Michigan State University

Go Green! The History of and the Recent Discoveries in Green Chemistry

Honors Option Paper Emily R. Bow CEM 351 001 Dr. Xuefei Huang November 30, 2012

Bow 2 Organic Chemistry: An Introduction Organic chemistry is defined as the study of carbon-based compounds, allowing it to be very relevant to our everyday lives (Stedmans Medical Dictionary). Carbon, although not an abundant element present in the universe, is essential for life. It is carbons unique properties that allow for incredible diversity among compounds related to life (Reusch). In fact, carbon is found in many molecules of which the human body is composed of: carbohydrates, proteins, nucleic acids (DNA), lipids, etc. The simple definition given to organic chemistry does not convey the complex divisions of it. There are many different branches of organic chemistry, including the following: synthesis, biocatalysis, bioorganic, nanoscience, immunology, and green chemistry (Chemistry.msu.edu). One branch of organic chemistry in particular, green chemistry, has proven to be of vital importance to our society in recent decades. The purpose of this essay is to discuss and explore the following questions: 1.) What is green chemistry, and why is it important to our everyday lives? 2.) What are some recent advances made within this branch of chemistry? What is up with the Environment? The chemical industry proves to be a very important and dominant industry in todays society, contributing to advances in pharmaceuticals, the food industry, etc. The demand for useful chemical products continues to increase, but at the same time, many concerns also arise: the depletion of nonrenewable resources, toxic discharge into the environment, short-term and long-term effects on human health, and the overall safety/condition of the environment and the humans exposed to it (Doble and Kruthiventi).

Bow 3 According to the Environmental Protection Agency, 7.1 billion pounds of toxic chemicals were released into the environment by the United States in 2000 (Doble and Kruthiventi). In 2006, a decrease in the amount of toxic chemicals over the next years began. However, in 2010, 3.93 billion pounds were released, 16% higher than the year before (Koch). In the past, the negative effects from the use of chemicals were not as concerning as they are today. As scientists learn more about the detrimental effects of these chemicals, the need to reduce these risks becomes vital. One branch of research, green chemistry, allows scientists to maximize the use of renewable resources, decrease the amount of harmful toxins being released into the environment, and overall improve the health and safety of humans. In the book Green Chemistry and Engineering, green chemistry is defined as the following:

a reduction in, or elimination of, the use of hazardous substances in a chemical process or the generation of hazardous or toxic intermediates or products. This includes feedstock, reagents, solvents, products, and byproducts. It also includes the use of sustainable raw material and energy sources for this manufacturing process. (Doble and Kruthiventi) A newer concept developed in the 1990s, green and sustainable chemistry, deals with, ...the development of processes and technologies that result in more efficient chemical reactions that generate little waste and fewer environmental emissions than traditional chemical reactions do (Doble and Kruthiventi). Instead of dealing with chemicals and their effects after they are already released into the environment, researchers in the field of green chemistry strive to eliminate risk at the source. Scientists and researches strive to execute an ideal process, which

Bow 4 ultimately leads to an ideal product (Doble and Kruthiventi). After an ideal process and ideal product is presented, an ideal user is also needed (see Figure 1 for reference). In the early 1990s, The Green Chemistry Movement was started by the US Environmental Protection Agency (Clark and Macquarrie). With the American Chemical Society, the EPA declared twelve basic principles of green chemistry. These principles are the following: 1. Prevention: Stop the pollutant at the source. 2. Atom economy: Strive for incorporation of all raw materials used to prevent unwanted/wasteful products. 3. Less hazardous chemical use: Substances should possess little or no toxicity to the environment. 4. Design for safer chemicals: Chemical products should be less toxic in short and long terms. 5. Safer solvents and auxiliaries: The use of auxiliary substances such as solvents or separation agents should not be used whenever possible. 6. Design for energy efficiency: If possible, all reactions should be conducted at mild temperature and pressure. Figure 1: Requirements for an ideal process, an ideal product, and an ideal user.

