The Catalyzed Photodissociation of Water

Chemical interactions between molecules in excited electronic, vibrational, or rotational states and surfaces is a new field of catalytic science. Until recently, catalysis of chemical reactions has only been considered for molecules in their thermodynamic ground states. Most of the surface reactions to be catalyzed were exothermic or thermodynamically downhill. In carrying out endothermic reactions, the only source of energy considered has been the addition of heat. This also assured that the molecules maintained an equilibrium energy distribution throughout the reaction.     

Possible Impact of Heterogeneous Photocatalysis on the Global Chemistry of the Earth's Atmosphere

Photochemistry is recognized to be important for various physicochemical processes in the atmosphere, such as formation of the ozone layer and smogs, degradation of waste substances, etc. [1]. However, up to the present the emphasis in atmospheric photochemistry has been mainly on the study of photochemical reactions that occur with molecules directly excited by absorption of light quanta. However, the major components and impurities of the earth's atmosphere (such as nitrogen, oxygen, water, carbon dioxide, methane, methane halides, etc.) are totally transparent to most solar radiation. Electronically excited states of these molecules are formed only upon absorption of vacuum ultraviolet light quanta with energy hv ≥ 5 eV (i.e., with wavelength λ ≤ 200 nm). Only a small portion of the energy of solar light is found in this spectral region. In other words, most of the energy of the solar flux cannot participate in such direct photochemical reactions.     

Possible Impact of Heterogeneous Photocatalysis on the Global Chemistry of the Earth's Atmosphere

Photochemistry is recognized to be important for various physicochemical processes in the atmosphere, such as formation of the ozone layer and smogs, degradation of waste substances, etc. [1]. However, up to the present the emphasis in atmospheric photochemistry has been mainly on the study of photochemical reactions that occur with molecules directly excited by absorption of light quanta. However, the major components and impurities of the earth's atmosphere (such as nitrogen, oxygen, water, carbon dioxide, methane, methane halides, etc.) are totally transparent to most solar radiation. Electronically excited states of these molecules are formed only upon absorption of vacuum ultraviolet light quanta with energy hv ≥ 5 eV (i.e., with wavelength λ ≤ 200 nm). Only a small portion of the energy of solar light is found in this spectral region. In other words, most of the energy of the solar flux cannot participate in such direct photochemical reactions.     

Quantum chemical studies of zeolite proton catalyzed reactions

Theoretical chemistry applied to zeolite acid catalysis is becoming an important tool in the understanding of the adsorption and interaction of guest molecules with the zeolitic lattice. Especially the understanding of the mechanisms by which zeolite catalyzed chemical reactions proceed becomes possible. It is shown here that the old interpretation of carbonium and carbenium ions as intermediates for zeolite catalyzed reactions has to be replaced by a new approach in terms of positively charged transition states that are strongly stabilized by the zeolitic lattice. The large deprotonation energy of the acidic zeolite is overcome by stabilization of the intermediate or transition state positive charge by the negative charge left in the lattice. The zeolitic sites responsible for the adsorption and/or reaction of guest molecules are the Brønsted-acid and Lewis-base sites. We also show that different transition states are responsible for different kinds of reactions, such as cracking, dehydrogenation, etc.     

Theoretical considerations on the sensitivities of electron beam resists

A theoretical study has been carried out in order to explain the sensitivities of electron beam and X-ray resists. A preliminary investigation reveals that the behavior of these resists, on irradiation by high energy radiation, may be considered to be the electronically-excited species in the polymer. To elucidate the chemical reactions in the excited states the adiabatic potential curves are calculated by the INDO/S procedure, which considers all the valence electrons and all the singly excited electronic configurations. Polyethylene and polyisobutylene were chosen as representative of crosslinkable and degradable polymers, respectively, since there is a parallelism between the beam sensitivity of resists and the effects of high energy radiation on polymers. Polyisobutylene has many antibonding curves favorable for the main chain scission in the excited states and polyethylene does not except for one improbable state. It was concluded that degradability is explainable by the ease of bond fission in the excited states; the crosslinkability is considered to be nondegradable property.     

Perennial Electron Mobility for Quantum Molecular Induction Period in Molecular Oxygenation and Oxygenation Trio of Pure Substances Under Controlled Conditions

The perennial electron mobility varying in degrees for certain selected substances, has given rise to the interesting features of information only to establish the molecule to molecule concepts of initial oxygenation. The induction period has been found to be distinct from antioxidant has been shown to have its own realm of molecular action with intermolecular electron mobility to other protected molecules and induction period with intramolecular electron mobility of the particular substance concerned under T-t adjustments. The possible seven states of an antioxidant in action over the whole spectrum of autoxidation reactions, have been described to establish its effective molecular functions. The concepts of induction, have been broadened to encompass other aspects, particularly those of biology, the perennial source of transition states and complexes for various life phenomena and processes.     

