Environment at MIT - Research and Academic Programs

Research and Resources

GREEN CHEMISTRY RESEARCH

Green Chemistry in Universities

Green Chemistry at Massachusetts Institute of Technology

Professor Angela Belcher (Department of Materials Science and Engineering and Biological Engineering)

Research includes using the principles of materials engineering, chemistry, molecular biology, and electrical engineering to design growth processes of nanomaterials that mimic natural self-assembly processes. In collaboration with professors Paula Hammond and Yet-Ming Chiang, her group has already created the first virus-assembled nanoelectrode and virus-assembled battery,
Professor Rick Danheiser (Department of Chemistry)
One area of research focuses on "environmentally-benign" organic synthesis. This includes the application of supercritical fluids as organic synthesis solvents and the promotion of synthetic reactions using microwave irradiation. Research is also being directed toward environmentally friendly pest control.

Dunetz, J. R.; Ciccolini, R. P.; Froling, M.; Paap, S. M.; Allen, A. J.; Holmes, A. B.; Tester, J. W.; Danheiser, R. L. Pictet-Spengler reactions in multiphasic supercritical carbon dioxide/CO2-expanded liquid media. In situ generation of carbamates as a strategy for reactions of amines in supercritical carbon dioxide. Chemical Communications. 2005, (35), 4465-4467.
Timko, Michael T.; Diffendal, Jason M.; Tester, Jefferson W.; Smith, Kenneth A.; Peters, William A.; Danheiser, Rick L.; Steinfeld, Jeffrey I. Ultrasonic Emulsification of Liquid, Near-Critical Carbon Dioxide-Water Biphasic Mixtures for Acceleration of a Hydrolysis Reaction. Journal of Physical Chemistry A. 2003, 107(29), 5503-5507.
Tester, Jefferson W.; Danheiser, Rick L.; Weintstein, Randy D.; Renslo, Adam; Taylor, Joshua D.; Steinfeld, Jeffrey I. Supercritical fluids as solvent replacements in chemical synthesis. ACS Symposium Series (2000), 767(Green Chemical Syntheses and Processes), 270-291.
Weinstein, Randy D.; Renslo, Adam R.; Danheiser, Rick L.; Tester, Jefferson W. Silica-Promoted Diels-Alder Reactions in Carbon Dioxide from Gaseous to Supercritical Conditions. Journal of Physical Chemistry B. 1999, 103(15), 2878-2887.
Renslo, Adam R.; Weinstein, Randy D.; Tester, Jefferson W.; Danheiser, Rick L. Concerning the Regiochemical Course of the Diels-Alder Reaction in Supercritical Carbon Dioxide. Journal of Organic Chemistry. 1997, 62(13), 4530-4533.
Weinstein, Randy D.; Renslo, Adam R.; Danheiser, Rick L.; Harris, Jonathan G.; Tester, Jefferson W. Kinetic Correlation of Diels-Alder Reactions in Supercritical Carbon Dioxide. Journal of Physical Chemistry. 1996, 100(30), 12337-12341.

Professor Catherine Drennan (Department of Chemistry)
A study of Ni-Fe-S-dependent CODHs could lead to biomimetic catalysts that can decrease CO levels in heavily polluted areas.

Drennan, C.L., Doukov, T.I., and Ragsdale, S.W. The Metalloclusters of Carbon Monoxide Dehydrogenase/ Acetyl-CoA Synthase: A Story in Pictures. Journal of Biological Inorganic Chemistry. 2004, 9, 511-515.
Drennan, C.L. and Peters, J. W. Surprising Cofactors in Metalloenzymes. Current Opinion in Structural Biology. 2003, 13, 220–226.
Doukov, T.I., Iverson, T.M., Seravalli, J., Ragsdale, S.W., and Drennan, C.L. A Ni-Fe-Cu Center in a Bifunctional Carbon Monoxide Dehydrogenase/Acetyl-CoA Synthase. Science. 2002, 298, 567–572.
Drennan, C.L., Heo, J., Sintchak, M.D., Schreiter, E., Ludden, P.W. Life on Carbon Monoxide: X-ray Structure of Rhodospirillum rubrum Ni-Fe-S Carbon Monoxide Dehydrogenase. Proceedings of the National Academy of Sciences U.S.A. 98, 2001, 11973–11978.

