|Center for Catalytic Science & Technology|
|Comprised of the following departments: Chemical & Biomolecular Engineering :: Chemistry & Biochemistry :: Materials Science & Engineering|
The design and synthesis of 3D covalent organic frameworks (COFs) have been considered a challenge, and the demonstrated applications of 3D COFs have so far been limited to gas adsorption. Herein we describe the design and synthesis of two new 3D microporous base-functionalized COFs, termed BF-COF-1 and BF-COF-2, by the use of a tetrahedral alkyl amine, 1,3,5,7-tetraaminoadamantane (TAA), combined with 1,3,5-triformylbenzene (TFB) or triformylphloroglucinol (TFP). As catalysts, both BF-COFs showed remarkable conversion (96 % for BF-COF-1 and 98 % for BF-COF-2), high size selectivity, and good recyclability in base-catalyzed Knoevenagel condensation reactions. This study suggests that porous functionalized 3D COFs could be a promising new class of shape-selective catalysts.
A new route from 5-hydroxymethylfurfural and isopropanol to 2,5-bis[(1-methylethoxy)methyl]furan, a potential biodiesel additive has been discovered by Jungho Jae, Eyas Mahmoud, and Profs. Vlachos and Lobo. Their discovery has been highlighted as the back cover of the latest ChemCatChem issue. In their paper on p.508 of this issue, Jae et al. describe the process, which applies Lewis acid zeolites, such as Sn- or Zr-Beta, as catalysts in a liquid-phase transfer hydrogenation and etherification cascade reaction. The use of Sn-Beta and secondary alcohols gives the products in the highest selectivities (>85%) in yields of over 80%. This chemistry opens a new opportunity to the production of biodiesel from biomass derived sugars.
A team of researchers at the University of Delaware has developed a highly selective catalyst capable of electrochemically converting carbon dioxide — a greenhouse gas — to carbon monoxide with 92 percent efficiency. The carbon monoxide then can be used to develop useful chemicals. The researchers recently reported their findings in Nature Communications.
The renewable production of chemicals and fuels from biomass is inherently difficult due to competing side reactions. Eyas Mahmoud and Raul Lobo at the CCST have recently demonstrated the selective production of phthalic anhydride, a chemical used for the manufacture of plasticizers, unsaturated polyesters, and resins in the millions of tonnes per year, from biomass by using mixed sulfonic-carboxylic anhydrides as reaction intermediates. The reaction starts by the Diels-Arder reaction of maleic anhydride and furan, and the product is effectively dehydrated by the mixed anhydrides. This result opens the door to the possibility of production of 'green' phthalic anhydride from renewable sources.
Professor Joel Rosenthal, in the Department of Chemistry and Biochemistry, has recently reported in the Journal of the American Chemical Society that bismuth modified glassy-carbon electrodes are excellent electrocatalysts for the electroreduction of carbon dioxide into carbon monoxide. Bismuth is a widely available metal the byproduct of the production of lead, copper and tin. In the JACS report, Rosenthal shows that Bi-modified carbon electrodes (see figure on left) are effective and selective devices for the conversion of CO2 to CO on a variety of solvents, but are especially effective in imidazonium-based ionic liquids. Low over-potentials and Faradaic efficiencies of nearly 95% yield excellent energy efficiency for CO production, comparable to what has been observed using expensive catalysts like silver or gold.
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CCST is happy to announce that Nima Nikbin is the recipient of the 2013 Eastman Chemical Student Award. Nima's work deals with the applications of quantum chemical calculations and theoretical chemistry to the analysis of catalysis problems of biomass derived molecules. He has investigated the difficult problem of understanding the molecular basis for catalytic activity and selectivity in the liquid phase for molecules as complex as fructose. This award recognizes his research accomplishments and the breath of his research activities. As a result of this award, Nima will give a summary of recent research results at the next CCST Annual Research Review and will receive a plaque and a gift at the Annual Review.
Donald Watson, an assistant professor and organic chemist in UD’s Department of Chemistry and Biochemistry has received the NSF Career and Cottrell Scholar Awards. His research focuses on the development of new reactions that enable the synthesis of complex organic molecules. Part of the Watson Research Group’s effort has been dedicated to creating new methods to prepare organosilanes. His interest in developing new routes to such compounds stems from their extreme utility and widespread applications in drug synthesis, agrochemical synthesis and material science. The NSF Career Award funds Watson to examine new ways to construct vinyl and allyl silanes using simple alkene starting materials. This Silyl-Heck Reaction, as he has termed it, is a very simple method to prepare these two types of important organosilanes. In the new method, his group adds silicon to unfunctionalized, alkenes, which are cheap and widely available. The research builds off the Nobel Prize-winning work of UD’s Richard Heck, Willis F. Harrington Professor Emeritus of Chemistry and Biochemistry, whose pioneering developments of reactions to form carbon-carbon bonds through palladium catalysis enabled chemists to make molecules as complex as those created by nature itself.
