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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OVERVIEW OF THE CATALYSIS SCIENCE PROGRAM PORTFOLIO 31 3 Overview of the Catalysis Science Program Portfolio This chapter provides an overview of the U.S. Department of Energy (DOE) Office of Basic Energy Science (BES) Catalysis Science Program’s re- search portfolio in terms of the number and value of research grants and the characteristics of the principal investigators that have been funded by the pro- gram since 1987. The review is mainly based on the grant information (institu- tion, project title, and principal investigator) provided by the program manager and on information from the DOE Office of Science Web site.1 However, demo- graphic data on grantees were obtained from the online version of the American Chemical Society Directory of Graduate Research and other Web sites. BES provided the committee with lists of grantees and project titles for the fiscal years (FYs) 1987 to 2007. In addition, BES designated each grant for FY 1999 to FY 2007 as belonging to one of eight categories: biorelated cataly- sis, catalysis science, homogeneous catalysis, heterogeneous catalysis, nanoscience, surface science, theory, and other initiatives. However, the com- mittee chose to analyze the portfolio according to the two main kinds of cataly- sis: heterogeneous (including catalysis science, nanoscience, surface science, theory, and other initiatives) and homogeneous catalysis (including biorelated catalysis). Heterogeneous catalysis. Grants to study multiphase catalytic reac- tions, which may contain heterogeneized molecular complexes, with a focus on the role played by the support to which the catalyst is at- tached. The grants also include those related to surface science, nanoscience, and special funding initiatives, which will be discussed in more detail later in this chapter. 1 Office Of Basic Energy Sciences. U.S. Department of Energy. Online. Available at http://www.sc.doe.gov/bes/. Accessed February 5, 2009. 31 

32 CATALYSIS FOR ENERGY Homogeneous catalysis. Grants to study single-phase reactions involv- ing well-defined molecular catalysts. The research may include hetero- geneized molecular catalysts and focus on ligand design. The grants will also be used to study biorelated topics, including biocatalysis, en- zyme catalysis, biomimetics, and conversion of biofeedstocks with syn- thetic catalysts or biological catalysts. RESEARCH GRANTS For FY 1999 to FY 2007, in terms of funding and the numbers of grants, heterogeneous catalysis and homogeneous catalysis comprised an aver- age of 70 percent and 30 percent of the Catalysis Science Program portfolio, respectively (Table 3-1). The dollar amount of the grants has been split evenly between national laboratories and universities; however, national laboratories received approximately 17 percent of the grants. This disparity relates to differ- ences between the funding structures of the two types of institutions: national laboratories tend to have greater salary expenditures and higher overhead costs than universities. BES staff designated the FY 2007 projects (140 projects and 276 prin- cipal investigators) by more specific subject of research, as shown in Table 3-2. BES staff also designated the FY 2007 projects by type of catalyst as follows: • Inorganic, organic complex catalysts (28 percent) • Interfacial, porous, hybrid catalysts (35 percent) • Nanostructured, supramolecular catalysts (27 percent) • Bioinspired catalysts (3 percent) • Theory, modeling, simulation relevant to catalysis (7 percent) Industrial Relevance The committee members solicited input from their industry contacts (see Appendix D) about the most important breakthroughs in catalysis. Each committee member asked 5 to 10 people in industry who are leaders in catalysis research the question: What has been the most important breakthrough in cataly- sis within last 20 years? The 32 responses that related to catalysis fell into the following categories, which are roughly aligned with the distribution of the FY 2007 grants mentioned above: • New materials (e.g., zeolites; nano, micro, meso, macro-porous materials; mixed metal oxides) 

