AdsorptionAdsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid (the absorbate) is dissolved by or permeates a liquid or solid (the absorbent). Adsorption is a surface phenomenon and the adsorbate does not penetrate through the surface and into the bulk of the adsorbent, while absorption involves transfer of the absorbate into the volume of the material, although adsorption does often precede absorption.
Langmuir adsorption modelThe Langmuir adsorption model explains adsorption by assuming an adsorbate behaves as an ideal gas at isothermal conditions. According to the model, adsorption and desorption are reversible processes. This model even explains the effect of pressure i.e. at these conditions the adsorbate's partial pressure, , is related to the volume of it, V, adsorbed onto a solid adsorbent. The adsorbent, as indicated in the figure, is assumed to be an ideal solid surface composed of a series of distinct sites capable of binding the adsorbate.
Photoemission spectroscopyPhotoemission spectroscopy (PES), also known as photoelectron spectroscopy, refers to energy measurement of electrons emitted from solids, gases or liquids by the photoelectric effect, in order to determine the binding energies of electrons in the substance. The term refers to various techniques, depending on whether the ionization energy is provided by X-ray, XUV or UV photons. Regardless of the incident photon beam, however, all photoelectron spectroscopy revolves around the general theme of surface analysis by measuring the ejected electrons.
SurfaceA surface, as the term is most generally used, is the outermost or uppermost layer of a physical object or space. It is the portion or region of the object that can first be perceived by an observer using the senses of sight and touch, and is the portion with which other materials first interact. The surface of an object is more than "a mere geometric solid", but is "filled with, spread over by, or suffused with perceivable qualities such as color and warmth".
X-ray photoelectron spectroscopyX-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic technique based on the photoelectric effect that can identify the elements that exist within a material (elemental composition) or are covering its surface, as well as their chemical state, and the overall electronic structure and density of the electronic states in the material. XPS is a powerful measurement technique because it not only shows what elements are present, but also what other elements they are bonded to.
ChemisorptionChemisorption is a kind of adsorption which involves a chemical reaction between the surface and the adsorbate. New chemical bonds are generated at the adsorbent surface. Examples include macroscopic phenomena that can be very obvious, like corrosion, and subtler effects associated with heterogeneous catalysis, where the catalyst and reactants are in different phases. The strong interaction between the adsorbate and the substrate surface creates new types of electronic bonds.
Surface tensionSurface tension is the tendency of liquid surfaces at rest to shrink into the minimum surface area possible. Surface tension is what allows objects with a higher density than water such as razor blades and insects (e.g. water striders) to float on a water surface without becoming even partly submerged. At liquid–air interfaces, surface tension results from the greater attraction of liquid molecules to each other (due to cohesion) than to the molecules in the air (due to adhesion). There are two primary mechanisms in play.
Low-energy electron diffractionLow-energy electron diffraction (LEED) is a technique for the determination of the surface structure of single-crystalline materials by bombardment with a collimated beam of low-energy electrons (30–200 eV) and observation of diffracted electrons as spots on a fluorescent screen. LEED may be used in one of two ways: Qualitatively, where the diffraction pattern is recorded and analysis of the spot positions gives information on the symmetry of the surface structure.
Surface plasmon resonanceSurface plasmon resonance (SPR) is a phenomenon that occurs where electrons in a thin metal sheet become excited by light that is directed to the sheet with a particular angle of incidence, and then travel parallel to the sheet. Assuming a constant light source wavelength and that the metal sheet is thin, the angle of incidence that triggers SPR is related to the refractive index of the material and even a small change in the refractive index will cause SPR to not be observed.
Surface plasmonSurface plasmons (SPs) are coherent delocalized electron oscillations that exist at the interface between any two materials where the real part of the dielectric function changes sign across the interface (e.g. a metal-dielectric interface, such as a metal sheet in air). SPs have lower energy than bulk (or volume) plasmons which quantise the longitudinal electron oscillations about positive ion cores within the bulk of an electron gas (or plasma). The charge motion in a surface plasmon always creates electromagnetic fields outside (as well as inside) the metal.
Heterogeneous catalysisHeterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Phase distinguishes between not only solid, liquid, and gas components, but also immiscible mixtures (e.g. oil and water), or anywhere an interface is present. Heterogeneous catalysis typically involves solid phase catalysts and gas phase reactants.
Electron diffractionElectron diffraction refers to changes in the direction of electron beams due to interactions with atoms. Close to the atoms the changes are described as Fresnel diffraction; far away they are called Fraunhofer diffraction. The resulting map of the directions of the electrons far from the sample (Fraunhofer diffraction) is called a diffraction pattern, see for instance Figure 1. These patterns are similar to x-ray and neutron diffraction patterns, and are used to study the atomic structure of gases, liquids, surfaces and bulk solids.
Localized surface plasmonA localized surface plasmon (LSP) is the result of the confinement of a surface plasmon in a nanoparticle of size comparable to or smaller than the wavelength of light used to excite the plasmon. When a small spherical metallic nanoparticle is irradiated by light, the oscillating electric field causes the conduction electrons to oscillate coherently. When the electron cloud is displaced relative to its original position, a restoring force arises from Coulombic attraction between electrons and nuclei.
TemperatureTemperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied on various reference points and thermometric substances for definition. The most common scales are the Celsius scale with the unit symbol °C (formerly called centigrade), the Fahrenheit scale (°F), and the Kelvin scale (K), the latter being used predominantly for scientific purposes.
State functionIn the thermodynamics of equilibrium, a state function, function of state, or point function for a thermodynamic system is a mathematical function relating several state variables or state quantities (that describe equilibrium states of a system) that depend only on the current equilibrium thermodynamic state of the system (e.g. gas, liquid, solid, crystal, or emulsion), not the path which the system has taken to reach that state. A state function describes equilibrium states of a system, thus also describing the type of system.
Thermodynamic temperatureThermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Lord Kelvin in terms of a macroscopic relation between thermodynamic work and heat transfer as defined in thermodynamics, but the kelvin was redefined by international agreement in 2019 in terms of phenomena that are now understood as manifestations of the kinetic energy of free motion of microscopic particles such as atoms, molecules, and electrons.
MoleculeA molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and biochemistry, the distinction from ions is dropped and molecule is often used when referring to polyatomic ions. A molecule may be homonuclear, that is, it consists of atoms of one chemical element, e.g. two atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of more than one element, e.
Transmission electron microscopyTransmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through a specimen to form an image. The specimen is most often an ultrathin section less than 100 nm thick or a suspension on a grid. An image is formed from the interaction of the electrons with the sample as the beam is transmitted through the specimen. The image is then magnified and focused onto an imaging device, such as a fluorescent screen, a layer of photographic film, or a sensor such as a scintillator attached to a charge-coupled device.
AdatomAn adatom is an atom that lies on a crystal surface, and can be thought of as the opposite of a surface vacancy. This term is used in surface chemistry and epitaxy, when describing single atoms lying on surfaces and surface roughness. The word is a portmanteau of "adsorbed atom". A single atom, a cluster of atoms, or a molecule or cluster of molecules may all be referred to by the general term "adparticle". This is often a thermodynamically unfavorable state. However, cases such as graphene may provide counter-examples.
Surface diffusionSurface diffusion is a general process involving the motion of adatoms, molecules, and atomic clusters (adparticles) at solid material surfaces. The process can generally be thought of in terms of particles jumping between adjacent adsorption sites on a surface, as in figure 1. Just as in bulk diffusion, this motion is typically a thermally promoted process with rates increasing with increasing temperature. Many systems display diffusion behavior that deviates from the conventional model of nearest-neighbor jumps.
