Simon R Bare

All Publications

• Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations. Journal of the American Chemical Society Wrasman, C. J., Boubnov, A., Riscoe, A. R., Hoffman, A. S., Bare, S. R., Cargnello, M. 2018

  Abstract

  Selective oxidations are crucial for the creation of valuable chemical building blocks but often require expensive and unstable stoichiometric oxidants such as hydroperoxides and peracids. To date, many catalysts that contain a single type of active site have not been able to attain the desired level of selectivity for partially oxidized products over total combustion. However, catalysts containing multiple types of active sites have proven to be successful for selective reactions. One category of such catalysts is bimetallic alloys, in which catalytic activity and selectivity can be tuned by modifying the surface composition. Traditional catalyst synthesis methods using impregnation struggle to create catalysts with sufficient control over surface chemistry to accurately tune the ensemble size of the desired active sites. Here we describe the synthesis of colloidal nanocrystals of dilute alloys of palladium and gold. We show that when supported on titania (TiO2), tuning the composition of the Pd/Au nanocrystal surface provides a synergistic effect in the selective oxidation of 2-propanol to acetone in the presence of H2 and O2. In particular, we show that certain Pd/Au surface ratios exhibit activity and selectivity far superior to Pd or Au individually. Through precise structural characterization we demonstrate that isolated atoms of Pd exist in the most active catalysts. The synergy between isolated Pd atoms and Au allows for the formation of reactive oxidizing species, likely hydroperoxide groups, responsible for selective oxidation while limiting oxygen dissociation and, thus, complete combustion. This work opens the way to more efficient utilization of scarce noble metals and new options for catalyzed selective oxidations.

  View details for PubMedID 30220200

• Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques Reaction Chemistry & Engineering Hoffman, A. S., Azzam, S., Zhang, K., Xu, Y., Liu, Y., Bare, S. R., Simonetti, D. A. 2018; 3: 668-675

  View details for DOI 10.1039/C8RE00020D

• Low-Temperature Restructuring of CeO2-Supported Ru Nanoparticles Determines Selectivity in CO2 Catalytic Reduction. Journal of the American Chemical Society Aitbekova, A. n., Wu, L. n., Wrasman, C. J., Boubnov, A. n., Hoffman, A. S., Goodman, E. D., Bare, S. R., Cargnello, M. n. 2018; 140 (42): 13736–45

  Abstract

  CO2 reduction to higher value products is a promising way to produce fuels and key chemical building blocks while reducing CO2 emissions. The reaction at atmospheric pressure mainly yields CH4 via methanation and CO via the reverse water-gas shift (RWGS) reaction. Describing catalyst features that control the selectivity of these two pathways is important to determine the formation of specific products. At the same time, identification of morphological changes occurring to catalysts under reaction conditions can be crucial to tune their catalytic performance. In this contribution we investigate the dependency of selectivity for CO2 reduction on the size of Ru nanoparticles (NPs) and on support. We find that even at rather low temperatures (210 °C), oxidative pretreatment induces redispersion of Ru NPs supported on CeO2 and leads to a complete switch in the performance of this material from a well-known selective methanation catalyst to an active and selective RWGS catalyst. By utilizing in situ X-ray absorption spectroscopy, we demonstrate that the low-temperature redispersion process occurs via decomposition of the metal oxide phase with size-dependent kinetics, producing stable single-site RuO x/CeO2 species strongly bound to the CeO2 support that are remarkably selective for CO production. These results show that reaction selectivity can be heavily dependent on catalyst structure and that structural changes of the catalyst can occur even at low temperatures and can go unseen in materials with less defined structures.

  View details for PubMedID 30252458

• High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts CHEMISTRY-A EUROPEAN JOURNAL Hoffman, A. S., Sokaras, D., Zhang, S., Debefve, L. M., Fang, C., Gallo, A., Kroll, T., Dixon, D. A., Bare, S. R., Gates, B. C. 2017; 23 (59): 14760–68

  Abstract

  We report high-energy-resolution X-ray absorption spectroscopy detection of ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO supports. The data are supported by density functional theory and FEFF X-ray absorption near-edge modelling, together with infrared (IR) spectra. The results demonstrate that high-energy-resolution X-ray absorption spectra near the iridium LIII (2p3/2 ) edge provide clearly ascribable, distinctive signatures of the ethylene and CO ligands and illustrate effects of supports and other ligands. This X-ray absorption technique is markedly more sensitive than conventional IR spectroscopy for characterizing surface intermediates, and it is applicable to samples having low metal loadings and in reactive atmospheres and is expected to have an increasing role in catalysis research by facilitating the determination of mechanisms of solid-catalyzed reactions through identification of reaction intermediates in working catalysts.