OVERVIEW OF THE CATALYSIS SCIENCE PROGRAM PORTFOLIO 33 • Theory (e.g., density functional theory) and mechanistic under- standings • New methods (analytical, e.g., XAFS; operando) • New oxidation processes and catalysts (e.g., Au, Pd/Au) • Environmental catalysis (catalytic converters, emission control catalyst, lean NOx, low sulfur). On the basis of the information provided above, the Catalysis Science Program portfolio appears to have a good distribution overall in its funding of basic research in the broad categories of homogeneous catalysis and heterogene- ous catalysis. During the time period studied, BES staff did a good job of main- taining the balance between experienced and new researchers within the portfo- lio by providing stable funding for established researchers while bringing new researchers and topics into the program. However, there are variations in the quality and relevance of the research in the portfolio, which will be discussed in detail in Chapter 5. TABLE 3-1 Funding and Number of Catalysis Science Program Grants for Research in Homogeneous and Heterogeneous Catalysis, FYs 1999–2001, 2002–2004, 2005–2007 Funding Percentage (millions of of Total dollars) Funding No. Grants Heterogeneous catalysis 1999–2001 48 67% 88 2002–2004 67 74% 102 2005–2007 79 73% 137 Homogeneous catalysis 1999–2001 24 33% 50 2002–2004 24 26% 39 2005–2007 $30 27% 62 NOTE: Grants for research in heterogeneous catalysis (multiphase reactions catalyzed by solid-state catalysts) include nanoscience, surface science, theory, and other initiatives. Grants for research in homogeneous catalysis (single- phase reactions catalyzed by molecular catalysts) include biocatalysis. Data in- clude individual, small-group, and conference grants. SOURCE: U.S. Department of Energy, Office of Basic Energy Sciences, Ca- talysis Science Program. 

34 CATALYSIS FOR ENERGY TABLE 3-2 Project Distribution by Subject of Research, FY 2007 No. Subject Grants C-H activation 34 Surface properties 31 Inorganic synthesis, inorganic single sites 22 Nanostructure synthesis, properties 21 Oxidation catalysis 20 Ab initio, multiscalar theory 19 Polymerization 12 Electroactivation 10 Surface design 9 X-Y activation 7 H2 production 7 Ultrafast chemical imaging facilities 5 CHO activation 5 Photocatalysis 5 C-X activation 4 Hybrid sites, cascade reactions 4 Biomass reactions 4 CO, small-molecule hydrogenation 4 Confined complexes 3 Chiral, stereoselective activation 3 Hydrogen storage 2 Aromatic reactions 2 Enzyme chemistry 2 Hydrotreating 2 NOTES: Some grants are related to more than one subject. SOURCE: Office of Basic Energy Sciences Catalysis Science Program staff. PRINCIPAL INVESTIGATORS This section describes the characteristics of the principal investigators who received funding from the Catalysis Science Program during the past eight years (FY 1999 to FY 2007). Table 3-3 shows the distribution of university- affiliated principal investigators according to academic title, and Table 3-4 

OVERVIEW OF THE CATALYSIS SCIENCE PROGRAM PORTFOLIO 35 2 shows the distribution according to years since receiving a Ph.D. The typical principal investigator was a full professor who had received a Ph.D. approxi- mately 20 years earlier. Twenty-four researchers (approximately 20–30 percent of all grantees) had been funded by the program since 1987. The program also funded a sizable number of junior faculty members; each year, an average of 20 percent of the principal investigators were assistant or associate professors, and 14 percent had received their Ph.D.’s less than 10 years before receiving pro- gram funding. TABLE 3-3 Catalysis Science Program University-Affiliated Principal Investi- gators by Academic Title, FYs 1999–2007 1999 2001 2003 2005 2007 Total 87 93 102 122 113 Assistant professor 8 7 9 12 5 Associate professor 8 10 10 15 19 Professor 63 67 70 82 77 Othera 8 9 13 13 12 a Chair, distinguished professor, adjunct professor, principal scientist, or emeritus professor. NOTES: Includes national laboratory personnel who are affiliated with a univer- sity. Duplicates and grants for conferences were removed from the original BES-supplied lists. SOURCE: DGRweb 2007. American Chemical Society Directory of Graduate Research. Online. Available at http://dgr.rints.com. Accessed March 2008. TABLE 3-4 Catalysis Science Program University-Affiliated Principal Investi- gators by Years Since Receiving a Ph.D., FYs 1999–2007 1999 2001 2003 2005 2007 Total 87 93 102 122 113 Years Since Ph.D. ≤ 10 15 9 13 18 16 11–20 26 31 22 28 31 21–30 25 27 41 42 37 31–40 20 22 20 26 21 ≥ 41 1 4 6 8 8 SOURCE: DGRweb 2007. American Chemical Society Directory of Graduate Research. Online. Available at http://dgr.rints.com. Accessed March 2008. 2 The academic title and the year in which the Ph.D. was received were found by using DGRweb. Online version of the American Chemical Society Directory of Graduate Research. Online. Available at http://dgr.rints.com. Accessed March 2008. 