Professor Phil Gschwend (Department of Civil and Environmental Engineering)
The main goal of Professor Gschwend's research is to predict the fates of organic chemicals in natural and engineered environments. This involves evaluating the physical chemical properties of synthetic organic compounds, in order to establish their environmental distribution before large quantities are produced and released. One area of study is the role of "black carbon" as a sorbent of organic compounds such as polycyclic aromatic hydrocarbons (PAHs) and as a factor limiting those compounds' bioavailability.

Kawamoto, Katsuya; Arey, J. Samuel; Gschwend, Philip M. Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements. Journal of the Air & Waste Management Association. 2003, 53(12), 1426-1435.
Accardi-Dey, AmyMarie; Gschwend, Philip M. Explaining sorption with an organic carbon absorbent and a black carbon adsorbent. Abstracts of Papers, 224th ACS National Meeting, Boston, MA, United States, August 18-22, 2002, ENVR-036.
Accardi-Dey, Amy Marie; Gschwend, Philip M. Assessing the Combined Roles of Natural Organic Matter and Black Carbon as Sorbents in Sediments. Environmental Science and Technology. 2002, 36(1), 21-29.
Wick, Lukas Y.; McNeill, Kristopher; Rojo, Michael; Medilanski, Edi; Gschwend, Philip M. Fate of Benzene in a Stratified Lake Receiving Contaminated Groundwater Discharges from a Superfund Site. Environmental Science and Technology. 2000, 34(20), 4354-4362.
Gustafsson, Orjan; Gschwend, Philip M. Aquatic colloids: concepts, definitions, and current challenges. Limnology and Oceanography. 1997, 42(3), 519-528.

Professor T. Alan Hatton (Department of Chemical Engineering)
Looking to "tailor solvents for specific applications while at the same time reducing their propensity to enter the environment with air emissions and aqueous discharge streams"

Professor Klavs Jensen (Department of Chemical Engineering, Department of Materials Science and Engineering)
Professor Jensen's research focuses on microfabricated systems which enable "economical and environmentally benign chemical manufacturing." Advantages of microfabricated systems include new reaction pathways, increased mass and heat transfer, and the integration of chemical reactions with sensors and actuators.

Boccazzi, Paolo; Chen, Angela Y.; Jensen, Klavs F.; Szita, Nicolas; Zanzotto, Andrea; Zhang, Zhiyu. Apparatus and methods for simultaneous operation of miniaturized reactors. U.S. Pat. Appl. Publ. (2005), 95 pp., Cont.-in-part of U.S. Ser. No. 427,373.
Ratner, Daniel M.; Murphy, Edward R.; Jhunjhunwala, Manish; Snyder, Daniel A.; Jensen, Klavs F.; Seeberger, Peter H. Microreactor-based reaction optimization in organic chemistry-glycosylation as a challenge. Chemical Communications (Cambridge, United Kingdom) 2005, (5), 578-580.
Lu, Hang; Gaudet, Suzanne; Schmidt, Martin A.; Jensen, Klavs F. A Microfabricated Device for Subcellular Organelle Sorting. Analytical Chemistry. 2004, 76(19), 5705-5712.
Jensen, Klavs F. Towards integrated microsystems for chemical synthesis. Micro Total Analysis Systems 2002, Proceedings of the µ-TAS 2002 Symposium, 6th, Nara, Japan, Nov. 3-7, 2002, 2 642-645.

Professor Gregory McRae (Department of Chemical Engineering)
Research focuses on "the development of chemistries and molecular systems that avoid the occurrence of environmental problems in the first place." Computational chemistry offers the opportunity to design molecules with the desired physical and chemical properties.

Hoffmann, V., Hungerbühler, K., and McRae, G. Multiobjective Screening and Evaulation of Chemical Process Technologies. Ind. Eng. Chem. Res. 2001, 40(21), 4513 –4524.
Cano-Ruiz, A. and G.J. McRae. Environmentally Conscious Process Design. Annual Reviews of Energy and Environment. 1998, 23, 499-536.

