Catalysis: Volume 31
In Chapter 1, Fan Zeng and Keith L. Hohn (Kansas State University) review the conversion of bio-renewable chemical into liquid fuels, polymers and pharmaceutical products, to replace petrochemicals with novel platform chemicals derived from bio-based feedstock. Chemistry involving C4 chemicals have been studied to make a variety of products, including fuel additives and polymer building blocks. This chapter gives an overview of the catalytic synthesis of C4 products from bio-sustainable chemicals, including C4 diols, alkenes, ketones and alcohols, by reviewing the impact of catalyst composition on product selective and the speculated catalytic reaction mechanisms.
In Chapter 2, Songbo He (University of Groningen, The Netherlands) reviews catalytic wet oxidation, which includes the process and catalyst development, and the potential for the treatment of biomass pyrolysis wastewater. This chapter addresses the homogeneous CWO processes (Loprox, Ciba-Geigy, IT EnviroScience, ATHOS and ORCAN) and heterogeneous CWO processes (Osaka Gas, Nippon Shokubai, Kurita, CALIPHOX, DICP and Watercatox), and also the development on the homogeneous catalysts (cations and anions) and heterogeneous catalysts (supported noble metal catalysts and non-noble metal oxides). Treatment of the wastewater from the biomass pyrolysis for bio-based fuels and chemicals process is a relatively unexplored field, for which the potential of CWO is also discussed.
In Chapter 3, Nicolás A. Grosso-Giordano, Stacey I. Zones and Alexander Katz (University of California at Berkeley and Chevron Energy Technology Company) review recent reports on controlling catalysis by designing molecular environments around active sites. Opportunities for controlling molecular architecture of catalytic active sites supported on amorphous versus zeolitic silicate supports are critically examined, and the role that support crystallinity could play on catalytic properties is described. They summarize structural features of active sites on silicate supports and contrast the inherent disorder of amorphous silica surfaces to the order of crystalline zeotypes. Within the context of selected catalytic systems currently employed in industrial practice, they examine how these structures affect inner- and outer-sphere environments of isolated active sites, and how these environments could impact catalytic activity, from the perspective of developing next-generation catalysts.
In Chapter 4, Su Cheun Oh, Mann Sakbodin, and Dongxia Liu (University of Maryland, College Park, MD) review the past research and ongoing development on direct non-oxidative methane conversion (DNMC) reaction in membrane reactors. The catalyst, membrane material, reactor configuration and performance for DNMC in membrane reactors are discussed. The challenges, strategies to mitigate reactor deterioration during DNMC, as well as future research and development directions to advance this technology for one-step conversion of methane to C2+ hydrocarbon fuels and chemicals are presented.
In Chapter 5, Isao Ogino (Hokkaido University) reviews roles of ligands and effects of neighboring metal atoms in atomically dispersed supported metal catalysts. Reactivity, stability, and catalytic performance of metals in such catalysts are significantly influenced by ligands including those on supports. Understanding the structure–performance relationships of atomically dispersed supported metal catalysts not only helps to describe the technological importance of minimizing the use of expensive noble metal but also provides fundamental insights to develop new catalysts. In addition to fundamental understanding of the structure–performance relationships of atomically dispersed supported metal catalysts, examples from recent literature are provided to illustrate the importance of such catalysts and prospective opportunities for new catalytic technology that are potentially enabled by them.
In Chapter 6, J. A. Rodriguez (Brookhaven National Laboratory, State University of New York at Stony Brook), F. Zhang, Z. Liu, and S. D. Senanayake (Brookhaven National Laboratory) review research focused on in situ studies for the activation and conversion of methane on well-defined metal–oxide surfaces. They present works dealing with the binding of methane on oxide and metal/oxide surfaces at low temperatures (<400 K). This is followed by a discussion of studies focused on the two reactions that involve the transformation of methane and have been investigated on well-defined metal–oxide surfaces: Methane dry reforming and the direct conversion of methane to methanol.
In Chapter 7, V. A. Sadykov, M. V. Arapova, E. A. Smal, S. N. Pavlova, L. N. Bobrova, N. F. Eremeev, N. V. Mezentseva and M. N. Simonov (Boreskov Institute of catalysis, Russia; Novosibirsk State University, Russia) provide a critical review of the design and performance of stable and efficient catalysts for biogas/biofuel transformation into syngas and hydrogen. These processes are based on nanocrystalline oxides with fluorite, perovskite and spinel oxides and their nanocomposites promoted by nanoparticles of Pt group metals and Ni-based alloys. Tailor-made versions of these catalysts are based upon the relationships between their synthesis procedure, composition, real structure/microstructure, surface properties, oxygen mobility and reactivity, which is determined to a great extent by the metal–support interaction. This requires application of modern sophisticated structural, spectroscopic, kinetic (including in situ FTIRS and isotope transients) methods and mathematical modeling.
In Chapter 8, Kazumasa Murata, Kakuya Ueda, Yuji Mahara (Nagoya University), Junya Ohyama (Nagoya University, Kyoto University, and Kumamoto University), and Atsushi Satsuma (Nagoya University and Kyoto University) review the advances in “in situ” and “operando” analysis with emphasis on environmental catalysts, e.g., catalysts for combustion, selective reduction of NO, automotive three-way catalysis, and related materials. This covers a series of techniques in the chapter such as X-ray absorption, infrared (IR) spectroscopy, ultraviolet-visible (UV–vis) spectroscopy, and Raman scattering spectroscopy. However, each technique has scopes and limitations. The authors provided several examples to explain how these techniques should be used as complements to other methods.
In Chapter 9, Matthew Drewery, Gizelle Sanchez, Eric Kennedy and Michael Stockenhuber (University of Newcastle, Australia) review the development and establishment of a sustainable and profitable biodiesel industry using glycerol as a raw material. Here, the various potential uses and techniques required to ensure the required level of purity are described. Finding a suitable glycerol derivative that has significant market demand is essential, and glycerol valorization is one biodiesel process that has attracted attention.
Prof. Eduardo Wolf (Notre Dame, USA) and colleagues describe the use of a novel technique in catalysis known as Solution Combustion Synthesis (SCS) in Chapter 10. The basis of this method is the self-sustained chemical reaction accompanied by a rapid release of heat. Specifically, the result is a solid catalyst, producing a material with useful properties, which can be used in reactions such as the hydrogen generation from methanol and ethanol, followed by application to electrocatalysis for fuels cell utilization. The rudimentary steps of SCS were developed in the early 19th century, when exothermic reduction – oxidation reactions were used to produce metals. Using this technique, many materials have been used to make metals and alloys, but none include catalysts. Here, this chapter focuses on SCS for catalyst synthesis. The goal is to demonstrate that SCS can be used to synthesize both unsupported and supported catalysts with specific catalytic properties, particularly high stability.
James Spivey, Yi-Fan Han and Dushyant Shekhawat