What are Organic Chemists doing to save the World?

By Alessia Petti, Ph.D. candidate in electrosynthesis at the University of Greenwich, guest blog writer

According to the most recent UN report, the last decade (2011-2020) was the warmest on record with carbon dioxide emissions reaching 148 percent of preindustrial levels in 2019.[1] The demand for change is urgent and, as recently emphasized at the COP26 in Glasgow, the time to act is shorting. Given the global nature of the problem, we should all ask ourselves what we are doing/can do to save the Earth. With this post, we intend to answer this question from an organic chemist perspective by summarizing the most significant developments in the field that enable waste reduction and guide us towards a sustainable future.

Figure 1: Earth Warming Up. Credits to: https://www.un.org/en/climatechange/what-is-climate-change

3 ways of fighting Global Warming in Organic Chemistry

  1. Beyond Thermochemical Activation: Enlightened Syntheses

Organic reactions often require thermochemical conditions to take place. Nevertheless, these conditions become incredibly energy-consuming when transferred to large-scale industrial processes. Energy waste is often associated with material waste, especially in the case of conventional redox reactions wherein stoichiometric quantities of redox reagents are necessary. Electrochemistry and photochemistry represent two alternative ways of activating organic molecules in an almost reagent-less fashion. Inexpensive electricity or light, derived from renewable energy sources, allows obtaining extremely selective electron transfers[2,3] while unlocking unprecedented reactivities. Within this context, Britton’s group (Simon Fraser University) in collaboration with Merck reported a photocatalytic method for the C-H fluorination of γ-fluoroleucine, a key intermediate in the preparation of the osteoporosis drug Odanacatib (Figure 2).[4]

Figure 2: Photocatalytic C-H fluorination of γ-fluoroleucine derivative.[5]

While previous fluorination protocols involved a multistep synthesis and the use of hazardous reagents such as hydrofluoric acid, this pathway affords the desired product directly from the unprotected amino acid in high selectivity via UV-irradiation of a decatungstate-catalyst. High productivities were also achieved when translating the reaction in flow (90% yield, 45 g after 2 h of residence time). Although using minimum amounts of metal catalysts represents a substantial improvement, redox reactions can be performed without any catalyst at all. This is the case of direct electrochemical reactions such as the anodic synthesis of ureas[6] realised by Lam’s group (University of Greenwich) (Figure 3). In this work, the carbonyl derivatives are accessed at room temperature by in situ generation of isocyanates followed by the one-pot addition of an amine.

Figure 3: Anodic synthesis of ureas.[6]

Electrolysis is achieved in the presence of cheap carbon graphite electrodes and without using any supporting electrolyte. Additionally, when performing the reaction in flow, no purification is required with the urea products formed in only six minutes (0.3 mmol scale).

2. Cleaner solvents by following Nature’s lead

Solvents have a crucial role in most organic transformations. However, most of those currently used in organic chemistry are petroleum-based and pose serious risks due to their flammability, carcinogenicity, and explosivity. Moreover, their persistence in soils and aquatic ecosystems has a major detrimental impact on the environment.[7] On the other hand, using water as the main solvent represents a cheap, safe, and environmentally benign alternative. Additionally, nature has shown us over a billion years that achieving complex transformations in this medium is perfectly doable. Driven by these considerations, Professor Lipshutz (University of California, Santa Barbara) has developed new synthetic methods using water as a large reaction medium in combination with micellar catalysis. One of his latest works involves a Migita cross-coupling formation of thioethers performed in recyclable water in presence of the surfactant (TPGS-750-M) and low levels of Ni catalyst (Figure 4).[8]

Figure 4: Migita-Like C−S Cross-Couplings in Recyclable Water.[8]

Despite these encouraging results, we are still far from reaching nature’s perfection. For instance, the water along with additives recovered at the end of the process must be treated as “wastewater” and therefore recycled. Aspects involving the toxicity and biodegradability of the surfactant must also be considered.

3. Turning waste into gold

Finally, organic chemistry is often associated with polymer synthesis. Out of the 381 million tonnes of plastic waste per year, only 9% of single-use plastics are recycled.[9,10] This 9% is mostly recycled via mechanical methods which would inevitably convert the polymer into lower-quality materials. Furthermore, many polymers cannot be recycled via mechanical processes meaning that these materials are destined for incineration. In an effort to invert this trend, Professor McNeil (University of Michigan) is exploring the possibility of chemical recycling. In her recent publication[11], a new and mild route for recycling the acrylic-based superabsorbent material used in diapers is disclosed. The transformation into commercially relevant pressure-sensitive adhesives (PSAs) relies first on acid-catalyzed hydrolysis followed by an optional chain-shortening via sonication and lastly, esterification driven by hydrophobicity (Figure 5).

Figure 5: Syntheses of pressure-sensitive adhesives from petroleum feedstocks (industrial approach) compared to waste diaper-based feedstock.[11]

Life cycle assessments conducted on the adhesives synthesized via this approach outperformed the petroleum-derived counterparts on nearly every metric including carbon dioxide emissions and cumulative energy demand.

To conclude, each scientist and innovator has the power to influence our planet’s tomorrow. Hence, start experimenting and be the change that you want to see in the world!

References

[1]        “Climate Reports | United Nations,” can be found under https://www.un.org/en/climatechange/reports, n.d.

[2]        G. E. M. Crisenza, P. Melchiorre, Nat. Commun. 2020, 11, 1–4.

[3]        M. Yan, Y. Kawamata, P. S. Baran, Chem. Rev. 2017, DOI 10.1021/acs.chemrev.7b00397.

[4]        S. D. Halperin, D. Kwon, M. Holmes, E. L. Regalado, L. C. Campeau, D. A. Dirocco, R. Britton, Org. Lett. 2015, 17, 5200–5203.

[5]        G. E. M. Crisenza, A. Faraone, E. Gandolfo, D. Mazzarella, P. Melchiorre, Nat. Chem. 2021, 13, 575–580.

[6]        A. Petti, C. Fagnan, C. G. W. van Melis, N. Tanbouza, A. D. Garcia, A. Mastrodonato, M. C. Leech, I. C. A. Goodall, A. P. Dobbs, T. Ollevier, K. Lam, Org. Process Res. Dev. 2021, DOI 10.1021/acs.oprd.1c00112.