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Jeffrey Rimer (Ph.D. 2006) recently received the NSF CAREER Award for his proposal: "A Bio-Inspired Approach to Engineer Zeolite Catalysts". Awards are given to outstanding junior-level faculty members to help them launch long-term, successful research careers. They are among the most prestigious grants in the STEM fields (science, technology, engineering and mathematics). Jeffrey Rimer, assistant professor of chemical and biomolecular engineering at the University of Houston, won a five-year, $400,000 grant to expand his efforts to improve zeolites, a class of catalysts used in the petroleum and chemical industries to create a range of different products, from ion-exchange additives in detergents to gasoline and alternative fuels. He proposes in his CAREER Award study to develop a rational design strategy for improving the mass transport properties of zeolite catalysts, notably a reduction in the internal pore diffusion path length and an increase in the exterior pore surface area, which are known to markedly improve activity and stability. He completed his Ph.D. under the supervision of Professors Dion Vlachos and Raul F. Lobo.
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Professor Yushan Yan has received a new grant from the ARPA-e program from the Department of Energy for a total of $793,000. This Advanced Research Projects Agency- Energy (ARPA-E) program seeks to support science and technology with the potential to produce game-changing breakthroughs in energy technology, form the foundation of new industries and have large commercial impact. Professor Yan’s proposal is one of only 66 proposals funded by the ARPA-e program. Professor Yan’s group has developed a new concept in flow batteries, a device that is used to store electrical energy when there is surplus production, and to deliver this energy efficiently and rapidly when it is needed. The discoveries of the Yan’s group should allow efficient electricity storage needed to cope with the intrinsic irregularity of renewable wind and solar electricity generation.
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Transition-metal phosphate framework materials are very important due to their potential as oxygen evolution catalysts in solar fuel production devices, or as novel high energy, high power cathode materials for rechargeable lithium-ion batteries. In a recent report highlighted as the cover of Chemical Communications, the Jiao group reported a general approach to synthesize a wide range of transition metal phosphate frameworks in deep-eutectic solvents through tuning key reaction parameters including temperature, time, and water addition. Four new metal phosphate frameworks, DEL-1, DEL-2, DEL-3 and MnPO4-DFT were synthesized for the first time. The capability to apply this method to many more metal phosphate frameworks offers new opportunities in catalysis, energy conversion, and energy storage.
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John R. Kitchin, of Carnegie Mellon University, has been named by President Obama as one of 96 researcher recipients of the Presidential Early Career Awards for Scientists and Engineers, the highest honor bestowed by the United States Government on science and engineering professionals in the early stages of their independent research careers. Kitchen received his PhD degree in Chemical Engineering from the University of Delaware in 2004. He was co-advised by Mark Barteau and Jingguang Chen.
“Discoveries in science and technology not only strengthen our economy, they inspire us as a people.” President Obama said. “The impressive accomplishments of today’s awardees so early in their careers promise even greater advances in the years ahead.”
The Presidential early career awards embody the high priority the Obama Administration places on producing outstanding scientists and engineers to advance the Nation’s goals, tackle grand challenges, and contribute to the American economy. The recipients are employed or funded by the following departments and agencies: Department of Agriculture, Department of Commerce, Department of Defense, Department of Education, Department of Energy, Department of Health and Human Services, Department of the Interior, Department of Veteran Affairs, Environmental Protection Agency, National Aeronautics and Space Administration, and the National Science Foundation, which join together annually to nominate the most meritorious scientists and engineers whose early accomplishments show the greatest promise for assuring America’s preeminence in science and engineering and contributing to the awarding agencies' missions.
The awards, established by President Clinton in 1996, are coordinated by the Office of Science and Technology Policy within the Executive Office of the President. Awardees are selected for their pursuit of innovative research at the frontiers of science and technology and their commitment to community service as demonstrated through scientific leadership, public education, or community outreach.
Professor Yushan Yan’s group recently reported an important advance in the development of polymer hydroxide (OH–) exchange membranes (HEMs) for fuel cell applications. In contrast to proton exchange membranes (PEMs), HEMs have lower materials costs and durability problems and can be utilized in combination with electrocatalysts that are more abundant and inexpensive than precious metal catalysts used for PEM fuel cells. In HEM design there has been well-known trade-off between swelling control and ion conductivity. Yan’s group has largely overcome this problem by enhancing van der Waals interactions among polymer chains. Using large quaternary phosphonium-functionalized polymers and a high electron density polymer chain (see Scheme I), the Yan group was able to prepare a new membrane with low swelling, high hydroxide conductivity and excellent HEM fuel cell performance. This discovery was reported in the May issue ChemSusChem (2012, 5, 843-848) and was highlighted as the cover.
Professor Donald Watson and his team in the UD Department of Chemistry and Biochemistry have developed a chemical reaction that converts carbon-hydrogen bonds to carbon-silicon bonds using the metal palladium as a catalyst, yielding an important new tool for building new molecules. The potential industrial applications are broad, ranging from the manufacture of medicines to polymers. This reaction is illustrated in Scheme I.