Bow 5 7. Use of renewable feedstock: Raw materials should be renewable whenever practical (stay away from nonrenewable substances as much as possible). 8. Reduction of derivatives: Unnecessary derivatization should be minimized or avoided. 9. Catalysis: The use of heterogeneous catalysts is preferred over the use of homogeneous or liquid catalysts. 10. Design for degradation: Chemical products should break down, not persist in the environment. 11. Real-time analysis for pollution prevention: Analytical methodologies need to be improved. 12. Inherently safer chemistry for accident prevention: Chemical processes that minimize the potential for accidents, explosions, fires, etc. should be chosen. (Clark and Macquarrie) The interest in the field of green chemistry continues to grow today, and the reason behind it is clear. Green chemistry has an immense impact on our daily lives because it ultimately can reduce risks to the environment and human health caused by hazardous substances dealt with in certain chemical processes (Doble and Kruthiventi). Catalysis: A Closer Look Catalysis is often described as the mainstay of green chemistry and it is important to discuss this process more in depth (Doble and Kruthiventi). Many green chemistry researchers and experiments heavily deal with this kind of chemical process. Catalysis can be characterized by the following, as described by Dr. Mukesh Doble and Dr. Amir Kumar Kruthiventi in Green Chemistry and Engineering: 1.) Catalytic reagents reduce the energy of the transition state, thereby reducing the energy input required for a process.

Bow 6 2.) Catalysts are required in small quantities. In the case of biocatalysts, the number of catalysts needed compared to the quantity of reactants is very low. 3.) The regeneration and reversibility of catalysts are good for green processes. Two catalytic chemical processes in particular, Friedel-Crafts processes and aromatic nitration, have undergone extensive research in effort to green them (Clark and Macquarrie). Friedel-Crafts processes were developed in 1877 and can be categorized into two main types: alkylation and acylation. Friedel-Crafts alkylation is the alkylation of an aromatic ring with an alkyl halide by the use of a strong Lewis acid catalyst (see Figure 2 for reference). On the other hand, a Friedel-Crafts acylation is the acylation of an aromatic ring with an acyl chloride by the use of a strong Lewis acid catalyst (Clark and Figure 2: Typical Friedel-Crafts processes. Macquarrie). Aromatic nitration is a very important industrial process because aromatic nitro compounds are used, as intermediates for dyes, plastics and pharmaceuticals (Clark and Macquarrie). An example of this type of reaction is the process for ethylidene norbornene (ENB) from vinylidene norbornene (VNB) (see Figure 3 for reference). ENB is typically used as the diene in the reaction that produces EPDM (a rubber). Also, it is formed by a Diels-Alder reaction -- a reaction in which the HOMO (highest Figure 3: The rearrangement of ethylidene norbornene (ENB) from vinylidene norbornene (VNB).

Bow 7 occupied molecular orbital) of a diene reacts with the LUMO (lowest unoccupied molecular orbital) of a dienophile. In this case, cyclopentadiene reacts with 1, 3 - butadiene to form VNB, which rearranges to ENB by aromatic nitration. A relevant example of catalysis in the pharmaceutical world is the process in which the analgesic Ibuprofen (AdvilTM) is synthesized. Before a new catalytic process was discovered, the synthesis of Ibuprofen involved an atom-efficiency of less than 40%. The new catalytic process involves the use of BHC; it is composed of three steps and possesses an atom-efficiency of 80%. Atom-efficiency, also called atom economy, can be described as, the number of atoms of all the reactants that are converted into atoms of the desired product in a reaction (Doble and Kruthiventi). The higher the atom-efficiency percentage, the more efficient the process. With Ibuprofen being a medication frequently consumed and the atom-efficiency increasing by 40%, this shows how much of an important role green chemistry and catalysis can play in our daily lives. Homogeneous Catalysis vs. Heterogeneous Catalysis Catalysis can be categorized into two categories -- heterogeneous or homogenous. According to the principles of green chemistry, heterogeneous catalysis should be preferred whenever possible. However, what is the difference between these two kinds of catalyses? Homogenous catalysis can be defined as a catalysis reaction in which the catalyst is in the same phase as the reactants. In a typical homogenous catalysis, the catalyst and reactants are either, present as a gas or contained in a single liquid phase (Chemguide). An example of a homogeneous catalysis is the synthesis of (S) - naproxen via the hydrogenation (enantioselective) in the presence of the catalyst ruthenium-BINAP.

