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At least 91 records · Page 5

Deducing subnanometer cluster size and shape distributions of heterogeneous supported catalysts

Abstract Infrared (IR) spectra of adsorbate vibrational modes are sensitive to adsorbate/metal interactions, accurate, and easily obtainable in-situ or operando. While they are the gold standards for characterizing single-crystals and large nanoparticles, analogous spectra for highly dispersed heterogeneous catalysts consisting of single-atoms and ultra-small clusters are lacking. Here, we combine data-based approaches with physics-driven surrogate models to generate synthetic IR spectra from first-principles. We bypass the vast combinatorial space of clusters by determining viable, low-energy structures using machine-learned Hamiltonians, genetic algorithm optimization, and grand canonical Monte Carlo calculations. We obtain first-principles vibrations on this tractable ensemble and generate single-cluster primary spectra analogous to pure component gas-phase IR spectra. With such spectra as standards, we predict cluster size distributions from computational and experimental data, demonstrated in the case of CO adsorption on Pd/CeO 2 (111) catalysts, and quantify uncertainty using Bayesian Inference. We discuss extensions for characterizing complex materials towards closing the materials gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation studies on carbon supported catalysts for oxygen reduction in alkaline medium

This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.

Srinivasan, Vakula S.↗

Laser Synthesis of Supported Catalysts for Carbon Nanotubes

Four methods of laser assisted catalyst generation for carbon nanotube (CNT) synthesis have been tested. These include pulsed laser transfer (PLT), photolytic deposition (PLD), photothermal deposition (PTD) and laser ablation deposition (LABD). Results from each method are compared based on CNT yield, morphology and structure. Under the conditions tested, the PLT was the easiest method to implement, required the least time and also yielded the best pattemation. The photolytic and photothermal methods required organometallics, extended processing time and partial vacuums. The latter two requirements also held for the ablation deposition approach. In addition to control of the substrate position, controlled deposition duration was necessary to achieve an active catalyst layer. Although all methods were tested on both metal and quartz substrates, only the quartz substrates proved to be inactive towards the deposited catalyst particles.

VanderWal, Randall L.↗

Cross-linked polyvinyl pyridine coated glass particle catalyst support and aqueous composition or polyvinyl pyridine adducted microspheres

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Rembaum, Alan↗

Catalysts, catalyst supports and methods of making the same

The present disclosure relates to a composition that includes a core in the shape of a particle having a characteristic length between about one micron and about one millimeter, an active material that includes a noble metal deposited on a surface of the core, and a coating that includes a first metal-oxide, where the active material is positioned between the core and the coating, the active material has a diameter between about one nanometer and about 20 nanometers, and the coating has a thickness between greater than zero nanometers and about 20 nanometers.

Vardon, Derek Richard↗

Design and Characterization of ALD-Based Overcoats for Supported Metal Nanoparticle Catalysts

Supported metal nanoparticle (SMN) catalysts are enormously crucial for many catalytic applications. However, catalyst deactivation, caused by sintering and coke formation, is a ubiquitous problem that significantly undermines catalytic processing economics. The application of material overcoating onto supported metal nanoparticles by atomic layer deposition (ALD) offers the solution to inhibit catalyst deactivation. Herein, we discuss examples in which ALD has been used to stabilize SMN catalysts in gaseous and aqueous-phase reactions. We highlight the ALD tools and methods in coating high-surface-area catalysts. Besides, various techniques are introduced to understand better how to characterize the overcoating layer and the catalyst itself. Finally, the outlook for new techniques to characterize the ALD overcoated catalytic materials is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation

Solid supports play an indispensable role in heterogeneous catalysis, as they can directly affect the catalytic activity and selectivity of supported catalysts. However, the specific roles of such supports remain to be demystified owing to the difficulties in obtaining precise structural information on supported catalysts. To understand the effects of MOF topology, pore environment, and metal identity of node supports on the catalytic activity, a Ni catalyst was supported on eight Zr- or Hf-MOFs based on 8-connected nodes: namely M-NU-1200, M-NU-1000, M-NU-1008, and M-NU-1010 (M = Zr, Hf). Single-crystal X-ray diffraction (SCXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the supported catalyst structures. To investigate the support effects on their activities, the supported Ni catalysts were evaluated by using ethylene hydrogenation as a model reaction. The results revealed that all Hf-based-MOF-supported Ni catalysts exhibited higher catalytic reactivity with TOF (turnover frequency) values at least double of those isostructural Zr counterparts. Additionally, MOFs with less congested metal anchoring sites, as a result of the topology and surrounding pore environment, yielded higher TOFs, suggesting the importance of supports in dictating both the catalyst accessibility and activity. Computational analysis complemented the experimental observations and provided insights into reaction barrier differences and their performance variation. Furthermore, this study demonstrates the essential role of the supports and provides a thought for selecting/designing suitable supports in heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flame Synthesis Of Single-Walled Carbon Nanotubes And Nanofibers