Perpetual Electron Mobility in the Molecule to Molecule Reaction Process of Methyl Linoleate as Ideal Substance in View of Entropy of Activation under Aegis of Modern Quantum Mechanics

The oxygenation, bromination and hydrogenation processes have hinted to three-dimensional attack and reaction involving various types of conformation, both in reactants and their active states for reaction. The 5-C unsaturated system in methyl linoleate has been found to indicate intra- and intermolecular forces not understood so far in molecules at close approach. The new molecular forces have been proposed to explain the same under aegis of modern quantum mechanics. The time and temperature effects under controlled conditions have clearly set out ten periods of oxygenation pointing to different types of reactions in each. This has given rise to seven kinds of chemical forces shown to play important roles in the periods according to energy conditions involved by time and temperature effects. Such new molecular forces have been found to cast some doubts on the approach to dot-dash-arrow representations in chemistry.     

Insights into the intrinsic interaction between series of C1 molecules and surface of NiO oxygen carriers involved in chemical looping processes

Understanding and modulating the interaction between various reactive molecules and oxygen carriers are the key issue to achieve process intensification of chemical looping technology. C1 chemical molecules play an important role in many reactions involved with chemical looping processes. However, up to now, there is still a lack of systematic and in-depth understanding of the adsorption mechanism of C1 molecules on the surface of oxygen carriers (OCs). In this work, the intrinsic interaction between a series of C1 molecules composed of CH₄, CO, CO₂, CH₃OH, HCHO and HCOOH and surface of NiO OCs in the chemical looping process have been studied using density functional theory calculations. Various adsorption configurations of C1 molecules and also different adsorption sites of NiO have been considered. The structural features of stable configuration of C1 molecules on the surface of NiO OCs have been obtained. Further, the interacted sites, types and strengths of C1 molecules on the surface of NiO have been directly pictured by the independent gradient model methods. Also, the nature of the interaction between C1 molecule and NiO surface has been investigated with the aid of energy decomposition analysis from a quantitative view.     

Photoinitiated Electron Transfer in Carotenoporphyrin-Quinone Triads: Enhanced Quantum Yields via Control of Reaction Exergonicity

Carotenoporphyrin-quinone triad molecules have previously been found to successfully mimic many aspects of photosynthetic electron and energy transfer. These molecules generate long-lived, energetic charge-separated states via a biomimetic multistep electron transfer scheme. In many of these molecules, the overall quantum yield for charge separation has been limited by an unfavorable partitioning of an intermediate charge-separated state between charge recombination and further reaction to yield the desired species. One strategy for overcoming this limitation is based on the fact that, in general, electron transfer rate constants do not depend linearly on reaction free energy change. In the triads, raising the energy of the intermediate charge-separated state would be expected to speed up the desired electron transfer (“normal” Marcus behavior), but slow down charge recombination (which formally lies in the “inverted” region). Laser flash photolysis and transient fluorescence measurements on two new triad molecules reveal enhanced quantum yields of long-lived charge-separated states which are consistent with this expectation.     

Insights into the intrinsic interaction between series of C1 molecules and surface of NiO oxygen carriers involved in chemical looping processes

Understanding and modulating the interaction between various reactive molecules and oxygen carriers are the key issue to achieve process intensification of chemical looping technology. C1 chemical molecules play an important role in many reactions involved with chemical looping processes. However, up to now, there is still a lack of systematic and in-depth understanding of the adsorption mechanism of C1 molecules on the surface of oxygen carriers (OCs). In this work, the intrinsic interaction between a series of C1 molecules composed of CH₄, CO, CO₂, CH₃OH, HCHO and HCOOH and surface of NiO OCs in the chemical looping process have been studied using density functional theory calculations. Various adsorption configurations of C1 molecules and also different adsorption sites of NiO have been considered. The structural features of stable configuration of C1 molecules on the surface of NiO OCs have been obtained. Further, the interacted sites, types and strengths of C1 molecules on the surface of NiO have been directly pictured by the independent gradient model methods. Also, the nature of the interaction between C1 molecule and NiO surface has been investigated with the aid of energy decomposition analysis from a quantitative view.     