[7]        M. Cortes-Clerget, J. Yu, J. R. A. Kincaid, P. Walde, F. Gallou, B. H. Lipshutz, Chem. Sci. 2021, 12, 4237–4266.

[8]        T.-Y. Yu, H. Pang, Y. Cao, F. Gallou, B. H. Lipshutz, Angew. Chemie Int. Ed. 2021, 60, 3708–3713.

[9]        “100+ Plastic in the Ocean Statistics & Facts (2020-2021),” can be found under https://www.condorferries.co.uk/plastic-in-the-ocean-statistics, n.d.

[10]     “The world’s plastic problem in numbers | World Economic Forum,” can be found under https://www.weforum.org/agenda/2018/08/the-world-of-plastics-in-numbers, n.d.

[11]     P. T. Chazovachii, M. J. Somers, M. T. Robo, D. I. Collias, M. I. James, E. N. G. Marsh, P. M. Zimmerman, J. F. Alfaro, A. J. McNeil, Nat. Commun. 2021, 12, 1–6.

The Looming Problem of Lithium-Ion Battery Waste

By Eloi Grignon, Ph.D. student, Member-at-Large for the GCI

Since their commercialization in 1991, lithium-ion batteries (LIBs) have gradually come to pervade our daily lives. Their ubiquity is achieved through our phones and laptops (you are likely reading these words via energy supplied by a LIB), where they are used to power not only our communication with one another, but also the myriad other tasks that we have come to delegate to our devices. Increasingly, LIBs are powering how we move, too, as is evidenced by the several million battery electric vehicles already on the road.1 With the production of electric vehicles set to skyrocket – the British and French governments have already pledged to ban sales of fossil-powered vehicles by 2040 – and the possibility of using LIBs for storage of grid electricity, it is clear that LIBs are not going anywhere, either.2 Indeed, spent batteries are expected to be generated at a rate of 2 million metric tons per year by 2030.3

And yet, there is no clear idea of what is to happen to these batteries once they’ve served their purpose. Currently, fewer than 5% of LIBs in the US and Europe are recycled while the rest end up in landfills.3

Since a LIB is densely comprised of several costly metals (Figure 1), it is fair to liken used batteries to enriched ore.3 It follows, then, that complete disposal of millions of metric tons of such a material represents a tremendous waste.

Figure 1.

Figure 1. Breakdown of LIB constituents. From Ref [3].

Recycling could curb the waste by salvaging this ‘ore’ and supplying it to LIB manufacturers at a cheaper price than that of virgin materials, thereby reducing LIB cost. Moreover, less of the material would have to be mined and treated in the first place. This is especially important when considering the impacts of both processes: mining has obvious environmental consequences while ore treatment is typically energy-intensive and can release harmful gases such as SOx.4 Furthermore, 10-25% of global cobalt production is mined by ‘artisanal’ workers in the DRC, many of whom lack proper wages and equipment. The UNICEF estimated in 2012 that 40,000 children were employed in such mines.5 From this perspective, LIB landfilling has a heavy economic, environmental, and moral opportunity cost attached.

In addition to wastefulness, landfilling LIBs also has direct negative consequences. Over time, the toxic constituents of the LIBs tend to flow into the soil, eventually leaching into the groundwater and accumulating in various organisms. These toxins can make their way up to humans, thus extending the health hazard to people. The harm imposed by discarded LIBs on the environment is not without some degree of irony, as LIBs have long been celebrated as a key cog in the establishment of a greener future. Evidently, this detrimental end-of-life scenario presents an incongruity.

Given the benefits of LIB recycling, it is clear that technical and economic barriers, rather than lack of purpose, are responsible for the poor recycling rates.

One such barrier results from the complicated composition within LIBs, which renders separation and recovery of all components difficult. For instance, smelting can effectively recover the heavy metals nickel, cobalt, and copper but fails to salvage lithium and the electrolyte. While hydrometallurgical (chemical leaching) methods can recover more components, they necessitate acids, hydrogen peroxide, and 7 m3 of water per ton of LIB.6 Needless to say, this is not ideal.

Another technical issue is the great variability between LIBs – different manufacturers tend to use different components and so there is no one universal composition (this pertains mainly to vehicles). As such, a recycling firm is at the mercy of its feedstock – for an input collected from many sources, there is no guarantee that 1 ton of batteries will yield a given amount of, say, cobalt.

These issues appear blatant when considering as a counterexample the success story of lead-acid battery recycling, whose simple and standardized composition – about 60% lead – enables an easy recycling process that claims nearly all (99%!) of used batteries.4

The low recycling rates are also due to economic factors. The end-to-end recycling process is energy-intensive and requires many steps, thus increasing costs. A firm operating such a process must carefully assess whether their repurposing protocol is cheap enough to supply materials that are price-competitive with mined materials. Due to the lack of LIB standardization and high volatility of constituent prices, this assessment is far from trivial and the business represents a clear risk. This risk is further exacerbated by the uncertainty of what the future of energy storage may resemble. In the arms race for higher energy density, new technologies arise frequently, thus threatening to render state-of-the-art materials (and so, recycling processes) obsolete.

While the above paragraphs appear rather pessimistic, it should be noted that we are only at the onset of the LIB boom. Indeed, the field of LIB recycling is still gaining traction and it is expected that serious investments will aid in the development of more efficient recycling techniques. To this end, the US DoE (through the $15 million ReCell Center) and the UK-based ReLib project have pledged to fund and support R&D in LIB recycling.3

There is also a clear interest from the private sector as is evidenced by the numerous startup firms currently designing their own protocols, including the Toronto-based company Li-Cycle.7

Another approach to sustainable energy storage is to circumvent the need for recycling breakthroughs altogether by designing the LIB differently from the start. For instance, the use of organic materials that are easily recyclable is increasingly explored for use in devices.1 Not only are these materials favourable in the end-of-life stage, but their production is also cheap, accessible, and environmentally benign.

In any case, scientists, engineers, and policymakers must come together to address the issues caused by LIB landfilling. And quickly, too, because the storm is coming (Figure 2).

Figure 2. A possible scenario for the growth of electric vehicle sales in the next decade. PLDVs = passenger light duty vehicles; LCVs = light commercial vehicles; BEVs = battery electric vehicles; PHEV = plug-in hybrid electric vehicles. From Ref [1].

