https://www.chem.ccu.edu.tw/~joyce/referance/gump/IL/Chem.%20Rev.%201999,%2099,%202071.pdf

Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis

BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.

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Combining theory and experiment in electrocatalysis: Insights into materials design

The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids.

It is possible to say that zeolites are the most widely used catalysts in industry They are crystalline microporous materials which have become extremely successful as catalysts for oil refining, petrochemistry, and organic synthesis in the production of fine and speciality chemicals, particularly when dealing with molecules having kinetic diameters below 10 A The reason for their success in catalysis is related to the following specific features of these materials:1 (1) They have very high surface area and adsorption capacity (2) The adsorption properties of the zeolites can be controlled, and they can be varied from hydrophobic to hydrophilic type materials (3) Active sites, such as acid sites for instance, can be generated in the framework and their strength and concentration can be tailored for a particular application (4) The sizes of their channels and cavities are in the range typical for many molecules of interest (5-12 A), and the strong electric fields2 existing in those micropores together with an electronic confinement of the guest molecules3 are responsible for a preactivation of the reactants (5) Their intricate channel structure allows the zeolites to present different types of shape selectivity, ie, product, reactant, and transition state, which can be used to direct a given catalytic reaction toward the desired product avoiding undesired side reactions (6) All of these properties of zeolites, which are of paramount importance in catalysis and make them attractive choices for the types of processes listed above, are ultimately dependent on the thermal and hydrothermal stability of these materials In the case of zeolites, they can be activated to produce very stable materials not just resistant to heat and steam but also to chemical attacks Avelino Corma Canos was born in Moncofar, Spain, in 1951 He studied chemistry at the Universidad de Valencia (1967−1973) and received his PhD at the Universidad Complutense de Madrid in 1976 He became director of the Instituto de Tecnologia Quimica (UPV-CSIC) at the Universidad Politecnica de Valencia in 1990 His current research field is zeolites as catalysts, covering aspects of synthesis, characterization and reactivity in acid−base and redox catalysis A Corma has written about 250 articles on these subjects in international journals, three books, and a number of reviews and book chapters He is a member of the Editorial Board of Zeolites, Catalysis Review Science and Engineering, Catalysis Letters, Applied Catalysis, Journal of Molecular Catalysis, Research Trends, CaTTech, and Journal of the Chemical Society, Chemical Communications A Corma is coauthor of 20 patents, five of them being for commercial applications He has been awarded with the Dupont Award on new materials (1995), and the Spanish National Award “Leonardo Torres Quevedo” on Technology Research (1996) 2373 Chem Rev 1997, 97, 2373−2419

From Microporous to Mesoporous Molecular-Sieve Materials and Their Use in Catalysis

Beyond Oil and Gas: The Methanol Economy

Nature’s photosynthesis uses the sun’s energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. In contrast, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products can be achieved via its capture and subsequent reductive hydrogenative conversion. The present Perspective reviews this new approach and our research in the field over the last 15 years. Carbon recycling represents a significant aspect of our proposed Methanol Economy. Any available energy source (alternative energies such as solar, wind, geothermal, and atomic energy) can be used for the production of needed hydrogen and chemical conversion of CO2. Improved new methods for the efficient reductive conversion of CO2 to methanol and/or DME that we have developed include bireformin...

/pdf/chemical-recycling-of-carbon-dioxide-to-methanol-and-8lhsh2jg05.pdf

Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons.

