Catalysis for Energy: Fundamental Science and Long-Term Impacts of the U.S. Department of Energy Basic Energy Sciences Catalysis Science Program (2009)

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1 Introduction This report presents an in-depth analysis of the investment in catalysis basic research by the U.S. Department of Energy (DOE) Office of Basic Energy Sciences (BES) Catalysis Science Program during the fiscal years 1999 to 2007. The review examines the BES research portfolio in catalysis and identifies whether and how it has advanced fundamental science and discusses how it con- tributes and is likely to contribute to immediate and long-term national energy goals, such as reducing the nation’s dependence on foreign sources of energy. First, however, it is important to understand what catalysis is and why it is im- portant to chemical transformations, global energy issues, and DOE. CATALYSIS AND CHEMICAL TRANSFORMATIONS Catalysis is a process by which a substance (a catalyst) increases the rate of a chemical reaction. Unlike the reactants, the catalyst remains essentially unchanged, relative to its initial state, at the end of the chemical reaction that it facilitates. Catalytic processes are typically categorized as heterogeneous or homogeneous: • In heterogeneous catalysis, the catalyst (typically a solid) is in a different phase from the reactants. • In homogeneous catalysis, the catalyst is in the same phase (typi- cally liquid) as the reactants. Catalysts vary in composition from solid metal surfaces to enzymes in solution, and they are involved in chemical transformations as different as the refining of petroleum and the synthesis of pharmaceuticals. Catalysis affects almost every aspect of our economy, health, and way of life as documented 13 

14 CATALYSIS FOR ENERGY etensively in the 1992 National Research Council report, Catalysis Looks to the Future.1 Catalysis is especially critical in the chemical and petroleum- processing industries, which are the two largest industrial energy users in the United States. 2 The U.S. chemical industry alone is estimated to account for approximately a quarter of global chemical production ($450 billion per year),3 thus the impact of catalysis on the U.S. economy is substantial. Furthermore, success in catalysis research has contributed to the strong position of the U.S. chemical industry. Examples of industrially important catalysts include Single-site polymerization catalysts, organometallic-based catalysts used in U.S. industry to produce over 2 billion pounds of polyolefins every year. Some of the polyolefins include long-chain branched copolymers of ethylene with α- olefins, new elastomers, and ones produced as a result of a new process for eth- ylene propylene diene monomer (EPDM) rubber. The new EPDM polymeriza- tion processes are more efficient, use less energy, and use less capital than prior technology. As a result, most of the world production of EPDM materials now uses the single-site polymerization catalysts. Platinum-group metal catalysts, which have been used in catalytic converters to reduce automobile tailpipe emissions. Catalytic converters have been used on all new cars since the mid 1970s. On the basis of measurements by the Envi- ronmental Protection Agency at over 250 sites, the average carbon monoxide (CO) concentration has dropped by 60 percent from 1990 to 2005—largely be- cause of the use of catalytic converters. Most cars today are equipped with three- way catalytic converters, which use newer catalysts that reduce emissions of CO, hydrocarbons or volatile organic compounds, and nitrogen oxides. Unfor- tunately, the optimal fuel mix for effective catalytic converter operation is often not the same as the optimal fuel efficiency mix, increasing carbon dioxide pro- duction. Zeolite catalysts, crystalline microporous materials that are used in a wide vari- ety of industries, from oil refining to production of fine chemicals.4 Zeolites are key catalysts in the petroleum refinery units known as fluid catalytic crackers, which are at the heart of gasoline and diesel production. Zeolites have enabled 1 National Research Council. 1992. Catalysis Looks to the Future. Washington, DC: National Academy Press. 2 2002 Manufacturing Energy Data Tables. Energy Information Administration. http://www.eia.doe.gov/emeu/mecs/mecs2002/data02/shelltables.html. Accessed February 2, 2009. 3 Industrial Technologies Program: Chemicals Industry of the Future. U.S. Department of En- ergy. http://www1.eere.energy.gov/industry/chemicals/. Accessed May 9, 2008. 4 Davis, M.E. 2003. Materials Science: Distinguishing the (Almost) Indistinguishable. Science 300(5618):438-439. 