References

  1. Poizot, P.; Gaubicher, J.;  Renault, S.;  Dubois, L.;  Liang, Y.; Yao, Y. J. C. R., Opportunities and Challenges for Organic Electrodes in Electrochemical Energy Storage. 2020.
  2. Gardiner, J. J. T. G., The rise of electric cars could leave us with a big battery waste problem. 2017, 10.
  3. It’s time to recycle lithium-ion batteries. C&EN Global Enterprise 2019, 97 (28), 29-32.
  4. Gaines, L. J. S. M.; Technologies, The future of automotive lithium-ion battery recycling: Charting a sustainable course. 2014, 1, 2-7.
  5. Frankel, T. C.; Chavez, M. R.; Ribas, J. J. T. W. P., The cobalt pipeline. Tracing the path from deadly hand-dug mines in Congo to consumers’ phones and laptops. 2016, 30.
  6. Larcher, D.; Tarascon, J.-M. J. N. c., Towards greener and more sustainable batteries for electrical energy storage. 2015, 7 (1), 19-29.
  7. https://li-cycle.com/about-us/.
Just Keep Flowing

Just Keep Flowing

By Nour Tanbouza (twitter @Nour_Tanbouza), PhD student, Laval University

Flow chemistry is a synthetic technique that enables chemical reactions to take place in a continuously flowing manner as opposed to running a reaction in a flask, sometimes termed batch chemistry. It has become incredibly mainstream and has been adopted by many chemical industries as a means to increase efficiency of large-scale reactions in highly controlled setups.1 What is flow chemistry, and why is it important? Furthermore, the main question, how does it contribute to sustainability?

Let us start by putting on a lab coat and safety goggles and strolling through a modern synthetic chemistry lab. Now, have a look around. What you will absolutely recognize and remember is a vast space of fume hoods and benches with different apparatus lying around like round bottom flasks, chromatography columns, stirrers, hot plates, etc. After that, take a browse through images of those same types of laboratories from the 1900s or even from the 1700s. Surely you will notice some improved safety features but what will strike you the most is how similar they are in terms of the equipment used then and now. We indeed currently have better stirring and heating equipment etc., but we still do reactions in round bottom flasks as batches.

Figure 1. on the left: 18th century laboratory used by Antoine Lavoisier (credits Sandstein / CC BY (https://creativecommons.org/licenses/by/3.0)); on the right: Modern synthetic chemistry laboratory ( credits Elrond / CC BY-SA (https://creativecommons.org/licenses/by-sa/4.0)

In 2005, the catastrophic T2 laboratories explosion occurred after a thermal runaway and high-pressure build-up of their 2,500-gallon batch reactor producing MMT (methylcyclopentadienyl manganese tricarbonyl).2 These types of accidents pose a huge risk to human life and the environment in addition to the legal and financial troubles that the company could face. Thus, there is an exigent need for safe and practical technologies that enable an efficient scale up of chemical reactions. These pursuits explain the recent uptake of flow chemistry by many manufacturing companies, especially those in the pharmaceutical industry.

Picture3

Figure 2. Aerial view of T2 Laboratories explosion

Flow chemistry can be thought of as a bench chemist’s very own cherry tree. The raw material is fed into the roots (pumps). Roots are the heart of the tree, and the same holds for the pumps of a flow system, so it is pivotal that they are well taken care of and are in perfect shape. Those nice healthy roots then flow the raw material over a large surface area up into the stems and leaves where reaction conditions are highly controlled and in perfect balance to elute the desired product continuously. Thus, whether targeting a few milligrams or multi-kilograms of product, it is dependent on how much feed material is flowed into the reactor. A flow reactor can be as small as a chip and still produce the needed amount of product. In 2019, flow chemistry was announced by the IUPAC (International Union of Pure and Applied Chemistry) as one of the ten chemical innovations that will change our world.3 There has been a significant paradigm shift by many industries, especially the pharmaceutical industry, to adopt flow chemistry. It is a technology that promises on-demand drug production, which is vital primarily for developing countries to access drugs in a decentralized manner.1

Picture4

Figure 3. An academic flow system (equipped with a photoreactor)

Green chemistry principles and a chemical industry’s agenda align when it comes to large scale reactions. Thus, it is not so surprising to see a significant uptake of flow chemistry by many companies. This kind of endorsement has helped spark research in continuous flow which is beginning to become a dominating area of study. Among the UN Sustainability Goals is responsibility for consumption and production, which is achieved in flow because it minimizes the amount of material needed for screening and allows reactions to take place in highly concentrated media. Reaction conditions being highly controlled (such as temperatures, pressure, mixing, etc.), allow reactions to be more selective and thus decreases any by-products and increases productivity.4 Also, hazardous chemicals can be safely manipulated in flow because there is no significant build-up at any given time. It is very versatile and modular where multiple reactions can be installed in sequence to consume any reactive intermediates in situ, and purification systems can be added directly as well. A reaction can be run at extremely high temperatures that go above boiling points which can enable reactions to proceed faster while being inherently safer and consuming significantly less energy when compared to a batch reactor.

Picture5

Figure 4. Illustration of a flow chemistry setup

This type of “thinking outside the flask” means stepping outside of a long-standing comfort zone which is not always trivial. However, this type of venture and side-by-side work of engineers and chemists is what made flow chemistry possible, and it is changing our world. Flow chemistry is still in its early stages, yet so much innovation has already been introduced. Give it a few years, and when you walk back into that synthetic chemistry lab, prepare to be flabbergasted by a space that resembles nothing of the past.

 

References:

  1. Malet-Sanz, L.; Susanne, F., Continuous flow synthesis. A pharma perspective. J. Med. Chem. 2012, 55, 4062-4098.
  2. http://www.csb.gov/UserFiles/file/T2%20Final%20Report.pdf
  3. Gomollón-Bel, F., Ten Chemical Innovations That Will Change Our World. Chemistry International 2019.
  4. Jensen, K. F.; Rogers, L., Continuous manufacturing – the Green Chemistry promise? Green Chemistry 2019, 21, 3481-3498.

