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Green Chemistry, Communication &

Research OpportunitiesFran Kerton, fkerton@mun.ca, @ChemMouseChris Kozak, ckozak@mun.ca, @kozycanuck

https://greenchem.wordpress.com/

Thank you to the Government of Canada for funding our visit to UWI (ELAP Faculty Mobility Grant)

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Outline• Monday:

• Background, Introduction to Green Chemistry and Goals of UWI-MUN Boot-camp• 12 Principles of Green Chemistry and the Green Chem Toolkit• How green is green? Metrics in Green Chemistry• 1st steps in evaluating work for ‘greenness’• Opportunities in Green Chemistry & Beyond

• Tuesday:• ‘Green’ solvents: Why? How? And Everywhere!• Critiquing published work for ‘greenness’ (is it green? could a green solvent be

used?)• Work on e-posters in small groups e-posters (chance to ask for help, share/get

ideas etc.)

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Outline• Wednesday:

• Overview of Catalysis: Homogeneous, Heterogeneous, Biocatalysis…• Critiquing published work for ‘greenness’• Work on e-posters in small groups

• Friday:• Green Materials and Design for Degradation• Final work on e-posters• Share posters with each other for last-minute edits• Share your green chemistry story with the world. #GreenChemUWI

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Background and history– Green chemistry & me

• Anastas & Warner (1998)• “The design of products and processes that minimize the use and

generation of hazardous substances”• My inspiration: Prof. Martyn Poliakoff (Nottingham, UK) & our planet• My mentor: Prof. James Clark (York, UK) – Inaugural editor of the

journal Green Chemistry• Initial experiences in using supercritical carbon dioxide• Published two editions of the text: Alternative Solvents for Green

Chemistry with RSC Publishing• Tried to find a relatively underexplored ‘niche’ – ocean-sourced

biomass4

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Introduction to Green Chemistry• DISCUSSION• What is Green Chemistry?• Why does it exist?• What is your motivation?

• Note: images from pixabay.com

• Chinese Proverb:Tell me and I'll forget; show me and I may remember; involve me and I'll understand

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12 Principles of Green Chemistry• Participation expected!

1. PreventionIt is better to prevent waste than to treat or clean up waste after it has been created.

2. Atom EconomySynthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.

3. Less Hazardous Chemical SynthesesWherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment.

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• Reminder…Participation expected!

4. Designing Safer ChemicalsChemical products should be designed to effect their desired function while minimizing their toxicity.

5. Safer Solvents and AuxiliariesThe use of auxiliary substances (e.g., solvents, separation agents, etc.) should be made unnecessary wherever possible and innocuous when used.

6. Design for Energy EfficiencyEnergy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized. If possible, synthetic methods should be conducted at ambient temperature and pressure.

7. Use of Renewable FeedstocksA raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable.

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8. Reduce DerivativesUnnecessary derivatization (use of blocking groups, protection/ deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste.

9. CatalysisCatalytic reagents (as selective as possible) are superior to stoichiometric reagents.

10. Design for DegradationChemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment.

11. Real-time analysis for Pollution PreventionAnalytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.

12. Inherently Safer Chemistry for Accident PreventionSubstances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires.

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Objective for the week:*Prepare an e-poster on an aspect of green chemistry*• Make a mini-review on a particular principle or aspect/use of green

chemistry• Can you apply any of the principles in your research? Do you already

use them?• RSC twitter poster website has good tips, also search on twitter for

#RSCposter,the winners are also linked on this page https://blogs.rsc.org/rscpublishing/2018/12/10/rsc-twitter-poster-conference-2019/

• We are available to help/provide advice most afternoons in Dr. Jalsa’soffice (Building C1, room 305)

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Exam

ple

post

ers

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Some green chemistry resources• US EPA: https://www.epa.gov/greenchemistry/green-chemistry-

resources

• American Chemical Society: https://www.acs.org/content/acs/en/greenchemistry.html

• Beyond Benign: https://www.beyondbenign.org/about-green-chemistry/

• FREE IMAGES: https://pixabay.com/11

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Some questions to think about?• …possible starting point for a poster:• Do we need to use organic solvents at all? Is LC essential in analysis? Can a

catalyst be used in place of a reagent?• Is there a viable alternative to using protecting groups? Can we use a less

hazardous raw material?• Is the proposed reactor the most efficient, from an energy efficiency and waste

minimisation point of view?• Is there a viable alternative to using an elimination reaction?• What is the reason for lack of selectivity for a given reaction? Can it be

overcome?• Are processing aids, such as filter aids necessary?• Can any waste or by-products be recovered for use in another process or

product?12

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Alternative Solvents

Renewable Feedstocks

CatalysisAlternative Energy

New Reactions

Innovative engineering

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How green is green? Metrics in green chem• Atom economy/efficiency

• AE = Sum of MW Desired Product(s)/ Sum of MW Reactants x 100%• Some reactions are inherently 100% AE (addition vs. elimination/substitution)

Examples?• i.e. Atom economy assumes that all other material used in the reaction (e.g.

solvents) is recycled with 100% efficiency?!