INTRODUCTION 15 the petroleum industry to increase the gasoline obtained from a barrel of oil (1 barrel = 42 gal) from 14 gal in the 1960s to 20 gal in the late 1980s.5 CATALYSIS AND ENERGY For fossil fuels (petroleum, natural gas, and coal) to be used with en- ergy technologies (such as internal-combustion engines in automobiles), raw materials must be chemically modified. In the case of petroleum, for example, the petroleum-refining industry (much like the chemical industry) relies heavily on catalysis to achieve the desired chemical form of the desired final product. Beyond the manufacture of the fuel, catalysis plays a critical role in mitigating the impact of the use of fossil fuel, as illustrated by the dramatic improvement in urban air quality as a result of using platinum-group catalysts in catalytic con- verters. There is no doubt that catalysis plays a critical role in today’s energy technologies. Catalysis is also linked to energy with respect to the large amount of fossil fuel consumed by the chemical industry, estimated by DOE to be almost 30 percent of all U.S. industrial energy consumption.6 Over half of that “energy” is fuel, such as natural gas, used as chemical feedstocks for the manufacture of more valuable products, and the rest is consumed primarily to generate electric- ity and heat for manufacturing processes. More efficient catalytic processes have the potential to decrease fossil-fuel consumption in both feedstocks and process heat. That is, catalysis that produces the desired end products at higher yields reduces consumption of the raw materials, and catalysis that increases reaction rates reduces the heat required to drive a process. Catalysis will be critical for converting other resources such as biomass and sunlight to usable sources of energy, and for developing new efficient proc- esses for using them in fuel cells and other new technologies. Catalysis is thus fundamentally linked to both energy delivery and energy use. The importance of catalysis related to energy is extensively covered in the 2008 DOE report, Basic Research Needs: Catalysis for Energy,7 and underlies DOE’s financial support for research in catalysis, which will be discussed in more detail below. 5 Katz, R. N. 2001. Advanced ceramics: Zeolites = More miles per barrel. Ceramic Industry Magazine. http://www.ceramicindustry.com/. Accessed January 31, 2009. 6 Industrial Technologies Program: Chemicals Industry of the Future. U.S. Department of En- ergy. http://www1.eere.energy.gov/industry/chemicals/. Accessed May 9, 2008. 7 Basic Research Needs: Catalysis for Energy. U.S. Department of Energy Basic Energy Sci- ences Workshop. http://www.sc.doe.gov/bes/reports/files/CAT_rpt.pdf. Accessed January 31, 2009. 

16 CATALYSIS FOR ENERGY CATALYSIS AND THE DEPARTMENT OF ENERGY MISSION DOE’s overarching mission is to advance the national, economic, and energy security of the United States. The agency also seeks to promote scien- tific and technologic innovation in support of that mission and to ensure the en- vironmental cleanup of the national nuclear-weapons complex.8 Catalysis sci- ence is relevant to the mission of DOE and the welfare of the nation in that, as stated earlier, catalysts are needed for the processes that convert crude oil, natu- ral gas, coal, and biomass into clean-burning fuels; catalysts are crucial for en- ergy conservation in creating new, less energy-demanding routes for the produc- tion of basic chemical feedstocks and value-added chemicals; and catalysis science has affected the technology that is used to clean up environmental pol- lutants, such as unwanted emissions from chemical production or combustion, and has provided a means of replacing undesirable chemicals with more benign ones, for example, the displacement of chlorofluorocarbons with more environ- mentally acceptable refrigerants.9 The origin of DOE traces back to the 1940s and the development of nu- clear weapons during World War II. However, it was not until 1977, soon after the 1973 oil embargo crisis, that DOE was created “to provide a framework for a comprehensive and balanced national energy plan by coordinating and adminis- tering the energy functions of the federal government. The DOE undertook re- sponsibility for long-term, high-risk research and development of energy tech- nology, federal power marketing, energy conservation, the nuclear weapons program, energy regulatory programs, and a central energy data collection and analysis program.”10 Support for catalysis research at DOE also began at that time as part of the Chemical Energy Program. The Chemical Energy Program encompassed “organic, inorganic, physical and electrochemistry; thermochemistry and reac- tion mechanisms and dynamics; coal and hydrocarbon fuel chemistry, heteroge- neous and homogeneous catalysis, chemistry of hydrogen production and stor- age, biomass conversions.”11 Most of the support for catalysis basic research at DOE resides in the Catalysis Science Program, but catalysis-related research is also carried out in other programs in BES. Solar photochemistry, energy biosci- ences, chemical physics, and materials chemistry programs also fund catalysis- related projects, although catalysis does not have the highest priority in these programs. 8 About DOE. U.S. Department of Energy. http://www.doe.gov/about/index.htm. Accessed January 31, 2009. 9 Based on CRA-Catalysis Science-2008, program description, February 2008. 10 Origins and Evolution of the Department of Energy. U.S. Department of Energy. http://www.doe.gov/about/origins.htm. Accessed July 15, 2008. 11 U.S. Department of Energy. 1979. DOE/ER-0024, Summaries of FY 1978 Research in the Chemical Sciences, April 1979, National Technical Information Service. 