The Great Step Backwards: Polymer to Monomer

By Hyungjun Cho, member-at-large for the GCI

There is a movement to develop a new type of product life system called ‘the circular economy’ [3]. Part of this movement aims to manufacture products from recycled or raw materials, and after its useful lifetime, re-introduce the product (now considered waste) as recycled material. The motivation for the introduction of the circular economy is to minimize the need for virgin raw material, especially when it originates from non-renewable resources. This effort is being spearheaded by the Ellen MacArthur Foundation with major industry partners like Google, Unilever, Solvay, and Philips, among others [3]. A critical component to the function of the circular economy is developing the capability to turn waste into a desirable product.

There are several methods of recycling all the different types of materials we use in every day life. This blog will discuss a niche in the ‘plastic to monomer’ field. Evidently, in April of 2019, IUPAC named ‘plastic to monomer’ as part of the 10 chemical innovations that could have high impact in society [6]. Before discussing ‘plastic to monomer’, I must clarify the term ‘plastic’. Generally, plastic is made up of many polymer chains that are physically entangled with one another. A macroscopic analogy is when many electrical wires (think of Christmas tree lights) become entangled: the wires are stuck to each other and the rigidity of the ball of wire is greater than the rigidity of a single wire.

Much like the type of wire influences the tangled ball it forms, the chemical structure of the polymer influences the material properties of the plastic. Examples of properties of plastics include rigidity, elasticity, malleability, gas permeability, friction to skin, transparency, and many others. The polymers that are used for commercial plastic products have been studied and developed for decades to be able perform a specific function. For example, polyvinyl chloride and polystyrene were initially discovered in the 1800s [2,8]. Thus, it would be ideal if the currently used polymers can be de-polymerized back into monomers for recycling purposes. This would be a major move by the plastics industry to become environmentally friendly.

The conventional method to turn polymers into monomer is thermal decomposition. Samples of polymer can be heated to high temperature (typically 220-500 °C) to break some of the bonds that hold the monomers together [10]. When this occurs, radicals can form at the site of the broken bond, which can lead to de-polymerization [10]. The required temperature and how much monomer is formed is dependent on the chemical structure of the monomers that are formed. Thermal decomposition to recover monomer is suitable only for a few types of polymers, such as poly(α-methylstyrene), which has ceiling temperature of 66 °C to propagate depolymerization; the monomer recovery after thermal decomposition of poly(α-methylstyrene) is excellent at 95% [11]. However, for polymers like polyethylene (PE, the most produced polymer) and polypropylene (PP, 2nd most produced polymer), the monomer recovery yield is poor (0.025-2%) [11]. In some cases such as polyvinylchloride (PVC, 3rd most produced polymer), thermal decomposition is even more problematic because PVC will release harmful hydrochloric acid and vinylenes upon heating [11]. Thus, the monomer recovery is poor (1 %) and the process is highly corrosive.

Therefore, one of the key challenges to address for ‘polymer to monomer’ is to perform de-polymerization at a low temperature. There are 4 recent publications that explore this challenge [5,7,9,12]. In general, the authors synthesized polymers using reversible-deactivation radical polymerization (RDRP) techniques and explored the de-polymerization reactions they encountered. Below is a brief highlight from the publications from the Haddleton group [9] and the Gramlich group [5].

Picture1

Scheme 1: De-polymerization of RAFT polymers with trithioester end-group [5]. Reproduced from ref. [5] with permission from The Royal Society of Chemistry.

Flanders et al. polymerized methacrylate monomers, including methylmethacrylate (MMA), using reversible addition-fragmentation chain-transfer (RAFT) polymerization with a trithioester chain-transfer agent (CTA) [5]. This type of polymerization places trithioester end-group at end of the polymer chain (Scheme 1). Typically, this end-group is used to re-start the polymerization at the trithioester end of the polymer. However, as we will see, it may have another function. The authors isolated the polymer, then re-dissolved the polymer in 1,4-dioxane at 70 °C (Scheme 1). This caused monomers to be released from the polymer chains at a temperature much less than the ceiling temperature of MMA, which is 227 °C [13]. Analysis of the polymer after partial de-polymerization demonstrated that the trithioester end-group was still attached to the polymer and the size dispersity (range of polymer ‘molecular weight’) was low, which suggested that the de-polymerization was moderated by the trithioester end-group. The authors observed 10-35% de-polymerization after heating at 70 °C for 12-60 hrs.

Picture2

Scheme 2: ATRP of NIPAM in carbonated water, followed by de-polymerization [9]. Reproduced from ref. [9] with permission from The Royal Society of Chemistry.

Lloyd et al. used an alkylbromide initiator, Cu-based catalyst system to polymerize N-isopropylacrylamide (NIPAM) in Highland Spring carbonated water at 0 °C (Scheme 2) [9]. This type of polymerization places a halide at the end of the polymer chain. The authors monitored the monomer conversion into polymer using 1H-NMR spectroscopy. They measured that ca. 99% of the monomer was converted into polymer chains within 10 min. Unexpectedly, in the next 50 min. the authors observed 50% de-polymerization. The authors attempted to optimize de-polymerization conditions by changing the pH, using dry ice in HPLC grade water instead of Highland Spring carbonated water, etc. which led to 34-71% de-polymerization after 0.5-24 hrs. Years later, the same group used a very similar polymerization condition to polymerize NIPAM [1]. This time, non-carbonated water was used as the solvent and they did not report any de-polymerization.

The reports on RDRP followed by de-polymerization highlighted here are not yet ready to make an impact to ‘plastic to monomer’. The authors admit that the mechanism of de-polymerization is unknown. However, these seem to be the first set of reports on de-polymerization occurring at low temperatures. Perhaps these publications could be the birth of the reversible-deactivation radical de-polymerization (RDRDe-P) field. This is especially intriguing because RDRP have already been studied for decades in academia and are being adopted by the polymer industry [4]. Companies like BASF, Solvay, DuPont, L’Oréal, Unilever, 3 M, Arkema, PPG Industries, etc. already claimed patents for technology and products based on RDRP [4]. Somewhat ironically, RDRP was also part of the IUPAC’s 10 chemical innovations for impact on society but not for its potential to recycle polymer [6].

The polymers of the future may not be made from monomers abundantly used today, but the polymers of the future may be degradable through a low energy process.

