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This book is based on a graduate course and suitable as a primer for any newcomer to the field, this book is a detailed introduction to the experimental and computational methods that are used to study how solid surfaces act as catalysts. Features include: * First comprehensive description of modern theory of heterogeneous catalysis * Basis for understanding and designing experiments in the field * Allows reader to understand catalyst design principles * Introduction to important elements of energy transformation technology * Test driven at Stanford University over several semesters

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].

Retro-aldol reactions have been implicated as the limiting steps in catalytic routes to convert biomass-derived hexoses and pentoses into valuable C₂, C₃, and C₄ products such as glycolic acid, lactic acid, 2-hydroxy-3-butenoic acid, 2,4-dihydroxybutanoic acid, and alkyl esters thereof. Due to a lack of efficient retro-aldol catalysts, most previous investigations of catalytic pathways involving these reactions were conducted at high temperatures (≥160 °C). Here, we report moderate-temperature (around 100 °C) retro-aldol reactions of various hexoses in aqueous and alcoholic media with catalysts traditionally known for their capacity to catalyze 1,2-intramolecular carbon shift (1,2-CS) reactions of aldoses, i.e., various molybdenum oxide and molybdate species, nickel(II) diamine complexes, alkali-exchanged stannosilicate molecular sieves, and amorphous TiO₂–SiO₂ coprecipitates. Solid Lewis acid cocatalysts that are known to catalyze 1,2-intramolecular hydride shift (1,2-HS) reactions that enable the formation of α-hydroxy carboxylic acids from tetroses, trioses, and glycolaldehyde, but cannot readily catalyze retro-aldol reactions of hexoses and pentoses at these moderate temperatures, are shown to be compatible with the aforementioned retro-aldol catalysts. The combination of a distinct retro-aldol catalyst with a 1,2-HS catalyst enables lactic acid and alkyl lactate formation from ketohexoses at moderate temperatures (around 100 °C), with yields comparable to best-reported chemocatalytic examples at high temperature conditions (≥160 °C). The use of moderate temperatures enables numerous desirable features such as lower pressure and significantly less catalyst deactivation.

fac-Re(2,2’-bipyridine)(CO)[sub.3]Cl] (denoted as ReCC) is an efficient molecule-catalyst with high selectivity in the photoreduction of CO[sub.2] to CO in a homogeneous system. However, the two major drawbacks of Re(I) complexes in the homogeneous system, easy degradation and difficult separation, seriously hinder its development in the field of industrial applications. In this paper, we designed and prepared two different Re-complex fixation systems (denoted as ReCC@TiO[sub.2]-5 wt% and ReCC-TiO[sub.2]-5 wt%) based on TiO[sub.2] gel via the sensitization method and sol–gel method, respectively. Compared with a pure ReCC complex, both of them exhibited excellent photocatalytic reduction activity. In particular, the sol–gel hybrid system (ReCC-TiO[sub.2]-5 wt%) displayed outstanding positive synergistic effects on the photocatalytic activity and the long durability of the photocatalytic process. A series of characterizations were carried out to explore the probable photocatalytic reduction process mechanism, which provides the theoretical basis and technical support for the Re complex fixation method.

The isomerization of geraniol using natural, acid-modified minerals such as vermiculite presents a promising approach aligned with the principles of green chemistry. Vermiculite, a naturally abundant layered silicate mineral, was subjected to the acid activation and thoroughly characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). These methods allowed the evaluation of crystallinity, structural stability, and surface morphology, which are critical parameters in the heterogeneous catalysis. The catalytic performance of the modified vermiculite was examined in the transformation of geraniol under mild conditions. The study systematically investigated the influence of key process parameters—temperature, reaction time, and catalyst content—on the conversion of geraniol and products selectivities. Optimization using the response surface methodology (RSM), enabled the identification of conditions leading to high conversion of geraniol (up to 85%) and allowing us to obtain favorable selectivities toward linalool, thunbergol, and 6,11-dimethyl-2,6,10-dodecatrien-1-ol. The results indicate that the acid-treated vermiculite exhibits sufficient surface acidity to effectively catalyze isomerization and cyclization reactions, without requiring additional promoters or metal-based systems. Moreover, the use of RSM provided the efficient framework for optimization reaction conditions, reducing experimental workload, and enhancing process efficiency. This study demonstrates the viability of natural, low-cost minerals as environmentally friendly catalysts and supports their integration into sustainable and “green” chemical technologies.

Most catalysts consist of nanometer-sized particles dispersed on a high-surface-area support. Advances in characterization methods have led to a molecular-level understanding of the relationships between nanoparticle properties and catalytic performance. Together with novel approaches to nanoparticle synthesis, this knowledge is contributing to the design and development of new catalysts.

Tungsten carbide is one of the most promising electrocatalysts for the hydrogen evolution reaction, although it exhibits sluggish kinetics due to a strong tungsten-hydrogen bond. In addition, tungsten carbide’s catalytic activity toward the oxygen evolution reaction has yet to be reported. Here, we introduce a superaerophobic nitrogen-doped tungsten carbide nanoarray electrode exhibiting high stability and activity toward hydrogen evolution reaction as well as driving oxygen evolution efficiently in acid. Nitrogen-doping and nanoarray structure accelerate hydrogen gas release from the electrode, realizing a current density of −200 mA cm −2 at the potential of −190 mV vs. reversible hydrogen electrode, which manifest one of the best non-noble metal catalysts for hydrogen evolution reaction. Under acidic conditions (0.5 M sulfuric acid), water splitting catalyzed by nitrogen-doped tungsten carbide nanoarray starts from about 1.4 V, and outperforms most other water splitting catalysts. Water electrolysis can generate carbon-neutral hydrogen gas from water, yet the required catalysts are often expensive, scarce, and poor at gas release. Here, the authors prepared nitrogen-doped carbon tungstide nanoarrays with high water-splitting activities and bubble-releasing surfaces.

This book, unique in its field, is a comprehensive description of all the methodologies reported for carrying out conjugate addition reactions in a stereoselective way, using small chiral organic molecules as catalysts (organocatalysts). In the last 3-4 years, this has been a rapidly growing field in organic chemistry, and many papers have appeared reporting excellent protocols for carrying out these highly efficient transformations that compete well with other classical approaches using transition metal catalysts. A particularly attractive feature of this transformation relies upon the fact that the conjugate addition (Michael and Hetero-Michael reactions) is an extraordinarily effective means to initiate cascade processes which result in the formation of complex molecules from very small and simple starting blocks. The book, written by noted experts, covers all recent advances in this hot topic, and provides a good state-of-the-art review for organic chemists working in this field and all those who wish to start projects in this area.

Surface science studies allow processes important for heterogeneous catalysis to be investigated in greatest detail. Starting from the simplest model of a catalytic surface, a metal single-crystal surface under ultrahigh vacuum conditions, enormous progress has been made in the last decades towards extending the surface science of catalysis to technically more relevant dimensions. In this perspective, we highlight recent work, including our own, dealing with the influence of water on metal-support interactions in surface science studies of oxide-supported metal nanoparticle model catalysts. In particular, the effect of hydroxyl groups on nucleation and sintering of metal nanoparticles, and surface science investigations into catalyst preparation using wet-chemical procedures are addressed. Graphical Abstract

This book reviews chiral polymer synthesis and its application to asymmetric catalysis. It features the design and use of polymer-immobilized catalysts and methods for their design and synthesis. Chapters cover peptide-catalyzed and enantioselective synthesis, optically-active polymers, and continuous flow processes. It collects recent advances in an important field of polymer and organic chemistry, with leading researchers explaining applications in academic and industry R & D.