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Photoredox Catalysis
Photoredox catalysis is a branch of photochemistry that uses single-electron transfer. Photoredox catalysts are generally drawn from three classes of materials: transition-metal complexes, organic dyes, and semiconductors. While organic photoredox catalysts were dominant throughout the 1990s and early 2000s, soluble transition-metal complexes are more commonly used today. Photochemistry of transition metal sensitizers Sensitizers absorb light to give redox-active excited states. For many metal-based sensitizers, excitation is realized as a metal-to-ligand charge transfer, whereby an electron moves from the metal (e.g., a d orbital) to an orbital localized on the ligands (e.g. the π* orbital of an aromatic ligand). The initial excited electronic state relaxes to the lowest energy singlet excited state through internal conversion, a process where energy is dissipated as vibrational energy rather than as electromagnetic radiation. This singlet excited state can relax further by ...
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Photochemistry
Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet (wavelength from 100 to 400  nm), visible light (400–750 nm) or infrared radiation (750–2500 nm). In nature, photochemistry is of immense importance as it is the basis of photosynthesis, vision, and the formation of vitamin D with sunlight. Photochemical reactions proceed differently than temperature-driven reactions. Photochemical paths access high energy intermediates that cannot be generated thermally, thereby overcoming large activation barriers in a short period of time, and allowing reactions otherwise inaccessible by thermal processes. Photochemistry can also be destructive, as illustrated by the photodegradation of plastics. Concept Grotthuss–Draper law and Stark-Einstein law Photoexcitation is the first step in a photochemical process where the reactant is elevated ...
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Rudolph Marcus
Rudolph Arthur Marcus (born July 21, 1923) is a Canadian-born chemist who received the 1992 Nobel Prize in Chemistry "for his contributions to the theory of electron transfer reactions in chemical systems". Marcus theory, named after him, provides a thermodynamic and kinetic framework for describing one electron outer-sphere electron transfer. He is a professor at Caltech, Nanyang Technological University, Singapore and a member of the International Academy of Quantum Molecular Science. Education and early life Marcus was born in Montreal, Quebec, the son of Esther (born Cohen) and Myer Marcus. His father was born in New York and his mother was born in England. His family background is from Ukmergė.Marcus, Rudolph A. Interview by Shirley K. Cohen. Pasadena, California, December 1, 7, and 14, 1993. Oral History Project, California Institute of Technology Archives. Retrieved 2020 from the World Wide Web: http://resolver.caltech.edu/CaltechOH:OH_Marcus_R He is Jewish and grew up mo ...
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Ruthenium
Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemicals. Russian-born scientist of Baltic-German ancestry Karl Ernst Claus discovered the element in 1844 at Kazan State University and named ruthenium in honor of Russian Empire, Russia. Ruthenium is usually found as a minor component of platinum ores; the annual production has risen from about 19 tonnes in 2009Summary. Ruthenium
platinum.matthey.com, p. 9 (2009)
to some 35.5 tonnes in 2017. Most ruthenium produced is used in wear-resistant electrical contacts and thick-film resistors. A minor application for ruthenium is in platinu ...
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Pauling Scale
Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the distance at which its valence electrons reside from the charged nucleus. The higher the associated electronegativity, the more an atom or a substituent group attracts electrons. Electronegativity serves as a simple way to quantitatively estimate the bond energy, and the sign and magnitude of a bond's chemical polarity, which characterizes a bond along the continuous scale from covalent to ionic bonding. The loosely defined term electropositivity is the opposite of electronegativity: it characterizes an element's tendency to donate valence electrons. On the most basic level, electronegativity is determined by factors like the nuclear charge (the more protons an atom has, the more "pull" it will have on electrons) and the number and location ...
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Phenylpyridine
2-Phenylpyridine is an organic compound with the formula C6H5C5H4N (or C11H9N). It is a colourless viscous liquid. The compound and related derivatives have attracted interest as precursors to highly fluorescent metal complexes of possible value as organic light emitting diodes (OLEDs). The compound is prepared by the reaction of phenyl lithium Phenyllithium or lithobenzene is an organometallic agent with the empirical formula C6H5Li. It is most commonly used as a metalating agent in organic syntheses and a substitute for Grignard reagents for introducing phenyl groups in organic synth ... with pyridine: :C6H5Li + C5H5N → C6H5-C5H4N + LiH The reaction of iridium trichloride with 2-phenylpyridine proceeds via cyclometallation to give the chloride-bridged complex: :4 C6H5-C5H4N + 2 IrCl3(H2O)3 → Ir2Cl2(C6H4-C5H4N)4 + 4 HCl This complex can be converted to the pictured tris(cyclometallated) derivative tris(2-phenylpyridine)iridium. References Further reading * {{DE ...