References

  1.  Alsubaie, F.; Liarou, E.; Nikolaou, V.; Wilson, P.; Haddleton, D. M. Thermoresponsive Viscosity of Polyacrylamide Block Copolymers Synthesised via Aqueous Cu-RDRP. European Polymer Journal 2019, 114, 326–331.
  2. Baumann, E. Ueber Einige Vinylverbindungen. Justus Liebigs Annalen der Chemie 1872, 163 (3), 308–322.
  3. Circular Economy – UK, USA, Europe, Asia & South America – The Ellen MacArthur Foundation https://www.ellenmacarthurfoundation.org/ (accessed Jan 5, 2020).
  4. Destarac, M. Industrial Development of Reversible-Deactivation Radical Polymerization: Is the Induction Period Over? Chem. 2018, 9 (40), 4947–4967.
  5. Flanders, M. J.; Gramlich, W. M. Reversible-Addition Fragmentation Chain Transfer (RAFT) Mediated Depolymerization of Brush Polymers. Chem. 2018, 9 (17), 2328–2335.
  6. Gomollón-Bel, F. Ten Chemical Innovations That Will Change Our World: IUPAC Identifies Emerging Technologies in Chemistry with Potential to Make Our Planet More Sustainable. Chemistry International 2019, 41 (2), 12–17.
  7. Li, L.; Shu, X.; Zhu, J. Low Temperature Depolymerization from a Copper-Based Aqueous Vinyl Polymerization System. Polymer 2012, 53 (22), 5010–5015.
  8. Liebig, J. Justus Liebig’s Annalen Der Chemie. Annalen der Chemie 1832, 1874-1978.
  9. Lloyd, D. J.; Nikolaou, V.; Collins, J.; Waldron, C.; Anastasaki, A.; Bassett, S. P.; Howdle, S. M.; Blanazs, A.; Wilson, P.; Kempe, K.; et al. Controlled Aqueous Polymerization of Acrylamides and Acrylates and “in Situ” Depolymerization in the Presence of Dissolved CO2. Commun. 2016, 52 (39), 6533–6536.
  10. Microwave-Assisted Polymer Synthesis. Springer eBooks 2016
  11. Moldoveanu, Șerban. Analytical Pyrolysis of Synthetic Organic Polymers; Techniques and instrumentation in analytical chemistry; Elsevier: Amsterdam ; Oxford, 2005.
  12. Sano, Y.; Konishi, T.; Sawamoto, M.; Ouchi, M. Controlled Radical Depolymerization of Chlorine-Capped PMMA via Reversible Activation of the Terminal Group by Ruthenium Catalyst. European Polymer Journal 2019, 120, 109181.
  13. SFPE Handbook of Fire Protection Engineering, 5th ed.; Hurley, M. J., Gottuk, D. T., Jr, J. R. H., Harada, K., Kuligowski, E. D., Puchovsky, M., Torero, J. L., Jr, J. M. W., Wieczorek, C. J., Eds.; Springer-Verlag: New York, 2016.
Boat Antifouling Technology: the problems and the green chemistry solutions!

Boat Antifouling Technology: the problems and the green chemistry solutions!

By Alana Rangaswamy (Vice-President, Dalhousie University Green Chemistry Initiative)

Picture1

The iconic Halifax Ferry is one of many boats to traverse the Harbour every day.

One great part of attending Dalhousie University is living steps away from the ocean. Much of Halifax’s history and development is due to its access to water, both as a naval base and port of call. With the massive amount of boat traffic seen daily by the harbour, marine industries strive to maximize the efficiency of travel. And one major way to do that is preventing small creatures from hitching a ride on your boat, causing drag and lowering the efficiency of your vessel. Enter antifoulants: coatings that kill organisms or otherwise block their ability to stick onto your ship. Antifouling is a necessary technology, but introducing biocidal agents into a marine environment, unsurprisingly, poses many environmental challenges. Let’s take a look at two commonly used antifoulants, their issues, and how scientists have tried to fix them:

Tributyltin 

You may have heard of tributyltin (TBT) as a biocidal agent. TBT is an excellent poison – effectively nonpolar due to its alkyl groups, it’s able to accumulate in organisms, rapidly killing them due to the high toxicity of SnIII. This property makes TBT an extremely effective antifouling agent, however, it easily leaches from boat hull paint into the ocean where it persists due to its high stability. Fortunately, the dangers TBT have been recognized worldwide and use as a biocidal agent has been banned as of 20081. Canada jumped on the bandwagon slightly earlier, with the last TBT-containing paint product registered in 1999.2 With this restriction, the industry is searching for alternatives that are as effective as TBT, without the environmental drawbacks.

Copper

Copper as a bulk metal is naturally antiseptic, promoting the formation of reactive hydroxyl radical species which lead to cell death in living systems.3 Copper has been used on boat hulls since the 1700s, and now usually shows up in paints as its metal oxide4 or as a suspension of copper powder.5 Although copper is less bioavailable than TBT, it persists and continually forms unstable radical species (and can, therefore. wreak ecological havoc) in a marine environment. Since copper is widely considered the new “gold” standard in antifouling, the sheer amount of it present on (and leaching off of) boat hulls today points to a long-term impact.

New Antifouling Tech

Green chemistry and engineering are all about designing cleaner systems that work as well as, or better than, the existing standard. TBT and copper are high bars to clear, but scientists are up to the challenge. As early as 1996, the environmentally benign Sea-Nine antifouling compound had received the Designing Greener Chemistry Award as part of the US EPA’s Presidential Green Chemistry Challenge.6 Sea-Nine is a derivative of isothiazolinone, a 5-membered heterocycle containing nitrogen and sulfur atoms. The compound is acutely toxic to marine organisms at the surface of boats, but biodegrades rapidly in marine environments through a ring-opening mechanism to form non-toxic by-products. Sea-Nine (and its derivatives) is currently present in commercial boat hull paints,7 however, degradation times may vary based on geographical location and local environment8 so our job isn’t done yet.

There are many newer studies in the works. For instance, investigation has been done into using natural products as antifouling agents. Natural products are secondary metabolites produced by microorganisms as a defence mechanism in response to stress. As such, they often have antimicrobial properties, while being naturally biodegradable. For example, 1-hydroxymyristic acid, a simple alpha-hydroxy fatty acid, was isolated from the marine bacterium Shwanella oneidensis. When panels were coated with paint containing the fatty acid, and subsequently immersed in a marine environment, no growth of foulants was observed even after 1.5 years.9 Other studies have added hydrophobic coatings which disrupt the binding interactions between the microorganism and the vessel’s hull, and promote detachment due to the natural flow of the water over the hull.10 Some research has diverted away from chemical modifiers altogether, using microtextures, which remove the flat surfaces required for spores to settle,10 to deter growth. UV-LEDs11 which are mutagenic and cytotoxic at a small scale, have also been used to reduce growth of foulants.