Professor Michael Rubner (Department of Materials Science and Engineering)
Biomimicry is the copying of a natural phenomenon's efficiency into a manufacturing process. One area of research is centered on designing a self-decontaminating surface coating inspired by the structure of lotus leaves. The surface would be biocidal, and capable of self-clean and self-renewal. Potential applications include self-cleaning fabrics and water-repellent windshields.

Professor Donald Sadoway (Department of Materials Science and Engineering)
Molten oxide electrolysis can be used for metal production; the only by-product would be oxygen gas. In contrast, in traditional electrolytic technologies, by-products include carbon dioxide, chlorine, and carbon tetrachloride.

"Towards Carbon-free Metals Production by Molten Oxide Electrolysis." Deepak Khetpal, Andrew Ducret and Donald R. Sadoway. Presented at TMS Annual Meeting, Charlotte, March, 2004.
"Titanium Extraction by Molten Oxide Electrolysis." Naomi A. Fried and Donald R. Sadoway. Presented at TMS Annual Meeting, Charlotte, March, 2004.

Professor Joseph Sadighi (Department of Chemistry)
Development of electrophilic fluorination processes using a metal catalyst, an alternative source of HF (instead of hazardous molecular fluorine), and a benign oxidant such as dioxygen.

Professor Gregory Stephanopoulos (Department of Chemical Engineering)
Production of polyhydroxybutyrate (PHB) from photosynthetic organisms, carbon dioxide, and light. For this case study, the unicellular freshwater cyanobacterium Synechocystis Sp. will be used to synthesize PHB.

Gill RT, Katsoulakis E, Schmitt W, Taroncher-Oldenburg G, Misra J, and Stephanopoulos G. Genome-Wide Dynamic Transcriptional Profiling of the Light-to-Dark Transition in Synechocystis Sp. Strain PCC 6803. J. Bacteriology. July 2002, 184(13), 3671-81.
Taroncher-Oldenburg, G., Nishina, K. and Stephanopoulos, G. Identification and analysis of the polyhydroxyalkanoate specific-ketothiolase and acetoacetyl-CoA reductase genes in the cyanobacterium Synechocystis sp. PCC6803. Applied Env. Microbiology. 2000, 66, 4440-4448.
G. Taroncher-Oldenburg and G. Stephanopoulos. Targeted, PCR-based gene disruption in cyanobacteria: Inactivation of the polyhydroxyalkanoic acid synthase genes in Synechocystis sp. PCC6803. Applied Microbiol. & Biotechnology. 2000, 54, 677-680.

Professor Jeff Tester (Department of Chemical Engineering)
Research is being conducted into chemical processes in supercritical fluids.

Dunetz, J. R.; Ciccolini, R. P.; Froling, M.; Paap, S. M.; Allen, A. J.; Holmes, A. B.; Tester, J. W.; Danheiser, R. L. Pictet-Spengler reactions in multiphasic supercritical carbon dioxide/CO2-expanded liquid media. In situ generation of carbamates as a strategy for reactions of amines in supercritical carbon dioxide. Chemical Communications. 2005, (35), 4465-4467.
DiNaro, J. L., Tester, J. W., Swallow, K. C. and Howard, J. B. Experimental Measurements of Benzene Oxidation in Supercritical Water. AIChE J. 2000, 46 (11), 2274-2284.
Taylor, J. D., Steinfeld, J. I. and Tester, J. W. Experimental Measurement of the Rate of Methyl tert‚Butyl Ether (MTBE) Hydrolysis in Sub‚and Supercritical Water. Ind. Eng. Chem. Research. 2000, 40(1), 67-74.
Renslo, A. R., Weinstein, R. D., Tester, J. W. and Danheiser, R. L. Concerning the Regiochemical Course of the Diels‚Alder Reaction in Supercritical Carbon Dioxide. Journal of Organic Chemistry. 1997, 62, 4530‚4533.
Weinstein, R. D., Renslo, A. R., Danheiser, R. L., Harris, J. G. and Tester, J. W. Kinetic Correlation of Diels‚Alder Reactions in Supercritical Carbon Dioxide. J. of Phys. Chem. 1996, 100(30), 12337-12341.
Meyer, J. C., Marrone, P. A. and Tester, J. W. Acetic Acid Oxidation and Hydrolysis in Supercritical Water. AIChE J. 1995, 41(9), 2108-2121.