INTRODUCTION 17 CATALYSIS AND BASIC RESEARCH FUNDING DOE funding for catalysis basic research is more than that of any other federal agency on the basis of the estimated number of grants that were funded in FY2005 (Table 1-1). In FY2005, DOE funded approximately $35 million in grants, or 54 percent of the total. The National Science Foundation (NSF) and the National Institutes of Health (NIH) also made sizable contributions to ca- talysis basic research. The three combined provided approximately $65 million. However, the focus of NIH projects is generally much different, that is, targeting synthesis of pharmaceuticals rather than commodity chemicals or energy. Figure 1-1 shows the decadal trend in the distribution of all catalysis- related basic-research grants by the three main funding agencies (based on in- formation from DOE, the NSF Web site, and the NIH CRISP database). It can be seen that the number of grants for catalysis research has been roughly con- stant over the past decade. TABLE 1-1 Estimated U.S. Federal Government Funding for Catalysis Basic Research, FY2005 Estimated % of No. % of Average Award Total Total Grants Grants Award Duration Funding Funding DOE 151 53% $235,000 3 years $35,485,000 54% NSF 76 27% $126,000 2–3 years $9,576,000 15% NIH 58 20% $360,000 3–4 years $20,880,000 32% Total 285 $65,941,000 SOURCE: Original analysis based on data from funding agencies. NSF data from Division of Chemical, Bioengineering, Environmental, and Transport Sys- tems and Division of Chemistry collected by searching Awards Database (http://www.nsf.gov/awardsearch/index.jsp); DOE data provided by Office of Basic Energy Sciences; NIH data from CRISP database (http://crisp.cit.nih.gov). 

18 CATALYSIS FOR ENERGY 300 250 Number of Grants 200 NIH 150 NSF DOE 100 50 0 1999 2000 2001 2002 2003 2004 2005 2006 2007 Fiscal Year FIGURE 1-1 Distribution of catalysis-related grants by three main government funding agencies. SOURCE: Original analysis based on data from agencies. NSF data from Divi- sion of Chemical, Bioengineering, Environmental, and Transport Systems and Division of Chemistry (http://dellweb.bfa.nsf.gov and http://www.nsf.gov/awardsearch/index.jsp); DOE data from Office of Basic Energy Sciences; NIH data from CRISP data- base (http://crisp.cit.nih.gov) and NIH Extramural Data Book, March 2008. The U.S. federal government investment in catalysis basic research ($65 million, of which $45 million is for nonpharmaceutical research) is similar to the levels of support for individual research institutes in other countries. For example, heterogeneous catalysis research in Europe, Japan, and other Asian countries (on the basis of visits to those countries) was recently summarized as follows:12 • Instituto de Tecnologia Quimica, Spain: $6 million budget, 25 re- search personnel (six principal investigators). • Fritz-Haber Institute, Germany: $35–40 million budget, 250–300 research personnel. • Dalian Institute of Chemical Physics, China: $15 million budget, 500 research personnel. 12 Davis, R. 2008. An International Assessment of Research in Catalysis by Nanostructured Ma- terials. Presentation to the Committee on the Review of Basic Energy Sciences Catalysis Program, March 17, 2008. 

INTRODUCTION 19 The funding mechanisms in those countries are quite different from those in the United States. For example, the Fritz-Haber Institute receives 60 percent of its funds from the Max Planck Society, and the Instituto de Tecnolo- gia Quimica receives approximately 80 percent of its budget from sources other than the federal government, including industrial contracts, intellectual property licensing fees, and European projects. In the United States, the main support for catalysis basic research conducted at universities and national laboratories comes from the federal government. As discussed in the benchmarking analyses conducted by the National Research Council, the maintenance of U.S. leadership and competitiveness in catalysis research may be threatened because of current levels of funding in the United States compared with those in other countries.13 SUMMARY Catalysis—the process by which a substance increases the rate of a chemical reaction—is involved in many chemical transformations of importance to the U.S. economy. The chemical transformations are in turn inextricably linked to production and use of energy. Thus, catalysis plays an essential role in the mission of DOE with respect to both current and long-term national energy goals. Support for catalysis basic research underlies the fundamental under- standing of chemical transformations involved in energy, human health, envi- ronmental, and other applications that address societal needs. DOE is the key provider of funding for catalysis basic research with relevance to energy in the United States. The primary mechanism by which DOE supports catalysis basic research is the Catalysis Science Program, which is the main subject of this re- port. An overview of the Catalysis Science Program will be provided in Chapter 2, followed by an overview of the research portfolio in Chapter 3, and a discussion of the key influences on the development of the portfolio in Chapter 4. The statement of task will be addressed largely in Chapters 5 and 6 with an in-depth analysis of the portfolio, its impact on fundamental science, and its contributions to reaching national energy goals. 13 National Research Council. 2007. The Future of U.S. Chemistry Research: Benchmarks and Challenges. Washington, DC: National Academies Press; National Research Council. 2007. Interna- tional Benchmarking of U.S. Chemical Engineering Research Competitiveness. Washington, DC: National Academies Press. 

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