Bow 8 In heterogeneous catalysis, the catalyst is present in a different phase than the phase in which the reactants are present. Typically, a solid catalyst is combined with either liquid or solid reactants. The steps in which heterogeneous catalysis occurs are as follows: 1.) The reactants adsorb to the active sites of the catalyst. 2.) The reaction occurs. 3.) The reactants desorb from the active sites of the catalyst. (Chemguide) Catalysts such as nickel and platinum are proven to be efficient catalysts because they allow the reactants to adsorb strongly, but at the same time allow for easy desorption. A very good example of a heterogeneous catalysis with the presence of nickel is the hydrogenation of a double bond, a reaction used on vegetable oils to make foods such as margarine (Chemguide). Heterogeneous catalysts are so useful in green chemistry because, they can be kept stationary while substrates are continuously added and pass through to yield a product that is continuously removed (Organic Chemistry Portal). Heterogeneous catalysts are recyclable and therefore can reduce the amount of waste produced by a chemical reaction. As substrates are Property Catalyst recovery Thermal stability Selectivity Homogeneous Difficult and expensive Poor Excellent/good - single active site Heterogeneous Easy and cheap Good Good/poor multiple active sites continuously added and heterogeneous catalysts are recycled, considerably less waste is produced; this is one of the main goals in the field of green chemistry. The less waste produced, the more efficient the process. Figure 4 depicts the pros and cons of heterogeneous catalysts and

Figure 4: The pros and cons of heterogeneous catalysts and homogeneous catalysts in chemical processes.

Bow 9 homogeneous catalysts (Di Monte, Kaspar, and Farnetti). Heterogeneous catalysts prove to be more preferred compared to homogeneous catalysts because they are easier to recover, cheaper, possess good thermal stability, and have multiple active sites (refer to Figure 4). Heterogeneous or not, catalysis proves to be an important process in green chemistry. It overall helps reduce the amount of side products formed, decreases the amount of energy needed, and ultimately decreases the amount of hazardous waste released into the environment. Discoveries in the field of Green Chemistry: Dr. James Jackson and Dr. Robert Maleczka Now that green chemistry and catalysis have been explored, it is important to discuss recent experiments/research done in the field of green chemistry. Two research professors at Michigan State University, Dr. James Jackson and Dr. Robert Maleczka, have done extensive research revolving around catalysis. Dr. Maleczka and his research group strive to develop reactions that ultimately reduce the need for tin, a nonrenewable resource. They developed a Stille reaction catalytic in tin (Maleczka). Since then, they have been recently studying the kinetics and mechanism of this process. In addition to minimizing the use of nonrenewable resources, Maleczkas group strives to create new synthetic methods, focusing on, the employment of organosilanes as both reagents and substrates in chemical transformations (Maleczka). Dr. Jackson explains that he and his research group, focus on adsorption, surface spectroscopy, and kinetic and quantum chemical modeling studies, complemented by classical mechanistic explorations of substituent effects, isotopic labeling, and variations in catalysts and conditions (Jackson). Two recent articles presented by Dr. Jackson (and other researchers) contribute some very interesting results that may open more doors in the field of green chemistry.