• E-factor• E-Factor = Kg waste/Kg Product• E-factor is not perfect – does not take into account energy use or hazards of

reagents/products etc. (Life Cycle Assessment is more thorough)• Many people ignore water when calculating E-factors. I include it. Why?

• LCA (Life cycle assessment/analysis)• Case study from our research on next slide

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Life cycle assessment• Comparing three routes to epoxidized fish oil (route 1: m-CPBA;

route 2: H2O2/H2SO4; route 3: formic acid) based on nine indices

• Acidification potential (AP), ozone depletion potential (OD), smog formation potential (SF), global warming potential (GW), human toxicity by inhalation (INHT) and ingestion (INGT) potentials, persistence (PER), bioaccumulation (BIOACC), and abiotic resource depletion potential (ADP) 15

Route IAP IOD ISF IGW IINHT IINGT PER BIOACC (log Kow) IAD

1 0 0.5 0.3 800 24 900,000 weeks 2.2 0.4

2 20 0.1 0.1 192 2,500 9,200 weeks 4.7 0.003

3 0 0 0.2 54 4,120 12,000 weeks 0.35 0.003

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Example AE calculation

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• Calculate the atom efficiency/economy for the reaction below:

OH

Bu

C5H10OMWt: 86.13

+

C8H8MWt: 104.15

catalystO

H Bu

C13H18OMolecular Weight: 190.29

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Example E-factor calculation

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• Calculate the E-factor (to 2 sig fig)

• Densities: 0.786 g/mL, 0.672 g/mL (hex), 0.90 g/mL• Identify 2 factors that could reduce this value

N

OH

MWt: 249.31 g/mol

N

O

H

MWt: 247.30 g/mol

+ 8 equiv. MnO2

MWt: 86.94 g/molAcetonitrile, 200 mL

5.00 g, 20.1 mmol 4.20 g

+ waste

Solvents used in purification:300 mL Hexane60 mL Ethyl Acetate

Celite, 20 gSilica, 40 g

Auxiliaries

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Don’t believe everything you read. Why you should be critical

• With increasing pressures on everyone around the world to publish more, you need to keep some skepticism in mind when reading the scientific literature.

• As a scientist, you need to be ethical and NOT ‘make up data’. Unfortunately, there are some bad scientists out there.

• https://retractionwatch.com/• New data can only be published once and it has to be your data• Always do a citation search to make sure the paper hasn’t been

‘corrected’ or ‘retracted’. Corrections are surprisingly frequent even for high impact papers in excellent journals.

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In terms of green chemistry: How to be critical

• Although Green Chemistry and ACS Sustainable Chemistry & Engineering require authors to consider metrics and justify solvent use – this doesn’t always happen!

• If a chemist is using highly flammable solvents and toxic/carcinogenic reagents – it is unlikely that the reaction could be performed on a large scale because of the risk of pollution and the risk to personnel/workers

• You should try to think about the method and reagents being used, and answer the questions listed below:

• Is the reaction atom efficient?• Are the reagents hazardous?• Are they renewable etc?• Are any of the principles of green chemistry already being employed?

• We will critique some papers in the next classes.

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Opportunities in Green Chemistry & Elsewhere

• Government of Canada (ELAP, CARICOM)• ACS Summer School on Green Chemistry & Sustainable Energy (funding

is provided for students/postdocs to attend from across the Americas)• Gordon Research Seminars (ahead of Gordon Research Conferences)

• Again, for students & postdocs: You can contact the chair to see if funding isavailable. They will sometimes waive the registration and provide a contribution towards travel expenses.

• ACS and RSC offer some travel funding opportunities to members e.g. to attend ACS meetings

• RSC has annual twitter poster conference• NESSE, IYCN and IUPAC (More later time permitting)• ACU Blue Charter (next slides)

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• The Commonwealth Blue Charter is an agreement by all 53 Commonwealth countries to actively co-operate to solve ocean-related problems and meet commitments for sustainable ocean development.

• Commonwealth Blue Charter Action Groups are member-driven, led by ‘Champion’ countries, and will guide the development of tools and training on nine topics identified as priorities:

• Commonwealth Clean Ocean Alliance; Coral Reef Protection and Restoration; Mangrove Ecosystems and Livelihoods; Marine Protected Areas

• Ocean Acidification; Ocean and Climate Change; Ocean Observation

• Sustainable Aquaculture; Sustainable Blue Economy

Commonwealth Blue Charter

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ACU Blue Charter Programme• Blue Charter Fellowships (2018 – Present)• Our Blue Charter Fellowships help to fulfil the objectives of the Commonwealth

MPRIF and support world-class research and innovation in marine plastics. Fellows are hosted by ACU member universities across the Commonwealth.

• Capacity Audit (2018-9)• Extensive online survey which aimed to identify loci and extent of existing

capacity, and capacity gaps in Commonwealth universities to conduct and support world-class R&I into marine plastics and their impacts

• Online Knowledge Exchange Training (2019 – 20)• Training on various methods of knowledge exchange, such as event planning

and online communication, with £90k of funding support available.

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Future considerations• Increase involvement from Small Island Developing

States/Countries

• Encourage South-South and North-South Fellowships

• Prioritise applications addressing development of sustainable alternatives to plastics and cleaning up the oceans

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