The long history and many methods developed to prevent boat hull fouling demonstrates that this is an important and challenging problem. But many results are promising, and green chemists and engineers are well on their way to solving it.

References:

  1. http://wwf.panda.org/?145704/tributyltin-canned
  2. Health Canada – Consumer Product Safety Registrar

http://pr-rp.hc-sc.gc.ca/ls-re/result-eng.php?p_search_label=antifouling+paint&searchfield1=ACT&operator1=CONTAIN&criteria1=tin&logicfield1=AND&searchfield2=NONE&operator2=CONTAIN&criteria2=&logicfield2=AND&searchfield3=NONE&operator3=CONTAIN&criteria3=&logicfield3=AND&searchfield4=NONE&operator4=CONTAIN&criteria4=&logicfield4=AND&p_operatordate=%3D&p_criteriadate=&p_status_reg=REGISTERED&p_status_hist=HISTORICAL&p_searchexpdate=EXP

  1. Grass, G., Rensing, C., and Solioz, M. Metallic copper as an antimicrobial surface. Environ. Microbiol. 2011, 77, 1541-1547. DOI: 10.1128/AEM.02766-10.
  2. https://www.chemistryworld.com/news/antifouling-coatings-cling-to-copper/3010011.article
  3. http://coppercoat.com/coppercoat-info/antifoul-how-it-works/
  4. https://www.epa.gov/greenchemistry/presidential-green-chemistry-challenge-1996-designing-greener-chemicals-award
  5. https://www.epaint.com/product/sn-1-antifouling-paint/
  6. Chen, L. and Lam, J. C. W. SeaNine 211 as an antifouling biocide: a coastal pollutant of emerging concern. Environ. Sci., 2017, 61, 68-79. DOI: 10.1016/j.jes.2017.03.040.
  7. Qian, P-Y., Xu, Y. and Fusetani, N. Natural products as antifouling compounds: recent progress and future perspectives. Biofouling, 2009, 26, 223-234. DOI: 10.1080/08927010903470815.
  8. Salta, M. et al. Designing biomimetic antifouling surfaces. Trans. R. Soc. A, 2010, 368, 4729-4757. DOI:10.1098/rsta.2010.0195
  9. https://www.pcimag.com/articles/104484-marine-fouling-prevention-solution-to-use-uv-led-technology

 

 

 

The plastic problem – accumulation before alternatives

The plastic problem – accumulation before alternatives

By Karlee Bamford, Treasurer for the GCI

Plastics undoubtedly play a central role in our daily lives and played a pivotal role in the development of consumer societies across the globe for over a century. Concurrent with newfound materials and newfound possibilities, unprecedented environmental problems have emerged as a result of our reliance on plastics. The accumulation of plastics in allocated disposal sites (e.g. landfills) and in otherwise uninhabited spaces (e.g. beaches, open ocean) present threats to human health, water security, and food supply. These challenges now impact communities globally, irrespective of their actual contribution to the generation of plastic waste, and affect individuals of all economic backgrounds.

Figure 1. Examples of waste plastic accumulation in landfills and the environment. Images source: Pixabay.

Given the scale and significance of these challenges, is there anything that chemists can do to resolve this panhuman problem? A recent blog post from the Green Chemistry Initiative (https://greenchemuoft.wordpress.com/category/author/molly-sung/) highlighted the advances that have been made in synthetic and materials chemistry towards plant-derived and biodegradable plastics as alternatives to traditional petroleum-derived plastics. While this is undoubtedly a crucial area of research as humanity has become permanently dependent on plastics, the design of next generation plastics that are inherently sustainable will not mitigate the overwhelming impacts of existing plastic waste. Arguably, attenuating the problem of plastic waste is more important than finding alternatives to traditional plastics. Indeed, the decomposition time for products made from the top four families of commodity plastics (PP, PE, PVC, PET), produced on a 224.6 million tonne-scale alone in 2017,1 is estimated at 1 to 600 years in marine environments2 and considerably longer in landfills due to lack of moisture.4

Figure 2. Examples of the top five most-produced commodity polymers and their production scale in 2017.1,3

Traditional plastic-recycling methods are not equipped to resolve the issue of waste plastic accumulation either. Recycling can be broken down into three distinct varieties: primary, secondary, and tertiary.5 Primary recycling, which is equivalent to repurposing or reusing, is used limitedly for products such as plastic bottles, typically made of PET, which be directly reused following the necessary sterilization. Secondary recycling involves mechanical processing of plastics into new materials and frequently results in reduction of the plastics overall quality or durability due to the thermal or chemical processes involved. Primary and secondary recycling account for the majority of recycling efforts, however, as a consequence of poor consumer compliance (e.g. <10 % in the US and 30-40 % in the EU)6 and the deteriorating value of plastics with repeated secondary recycling, all plastics eventually become waste. The last and most underutilized form of recycling is tertiary recycling, the degradation or depolymerization of plastics into useful chemicals or materials. In the last year alone, numerous high profile editorial and review articles have appeared in Science7,8,9 and Nature6,10 emphasizing the incredible potential of chemical (tertiary) recycling as means of reducing plastic waste and as a new, sustainable chemical feedstock for the polymer (plastics) industry.

The challenge of chemical recycling is immediately evident: plastics have been expertly designed to be highly durable and chemically resistant, and thus, plastics cannot be easily transformed chemically. Ideally, polymers used in plastics could be depolymerized to monomer for subsequent repolymerization. For condensation polymers, such as polyethylene terephthalate (PET), the reverse of the polymerization reaction is the addition of a small molecule to the polymer to reform monomer. While completely reversible on paper or in theory, such depolymerization strategies have had limited success for PET.

