Adsorption at an oxide surface is an essential step in any catalytic, electrocatalytic, or photocatalytic application of oxides, and in their use as sorbents. Among the most important properties one must know about adsorption are its fundamental thermodynamic parameters: the enthalpy and entropy of adsorption. Campbell and Sellers comprehensively review experimental measurements of the heats and entropies of adsorption on well-defined oxides surfaces, including thermodynamic studies of the adsorption of a variety of small molecules and metal atoms on the full range of oxides surfaces.
These data can serve as important benchmarks for validating new computational methods that are very actively being developed today to provide better energy accuracy in modeling the surface chemistry of oxides. Oxide surfaces are used in countless catalytic applications, but their catalytic reactions involving oxygenates are one of their most important application areas. Vohs reviews the current state of knowledge regarding the site requirements for the adsorption and reaction of oxygenates on metal oxide surfaces.
His interpretations of these studies serve as a great paradigm for understanding acid—base properties of oxide surfaces and their manifestation in catalytic reaction mechanisms and oxide surface phenomena in general. The very late transition metals, such as Pd, Pt, Rh, Ir, and Ru, are catalytically active for many reactions. They are usually dispersed across the surface of some oxide or carbon support as nanoparticles.
Because the oxides of these metals have very small heats of formation, they are very easily reducible and the metals are usually considered in their elemental state.
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However, recent evidence suggests that they are also active in their oxide form, and the surface chemical properties of their oxides are often important in the preparation, activation, and reactivation of catalysts. Weaver reviews the surface chemistry of well-ordered oxide surfaces of Pd, Pt, Rh, Ir, and Ru, with emphasis on their preparation, oxygen desorption energetics and kinetics, and chemisorption properties toward small molecules.
These oxides show some surprising behavior. For example, PdO can adsorb short alkanes much more strongly than most oxides and even more strongly than the metallic surfaces of Pd, and as a consequence, PdO is exceptionally reactive in cleaving the C—H bond in small alkanes. While the majority of this issue focuses on surface chemistry involving the interactions of very small molecules with oxide surfaces, where in-depth insight at the atomic scale can be obtained experimentally, the interactions of biopolymers with the oxide surface are extremely important for understanding a wide variety of areas, including material biocompatibility, biomineralization, bioanalytical chemistry and biomolecule sensing, biofouling, and drug delivery.
To give an insight into the fundamental surface chemical issues associated with this field, the review by Ugliengo, Rimola, Sodupe, Dominique, and Lambert of the adsorption of biomolecules on silica surfaces focuses on both computational modeling and experimental studies of this complex topic. Cellular complexity captured in durable silica biocomposites. When oxides are supported on metals and have dimensions that are only a few atomic layers thick, they take on unique new properties.
The review by Netzer, Surnev, and Fortunelli addresses ultrathin films of metal-supported oxides in the extreme nanoscale regime. They discuss how nanostructures of the supported oxide are electronically and elastically coupled to the underlying metal surface and how this can lead to the emergence of novel properties when the oxide film is in the two-dimensional 2-D thin film limit of 1—5 atomic layers or when present as one-dimensional 1-D oxide line structures and quasi zero-dimensional 0-D oxide clusters or nanodots. These emergent properties result from the hybrid character and the low dimensionality of these oxide nanostructures.
As mentioned above, mixed-metal oxides offer exciting possibilities as catalytic, electrocatalyic, photocatalytic, and energy storage materials.
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The review by Stacchiola, Senanayake, Liu, and Rodriguez shows that when an oxide surface is covered with a second oxide at coverages below one monolayer, new synergistic catalytic effects can be obtained. They generated and studied novel structures such as monomers of vanadia, 1D strips of ruthenia, dimers of ceria, and WO 3 3 clusters on TiO 2 Some of these have a strong influence on the activity of the material as a catalyst for the selective oxidation of alkanes and the dehydrogenation of alcohols.
These studies help provide a conceptual framework for controlling the chemical properties of mixed-metal oxides that can help us learn how to engineer new catalysts. This model analyzes the interactions between the dopant and the host oxide as well as the interactions of adsorbates with both types of centers in terms of acid—base interactions, and it provides several simple but very useful rules for interpreting and even predicting these interactions.
Henderson and Lyubinetsky review the deep molecular-level insights into photocatalysis that have been provided by scanning probe microscopy studies of photochemical reactions of small molecules on rutile TiO 2 surfaces, which again serve as a prototype system for understanding photochemical events at oxide surfaces.https://mightiposuta.cf
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To understand photocatalysis, photoelectrocatalysis, and dye-sensitized solar cells, one must have a theoretical description of the excited states of the oxide surfaces involved, both as extended oxide surfaces and in nanoparticle form, including both pure and doped oxide materials. Sousa, Tosoni, and Illas review the present state of the art in the theoretical description of excited states at such oxide surfaces. The review by Akimov, Neukirch, and Prezhdo summarizes the deep insights into photocatalysis and charge transfer at oxide surfaces that have been achieved through theoretical studies of these highly complex phenomena using a variety of well-chosen computational approaches.