  View details for PubMedID 28749554

• Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids ACS CATALYSIS Babucci, M., Fang, C., Hoffman, A. S., Bare, S. R., Gates, B. C., Uzun, A. 2017; 7 (10): 6969–72

  View details for DOI 10.1021/acscatal.7b02429

  View details for Web of Science ID 000412795700061

• Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability ACS CATALYSIS Goodman, E. D., Dai, S., Yang, A., Wrasman, C. J., Gallo, A., Bare, S. R., Hoffman, A. S., Jaramillo, T. F., Graham, G. W., Pan, X., Cargnello, M. 2017; 7 (7): 4372–80

  View details for DOI 10.1021/acscatal.7b00393

  View details for Web of Science ID 000405360800018

• Characterization of Coke on a Pt-Re/gamma-Al2O3 Re-Forming Catalyst: Experimental and Theoretical Study ACS CATALYSIS Bare, S. R., Vila, F. D., Charochak, M. E., Prabhakar, S., Bradley, W. J., Jaye, C., Fischer, D. A., Hayashi, S. T., Bradley, S. A., Rehr, J. J. 2017; 7 (2): 1452–61

  View details for DOI 10.1021/acscatal.6b02785

  View details for Web of Science ID 000393539200061

• Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography Schmidt, J. E., Poplawsky, J. D., Mazumder, B., Attila, O., Fu, D., de Winter, D., Meirer, F., Bare, S. R., Weckhuysen, B. M. WILEY-V C H VERLAG GMBH. 2016: 11173–77

  Abstract

  Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.

  View details for DOI 10.1002/anie.201606099

  View details for Web of Science ID 000383642300038

  View details for PubMedID 27485276

• Transmission and fluorescence X-ray absorption spectroscopy cell/flow reactor for powder samples under vacuum or in reactive atmospheres REVIEW OF SCIENTIFIC INSTRUMENTS Hoffman, A. S., Debefve, L. M., Bendjeriou-Sedjerari, A., Ouldchikh, S., Bare, S. R., Basset, J., Gates, B. C. 2016; 87 (7): 073108

  Abstract

  X-ray absorption spectroscopy is an element-specific technique for probing the local atomic-scale environment around an absorber atom. It is widely used to investigate the structures of liquids and solids, being especially valuable for characterization of solid-supported catalysts. Reported cell designs are limited in capabilities-to fluorescence or transmission and to static or flowing atmospheres, or to vacuum. Our goal was to design a robust and widely applicable cell for catalyst characterizations under all these conditions-to allow tracking of changes during genesis and during operation, both under vacuum and in reactive atmospheres. Herein, we report the design of such a cell and a demonstration of its operation both with a sample under dynamic vacuum and in the presence of gases flowing at temperatures up to 300 °C, showing data obtained with both fluorescence and transmission detection. The cell allows more flexibility in catalyst characterization than any reported.

  View details for DOI 10.1063/1.4958824

  View details for Web of Science ID 000382448600011

  View details for PubMedID 27475549

• Surface analysis of zeolites: An XPS, variable kinetic energy XPS, and low energy ion scattering study SURFACE SCIENCE Bare, S. R., Knop-Gericke, A., Teschner, D., Haevacker, M., Blume, R., Rocha, T., Schloegl, R., Chan, A. Y., Blackwell, N., Charochak, M. E., ter Veen, R., Brongersma, H. H. 2016; 648: 376–82

  View details for DOI 10.1016/j.susc.2015.10.048

  View details for Web of Science ID 000374198600054

• Aberration-Corrected Transmission Electron Microscopy and InSitu XAFS Structural Characterization of Pt/-Al2O3 Nanoparticles CHEMCATCHEM Sinkler, W., Sanchez, S. I., Bradley, S. A., Wen, J., Mishra, B., Kelly, S. D., Bare, S. R. 2015; 7 (22): 3779–87

  View details for DOI 10.1002/cctc.201500784

  View details for Web of Science ID 000365116400021

• Expanding Beyond the Micropore: Active-Site Engineering in Hierarchical Architectures for Beckmann Rearrangement ACS Catalysis Newland, S. H., Sinkler, W., Mezza, T., Bare, S. R., Carravetta, M., Haies, I. M., Levy, A., Keenan, S., Raja, R. 2015; 5 (11): 6587–93

  View details for DOI 10.1021/acscatal.5b01595

  View details for Web of Science ID 000364441300040

• Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Potter, M. E., Paterson, A. J., Mishra, B., Kelly, S. D., Bare, S. R., Cora, F., Levy, A. B., Raja, R. 2015; 137 (26): 8534-8540

  Abstract

  A combined electronic structure computational and X-ray absorption spectroscopy study was used to investigate the nature of the active sites responsible for catalytic synergy in Co-Ti bimetallic nanoporous frameworks. Probing the nature of the molecular species at the atomic level has led to the identification of a unique Co-O-Ti bond, which serves as the loci for the superior performance of the bimetallic catalyst, when compared with its analogous monometallic counterpart. The structural and spectroscopic features associated with this active site have been characterized and contrasted, with a view to affording structure-property relationships, in the wider context of designing sustainable catalytic oxidations with porous solids.

