Author: David Chi-Wai TangPublisher:
ISBN:
Category :
Languages : en
Pages : 562
Book Description
High Pressure Scanning Tunneling Microscopy Studies of Adsorbate Structure and Mobility During Catalytic Reactions
Author: David Chi-Wai TangHigh Pressure Scanning Tunneling Microscopy and High PressureX-ray Photoemission Spectroscopy Studies of Adsorbate Structure, Composition and Mobility During Catalytic Reactions on A Model SingleCrystal
Author: M. O. MontanoPublisher:
ISBN:
Category :
Languages : en
Pages :
Book Description
Our research focuses on taking advantage of the ability of scanning tunneling microscopy (STM) to operate at high-temperatures and high-pressures while still providing real-time atomic resolution images. We also utilize high-pressure x-ray photoelectron spectroscopy (HPXPS) to monitor systems under identical conditions thus giving us chemical information to compare and contrast with the structural and dynamic data provided by STM.
High Pressure Scanning Tunneling Microscopy Studies of AdsorbateStructure and Mobility During Catalytic Reactions
Author: Publisher:
ISBN:
Category :
Languages : en
Pages : 277
Book Description
The aim of the work presented therein is to take advantage of scanning tunneling microscope’s (STM) capability for operation under a variety of environments under real time and at atomic resolution to monitor adsorbate structures and mobility under high pressures, as well as to design a new generation of STM systems that allow imaging in situ at both higher pressures (35 atm) and temperatures (350 °C).
Adsorbate Structures and Catalytic Reactions Studied in the Torrpressure Range by Scanning Tunneling Microscopy
Author: Publisher:
ISBN:
Category :
Languages : en
Pages : 132
Book Description
High-pressure, high-temperature scanning tunneling microscopy (HPHTSTM) was used to study adsorbate structures and reactions on single crystal model catalytic systems. Studies of the automobile catalytic converter reaction [CO + NO → 1/2 N2 + CO2] on Rh(111) and ethylene hydrogenation [C2H4 + H2 → C2H6] on Rh(111) and Pt(111) elucidated information on adsorbate structures in equilibrium with high-pressure gas and the relationship of atomic and molecular mobility to chemistry. STM studies of NO on Rh(111) showed that adsorbed NO forms two high-pressure structures, with the phase transformation from the (2 x 2) structure to the (3 x 3) structure occurring at 0.03 Torr. The (3 x 3) structure only exists when the surface is in equilibrium with the gas phase. The heat of adsorption of this new structure was determined by measuring the pressures and temperatures at which both (2 x 2) and (3 x 3) structures coexisted. The energy barrier between the two structures was calculated by observing the time necessary for the phase transformation to take place. High-pressure STM studies of the coadsorption of CO and NO on Rh(111) showed that CO and NO form a mixed (2 x 2) structure at low NO partial pressures. By comparing surface and gas compositions, the adsorption energy difference between topsite CO and NO was calculated. Occasionally there is exchange between top-site CO and NO, for which we have described a mechanism for. At high NO partial pressures, NO segregates into islands, where the phase transformation to the (3 x 3) structure occurs. The reaction of CO and NO on Rh(111) was monitored by mass spectrometry (MS) and HPHTSTM. From MS studies the apparent activation energy of the catalytic converter reaction was calculated and compared to theory. STM showed that under high-temperature reaction conditions, surface metal atoms become mobile. Ethylene hydrogenation and its poisoning by CO was also studied by STM on Rh(111) and Pt(111). Poisoning was found to coincide with decreased adsorbate mobility. Under ethylene hydrogenation conditions, no order is detected by STM at 300 K, as hydrogen and ethylidyne, the surface species formed by gas-phase ethylene, are too mobile. When CO is introduced, the reaction stops, and ordered structures appear on the surface. For Rh(111), the structure is predominantly a mixed c(4 x 2), though there are some areas of (2 x 2). For Pt(111), the structure is hexagonal and resembles the Moire pattern seen when Pt(111) is exposed to pure CO. From these studies it is concluded that CO poisons by stopping adsorbate mobility. This lack of adsorbate mobility prevents the adsorption of ethylene from the gas phase by hindering the creation of adsorption sites.
Adsorbate Structures and Catalytic Reactions Studied in the Torr Pressure Range by Scanning Tunneling Microscopy
Author: Kevin Shao-Lin HwangPublisher:
ISBN:
Category :
Languages : en
Pages : 272
Book Description
Scanning Tunneling Microscopy in Surface Science, Nanoscience, and Catalysis
Author: Michael BowkerPublisher: John Wiley & Sons
ISBN: 9783527628834
Category : Science
Languages : en
Pages : 258
Book Description
Here, top international authors in the field of STM and surface science present first-class contributions on this hot topic, bringing the reader up to date with the latest developments in this rapidly advancing field. The focus is on the nanoscale, particularly in relation to catalysis, involving developments in our understanding of the nature of the surfaces of oxides and nanoparticulate materials, as well as adsorption, and includes in-situ studies of catalysis on such model materials. Of high interest to practitioners of surface science, nanoscience, STM and catalysis.