Catalytic hydrogenolysis on metals

Two issues of broad interest in catalysis are reaction mechanisms and comparisons of catalytic activities of different substances. Metal-catalyzed hydrogenolysis reactions of simple molecules provide examples in which both issues have been investigated in some detail. While hydrogenolysis of carbon-carbon bonds in alkanes has received most of the attention to date, some work has also been reported on the hydrogenolysis of carbon-nitrogen bonds in amines and of carbon-halogen bonds in alkyl halides. General mechanistic features of hydrogenolysis reactions on metals and comparisons of catalytic activities of metals for such reactions are considered in this brief review.     

Applications of phase-transfer catalytic reactions to fatty acids and their derivatives: Present state and future potential

Phase-transfer catalysts (PTC), which accelerate reactions between liquid(organic)-liquid(water) and liquidsolid heterogeneous states, have been investigated and developed. Several processes with PTC have succeeded in industrial processes involving fatty acids and their derivatives. For example, preparation of fatty alkyl glycidyl ethers, from which fatty alkyl glyceryl ethers and their derivatives can be obtained, has been carried out with PTC. However, some problems remain to be solved. For example, preparation of the fatty alkyl glycidyl ether by a PTC reaction was considered, but typical problems to be solved included: (i) how to reuse or recover the catalysts; (ii) how to control the heterogeneous reaction without obstacles to produce useful chemical materials; (iii) how to satisfy the environmental requirements for the catalysts; and (iv) are there more effective catalysts? We address these problems based on our own experiences with phase-transfer catalytic Williamson ether syntheses of fatty alkyl glycidyl ethers. Moreover, we describe recent developments in phase-transfer catalytic reactions related to oleochemistry, such as transition metal-catalyzed reactions of long-chain olefins in liquid(organic)-liquid(water) or liquid-solid heterogeneous states. Based on these results, we have considered the potential of PTC as a synthetic tool in oleochemistry.     

Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Selective Nanocatalysis of Organic Transformation by Metals: Concepts, Model Systems, and Instruments

Monodispersed transition metal (Pt, Rh, Pd) nanoparticles (NP) in the 0.8–15 nm range have been synthesized and are being used to probe catalytic selectivity in multipath organic transformation reactions. For NP systems, the turnover rates and product distributions depend on their size, shape, oxidation states, and their composition in case of bimetallic NP systems. Dendrimer-supported platinum and rhodium NPs of less than 2 nm diameter usually have high oxidation states and can be utilized for catalytic cyclization and hydroformylation reactions which previously were produced only by homogeneous catalysis. Transition metal nanoparticles in metal core (Pt, Co)––inorganic shell (SiO₂) structure exhibit exceptional thermal stability and are well-suited to perform catalytic reactions at high temperatures (>400 °C). Instruments developed in our laboratory permit the atomic and molecular level study of NPs under reaction conditions (SFG, ambient pressure XPS and high pressure STM). These studies indicate continuous restructuring of the metal substrate and the adsorbate molecules, changes of oxidation states with NP size and surface composition variations of bimetallic NPs with changes of reactant molecules. The facile rearrangement of NP catalysts required for catalytic turnover makes nanoparticle systems (heterogeneous, homogeneous and enzyme) excellent catalysts and provides opportunities to develop hybrid heterogeneous-homogeneous, heterogeneous-enzyme and homogeneous-enzyme catalyst systems.     

Elementary Reactions and Their Role in Gas-Phase Prebiotic Chemistry

The formation of complex organic molecules in a reactor filled with gaseous mixtures possibly reproducing the primitive terrestrial atmosphere and ocean demonstrated more than 50 years ago that inorganic synthesis of prebiotic molecules is possible, provided that some form of energy is provided to the system. After that groundbreaking experiment, gas-phase prebiotic molecules have been observed in a wide variety of extraterrestrial objects (including interstellar clouds, comets and planetary atmospheres) where the physical conditions vary widely. A thorough characterization of the chemical evolution of those objects relies on a multi-disciplinary approach: 1) observations allow us to identify the molecules and their number densities as they are nowadays; 2) the chemistry which lies behind their formation starting from atoms and simple molecules is accounted for by complex reaction networks; 3) for a realistic modeling of such networks, a number of experimental parameters are needed and, therefore, the relevant molecular processes should be fully characterized in laboratory experiments. A survey of the available literature reveals, however, that much information is still lacking if it is true that only a small percentage of the elementary reactions considered in the models have been characterized in laboratory experiments. New experimental approaches to characterize the relevant elementary reactions in laboratory are presented and the implications of the results are discussed.     