  View details for DOI 10.1021/jacs.5b03734

  View details for Web of Science ID 000357964400039

  View details for PubMedID 26076192

• Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography NATURE COMMUNICATIONS Perea, D. E., Arslan, I., Liu, J., Ristanovic, Z., Kovarik, L., Arey, B. W., Lercher, J. A., Bare, S. R., Weckhuysen, B. M. 2015; 6

  Abstract

  Zeolite catalysis is determined by a combination of pore architecture and Brønsted acidity. As Brønsted acid sites are formed by the substitution of AlO4 for SiO4 tetrahedra, it is of utmost importance to have information on the number as well as the location and neighbouring sites of framework aluminium. Unfortunately, such detailed information has not yet been obtained, mainly due to the lack of suitable characterization methods. Here we report, using the powerful atomic-scale analysis technique known as atom probe tomography, the quantitative spatial distribution of individual aluminium atoms, including their three-dimensional extent of segregation. Using a nearest-neighbour statistical analysis, we precisely determine the short-range distribution of aluminium over the different T-sites and determine the most probable Al-Al neighbouring distance within parent and steamed ZSM-5 crystals, as well as assess the long-range redistribution of aluminium upon zeolite steaming.

  View details for DOI 10.1038/ncomms8589

  View details for Web of Science ID 000358855900002

  View details for PubMedID 26133270

• Characterization of a Fluidized Catalytic Cracking Catalyst on Ensemble and Individual Particle Level by X-ray Micro-and Nanotomography, Micro-X-ray Fluorescence, and Micro-X-ray Diffraction CHEMCATCHEM Bare, S. R., Charochak, M. E., Kelly, S. D., Lai, B., Wang, J., Chen-Wiegart, Y. 2014; 6 (5): 1427–37

  View details for DOI 10.1002/cctc.201300974

  View details for Web of Science ID 000335926400037

• Pressure-Dependent Effect of Hydrogen Adsorption on Structural and Electronic Properties of Pt/gamma-Al2O3 Nanoparticles CHEMCATCHEM Mistry, H., Behafarid, F., Bare, S. R., Roldan Cuenya, B. 2014; 6 (1): 348–52

  View details for DOI 10.1002/cctc.201300783

  View details for Web of Science ID 000330636800044

• Interplay between nanoscale reactivity and bulk performance of H-ZSM-5 catalysts during the methanol-to-hydrocarbons reaction JOURNAL OF CATALYSIS Aramburo, L. R., Teketel, S., Svelle, S., Bare, S. R., Arstad, B., Zandbergen, H. W., Olsbye, U., de Groot, F. F., Weckhuysen, B. M. 2013; 307: 185–93

  View details for DOI 10.1016/j.jcat.2013.07.009

  View details for Web of Science ID 000327903900021

• Operando Effects on the Structure and Dynamics of PtnSnm/gamma-Al2O3 from Ab Initio Molecular Dynamics and X-ray Absorption Spectra JOURNAL OF PHYSICAL CHEMISTRY C Vila, F. D., Rehr, J. J., Kelly, S. D., Bares, S. R. 2013; 117 (24): 12446–57

  View details for DOI 10.1021/jp403931z

  View details for Web of Science ID 000320911100007

• EXAFS Model of 2-Dimensional Platinum Clusters Kelly, S. D., Charochak, M. E., Blackwell, N., Bare, S. R., Wu, Z. Y. IOP PUBLISHING LTD. 2013

  View details for DOI 10.1088/1742-6596/430/1/012061

  View details for Web of Science ID 000320464300061

• Electronic properties and charge transfer phenomena in Pt nanoparticles on gamma-Al2O3: size, shape, support, and adsorbate effects PHYSICAL CHEMISTRY CHEMICAL PHYSICS Behafarid, F., Ono, L. K., Mostafa, S., Croy, J. R., Shafai, G., Hong, S., Rahman, T. S., Bare, S. R., Roldan Cuenya, B. 2012; 14 (33): 11766–79

  Abstract

  This study presents a systematic detailed experimental and theoretical investigation of the electronic properties of size-controlled free and γ-Al(2)O(3)-supported Pt nanoparticles (NPs) and their evolution with decreasing NP size and adsorbate (H(2)) coverage. A combination of in situ X-ray absorption near-edge structure (XANES) and density functional theory (DFT) calculations revealed changes in the electronic characteristics of the NPs due to size, shape, NP-adsorbate (H(2)) and NP-support interactions. A correlation between the NP size, number of surface atoms and coordination of such atoms, and the maximum hydrogen coverage stabilized at a given temperature is established, with H/Pt ratios exceeding the 1 : 1 ratio previously reported for bulk Pt surfaces.