Carbon nanotubes are widely sought for a variety of applications including gas storage, intercalation media, catalyst support and composite reinforcing material [1]. Each of these applications will require large scale quantities of CNTs. A second consideration is that some of these applications may require redispersal of the collected CNTs and attachment to a support structure. If the CNTs could be synthesized directly upon the support to be used in the end application, a tremendous savings in post-synthesis processing could be realized. Therein we have pursued both aerosol and supported catalyst synthesis of CNTs. Given space limitations, only the aerosol portion of the work is outlined here though results from both thrusts will be presented during the talk. Aerosol methods of SWNT, MWNT or nanofiber synthesis hold promise of large-scale production to supply the tonnage quantities these applications will require. Aerosol methods may potentially permit control of the catalyst particle size, offer continuous processing, provide highest product purity and most importantly, are scaleable. Only via economy of scale will the cost of CNTs be sufficient to realize the large-scale structural and power applications on both earth and in space. Present aerosol methods for SWNT synthesis include laser ablation of composite metalgraphite targets or thermal decomposition/pyrolysis of a sublimed or vaporized organometallic [2]. Both approaches, conducted within a high temperature furnace, have produced single-walled nanotubes (SWNTs). The former method requires sophisticated hardware and is inherently limited by the energy deposition that can be realized using pulsed laser light. The latter method, using expensive organometallics is difficult to control for SWNT synthesis given a range of gasparticle mixing conditions along variable temperature gradients; multi-walled nanotubes (MWNTs) are a far more likely end products. Both approaches require large energy expenditures and produce CNTs at prohibitive costs, around $500 per gram. Moreover these approaches do not possess demonstrated scalability. In contrast to these approaches, flame synthesis can be a very energy efficient, low-cost process [3]; a portion of the fuel serves as the heating source while the remainder serves as reactant. Moreover, flame systems are geometrically versatile as illustrated by innumerable boiler and furnace designs. Addressing scalability, flame systems are commercially used for producing megatonnage quantities of carbon black [4]. Although it presents a complex chemically reacting flow, a flame also offers many variables for control, e.g. temperature, chemical environment and residence times [5]. Despite these advantages, there are challenges to scaling flame synthesis as well.

Wal, Randy L. Vander↗

Toward Rational Design of Supported Vanadia Catalysts of Lignin Conversion to Phenol

In sustainable chemical engineering, catalytic upgrading of lignocellulosic biomass has recently gained attention for producing renewable platform chemicals. To achieve maximal biomass utilization, upgrading the underutilized lignin components is essential. Among various catalysts for lignin upgrading, supported vanadia (V2O5) catalysts are promising because of their cost-effectiveness and tunability of either dopant metals or catalyst supports. Here, computational studies are conducted to derive rational design guidelines of supported V2O5 catalysts for accomplishing the high catalytic activity of lignin upgrading to phenol, a key compound for producing bioplastics and biofuel blendstocks. Guaiacol was used as the model compound since it comprises the highest portion of depolymerized lignin. Computational mechanistic studies for the catalytic guaiacol conversion to phenol were performed for the V2O5 catalysts on Titania (TiO2) and silica (SiO2) to explain higher experimental phenol yields on V2O5/SiO2 than V2O5/TiO2. The hydrogen migration from the methoxy group to the aryl ring was identified as a rate-determining step, and the overall activation energies on the two catalysts were compared. A structural analysis was carried out for the catalysts and rate-determining transition states to gain further insights from mechanistic studies. It was concluded that the tilt angle of the aryl group in the hydrogen migration transition state is a key descriptor determining the catalytic activity of phenol formation. These features correlate well with activation energies and experimental phenol yields, indicating that they provide design guidelines for supported metal catalysts for lignin upgrading before experiments.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Assessment and comparison of ordered & non-ordered supported metal oxide catalysts for upgrading propane to propylene

Propylene is an important chemical feedstock that is largely produced via cracking of oil-derived naphtha. Direct conversion of propane into propylene may be a more attractive alternative. Specifically, propane dehydrogenation (DH) and oxidative dehydrogenation (ODH) are promising for this transformation, albeit only DH has been industrially implemented. However, even the best DH catalysts (Pt-based) still suffer from deactivation. VO x - and BO x -based ODH catalysts result in significant over-oxidation and lack a mechanistic understanding. A common challenge in developing these catalysts is the broad distribution of surface species caused by the use of non-ordered catalyst supports. This hampers clear structure-performance correlations. Recent progress in the preparation of well-defined active sites on ordered supports has brought about improved catalysts, as well as fundamental insight into the working mechanism. This review will highlight recent advancements in the development of these catalysts and provide direction on the use of ordered supports for propane upgrading.

03 NATURAL GAS↗

Active-Site Determination and Mechanistic Insights in a MOF-Supported Polymerization Catalyst

The structural elucidation of catalyst active sites in heterogeneous catalysts when supported by traditional metal oxides remains a challenge despite the advanced characterization techniques that have been developed. The catalyst-deposition-site nonuniformity in metal oxides inhibits clear structural characterization through bulk spectroscopic methods and rules out the use of single-crystal X-ray diffraction. However, for metal-organic framework (MOF)-supported catalysts, the crystallinity and uniform structures of the underlying support enhance our ability to identify the precatalyst and catalytically active sites and open the door to using single-crystal X-ray diffraction coupled with spectroscopy under reaction conditions. Additionally, the use of in situ X-ray absorption spectroscopy identifies the catalytically active site in diethylaluminum chloride (DEAC)-pretreated Cr-SIM-NU-1000 to be a Cr-ethyl when used for ethylene polymerization. Further kinetic experiments elucidate the effects of ethylene pressure, temperature, catalyst loading, and cocatalyst loading, furthering mechanistic knowledge and helping to deconvolute the structure-function relationship.

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