticle size. Consequently, this leads to the loss of surface area and activity. While particle migration could be controlled through suitable structuring of catalyst supports, it is more difficult to control the mobility of atomically dispersed species. These insights into the mechanisms of sintering could help to develop sinter-resistant catalysts, with the ultimate goal of designing catalysts that are self-healing.

Relating rates of catalyst sintering to the disappearance of individual nanoparticles during Ostwald ripening.

Sintering of nanoparticles (NPs) of Ni supported on MgAl(2)O(4) was monitored in situ using transmission electron microscopy (TEM) during exposure to an equimolar mixture of H(2) and H(2)O at a pressure of 3.6 mbar at 750 °C, conditions relevant to methane steam reforming. The TEM images revealed an increase in the mean particle size due to disappearance of smaller, immobile NPs and the resultant growth of the larger NPs. A new approach for predicting the long-term sintering of NPs is presented wherein microscopic observations of the ripening of individual NPs (over a span of a few seconds) are used to extract energetic parameters that allow a description of the collective behavior of the entire population of NPs (over several tens of minutes).