Green Chemistry at the University of Oregon

The "Green" undergraduate chemistry curricula include a green organic chemistry lab course. There is also an emphasis on environmental and green chemistry topics in general chemistry courses. Their textbook, Green Organic Chemistry—Strategies, Tools and Laboratory Experiments, is available here.

Center for Green Chemistry at University of Massachusetts Lowell

Research is being conducted on reaction design, to improve the "greenness" of classical reactions. Other projects include bioinspired photopolymers and non-covalent derivatization (using crystal engineering as an environmentally benign method to control the physical properties of materials). Additional resources include a list of green undergraduate experiments and publications.

Green Chemistry at the University of Scranton: Scranton: PA

The university has developed green chemistry modules, which can be used in existing college-level chemistry classes. Examples include modules for general chemistry, polymer chemistry, and biochemistry. A joint project with the GCI is also underway, to assess the environmental and economic benefits of US industries in using green chemistry processes.

Institute for Green Oxidation Chemistry at Carnegie Mellon University

One major area of study is the development of new catalysts for the activation of H2O2. These catalysts are called TAML (TetraAmidoMacrocyclicLigand) activators, which can ameliorate or eradicate the environmental hazards in processes such as dye bleaching and peroxide wood pulp bleaching.

National Environmental Technology Institute (NETI): Green Chemistry at University of Massachusetts, Amherst

Projects funded by NETI include the replacement of oil-based primers (which involve petroleum-based solvents and VOC emissions) with water-based coatings, and the deposition of metals from supercritical CO2 (eliminating toxic agents such as hydrazine). In addition, NETI has established partnerships with industries; the industries provide funding or staff, and NETI provides faculty researchers to work with the industries. A list of current industry partners can be found here. In 2001, NETI co-sponsored a Green Chemistry Research Symposium. The research presentations can be found here.

Green Chemistry at Georgia Institute of Technology

Eckert-Liotta Joint Research Group
Their research is focused on "the interface between chemistry and chemical engineering." Topics and applications include solvent-free processes, energy conservation, bioseparations, reactions in supercritical fluids, and novel materials. In 2004, the group won the Presidential Green Chemistry Challenge Award for its work on using tunable solvents for sustainable technololgy.

Related papers:
- Xie, X.; Brown, J.S.; Bush, D.; Eckert, C.A. Bubble and Dew Point Measurements of the Ternary System Carbon Dioxide + Methanol + Hydrogen at 313.2 K. J. Chem. Eng. Data. 2005, 50, 780-783.
- Xie, X.; Liotta, C.L.; Eckert, C.A. CO2-Protected Amine Formation from Nitrile and Imine Hydrogenation in Gas-Expanded Liquids. Ind. Eng. Chem. Res. 2004, 43, 7907-7911.
- Eckert, C.A.; Liotta, C.L.; Bush, D.; Brown, J.S.; Hallett, J.P. Sustainable Reactions in Tunable Solvents. J. Phys. Chem. B. 2004, 108, 18108-18118.
- Nolen, S.A.; Liotta, C.L.; Eckert, C.A.; Glaeser, R. The Catalytic Opportunities of Near-Critical Water: A Benign Medium for Conventionally Acid and Base Catalyzed Condensations for Organic Synthesis. Green Chem. 2003, 5, 663-669.
- Ablan, C.D.; Hallett, J.P.; West, K.N.; Jones, R.S.; Eckert, C.A.; Liotta, C.L.; Jessop, P.G. Use and Recovery of a Homogeneous Catalyst with Carbon Dioxide as a Solubility Switch. Chemical Communications. 2003, 2972-2973.

Green Chemistry at the University of North Carolina at Chapel Hill

Professor DeSimone (Department of Chemistry, Department of Chemical Engineering)
One area of research is focused on supercritical CO2, which can replace volatile organic solvents in the foaming process of polymer processing.

