Thomas Willum Hansen

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.

Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction

Low-temperature fuel cells are limited by the oxygen reduction reaction, and their widespread implementation in automotive vehicles is hindered by the cost of platinum, currently the best-known catalyst for reducing oxygen in terms of both activity and stability. One solution is to decrease the amount of platinum required, for example by alloying, but without detrimentally affecting its properties. The alloy PtxY is known to be active and stable, but its synthesis in nanoparticulate form has proved challenging, which limits its further study. Herein we demonstrate the synthesis, characterization and catalyst testing of model PtxY nanoparticles prepared through the gas-aggregation technique. The catalysts reported here are highly active, with a mass activity of up to 3.05 A mgPt(-1) at 0.9 V versus a reversible hydrogen electrode. Using a variety of characterization techniques, we show that the enhanced activity of PtxY over elemental platinum results exclusively from a compressive strain exerted on the platinum surface atoms by the alloy core.

Enabling direct H2O2 production through rational electrocatalyst design.

Future generations require more efficient and localized processes for energy conversion and chemical synthesis. The continuous on-site production of hydrogen peroxide would provide an attractive alternative to the present state-of-the-art, which is based on the complex anthraquinone process. The electrochemical reduction of oxygen to hydrogen peroxide is a particularly promising means of achieving this aim. However, it would require active, selective and stable materials to catalyse the reaction. Although progress has been made in this respect, further improvements through the development of new electrocatalysts are needed. Using density functional theory calculations, we identify Pt-Hg as a promising candidate. Electrochemical measurements on Pt-Hg nanoparticles show more than an order of magnitude improvement in mass activity, that is, A g(-1) precious metal, for H2O2 production, over the best performing catalysts in the literature.

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).

Reliability of clinical ICD-10 schizophrenia diagnoses.

Concern has been expressed as to the reliability of clinical ICD-10 diagnosis of schizophrenia. This study was designed to assess the diagnostic reliability of the clinical ICD-10 diagnosis of schizophrenia in a random sample of Danish in- and outpatients with a history of psychosis. A sample of 100 subjects was assessed using the operational criteria OPCRIT checklist for psychotic and affective illness. The most recent principal and clinical ICD-10 diagnosis was compared with diagnoses generated by the OPCRIT instrument. Data documented very high sensitivity (93%) and positive predictive value (87%) of ICD-10 schizophrenia and an overall good agreement between clinical and OPCRIT-derived diagnoses (κ=0.60). An even higher positive predictive value was obtained when diagnoses were amalgamated into a diagnostic entity of schizophrenia-spectrum disorders (98%). Near perfect agreement was seen between OPCRIT-derived ICD-10 and DSM-IV diagnoses (κ=0.87). Thus, this study demonstrates high reliability of the clinical diagnosis of schizophrenia and even more so of the diagnosis of schizophrenia-spectrum disorder.

Chiral-Selective Growth of Single-Walled Carbon Nanotubes on Lattice-Mismatched Epitaxial Cobalt Nanoparticles

Controlling chirality in growth of single-walled carbon nanotubes (SWNTs) is important for exploiting their practical applications. For long it has been conceptually conceived that the structural control of SWNTs is potentially achievable by fabricating nanoparticle catalysts with proper structures on crystalline substrates via epitaxial growth techniques. Here, we have accomplished epitaxial formation of monometallic Co nanoparticles with well-defined crystal structure, and its use as a catalyst in the selective growth of SWNTs. Dynamics of Co nanoparticles formation and SWNT growth inside an atomic-resolution environmental transmission electron microscope at a low CO pressure was recorded. We achieved highly preferential growth of semiconducting SWNTs (~90%) with an exceptionally large population of (6, 5) tubes (53%) in an ambient CO atmosphere. Particularly, we also demonstrated high enrichment in (7, 6) and (9, 4) at a low growth temperature. These findings open new perspectives both for structural control of SWNTs and for elucidating the growth mechanisms.

Association analysis of schizophrenia on 18 genes involved in neuronal migration: MDGA1 as a new susceptibility gene

Several lines of evidence support the theory of schizophrenia (SZ) being a neurodevelopmental disorder. The structural, cytoarchitectural and functional brain abnormalities reported in patients with SZ, might be due to aberrant neuronal migration, since the final position of neurons affects neuronal function, morphology, and formation of synaptic connections. We have investigated the putative association between SZ and gene variants engaged in the neuronal migration process, by performing an association study on 839 cases and 1,473 controls of Scandinavian origin. Using a gene‐wide approach, tagSNPs in 18 candidate genes have been genotyped, with gene products involved in the neuron‐to‐glial cell adhesion, interactions with the DISC1 protein and/or rearrangements of the cytoskeleton. Of the 289 markers tested, 19 markers located in genes MDGA1, RELN, ITGA3, DLX1, SPARCL1, and ASTN1, attained nominal significant P‐values (P < 0.05) in either a genotypic or allelic association test. All of these genes, except transcription factor DLX1, are involved in the adhesion between neurons and radial glial cells. Eight markers obtained nominal significance in both tests, and were located in intronic or 3′UTR regions of adhesion molecule MDGA1 and previously reported SZ candidate RELN. The most significant result was attained for MDGA1 SNP rs9462341 (unadjusted association results: genotypic P = 0.00095; allelic P = 0.010). Several haplotypes within MDGA1, RELN, ITGA3, and ENAH were nominally significant. Further studies in independent samples are needed, including upcoming genome wide association study results, but our data suggest that MDGA1 is a new SZ susceptibility gene, and that altered neuronal migration is involved in SZ pathology.