36 CATALYSIS FOR ENERGY The impact of the Catalysis Science Program on fundamental catalysis science can be measured in part by the reputation of its funded researchers among their peers in the United States and abroad and by the quantity and qual- ity of their journal publications. Journal Citations Well-established and respected researchers are typically among the most-cited journal article authors, which appears to be the case for many of the principal investigators who have been funded by the program for a long time. According to the most recent update of the h-index3 for chemistry (Table 3-5), 18 principal investigators who are currently funded by the program are on the h- index list. More than half of these 18 investigators have received funding from the program for 20 years or more. These scientists are among the best-known chemists in the world and include Nobel laureates. However, the h-index is a measure of past contributions, not current contributions. U.S. researchers remain among the top performers in terms of number of journal citations, but U.S. representation in catalysis publications has been decreasing. In two of the leading catalysis journals, Journal of Catalysis and Applied Catalysis (Table 3-6), the number of U.S. papers increased from 1990– 1994 to 2000–2006, but the corresponding percentage of the total decreased.4 At the same time, the European Union share remained stable, and the Asian share increased. Among the 50 papers cited most frequently in these two jour- nals, the number of U.S.-originated papers declined from 27 to 12. In the same report, it was found that this general trend of decline in the share of U.S.-based participation in catalysis was also observed in an analysis of U.S. patents that originated in the United States. 3 In 2005, Jorge Hirsch, of the University of California, San Diego, devised an algorithm, known as the h-index, that calculates the impact of a scientist’s work. Chemistry World compiles and produces an h-index list of living chemists. A scientist’s h-index is equal to the highest number of papers that the person has published that has accrued at least that number of citations. For example, in Table 3-5, G. M. Whitesides has the highest h-index (as of March 28, 2008), 140. That means that he has published 140 papers that have each been cited at least 140 times. 4 National Research Council. 2007. International Benchmarking of U.S. Chemical Engineering Research Competitiveness. Washington, DC: National Academies Press. 

OVERVIEW OF THE CATALYSIS SCIENCE PROGRAM PORTFOLIO 37 TABLE 3-5 H-index ranking of select prominent chemists with relevance to the Catalysis Science Program, according to 2008 H-Index, H-Index Rank, and Field of Chemistry (other prominent chemists listed for comparison) Rank Name H-Index Field 1 G. M. Whitesides 140 Organic 16 G. Ertla 97 Physical 16 T. Marksb,c 97 Inorganic b 31 G. Somorjai 92 Physical 36 R. H. Grubbsb 90 Inorganic 44 R. R. Schrocka,b 87 Inorganic 55 G. A. Olaha 83 Organic 72 J. T. Yatesb 77 Physical b 82 L. Que 75 Biological 90 K. Morokuma 74 Theoretical 144 J. E. Bercawb,c 69 Inorganic 152 A. T. Bellb,c 68 Physical 152 R. J. Madixc,d 68 Physical b,c 167 R. G. Bergman 67 Inorganic 188 J. C. Crabtreeb,c 65 Inorganic 217 D. W. Goodmanb,c 63 Physical 217 K. N. Raymondb 63 Inorganic 232 H. Krotoa 62 Physical 253 W. J. Evansb 61 Inorganic b,c 272 C. P. Casey 60 Inorganic 286 W. Kohna 59 Theoretical 306 D. A. Dixonb 58 Theoretical 366 M. H. Chisholmb,c 55 Inorganic 366 R. M. Crooksb 55 Analytical 435 R. F. Curla 52 Physical 435 L. A. Curtissb 52 Theoretical 435 T. D. Tilleyb 52 Inorganic 463 T. B. Rauchfussb 51 Inorganic a Nobel laureate. b Receives research funding from the Catalysis Science Program. c Funded by the Catalysis Science Program since 1987. d Emeritus professor, previously funded by BES. NOTES: List of living chemists compiled by Henry Schaefer, with colleague Amy Peter- son, both of the University of Georgia, who assessed h-indexes of approximately 2,000 chemists. The list includes 560 names of those with an h-index greater than 50. SOURCE: Schaefer, Henry. 2008. H-index ranking of living chemists. Online. Chemistry World. Available at http://www.rsc.org/chemistryworld/News/2007/April/23040701.asp. Accessed October 22, 2008. 