Related papers:
- Ye, W. and DeSimone, J.M. Emulsion Polymerization of N-Ethylacrylamide in Supercritical Carbon Dioxide. Macromolecules. 2005, 38(6), 2180-2190.
- Hoggan, E.N., Flowers, D., Wang, K., DeSimone, J.M., and Carbonell, R.G. Spin Coating of Photoresists using Liquid Carbon Dioxide. Ind. Eng. Chem. Res. 2005, 43(9), 2113-2122.

Professor Meyer (Department of Chemistry)
His research involves molecular assemblies for studies in artificial photosynthesis, and designing chemical models for enzyme-catalyzed reactions, such as water oxidation and nitrite reduction.

Greening Your Own Laboratory

An Asymptotic Approach to the Development of a Green Organic Chemistry Laboratory

This article by Professor Thomas E. Goodwin of the Department of Chemistry at Hendrix College provides an analysis and overview of greening undergraduate laboratories based on his own laboratory’s transformation.

Goodwin, T.E. An Asymptotic Approach to the Development of a Green Organic Chemistry Laboratory. J. Chem. Edu. 2004, 81, 1187-1190.

Green Chemical Processing in the Teaching Laboratory: a Convenient Liquid CO2 Extraction of Natural Products

This article published in Green Chemistry describes a new way to incorporate green principles into the chemical laboratory through the extraction of natural products using liquid carbon dioxide. The method employed is inexpensive and uses standard laboratory materials.

GREEN CHEMISTRY RESOURCES

Green Chemistry Networks

EPA P3 Award: A Student Design Competition for Sustainability

P3 stands for People, Prosperity, and the Planet. All three are components of sustainability, which is the next step after P2—pollution prevention. The EPA launched the P3 Award in 2003, to promote innovative research and design towards sustainability. Research topics include agriculture, built environment, ecosystems, materials and chemistry, energy, water, and information resources.

Each year, student teams from colleges compete for $10,000 grants. This grant money is used to further their design projects during the school year. Grant recipients are then invited to Washington D.C. in the following spring, to present their projects. The highest-ranked teams receive the P3 Award, which includes additional funding to continue their design projects. Rules and facts about the P3 Award can be found here.

U.S. Environmental Protection Agency Green Chemistry Program

The green chemistry mission is to "promote innovative chemical technologies that reduce or eliminate the use or generation of hazardous substances in the design, manufacture, and use of chemical products." The EPA website gives an introduction to green chemistry, and lists the twelve principles. There are links to green chemistry documents and tools, conferences, international activities, programs and grants. This includes information on the EPA Presidential Green Chemistry Challenge, which promotes innovative methods for cleaner chemistry. The award winners—individuals, groups, and organizations—receive national recognition for their work. In order to be eligible, the nominated teams "must have reached a significant milestone within the past five years in the United States."

The American Chemical Society's Green Chemistry Institute

The site provides links to green chemistry awards, meetings, research, and resources. The GCI is directed by Paul Anastas, who originally developed the 12 principles of green chemistry. One part of the website deals with education, and how to raise green chemistry awareness in schools and research facilities. Resources include guides on how to incorporate green chemistry into the curricula, a set of green chemistry-related labs, and a book of case studies based on the Presidential Green Chemistry Challenge Awards.

Green Chemistry Network: Department of Chemistry, University of York

Launched by the Royal Society of Chemistry, the GCN aims to promote green chemistry awareness, education, training, and practice in industry, commerce, and schools. The site lists links, journals, awards, and events. The Industry section lists green chemistry success stories and workshops aimed at businesses.

Green Chemistry: Books and Journals

Green Chemistry Journal
Publishes "cutting-edge research" on green chemistry and its applications for research and industry. Links are available for related chemistry journals.

EPA's Green Engineering Textbook
This is a college graduate-level textbook, to be used as a stand-alone course or incorporated into existing chemical engineering classes. Sections of the book can be purchased individually, to create a customized version of the text. The introduction, lecture notes, and sample problems from each chapter are available here.

Go Green: Wiley Publishers
A list of books and journal articles related to green chemistry research, education, and product development. Links are available for other topics, such as biosciences, toxicology, environmental monitoring, and pesticides.

Energy Research Council

Energy Club

Campus Sustainability UROPs

Massachusetts Institute of Technology
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