A very important area which we have not included in this issue is the study of adsorption onto single-crystalline oxide surfaces from liquid solutions. An extensive overview of the beautiful work in this area has recently appeared Brown, G. In summary, while this issue does not give anywhere near full coverage to all the very exciting areas of research in oxide surface chemistry, it does provide a very broad and deep summary of this field that we hope will be useful both as an introductory text for new students in this field as well as a valuable reference for use by experienced researchers.
View the notice. The basic concepts surrounding various properties of surfaces such as structure, thermodynamics, dynamics, electrical properties, and surface chemical bonds are presented. The techniques of atomic and molecular scale studies of surfaces are listed with references to up-to-date review papers. For advanced readers, this book covers recent developments in in-situ surface analysis such as high- pressure scanning tunneling microscopy, ambient pressure X-ray photoelectron spectroscopy, and sum frequency generation vibrational spectroscopy SFG.
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Tables listing surface structures and data summarizing the kinetics of catalytic reactions over metal surfaces are also included. Ways to utilize new surface science techniques to study properties of polymers, reaction intermediates, and mobility of atoms and molecules at surfaces. Introduction to Surface Chemistry and Catalysis serves as a textbook for undergraduate and graduate students taking advanced courses in physics, chemistry, engineering, and materials science, as well as researchers in surface science, catalysis science, and their applications.
His current research interests include the oxidation of nanoparticles, the compensation effect in heterogeneous catalysis, and sum frequency generation vibrational spectroscopy at interfaces.
Introduction to Surface Chemistry and Catalysis. Gabor A. Somorjai , Yimin Li. Now updated-the current state of development of modern surface science Since the publication of the first edition of this book, molecular surface chemistry and catalysis science have developed rapidly and expanded into fields where atomic scale and molecular information were previously not available. The behavior of an electrode-electrolyte interface is affected by the distribution of ions in the liquid phase next to the interface forming the electrical double layer.
Adsorption and desorption events can be studied at atomically flat single crystal surfaces as a function of applied potential, time, and solution conditions using spectroscopy, scanning probe microscopy  and surface X-ray scattering. Geologic phenomena such as iron cycling and soil contamination are controlled by the interfaces between minerals and their environment. The atomic-scale structure and chemical properties of mineral-solution interfaces are studied using in situ synchrotron X-ray techniques such as X-ray reflectivity , X-ray standing waves , and X-ray absorption spectroscopy as well as scanning probe microscopy.
For example, studies of heavy metal or actinide adsorption onto mineral surfaces reveal molecular-scale details of adsorption, enabling more accurate predictions of how these contaminants travel through soils  or disrupt natural dissolution-precipitation cycles. Surface physics can be roughly defined as the study of physical interactions that occur at interfaces. It overlaps with surface chemistry.
Some of the topics investigated in surface physics include friction , surface states , surface diffusion , surface reconstruction , surface phonons and plasmons , epitaxy , the emission and tunneling of electrons, spintronics , and the self-assembly of nanostructures on surfaces. These include X-ray photoelectron spectroscopy , Auger electron spectroscopy , low-energy electron diffraction , electron energy loss spectroscopy , thermal desorption spectroscopy , ion scattering spectroscopy , secondary ion mass spectrometry , dual polarization interferometry , and other surface analysis methods included in the list of materials analysis methods.
Many of these techniques require vacuum as they rely on the detection of electrons or ions emitted from the surface under study. This is found by an order of magnitude estimate for the number specific surface area of materials and the impingement rate formula from the kinetic theory of gases. Purely optical techniques can be used to study interfaces under a wide variety of conditions. Reflection-absorption infrared, dual polarisation interferometry, surface enhanced Raman and sum frequency generation spectroscopies can be used to probe solid—vacuum as well as solid—gas, solid—liquid, and liquid—gas surfaces.
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Multi-Parametric Surface Plasmon Resonance works in solid-gas, solid-liquid, liquid-gas surfaces and can detect even sub-nanometer layers. Dual Polarization Interferometry is used to quantify the order and disruption in birefringent thin films. X-ray scattering and spectroscopy techniques are also used to characterize surfaces and interfaces.
While some of these measurements can be performed using laboratory X-ray sources , many require the high intensity and energy tunability of synchrotron radiation. Surface-extended X-ray absorption fine structure SEXAFS measurements reveal the coordination structure and chemical state of adsorbates.
X-ray photoelectron spectroscopy XPS is a standard tool for measuring the chemical states of surface species and for detecting the presence of surface contamination. Surface sensitivity is achieved by detecting photoelectrons with kinetic energies of about eV , which have corresponding inelastic mean free paths of only a few nanometers.
This technique has been extended to operate at near-ambient pressures ambient pressure XPS, AP-XPS to probe more realistic gas-solid and liquid-solid interfaces. Modern physical analysis methods include scanning-tunneling microscopy STM and a family of methods descended from it, including atomic force microscopy.
These microscopies have considerably increased the ability and desire of surface scientists to measure the physical structure of many surfaces. For example, they make it possible to follow reactions at the solid—gas interface in real space, if those proceed on a time scale accessible by the instrument. From Wikipedia, the free encyclopedia. For the journal, see Surface Science journal.
Interface chemistry Kelvin probe force microscope Micromeritics Surface modification of biomaterials with proteins Surface finishing Surface modification Surface phenomenon Tribology. Introduction to Surface Physics. Oxford University Press. Fundamentals of Interface and Colloid Science. Academic Press. February Surface Science.