At-Risk Variant in TCF7L2 for Type II Diabetes Increases Risk of Schizophrenia

BACKGROUND Schizophrenia is associated with increased risk of type II diabetes and metabolic disorders. However, it is unclear whether this comorbidity reflects shared genetic risk factors, at-risk lifestyle, or side effects of antipsychotic medication. METHODS Eleven known risk variants of type II diabetes were genotyped in patients with schizophrenia in a sample of 410 Danish patients, each matched with two healthy control subjects on sex, birth year, and month. Replication was carried out in a large multinational European sample of 4089 patients with schizophrenia and 17,597 controls (SGENE+) using Mantel-Haenszel test. RESULTS One type II diabetes at-risk allele located in TCF7L2, rs7903146 [T], was associated with schizophrenia in the discovery sample (p = .0052) and in the replication with an odds ratio of 1.07 (95% confidence interval 1.01-1.14, p = .033). CONCLUSION The association reported here with a well-known diabetes variant suggests that the observed comorbidity is partially caused by genetic risk variants. This study also demonstrates how genetic studies can successfully examine an epidemiologically derived hypothesis of comorbidity.

Maternally derived microduplications at 15q11-q13: implication of imprinted genes in psychotic illness

OBJECTIVE Rare copy number variants have been implicated in different neurodevelopmental disorders, with the same copy number variants often increasing risk of more than one of these phenotypes. In a discovery sample of 22 schizophrenia patients with an early onset of illness (10-15 years of age), the authors observed in one patient a maternally derived 15q11-q13 duplication overlapping the Prader-Willi/Angelman syndrome critical region. This prompted investigation of the role of 15q11-q13 duplications in psychotic illness. METHOD The authors scanned 7,582 patients with schizophrenia or schizoaffective disorder and 41,370 comparison subjects without known psychiatric illness for copy number variants at 15q11-q13 and determined the parental origin of duplications using methylation-sensitive Southern hybridization analysis. RESULTS Duplications were found in four case patients and five comparison subjects. All four case patients had maternally derived duplications (0.05%), while only three of the five comparison duplications were maternally derived (0.007%), resulting in a significant excess of maternally derived duplications in case patients (odds ratio=7.3). This excess is compatible with earlier observations that risk for psychosis in people with Prader-Willi syndrome caused by maternal uniparental disomy is much higher than in those caused by deletion of the paternal chromosome. CONCLUSIONS These findings suggest that the presence of two maternal copies of a fragment of chromosome 15q11.2-q13.1 that overlaps with the Prader-Willi/Angelman syndrome critical region may be a rare risk factor for schizophrenia and other psychoses. Given that maternal duplications of this region are among the most consistent cytogenetic observations in autism, the findings provide further support for a shared genetic etiology between autism and psychosis.

Surface Chemistry of Ag Particles: Identification of Oxide Species by Aberration-Corrected TEM and by DFT Calculations

In the 1990s, by means of spectroscopic methods, Ertl et al. found surface and subsurface oxygen atoms on and in Ag catalysts. Three species of atomic oxygen with distinct structural and energetic properties were identified. According to their TDS behavior (TDS: thermal desorption spectroscopy), a surface atomic species was termed the a form, and a bulk-dissolved species of lower interaction energy the b form. Finally, g-oxygen was identified as strongly interacting atomic oxygen with high electron density, incorporated into the top atomic surface layer of Ag. As silver catalysts are used in many reactions, for example, hydrogenation of unsaturated aldehydes, partial oxidation of methanol to formaldehyde, and oxidative coupling of methane to ethane and ethylene, the discovery of surface and subsurface oxygen atoms in Ag is of great significance for understanding the catalytic reaction steps and mechanisms of silver catalysts. However, the location of surface and subsurface oxygen atoms remains an unanswered question in Ag catalysis and, perhaps more importantly, it is unclear whether nonmodel industrial catalysts exhibit the same surface chemistry. High-resolution transmission electron microscopy (HRTEM) has been widely used to study the morphology and structure of catalysts. It provides detailed information on the microand nanostructure of catalysts. By aligning the normal of a given surface perpendicular to the incident electron beam, the surface structure and its relationship to the underlying bulk structure can be investigated. However, due to the artefacts caused by spherical aberration of magnetic imaging lenses, conventional TEM is not optimally suited to obtaining readily interpretable images of catalyst surfaces. One major artefact is the delocalization of image details, which appears as an extension of the perimeter of a sample beyond the actual surface. In this study, we investigated an Ag/SiO2 catalyst using a TEM with a sphericalaberration corrector that can compensate for these problems and thus provide detailed information about the structure of the surfaces of a silver-based catalyst. With the support of DFT calculations, the positions of aand g-oxygen on the surfaces of Ag particles have been determined for the first time. Furthermore, the presence of local surface oxygen atoms or oxide was verified. To investigate Ag particles by a direct imaging technique, spatial frequencies in the band between 4.24 and 4.89 nm 1 representing Ag(111) and Ag(200) lattice-plane distances of 0.236 and 0.204 nm, respectively, must be transferred with the same contrast. Under the experimental conditions shown in Figure 1 the acquired high-resolution electron micrograph makes the surface terminations of the Ag particle clearly observable (Figure S1 and Figure 2). The internal crystalline structure of the Ag particles extends to the surface, where it is terminated abruptly in different ways. Steps consisting of one or two atom rows on the (111) facet are observed.