Single molecule multiphotochromism with diarylethenes

In single photochromes, the two isomers that are interconverted in photoinduced reactions can serve as on and off states in a molecular switching device. The addition of several photochromic moieties onto a single molecule can allow the processing of more complex logical patterns. For example, an asymmetric triad could, in principle, store a byte, rather than a bit, of data. Because of the potential impact of multiphotochromic molecules in many research areas, over the past decade several groups have synthesized these coupled structures. The targets are easily addressable molecules that display increased contrast between the on and off states and in which all isomers have significantly distinguishable optical signatures. In this Account, we provide an overview of the multiswitchable molecular systems that incorporate at least one diarylethene group, which is the most successful thermally stable (P-type) organic photochrome. Up to this point, most systems have presented significant limitations. First of all, the reversibility of the processes is hindered by several side reactions more frequently than for single photochromes. Second, switching one part of the compound impedes the photoreactivity of other fragments in approximately 50% of the cases, and maximizing the electronic communication increases the probability of partial activity. In addition, most of the few synthesized operative systems only demonstrate cumulative absorption spectra rather than new features. Finally, it is impossible to selectively induce a chosen conversion because one wavelength might trigger several processes. We also emphasize the promising successes of asymmetric diarylethene dimers and trimers and molecules that combine two families of photochromes, such as diarylethene added to fulgimide or phenoxy-naphthacenequinone. In that framework, theoretical simulations offer complementary tools to investigate these structures, both to obtain structure/property relationships and to propose paths for the design of more efficient molecules. However, due to the size of the systems, researchers can only apply semiquantitative models. The investigation of the absorption spectra of the photochromes with time-dependent density functional theory (TD-DFT), the analysis of the topology of the LUMO + n (typically n = 1) of the closed-open hybrid, and an estimate of the steric stress in the hypothetical (ground-state) closed-closed structure serve as a useful combination of parameters to obtain initial insights regarding the photocyclization of the different open diarylethene groups. Nevertheless, because a first-order qualitative approach does not explore the potential energy surface of the photoexcited states, it remains inadequate for the investigation of some molecules.     

Practical implications of fatty acid topography modification by unsaturation

Unsaturated fatty acids are markedly different from their saturated counterparts in a number of areas that relate only to the physical properties given them by their topography. In systems where free single bond rotation is restricted, such as monolayers or biomembranes, the effectiveness of chain packing and the fluidity of the fatty chain region is critical and here may best be studied. Topography plays a role in many chemical reactions in terms of reaction rate and product stereochemistry, but is less critical here. Topography hindrances to reaction rate often may be overcome by raising the reaction temperature. When stereochemistry is important, however, the topography of the reactants must be considered. In tightly packed crystalline bulk or condensed monolayer states, the conformation assumed by the chain is its most stable one, excluding polymorphism. This conformation usually will approximate the one of greatest stability for the free molecule in a nonrestricting environment. However, because differences in energy between rotational conformers is generally small, departures from the preferred conformation will be abundant in the absence of constraints imposed by neighboring molecules. Therefore, in the absence of a restricting environment, topographical differences will be minimized. The counterpoint to this is that a large percentage of the fatty acids in use are in such restricting environments in biomembranes, soaps, wetting and foaming agents, fabric afteners, etc., or are purified through a process maiing use of differences in chain packing efficiency, crystallization, where their topography is the primary source of their utility.     

Formation of poly(butylene terephthalate): Secondary reactions studied by model molecules

The secondary reactions occurring in the formation poly(butylene terephthalate), leading to thermal degradation (in the temperature range 210°–280°C) or giving rise to tetrahydrofuran (in the temperature range 160°–190°C) have been kinetically studied with the aid of model molecules: 1,4-butylene dibenzoate and 4-hydroxybutyl benzoate. Some kinetic parameters have been determined; the effect of temperature and of catalysts and stabilizers has been considered and a mechanism is proposed for the formation of tetrahydrofuran from hydroxyl end groups.     

A fundamental principle and systematic procedures for process intensification in reactive distillation columns

A fundamental principle is developed for process intensification through internal mass and energy integration in reactive distillation columns and three systematic procedures are devised for process synthesis and design. For reactive distillation columns involving reactions with highly thermal effect, process intensification can be achieved with an exclusive consideration of internal energy integration between the reaction operation and separation operation involved. However, in the case of a highly endothermic reaction with an extremely low reaction rate and/or small chemical equilibrium constant, internal mass integration has also to be considered between the reactive section and stripping section. For reactive distillation columns involving reactions with negligibly or no thermal effect, process intensification can be performed with an exclusive consideration of internal mass integration. For reactive distillation columns involving reactions with moderately thermal effect, process intensification must be conducted with a careful trade-off between internal mass and energy integration. Five hypothetical and two real reactive distillation systems are employed to evaluate the principle and procedures proposed. It is demonstrated that intensifying internal mass and energy integration is really effective for process intensification. Not only can the thermodynamic efficiency be improved substantially, but also the capital investment can be further reduced.