Bow 10 Example 1: Supported mesoporous solid base catalysts for condensation of carboxylic acids Ketonization, the condensation of carboxylic acids to ketones, has proven to be an important process because ketones have the potential to be a high-energy-density and renewable biofuel. Ketonization is a green process because of its, non-polluting by-productsand no solvent or other elaborate reagents are necessary (Jackson). The ketonization of acetic acid to acetone can occur using different catalysts, but CeO2, MnO2, CdO, and La2O3 on SiO2 are the most active oxides for this reaction. Although, incorporation of the transition and nontransition metals into the silica network of mesoporous materials (MCM-41, HMS) has been reported, it is difficult for Ce to be incorporated into the molecular sieves due to size incompatibility (Jackson). This experiment focuses on the preparation of MnOx/CeO2, specifically by the citrate process (due to its efficiency compared to conventional co-precipitation) on two mesoporous silica catalysts -- CM-HMS and CM-MCM-41. The experiment also compares catalytic activities of CM-HMS and Cm-MCM-41 to unsupported MnOx/CeO2 for the ketonization of propionic acid and butyric acid (Jackson). In order to do this, the researchers performed the reactions and then took the following various measurements: FTIR spectra, powder x-ray diffraction, N2 adsorption, TEM images, EDX spectra, UV-vis spectroscopy, and CO2 Figure 5: Preparation of CM-HMS and CMMCM-41 scheme.

desorption. A scheme for the preparation of the two catalysts is shown in Figure 5.

Bow 11 The following conclusions were made from the corresponding measurements:

1.) FTIR spectra: during the preparation of CM-HMS and CM-MCM-41, the metal-citrate complex in HMS and MCM-41 is formed. Complex is then decomposed during calcination step. 2.) Powder x-ray diffraction: deorganization of mesoporous structure occurred upon addition of MnOx/CeO2, evidence that MnOx is fully dispersed as a solid solution in CeO2, and indication that some particles of CeO2 are dispersed on surface of HMS and MCM-41. 3.) N2 adsorption measurements: approximately 85% of the MnOx/ CeO2 is estimated to be deposited along the mesopore walls of HMS, while about 35% is deposited along the mesopore walls of MCM-41. 4.) TEM images: the CM-HMS and CM-MCM-41 catalysts retain the mesoporous framework of HMS and MCM-41. 5.) EDX spectra: Indication that most of the Ce and Mn are uniformly distributed into or onto the support materials. 6.) UV-vis: A more uniform dispersion of MnOx and CeO2 apparently forms on HMS and MCM-41 than in the bulk catalyst. 7.) CO2 desorption: CM-HMS and CM-MCM-41 possess only weak basic sites. (Jackson) From these results, it is confirmed that CM-HMS and CM-MCM-41 are very promising solid base catalysts in order to, upgrade carboxylic acids to higher value intermediates or biofuel components (Jackson). Example 2: Aqueous electrocatalytic hydrogenation of furfural using a sacrificial anode Furfural is an organic compound that can be used as an important building block for fuels and chemicals (or by itself). Furfural can be formed into furfuryl alcohol and 2-methylfuran by

Bow 12 electrocatalytic hydrogenation; this product is very useful in perfumery, pharmaceutical and polymer industries. The reaction scheme is shown in Figure 6. The focus on this experiment was to study the electrocatalytic hydrogenation of furfural to furfuryl alcohol and 2methylfuran. In order to do this, researchers ran an undivided cell in aqueous solution, with a sacrificial Ni or Ni-Fe alloy anode (Jackson). The following cathode materials were used: Al, Fe, Ni, Cu, and stainless steel (SS). The effect of pH on the reaction was studied along with the differentiation between the catalytic Figure 7: On the left, the undivided electrochemical cell. On the right, the divided Hcell. roles of the original cathode versus Ni deposited on cathode by reduction of anodederived Ni ions (scheme shown in Figure 7). The following results were concluded from the experiment: 1.) Nickel deposited on the cathode surface could flake off to become part of the precipitated particles and organic species were absorbed onto precipitate (Jackson). Data shown below. Figure 6: Electrocatalytic hydrogenation of furfural to furfuryl alcohol and 2methylfuran.