38 CATALYSIS FOR ENERGY TABLE 3-6 Papers by U.S. Authors in Journal of Catalysis and Applied Catalysis 1990–1994 1995–1999 2000–2006 No. Papers No. Papers No. Papers Total 2,255 3,932 6,859 U.S. Papers 747 (33%) 891 (23%) 1,047 (15%) SOURCE: National Research Council. 2007. International Benchmarking of U.S. Chemical Engineering Research Competitiveness. Washington, DC: Na- tional Academies Press. International Reputation The Catalysis Science Program funds the most-recognized names in catalysis research, especially in heterogeneous catalysis. This assessment is based on a reputation survey that was conducted for an earlier study to deter- mine the international standing of U.S. researchers in chemistry and chemical engineering.5 Surveys were carried out separately for heterogeneous and homo- geneous catalysis. A new analysis of these surveys that specifically addresses the reputation of Catalysis Science Program grantees is summarized below. Heterogeneous Catalysis A total of 331 researcher names, including duplicates, were provided: 140 (42 percent) from the United States and 191 from elsewhere. That 42 per- cent of the researchers are from the United States indicates that the United States is a leader in heterogeneous catalysis research. Twenty-two names appear on five or more organizer lists, and they are shown in alphabetical order in Table 3- 7. Of these, nine are from the United States, and all nine are funded by the Ca- talysis Science Program (and most with long-term funding). These data imply that the program has a significant impact on the international standing of U.S. research in catalysis and is essential to the success of a heterogeneous catalysis researcher. The dependence of heterogeneous catalysis basic research on the program underlines the crucial role of the program and places substantial re- sponsibility on the program to ensure that the best researchers are identified and supported. 5 See discussion of virtual congresses in National Research Council, 2007, The Future of U.S. Chemistry Research: Benchmarks and Challenges, Washington, DC: National Academies Press. 

OVERVIEW OF THE CATALYSIS SCIENCE PROGRAM PORTFOLIO 39 TABLE 3-7 Most-Recognized Heterogeneous Catalysis Virtual Congress Speakers (in alphabetical order) Name Affiliation Country Baiker, Alfons ETH Zurich Switzerland Barteau, Marka University of Delaware United States Bell, Alexisa University of California, Berkeley United States Corma, Avelino Universidad Politecnica de Valencia Spain Dumesic, Jamesa University of Wisconsin, Madison United States Ertl, Gerhard Fritz-Haber Germany Freund, Hans- Fritz-Haber Germany Joachim Gates, Brucea University of California, Davis United States Goodman, D. Texas A&M University United States Waynea Hutchings, Graham University of Wales UK Iglesia, Enriquea University of California, Berkeley United States Iwasawa, Yasuhiro University of Tokyo Japan Jacobs, P. Leuven University Belgium Lercher, Johannes Technical University of Munich Germany Li, Can Dalian Institute of Chemical Physics China Neurock, Matthewa University of Virginia United States Nørskov, Jens Denmark Technical University Denmark Prins, Roel ETH Zurich Switzerland Schmidt, Lanny D.a University of Minnesota United States Somorjai, Gabor A.a University of California, Berkeley United States Topsøe, Henrik Haldor Topsøe Denmark van Santen, Rutger Eindhoven University of Netherlands Technology a Receives research funding from the Catalysis Science Program. SOURCE: A summarized version of this information appears in National Re- search Council, 2007, The Future of U.S. Chemistry Research: Benchmarks and Challenges, Washington, DC: National Academies Press. Homogeneous Catalysis A total of 148 researcher names, including duplicates, were provided for this virtual congress: 77 (52 percent) from the United States and 71 from elsewhere. That 52 percent of researchers are from the United States indicates 