High Pressure, High Temperature Scanning Tunneling Microscopy Studies of CO, NO, and 02 on Pt(111) and Rh(111)
Author: Keith Benton RiderDynamics of Surfaces and Reaction Kinetics in Heterogeneous Catalysis
Author: G.F. FromentPublisher: Elsevier
ISBN: 0080530621
Category : Technology & Engineering
Languages : en
Pages : 611
Book Description
Many processes of the chemical industry are based upon heterogeneous catalysis. Two important items of these processes are the development of the catalyst itself and the design and optimization of the reactor. Both aspects would benefit from rigorous and accurate kinetic modeling, based upon information on the working catalyst gained from classical steady state experimentation, but also from studies using surface science techniques, from quantum chemical calculations providing more insight into possible reaction pathways and from transient experimentation dealing with reactions and reactors. This information is seldom combined into a kinetic model and into a quantitative description of the process. Generally the catalytic aspects are dealt with by chemists and by physicists, while the chemical engineers are called upon for mechanical aspects of the reactor design and its control. The symposium "Dynamics of Surfaces and Reaction Kinetics in Heterogeneous Catalysis" aims at illustrating a more global and concerted approach through a number of prestigious keynote lectures and severely screened oral and poster presentations.
In Situ Studies of Surface Mobility on Noble Metal Model Catalysts Using STM and XPS at Ambient Pressure
Author: Publisher:
ISBN:
Category :
Languages : en
Pages :
Book Description
High Pressure Scanning Tunneling Microscopy (HP-STM) and Ambient Pressure X-ray Photoelectron Spectroscopy were used to study the structural properties and catalytic behavior of noble metal surfaces at high pressure. HP-STM was used to study the structural rearrangement of the top most atomic surface layer of the metal surfaces in response to changes in gas pressure and reactive conditions. AP-XPS was applied to single crystal and nanoparticle systems to monitor changes in the chemical composition of the surface layer in response to changing gas conditions. STM studies on the Pt(100) crystal face showed the lifting of the Pt(100)-hex surface reconstruction in the presence of CO, H2, and Benzene. The gas adsorption and subsequent charge transfer relieves the surface strain caused by the low coordination number of the (100) surface atoms allowing the formation of a (1 x 1) surface structure commensurate with the bulk terminated crystal structure. The surface phase change causes a transformation of the surface layer from hexagonal packing geometry to a four-fold symmetric surface which is rich in atomic defects. Lifting the hex reconstruction at room temperature resulted in a surface structure decorated with 2-3 nm Pt adatom islands with a high density of step edge sites. Annealing the surface at a modest temperature (150 C) in the presence of a high pressure of CO or H2 increased the surface diffusion of the Pt atoms causing the adatom islands to aggregate reducing the surface concentration of low coordination defect sites. Ethylene hydrogenation was studied on the Pt(100) surface using HP-STM. At low pressure, the lifting of the hex reconstruction was observed in the STM images. Increasing the ethylene pressure to 1 Torr, was found to regenerate the hexagonally symmetric reconstructed phase. At room temperature ethylene undergoes a structural rearrangement to form ethylidyne. Ethylidyne preferentially binds at the three-fold hollow sites, which are present on the Pt(100) hex reconstructed phase, but not the (100)-(1x1) surface. The increase in ethylene pressure caused the adsorbate interactions to dominate the crystal morphology and imposed a surface layer structure that matched the ethylidyne binding geometry. The STM results also showed that the surface was reversibly deformed during imaging due to increases in Pt mobility at high pressure. The size dependence on the activity and surface chemistry of Rh nanoparticles was studied using AP-XPS. The activity was found to increase with particle size. The XPS spectra show that in reaction conditions the particle surface has an oxide layer which is chemically distinct from the surface structure formed by heating in oxygen alone. This surface oxide which is stabilized in the catalytically active CO oxidation conditions was found to be more prevalent on the smaller nanoparticles. The reaction-induced surface segregation behavior of bimetallic noble metal nanoparticles was observed with APXPS. Monodisperse 15 nm RhPd and PdPt nanoparticles were synthesized with well controlled Rh/Pd and Pd/Pt compositions. In-situ XPS studies showed that at 300 C in the presence of an oxidizing environment (100 mTorr NO or O2) the surface concentration of the more easily oxidized element (Rh in RhPd and Pd in PdPt) was increased. Switching the gas environment to more reducing conditions (100 mTorr NO and 100 mTorr CO) caused the surface enrichment of the element with the lowest surface energy in its metallic state. Using in-situ characterization, the redox chemistry and the surface composition of bimetallic nanoparticle samples were monitored in reactive conditions. The particle surfaces were shown to reversibly restructure in response to the gas environment at high temperature. The oxidation behavior of the Pt(110) surface was studied using surface sensitive in-situ characterization by APXPS and STM. In the presence of 500 mTorr O2 and temperatures between 25 and 200 C, subsurface oxygen was detected in the surface layer. STM images show that these conditions were found to cause a roughened surface decorated with 1 nm islands. The formation of this surface oxide is a high pressure phenomenon and was not detected in 50 mTorr O2. After forming the surface oxide at high pressure, its chemical activity was measured through the reaction with CO at low pressure while continuously monitoring the oxygen species with XPS. The subsurface oxygen was removed by CO oxidation at a comparable rate to the chemisorbed oxygen at 2 C. Repeating the experiment at -3 C reduced the reaction rate, but not the relative activity of the two chemical species suggesting that neither species is significantly more active for the CO oxidation reaction. These studies use molecular level surface characterization in the presence of gases to show the structural changes induced by gas adsorption at high pressure.
The Development of Catalysis
Author: Adriano ZecchinaPublisher: John Wiley & Sons
ISBN: 1119181305
Category : Science
Languages : en
Pages : 352
Book Description
This book gradually brings the reader, through illustrations of the most crucial discoveries, into the modern world of chemical catalysis. Readers and experts will better understand the enormous influence that catalysis has given to the development of modern societies. • Highlights the field's onset up to its modern days, covering the life and achievements of luminaries of the catalytic era • Appeals to general audience in interpretation and analysis, but preserves the precision and clarity of a scientific approach • Fills the gap in publications that cover the history of specific catalytic processes