In a recent report in Angew. Chemie Int. Ed., the Watson group demonstrated a high-yielding protocol for the silyl-Heck reaction of alkenes. Key to this discovery was the identification of tBuPPh2 as a uniquely effective ligand for this catalyst. This method allows the direct silylation of monosubstituted alkenes. In the case of substrates that lack allylic hydrogen atoms, such as styrenes, high yields of E-vinyl silanes result. Substrates that contain allylic hydrogen atoms are transformed into terminal allyl silanes in good yields and with good levels of E/Z stereocontrol. When combined with existing methods, the conversion of a-olefins into allyl silanes allows the facile and selective functionalization of the allylic position, which results in a rapid increase of molecular complexity from simple starting materials.
McAtee, J.R. et al, “Preparation of Allyl and Vinyl Silanes by the Palladium-Catalyzed Silylation of Terminal Olefins: A Silyl-Heck Reaction” in Angew. Chemie-Int. Ed., 2012, 51, 3663-3667.
The three-year grant builds on work initiated by UD Prof. Jingguang Chen in 2005 when he co-founded the synchrotron catalysis consortium (SCC). SCC promotes the use of synchrotron techniques for cutting-edge catalysis research under in-situ conditions. Chen is the consortium’s lead principal investigator.
Synchrotron spectroscopies demonstrate unique advantages over conventional techniques, including higher detection sensitivity and molecular specificity, faster detection rate and more in-depth information about structural, electronic and catalytic properties under actual reaction conditions.
Since 2005, the SCC has designed over a dozen specialized in situ reaction cells and advanced optics particularly tailored to catalysis research; work that has impacted more than 100 U.S. research groups in the catalysis community.
DOE recently invested $1 billion in a stronger synchrotron installation at BNL. Under the current renewal, Chen’s group will aid the transition to the new synchrotron system, enabling further insight into the chemical and physical structure of materials.
“The consortium’s role is to ensure that catalysis remains well represented in this new synchrotron facility,” remarked Chen.
Catalysis has played a significant role in the chemical and petroleum industries over the past several decades, and more recently has been applied to a number of new areas, including environmental and bioengineering applications.
UD has had an active and vital research program in catalysis since the Center for Catalytic Science and Technology (CCST) was founded in 1978. Chen and his colleagues are investigating the use of less-expensive, more stable catalytic materials for applications ranging from fuel cells to biomass utilization.
Jingguang Chen is the Claire D. LeClaire Professor of Chemical and Biomolecular Engineering and the co-director of the DOE Energy Frontier Research Center at UD. He served as the director of CCST from 2000 through 2007 and as the interim director of the UD Energy Institute (UDEI) from 2008 through 2010.
Anatoly Frenkel, professor of physics at Yeshiva University, and Radoslav Adzic, senior chemist at BNL, are co-principal investigators on the grant. UD research team members on location full-time at BNL include Emily Carino, Ned Marinkovic and Adele Wang.
Article by Karen B. Roberts
Thomas F. Degnan, Jr., of ExxonMobil Research and Engineering Company and a University of Delaware/CCST alum, is the 2012 recipient of the ACS Award in Industrial Chemistry sponsored by the ACS Division of Business Development and Management and the ACS Division of Industrial & Engineering Chemistry. Mr. Degnan will be honored at an Awards Ceremony on Tuesday, March 27, 2012, in conjunction with the 243rd ACS National Meeting in San Diego, CA.
Yushan Yan joined the Chemical and Biomolecular Engineering Department in July 2011, as Distinguished Professor of Engineering and is now part of the CCST faculty. Yushan received his bachelor's degree in chemical physics from the University of Science and Technology of China in 1988. After studying for a few years at the Dalian Institute of Physical Chemistry, he moved to the United States where he earned his master's and doctoral degrees in chemical engineering from the California Institute of Technology in 1995 and 1997, respectively. He worked at Allied Signal for two years before joining the faculty of the University of California at Riverside where he also served as Presidential Chair of the Chemical Engineering Department from 2008 to 2011 before joining the faculty of the University of Delaware.
We are delighted to have Yushan at the CCST. His research program has produced multiple and important innovations in the science and application of zeolites and other porous materials into unconventional areas such as water purification, low-k electronics, corrosion resistance zeolite membranes and novel electrochemical systems. He has been a pioneer in the development of novel concepts in electrochemical energy conversion and has developed effective and stable hydroxide-based exchange polymer membranes. These materials have great potential for novel applications in fuel cells, batteries and other electrochemical devices. He is the inventor of a large number of issued or pending patents, several of which he has licensed to form startup companies. He is the recipient of numerous awards including recently the Breck Award from the International Zeolite Association and the 27th Outstanding Alumni Lecture, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
The CCST faculty is very enthusiastic about Yushan’s contributions to catalysis and catalysis technology and look forward to working with him in the years to come.