2.) The overall electrochemical efficiency based on the two products was highest at a pH of 5.0 (Jackson). Data shown below.

Bow 13 Ultimately, the researchers succeeded with electrocatalyic hydrogenation of furfural using an undivided electrolytic cell. Furfuryl alcohol was the major product, and 2-methylfuran was the minor. It was determined that nickel and iron gave best results for the reaction, and a pH of 5.0 produced maximum yield. The researchers concluded the following: Based on this investigation, electrocatalytic hydrogenation of furfural using a sacrificial anode could be a very promising process for furfuryl alcohol production (Jackson). Green Chemistry: A Truly Great Thing The papers/experiments just briefly discussed are only two contributions of the thousands of important contributions to the ever-growing field of green chemistry. Green chemists are continuing to question more, test more, and learn more about alternate ways to produce efficient and important products with less or no hazardous waste as the by-products. There are a lot more opportunities to make the environment safer, and many researchers are seizing that opportunity. Green chemistry is vitally important to our everyday lives because it ultimately allows for the following: 1.) A reduction/elimination in the use of hazardous substances in chemical processes. 2.) A reduction/elimination in the generation of hazardous or toxic products into the environment. 3.) An increase in the use of more efficient, renewable resources. 4.) An opportunity for a safer environment in which we live. The need for less hazardous waste, more renewable resources, and a safer environment is only growing; and green chemistry and its positive effects seem to also be sticking around for a while.

Bow 14 Works Cited Anastas, Paul, et al. Handbook of Green Chemistry - Green Catalysis. New Jersey: John Wiley & Sons: 2009. Wiley Online Library. Web. 26. Nov. 2012. Chemistry Department. Michigan State University, n.d. Web. 17 Nov. 2012. Clark, James and Duncan Macquarrie. Handbook of Green Chemistry and Technology. Oxford: Wiley-Blackwell: 2002. Wiley Online Library. Web. 21. Nov. 2012. Di Monte, Roberta, et al. Homogeneous and Heterogeneous Catalysis. Encyclopedia of Life Support Systems, n.d. Web. 26 Nov. 2012. Doble, Mukesh, and Anil Kumar Kruthiventi. Green Chemistry and Engineering. Burlington: Academic Press: 2007. Ebrary Reader. Web. 21 Nov. 2012. Faculty Research Interests. Chemistry.msu.edu. Michigan State University, n.d. Web. 17 Nov. 2012. Green Chemistry. Organic-chemistry.org. Organic Chemistry Portal, n.d. Web. 26 Nov. 2012. Jackson, James, et al. Aqueous electrocatalytic hydrogenation of furfural using a sacrificial anode. Electrochimica Acta 64 (2012): 87-93. Web. 17 Nov. 2012. Jackson, James, Miller, Dennis J., and Ambareesh D. Murkute. Supported mesoporous solid base catalysts for condensation of carboxylic acids. Journal of Catalysis 278 (2011): 189-199. Web. 17 Nov. 2012. James Jackson. Chemistry.msu.edu. Michigan State University, n.d. Web. 17 Nov. 2012. Koch, Wendy. EPA: Toxic chemical releases rise 16% in 2010. USA Today. USA Today, 6 Jan. 2012. Web. 17 Nov. 2012. "Organic Chemistry." The American Heritage Stedmans Medical Dictionary. Boston: Houghton Mifflin Company, 1995. Dictionary.com. Web. 17 Nov. 2012.

Bow 15 Reusch, William. Welcome to Introduction to Organic Chemistry. Introduction to Organic Chemistry. Kendall Hunt Publishing, n.d. Web. 21 Nov. 2012. Robert Maleczka. Chemistry.msu.edu. Michigan State University, n.d. Web. 17 Nov. 2012. Types of Catalysis. Chemguide.co.uk. Chemguide, n.d. Web. 26 Nov. 2012.