Reacting the polymeric PET material with protic reagents (e.g. amines, alcohols) followed by hydrolysis to give monomers that can be repolymerized, if of sufficient purity (Figure 3), requires high temperature (250-300 °C) and high pressure (0.1-4 MPa) conditions unless additives, such as strong acids and bases or metal salts, are used.11 The action of many additives is not well understood, thus precluding rational improvement of the system. Hydrolysis of PET itself, especially at neutral pH, is the most challenging approach to PET chemical recycling as water is a relatively poor nucleophile. Hence stronger nucleophiles, such as ethylene glycol, are preferred.

Figure 3. Depolymerization of PET by glycolysis.

One practical problem in the chemical recycling of any plastic is its insolubility. Phase transfer catalysts –  species capable of transferring from one phase to another – have been used to address the insolubility of PET12 and have permitted the direct hydrolysis of PET at operating temperatures as low as 80 °C, as in the work of Karayannidis and coworkers (Figure 4). The phases in these systems are the insoluble PET polymer (the organic phase) and the basic solution (the aqueous phase) surrounding it.13

Figure 4. Phase transfer catalyzed hydrolysis of PET (catalyst shown in blue).

Addition polymers, such as polypropylene (PP) or polyethylene (PE), cannot be depolymerized to monomer form using the above strategies as their polymerization does not involve the loss of small molecules. Until very recently, the best end-of-life purpose for the majority of plastics has been energy recovery through incineration. The work of Huang and coworkers on the chemical degradation of PE plastics is a break-through for the field of plastic recycling. While previous studies have reported that thermolysis of PE yields poorly defined mixtures of hydrocarbons, these authors have found a remarkable, highly targeted method for converting PE to a narrow distribution of fuels (3 to 30 carbons in length) using a dehydrogenative metathesis strategy (Figure 5).14 The homogeneous iridium catalysts employed were previously reported in the literature for alkane dehydrogenation (step 1) and hydrogenation (step 3), but no such polymer substrates had apparently been attempted for main-chain dehydrogenation. Similarly, the authors used a previously-established rhenium oxide/aluminium oxide catalyst for olefin metathesis (step 2).

Figure 5. The transition-metal catalyzed degradation of PE to liquid fuels reported by Huang and Guan (catalysts shown in blue).14

The chemical recycling of PET by phase transfer catalysis and of PE by dehydrogenative-metathesis have very little in common with one another on a technical level. What unites these two strategies is the desire to transform the problematic, highly abundant and inexpensive resource that is waste plastic into useful commodities. Perhaps more importantly, these two examples both take revolutionary approaches to old problems through inspiration from fundamental research and parallels found in small molecule catalysis. Rethinking the plastic problem into a challenge for catalysis, rather than solely a call for clever materials design, is critical if we wish to reduce the threats that waste plastics pose to our health and our environment.

References:

  1. Tavazzi, L., et al., The Excellence of the Plastics Supply Chain in Relaunching Manufacturing in Italy and Europe, The European House, Ambrosetti, 2013 (as cited in Bühler‐Vidal, J. O. The Business of Polyethylene. In Handbook of Industrial Polyethylene and Technology; Spalding, M. A.; Chatterjee, A. M., Eds.; John Wiley & Sons: Hoboken, NJ, 2017; p. 1305).
  2. Mote Marine Laboratory Biodegradation Timeline; 1993. Available from: https://www.mass.gov/files/documents/2016/08/pq/pocket-guide-2003.pdf ; accessed July 10, 2018.
  3. Image sources: Image sources: (Plastic recycling symbols) http://naturalsociety.com/recycling-symbols-numbers-plastic-bottles-meaning/ ; (PP) https://www.screwfix.com/p/stranded-polypropylene-rope-blue-6mm-x-30m/98570 ; (LLDPE) https://www.polymersolutions.com/blog/differences-between-ldpe-and-hdpe/ ; (HDPE) https://chemglass.com/bottles-high-density-polyethylene-hdpe-wide-mouths ; (PVC) https://omnexus.specialchem.com/selection-guide/polyvinyl-chloride-pvc-plastic ; (PET) https://ecosumo.wordpress.com/2009/06/04/what-does-the-recycle-symbol-mean-part-2/
  4. Andrady, A. L. Journal of Macromolecular Science, Part C: Polymer Reviews, 1994, 34(1), 25-76.
  5. Hopewell, J.; Dvorak, R.; Kosior, E. Trans. R. Soc. B, 2009, 364, 2115–2126.
  6. Rahimi, A.; García, J. M. Nature Reviews Chemistry, 2017, 1, 0046.
  7. MacArthur, E. Science, 2017, 358 (6365), 843.
  8. García, J. M.; Robertson, M. L. Science, 2017, 358(6365), 870-872.
  9. Sardon, H.; Dove, A. P. Science, 2018, 360(6387), 380-381.
  10. The Future of Plastic. Nature Communications, 2018, 9, 2157.
  11. Venkatachalam, S.; Nayak, S. G.; Labde, J. V.; Gharal, P. R.; Rao, K.; Kelkar, A. K. Degradation and Recyclability of Poly (Ethylene Terephthalate). In Polyester; Saleh, H. E. M., Ed.; InTech: London, 2004; p. 78.
  12. Glatzer, H. J.; Doraiswamy, L. K. Eng. Sci. 2000, 55(21), 5149-5160.
  13. Kosmidis, V. A.; Achilias, D. S.; Karayannidis, G. P. Mater. Eng. 2001, 286(10), 640-647.
  14. Jia, X.; Qin, C.; Friedberger, T.; Guan, Z.; Huang, Z. Science Advances 2016, 2(6), e1501591.

Issues of Sustainability in Laboratories Outside the Field of Chemistry: Pipette Tips

Issues of Sustainability in Laboratories Outside the Field of Chemistry: Pipette Tips

By David Djenic, Member-at-Large for the GCI

As a biochemistry student in the Green Chemistry Initiative, I’m interested in looking at how to implement the principles of green chemistry in molecular biology and biochemistry labs. While molecular biology labs focus more on studying biological systems and molecules rather than synthesizing new molecules, like in synthetic chemistry, there are still problems when it comes to performing environmentally sustainable research.

Pipette tips and pipette tip racks are major contributors to non-chemical waste in biomedical labs because of the volume of tips thrown out and the lack of recycling programs to deal with tips and racks. Pipette tip racks are commonly used because they reduce the risk of contaminating pipette tips. Pipette tip racks are made of #5 plastic (polypropylene), the same material as yogurt cups, medicine bottles and David_blog 1microwavable containers, making them lightweight and very safe to use [1].
However, #5 plastics are rarely accepted by curbside recycling programs and are placed in landfills and incinerators instead [2]. The plastic from the empty polypropylene racks take hundreds, if not thousands, of years to degrade [3].