40 CATALYSIS FOR ENERGY TABLE 3-8 Most-Recognized Homogeneous Catalysis Virtual Congress Speakers (in alphabetical order) Name Affiliation Country Bercaw, John E.a California Institute of Technology United States Bergman, Robert G. a University of California, Berkeley United States Bianchini, Claudio Florence Italy Brookhart, Maurice University of North Carolina, Chapel Hill United States Buchwald, S. Massachusetts Institute of Technology United States Casey, Charles P. a University of Wisconsin United States Crabtree, Roberta Yale University United States Erker, G. Munster University Germany Ferringa, Ben Groningen Netherlands Fu, Gregory Massachusetts Institute of Technology United States Fürstner, Alois Mülheim Germany Gibson, Vernon London UK Grubbs, Robert H. a California Institute of Technology United States Hartwig, John A. a University of Illinois United States Jacobsen, Erik Harvard University United States Jordan, Richard F. a University of Chicago United States Marks, Tobina Northwestern United States Milstein, David Weizmann Institute Israel Noyori, Ryoji Nagoya Japan Okuda, Jun RWTH Aachen Germany Oro, Luis Zaragoza Spain Reetz, Manfred T. Mülheim Germany Schrock, Richard R. a Massachusetts Institute of Technology United States Togni, Antonio ETH Zürich Switzerland Trost, Barry M. Stanford University United States Van Koten, G. Utrecht University Netherlands Ziegler, Tom University of Calgary Canada a Receives research funding from the Catalysis Science Program. SOURCE: A summarized version of this information appeared in National Research Council, 2007, The Future of U.S. Chemistry Research: Benchmarks and Challenges, Washington, DC: National Academies Press. that the United States is also a leader in homogeneous catalysis research. Twenty-seven names appear on two or more organizer lists, and they are shown in alphabetical order in Table 3-8. The impact of the Catalysis Science Program on the international standing of U.S. research in homogeneous catalysis is not as evident as in the case of heterogeneous catalysis. Although the percentage of U.S. scientists in the list is higher than the percentage of heterogeneous catalysis researchers, only 8 of the 14 U.S. researchers on the list are currently funded by the program. This is probably due to the fact that multiple sources of funding for homogeneous catalysis research exist in the United States, particularly at the National Institutes of Health. However, several BES-funded principal investiga- tors on the list (such as Bercaw, Bergman, Marks, and Schrock) have made some of the most important contributions to the fundamental understanding of 

OVERVIEW OF THE CATALYSIS SCIENCE PROGRAM PORTFOLIO 41 catalysis and to addressing energy needs, which will be discussed in greater de- tail in Chapters 5 and 6. CONCLUSIONS The United States’ strong international reputation in catalysis research is built on the records of many established, principal investigators who receive funding from the Catalysis Science Program. However, trends in journal publi- cations indicate that the United States is losing its competitive edge in catalysis, because of increased funding and research efforts in other countries.6 There is some indication that a gap in contributions from midcareer researchers, espe- cially in heterogeneous catalysis (owing to the downturn in the1980s’ job mar- ket), has affected the international standing of U.S. research. Overall, the Catalysis Science Program portfolio (research grants and principal investigators) is appropriately distributed in its funding of basic re- search in the broad fields of homogeneous and heterogeneous catalysis. During the time period studied, BES staff did a good job of maintaining a balance within the portfolio and of providing stable funding for established researchers while bringing new researchers and topics into the program. However, there are variations in the quality and relevance of the research in the BES portfolio, which will be discussed in more detail in Chapter 5. 6 National Research Council, 2007, The Future of U.S. Chemistry Research: Benchmarks and Challenges, Washington, DC: National Academies Press. 

42 CATALYSIS FOR ENERGY