  View details for DOI 10.1039/c2cp41928a

  View details for Web of Science ID 000307017800023

  View details for PubMedID 22828479

• Controlled one-step synthesis of hierarchically structured macroscopic silica spheres MICROPOROUS AND MESOPOROUS MATERIALS Scholz, S., Bare, S. R., Kelly, S. D., Lercher, J. A. 2011; 146 (1-3): 18–27

  View details for DOI 10.1016/j.micromeso.2011.04.036

  View details for Web of Science ID 000295769400004

• Density functional theory study of the effect of subsurface H, C, and Ag on C2H2 hydrogenation on Pd(1 1 1) CATALYSIS TODAY Tiruppathi, P., Low, J. J., Chan, A. Y., Bare, S. R., Meyer, R. J. 2011; 165 (1): 106–11

  View details for DOI 10.1016/j.cattod.2011.02.029

  View details for Web of Science ID 000289789800015

• Experimental (XAS, STEM, TPR, and XPS) and Theoretical (DFT) Characterization of Supported Rhenium Catalysts JOURNAL OF PHYSICAL CHEMISTRY C Bare, S. R., Kelly, S. D., Vila, F. D., Boldingh, E., Karapetrova, E., Kas, J., Mickelson, G. E., Modica, F. S., Yang, N., Rehr, J. J. 2011; 115 (13): 5740–55

  View details for DOI 10.1021/jp1105218

  View details for Web of Science ID 000288885900068

• Simultaneous XAFS measurements of multiple samples JOURNAL OF SYNCHROTRON RADIATION Ravel, B., Scorzato, C., Siddons, D. P., Kelly, S. D., Bare, S. R. 2010; 17: 380–85

  Abstract

  A four-channel ionization chamber has been designed, constructed and tested. This ionization chamber allows X-ray absorption spectra to be collected in transmission from up to four samples simultaneously. This results in spectra that are free of systematic uncertainty in relative energy alignment introduced by scan-to-scan stability of the monochromator or of numerical uncertainty associated with a post-processing alignment algorithm, allowing, in a single shot, an absolute measure of edge shift between four samples of different valence. As four samples can be measured in parallel, the time expended over the course of an experiment to cycle the measurement environment between its rest state and the measurement condition is substantially reduced. The ionization chamber is simple in design and could be implemented at virtually any XAFS beamline with a horizontal fan of radiation such as that provided by a bend magnet or wiggler.

  View details for DOI 10.1107/S0909049510006230

  View details for Web of Science ID 000276785600012

  View details for PubMedID 20400837

• Characterizing industrial catalysts using in situ XAFS under identical conditions PHYSICAL CHEMISTRY CHEMICAL PHYSICS Bare, S. R., Kelly, S. D., Ravel, B., Greenlay, N., King, L., Mickelson, G. E. 2010; 12 (27): 7702–11

  Abstract

  In situ X-ray absorption spectroscopy (XAS) in catalysis research has traditionally been conducted by making one measurement at a time on a single sample. In an industrial research environment this is especially limiting as sample throughput (productivity) and turnaround time (direct project relevance) are critical issues in the use of XAS in a fast-moving technology delivery project. In order to address these issues we have developed and implemented a four-channel ionization chamber combined with two different in situ cells that allows XAS data to be collected simultaneously from four samples, or four regions, in transmission geometry without any sample or detector movement. In the development of this new capability it was realized that there are other benefits from this simultaneous detection in addition to increased productivity. Namely, (i) the use of EXAFS to determine the structure of a catalyst in situ axially at four different positions down a catalyst bed; (ii) the ability to collect up to four XAFS spectra simultaneously and thereby avoid any scan-to-scan uncertainties, and (iii) the added confidence in the ability to discriminate small differences in similarly prepared catalysts which is typical in the development of a commercial catalyst. Specific illustrations of each of these applications are shown. The methodology is simple to implement and could be used on any XAFS beamline with a horizontal fan of radiation, such as at a typical bending magnet or wiggler source beamline.

  View details for DOI 10.1039/b926621f

  View details for Web of Science ID 000279514500045

  View details for PubMedID 20505854