Biomedical companies have worked in the past 10 years to reduce the amount of waste from pipette tip racks. For example, Anachem, a pipette and pipette tip manufacturing company in the UK, has collaborated with a plastic recycling company to collect racks from qualifying laboratories, ground them down, melt them, and remould into new products [3]. A similar program is run at the Environment, Health and Safety (EHS) division of the National Cancer Institute at Frederick (NCI-Frederick), where, from 2003 to 2006, approximately 8,400 pounds of pipette tip boxes were recycled, saving approximately $7,400 in medical waste contract money [4].

David_blog 2

Pipette tip box waste to be recycled through the EHS program [4].

There aren’t many statistics on the waste produced by the pipette tips themselves. But whenever I’m in a biochemistry lab course, the orange bins where used tips are thrown are filled to the brim with pipette tips, microcentrifuge tubes, Falcon tubes, etc. It is more difficult to reduce and recycle tips rather than tip racks because they are heavily contaminated after use. GreenLabs at the University of Chicago offers some interesting suggestions on reducing pipette waste, such as using pipette tip refills, buying pipette tips made from sustainable material, and generally reducing pipette tip use when possible. However, more research on pipette tip waste is needed to quantifiably analyze the impact of tips and come up with solutions to reduce potential waste.

I think undergraduate biomedical teaching and research labs do apply basic green chemistry principles, even if they are not explicitly brought up. Many of the reactions are done in very small, precise quantities and waste is generally disposed of in the proper place. However, there does not seem to be much exposure, if at all when it comes to green chemistry issues; biochemistry and biomedical students aren’t aware of the environmental impact they generate in labs. Introducing green chemistry education in biomedical laboratories at U of T, especially when it comes to the issue of pipette tips and racks, would help U of T reduce its environmental impact even more.

 

References

[1] http://www.davidsuzuki.org/publications/downloads/2010/plasticsbynumber.pdf

[2] http://earth911.com/home/recycling-mysteries-5-plastics/

[3] http://www.labnews.co.uk/features/consumables-dont-cost-the-earth-01-07-2005/

[4] G. A. Ragan, J. Chem. Health Saf. 2007, 14, (6) 17-20.  http://www.sciencedirect.com/science/article/pii/S1871553206001344

Recycling Perovskite Solar Cells

Recycling Perovskite Solar Cells

By Judy Tsao, Member-at-Large for the GCI

Solar energy is arguably the most abundant and environmentally friendly source of energy that we have access to. In fact, crystalline silicon solar cells have been employed in parts of the world at a comparable cost to the price of electricity derived from fossil fuels.1 The large-scale employment of solar cells, however, remains challenging as the efficiency of existing solar cells still needs to be improved significantly.

An important recent breakthrough the field of solar cells is the use of perovskite solar cells (PSC), which includes a perovskite-structured compound as the light-harvesting layer in the device (Figure 1). Perovskite is a name given to describe the specific 3-D arrangement of atoms in such materials. Even though the first PSC was reported only in 2009, its power conversion efficiency (PCE) has already been reported to exceed 20%, a milestone in the development of any new solar cells which typically takes decades of optimization to achieve.2

judy-blog-1

Figure 1. Thin-film perovskite solar cell manufactured by vapour deposition (photo credit: Boshu Zhang, Wong Choon, Lim Glenn & Mingzhen Liu)

PSC has several advantages compared with traditional solar cells, including low weight, flexibility, and low cost.3 There are, however, several challenges that must be overcome before PSC can be brought to the market. The most common PSC to date includes CH3NH3PbI3 and related materials, which contain soluble lead (II) salts that are toxic and strictly regulated.

Interestingly, there has been a consensus in the literature that the lead content in the perovskite layer is not actually the main issue in the environmental impact of PSC production.4 Part of the reason for this conclusion is simply that the thickness of perovskite layer required would amount to less than 1000 mg of lead in one square meter of material. This value is only modest compared to lead pollution from other human sources such as lead paints or lead batteries.5

The main environmental concerns regarding PSCs appear to lie in the use of gold and high temperature processes during the manufacturing of the devices.6 It has thus been suggested that, in order to reduce the environmental impact of PSCs, recycling of raw materials is very important. In a recent study by Kadro et al., 7 a facile protocol for the recycling of perovskite solar cell was developed. The entire procedure takes place at room temperature and takes less than 10 minutes (Figure 2).

judy-blog-2

Figure 2. Schematic process for recycling PSC components [7].

As it turns out, components of a fully assembled PSC can be extracted by sequentially placing the device in different solvents. Step 1 of the procedure uses chlorobenzene to remove the gold layer, while step two uses ethanol to dissolve CH3NH3I. This then leaves PbI2 to be the only component remaining on the device, which can be removed by just a few drops of N,N-dimethylformamide. It is also worth noting that the recycled materials can be fabricated into a complete PSC again without significant drop in performance.

Even though the discovery of PSC has only been made less than a decade ago, its potential in applications in photovoltaics has been underlined by numerous studies. It is especially gratifying to see that the environmental impacts of such devices are already under active research before PSCs are introduced to the market. While these studies have demonstrated that PSCs have low environmental impacts when properly recycled, there are other challenges still facing researchers in this field. In particular, the short lifetime of such devices needs to be improved to match that of traditional silicon-based solar cells. Nevertheless, the facile method of recycling PSCs without compromising the performance will certainly make them even more competitive than traditional solar cells.

References:

  1. Branker, K. et al. Renewable Sustainable Energy Rev. 2011, 15, 4470.
  2. Yang, W. S. et al. Science, 2015, 348, 1234.
  3. Snaith, H. J. Phys. Chem. Lett. 2013, 4, 3623.
  4. Serrano-Lujan, L. et al. Energy Mater. 2015, 5, 150119.
  5. Dabini, D. Phys., 2015, 6, 3546.
  6. Espinosa, N. et al. Adv. Energy Mater. 2015, 5, 1.
  7. Kadro, J. M. et al. Energy, Environ. Sci. 2016, 9, 3172.