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2,2'-bipyridine
The comma is a punctuation mark that appears in several variants in different languages. It has the same shape as an apostrophe or single closing quotation mark () in many typefaces, but it differs from them in being placed on the baseline of the text. Some typefaces render it as a small line, slightly curved or straight, but inclined from the vertical. Other fonts give it the appearance of a miniature filled-in figure on the baseline. The comma is used in many contexts and languages, mainly to separate parts of a sentence such as clauses, and items in lists mainly when there are three or more items listed. The word ''comma'' comes from the Greek (), which originally meant a cut-off piece, specifically in grammar, a short clause. A comma-shaped mark is used as a diacritic in several writing systems and is considered distinct from the cedilla. In Byzantine and modern copies of Ancient Greek, the " rough" and "smooth breathings" () appear above the letter. In Latvian, R ...
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Sinusoidally
A sine wave, sinusoidal wave, or just sinusoid is a mathematical curve defined in terms of the ''sine'' trigonometric function, of which it is the graph. It is a type of continuous wave and also a smooth periodic function. It occurs often in mathematics, as well as in physics, engineering, signal processing and many other fields. Formulation Its most basic form as a function of time (''t'') is: y(t) = A\sin(2 \pi f t + \varphi) = A\sin(\omega t + \varphi) where: * ''A'', ''amplitude'', the peak deviation of the function from zero. * ''f'', ''ordinary frequency'', the ''number'' of oscillations (cycles) that occur each second of time. * ''ω'' = 2''f'', ''angular frequency'', the rate of change of the function argument in units of radians per second. * \varphi, ''phase'', specifies (in radians) where in its cycle the oscillation is at ''t'' = 0. When \varphi is non-zero, the entire waveform appears to be shifted in time by the amount ''φ''/''ω'' seconds. A negative value repr ...
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Voltammetry
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram which plots the current produced by the analyte versus the potential of the working electrode. Theory Voltammetry is the study of current as a function of applied potential. Voltammetric methods involve electrochemical cells, and investigate the reactions occurring at electrode/electrolyte interfaces. The reactivity of analytes in these half-cells is used to determine their concentration. It is considered a dynamic electrochemical method as the applied potential is varied over time and the corresponding changes in current are measured. Most experiments control the potential(volts) of an electrode in contact with the analyte while measuring the resulting current (amperes). ...
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Work Function
In solid-state physics, the work function (sometimes spelt workfunction) is the minimum thermodynamic work (i.e., energy) needed to remove an electron from a solid to a point in the vacuum immediately outside the solid surface. Here "immediately" means that the final electron position is far from the surface on the atomic scale, but still too close to the solid to be influenced by ambient electric fields in the vacuum. The work function is not a characteristic of a bulk material, but rather a property of the surface of the material (depending on crystal face and contamination). Definition The work function for a given surface is defined by the difference :W = -e\phi - E_, where is the charge of an electron, is the electrostatic potential in the vacuum nearby the surface, and is the Fermi level (electrochemical potential of electrons) inside the material. The term is the energy of an electron at rest in the vacuum nearby the surface. In practice, one directly controls by ...
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Cyclic Voltammetry
Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV experiment, the working electrode's potential is ramped in the opposite direction to return to the initial potential. These cycles of ramps in potential may be repeated as many times as needed. The current at the working electrode is plotted versus the applied voltage (that is, the working electrode's potential) to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution or of a molecule that is adsorbed onto the electrode. Experimental method In cyclic voltammetry (CV), the electrode potential ramps linearly versus time in cyclical phases (Figure 2). The rate of voltage change over time during each of these phases is known as the experiment ...
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Photocatalyst Cycle
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalyzed photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the photocatalytic activity depends on the ability of the catalyst to create electron–hole pairs, which generate free radicals (e.g. hydroxyl radicals: •OH) able to undergo secondary reactions. Its practical application was made possible by the discovery of water electrolysis by means of titanium dioxide (). History Early mentions (1911–1938) The earliest mention came in 1911, when German chemist Dr. Alexander Eibner integrated the concept in his research of the illumination of zinc oxide (ZnO) on the bleaching of the dark blue pigment, Prussian blue. Around this time, Bruner and Kozak published an article discussing the deterioration of oxalic acid in the presence of uranyl salts under illumination, while in 1913, Landau published an article explaining the phenomenon of pho ...
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