Friedel-Crafts and related reactions

Chapter 1: Introduction. Chapter 2: Coal in the Industrial Revolution, and Beyond. Chapter 3: History of Oil and Natural Gas. Oil Extraction and Exploration. Natural Gas. Chapter 4: Fossil Fuel Resources and Uses. Coal. Oil. Tar Sands. Oil Shale. Natural Gas. Coalbed Methane. Tight Sands and Shales. Methane Hydrates. Outlook. Chapter 5: Diminishing Oil and Gas Reserves. Chapter 6: The Continuing Need for Hydrocarbons and their Products. Fractional Distillation. Thermal Cracking. Chapter 7: Fossil Fuels and Climate Change. Mitigation. Chapter 8: Renewable Energy Sources and Atomic Energy. Hydropower. Geothermal Energy. Wind Energy. Solar Energy: Photovoltaic and Thermal. Electricity from Photovoltaic Conversion. Solar Thermal Power for Electricity Production. Electric Power from Saline Solar Ponds. Solar Thermal Energy for Heating. Economic Limitations of Solar Energy. Biomass Energy. Electricity from Biomass. Liquid Biofuels. Ocean Energy: Thermal, Tidal, and Wave Power. Tidal Energy. Waves. Ocean Thermal Energy. Nuclear Energy. Energy from Nuclear Fission Reactions. Breeder Reactors. The Need for Nuclear Power. Economics. Safety. Radiation Hazards. Nuclear Byproducts and Waste. Emissions. Nuclear Power: An Energy Source for the Future. Nuclear Fusion. Future Outlook. Chapter 9: The Hydrogen Economy and its Limitations. The Discovery and Properties of Hydrogen. The Development of Hydrogen Energy. The Production and Uses of Hydrogen. Hydrogen from Fossil Fuels. Hydrogen from Biomass. Photobiological Water Cleavage. Water Electrolysis. Hydrogen Production Using Nuclear Energy. The Challenge of Hydrogen Storage. Liquid Hydrogen. Compressed Hydrogen. Metal Hydrides and Solid Absorbents. Other Means of Hydrogen Storage. Hydrogen: Centralized or Decentralized Distribution? Safety of Hydrogen. Hydrogen in Transportation. Fuel Cells. History. Fuel Cell Efficiency. Hydrogen-Based Fuel Cells. PEM Fuel Cells for Transportation. Regenerative Fuel Cells. Outlook. Chapter 10: The "Methanol Economy": General Aspects. Chapter 11: Methanol as a Fuel and Energy Carrier. Properties and Historical Background. Present Uses of Methanol. Use of Methanol and Dimethyl Ether as Transportation Fuels. Alcohol as a Transportation Fuel in the Past. Methanol as Fuel in Internal Combustion Engines (ICE). Methanol and Dimethyl Ether as Diesel Fuels Substitute in Compression Ignition Engines. Biodiesel Fuel. Advanced Methanol-Powered Vehicles. Hydrogen for Fuel Cells from Methanol Reforming. Direct Methanol Fuel Cell (DMFC). Fuel Cells Based on Other Fuels and Biofuel Cells. Regenerative Fuel Cell. Methanol for Static Power and Heat Generation. Methanol Storage and Distribution. Methanol Price. Methanol Safety. Emissions from Methanol-Powered Vehicles. Methanol and the Environment. Methanol and Issues of Climate Change. Chapter 12: Production of Methanol from Syn-Gas to Carbon Dioxide. Methanol from Fossil Fuels. Production via Syn-Gas. Syn-Gas from Natural Gas. Methane Steam Reforming. Partial Oxidation of Methane. Autothermal Reforming and Combination of Steam Reforming and Partial Oxidation. Syn-Gas from CO2 Reforming. Syn-Gas from Petroleum and Higher Hydrocarbons. Syn-Gas from Coal. Economics of Syn-Gas Generation. Methanol through Methyl Formate. Methanol from Methane Without Syn-Gas. Selective Oxidation of Methane to Methanol. Catalytic Gas-Phase Oxidation of Methane. Liquid-Phase Oxidation of Methane to Methanol. Methanol Production through Mono-Halogenated Methanes. Microbial or Photochemical Conversion of Methane to Methanol. Methanol from Biomass. Methanol from Biogas. Aquaculture. Water Plants. Algae. Methanol from Carbon Dioxide. Carbon Dioxide from Industrial Flue Gases. Carbon Dioxide from the Atmosphere. Chapter 13: Methanol-Based Chemicals, Synthetic Hydrocarbons and Materials. Methanol-Based Chemical Products and Materials. Methanol Conversion to Olefins and Synthetic Hydrocarbons. Methanol to Olefin (MTO) Process. Methanol to Gasoline (MTG) Process. Methanol-Based Proteins. Outlook. Chapter 14: Future Perspectives. The "Methanol Economy" and its Advantages. Further Reading and Information. References. Index.

Starting with coal, followed by petroleum oil and natural gas, the utilization of fossil fuels has allowed the fast and unprecedented development of human society. However, the burning of these resources in ever increasing pace is accompanied by large amounts of anthropogenic CO2 emissions, which are outpacing the natural carbon cycle, causing adverse global environmental changes, the full extent of which is still unclear. Even through fossil fuels are still abundant, they are nevertheless limited and will, in time, be depleted. Chemical recycling of CO2 to renewable fuels and materials, primarily methanol, offers a powerful alternative to tackle both issues, that is, global climate change and fossil fuel depletion. The energy needed for the reduction of CO2 can come from any renewable energy source such as solar and wind. Methanol, the simplest C1 liquid product that can be easily obtained from any carbon source, including biomass and CO2, has been proposed as a key component of such an anthropogenic carbon cycle in the framework of a “Methanol Economy”. Methanol itself is an excellent fuel for internal combustion engines, fuel cells, stoves, etc. It's dehydration product, dimethyl ether, is a diesel fuel and liquefied petroleum gas (LPG) substitute. Furthermore, methanol can be transformed to ethylene, propylene and most of the petrochemical products currently obtained from fossil fuels. The conversion of CO2 to methanol is discussed in detail in this review.

George A. Olah

Papers

Beyond Oil and Gas: The Methanol Economy

Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons.

Friedel-Crafts and related reactions

Beyond Oil and Gas: The Methanol Economy

Recycling of carbon dioxide to methanol and derived products – closing the loop