Adsorbents for Environmental Remediation March 22, 2018 Saskatoon, - PowerPoint PPT Presentation

Modified Biopolymer Adsorbents for Environmental Remediation March 22, 2018 Saskatoon, SK. SustainTech 2018 Lee D. Wilson Department of Chemistry lee.wilson@usask.ca o UNIVERSITY OF SASKATCHEWAN Saskatoon, Saskatchewan, Canada. www.usask.ca

Wilson Research Group

Overview  Background  Overview of “polysaccharide m aterials” & selected studies Part 1. Conventional cross-linked cyclodextrin biopolymers Part 2. Responsive & hierarchical functional materials Future Work & Conclusions 3

At current usage rates, the world will have 40% less fresh water than it needs in 15 years , according to the United Nations World Water Assessment Program in its 2015 report (March 22/15). http://www.unesco.org 4

Actual & Projected (2030) Usage on Global Water Stress Sources: OECD. 2008 Environmental outlook to 2030 . Paris, France: OECD Publishing. Water Resources Group. 2009 Charting our water future: economic frameworks to inform decision-making. See http://www.2030wrg.org/wp-content/uploads/2014/07/Charting- Our-Water-Future-Final.pdf. FAO. 2015Water uses. See http://www.fao.org/nr/water/aquastat/water_use

http://www.unesco.org 6

Applications of Biopolymer Materials Remediation Issues Agriculture & Bioresources Mining & Minerals Oil/gas & Energy Water/Food/Energy Security

Adsorption Processes  Chemical separation based on surface area & surface chemical interactions  Adsorption methods are low-cost, efficient, and are often limited by the nature of the adsorbent phase K Ads 1-  = unoccupied  = occupied 8

Molecular Sponges: Tunable Materials by Design Bifunctional Linker Polyfunctional Molecular Carbohydrate Crosslinked Sponge Framework Figure 1. Design of a molecular sponge material through crosslinking of a multifunctional carbohydrate (triangle) and a bifunctional (rectangle) linker unit to form a porous network. 9 Mohamed et al., Carbohydrate Research , 2011 , 346, 219-229

Molecular Sponge Materials Adsorption Desorption Wilson et al. Materials (Basel) , 2011 , 4, 1-15. J. Colloid & Interface Sci . 2012 , 387, 250-261 Key Findings: Molecular sponge materials can be prepared with rational design for the controlled removal of 10 environmental contaminants from water

Beyond Molecular Sponge Materials: Biopolymers from Alternative Sources

Highlights and Case Studies in Environmental Remediation Agriculture & Bioresources Energy: Oil-Water Separation Mining & Minerals Biotechnology & Chemical Separations Smart & Dual-Function Materials CASE STUDIES (1-3) 12

Application of Cross-Linked Biopolymers Remediation of Pesticides and Petrochemicals CASE STUDY #1 13

Grand Challenges Canada Adsorptive Removal of Pesticides Mohamed et al . Adsorption , 2016 , DOI 10.1007/s10450-016-9796-7 Mohamed et al. Chemosphere 2015 , 136, 252 – 258

Biofuels Processing Scheme 1: Water-ethanol separation of biofuel mixtures. publication: Dehabadi & Wilson, Energy Fuels 2016 , 30, 5684 − 5692. Energy & Fuels, 2015, 29, 6512-6521. 15 SREDA Finalist for “Best Project” Award in 2017

Tar Sands and Naphthenic Acids (NAs) O ( ) n Z=0 OH R R O O Z=-2 ( ) n ( ) n OH OH R R R O O O Z=-4 ( ) n OH ( ) n OH ( ) OH n R R OH ( ) R n R O O O O Z=-6 ( ) ( ) ( ) OH OH OH n n n Wilson, L. D.; Mohamed, M. H.; Headley, J. V.; Peru, K M. IChemE: Process Safety and Environmental Protection, 2008 , 86, 237-243. Mohamed, M. H.; Wilson, L. D. * ; Headley, J. V.; Peru, K. M. 16 Phys. Chem. Chem. Phys . 2010 , 13, 1112-1122.

Mass Spectrometry Results: Molecular Selectivity Commercial Commercial Industrial Rev. Environ. Health 2014 , 29, 5-8. NAs HDI-1 CDI-1 17

Modified Chitosan via Cross-linking for OSPW S1: 2-hexydecanoic acid RSC Adv ., 2015 , 5, 82065 – 82077 (Chitosan) Carbohydrate Polymers , 2016 , 136, 329-340 (Cellulose) 18

Surface vs. Micropore Sites : molecular sieving effects “Pillared” Biopolymers Molecular imprinting via cross-linking with IF values ca . 43- to 83-fold 19 Mohamed, Udoetok, et al. RSC Adv ., 2015 , 5, 82065 – 82077

Molecular Selective Fractionation of Mixtures S1 S2 S3 RSC Adv ., 2015 , 5, 82065 – 82077 20 Udoetok, et al. Carbohydrate Polymers , 2016 , 136, 329-340

Application of Cross-Linked Biopolymers Remediation of Fertilizer Nutrients & Minerals CASE STUDY #2 21

Adsorbents for the removal of fertilizer run-off? • Algal blooms due to build up of N- and P- 15,000 km 2 in 2007 • 23 DEPARTMENT OF CHEMISTRY

Modified Chitosan for Urea Capture Wilson & Xue, J. Appl. Polym. Sci . 2013, 128, 667-675 . Cu(II) imbibed Chi-Glu copolymers copolymers 24 Low Low + Cu (II) High

Sorption of Urea: Role of Cross-linking & Cu (II) Urea Uptake Chi-Glu Copolymer/Cu(II) Materials Key Results:  Cross-linking and Cu (II) results in  urea sorption Wilson & Xue, J. Appl. Polym. Sci . 2013 , 128, 667-675 . 25

“One - Pot” Urea Uptake Kinetics Xue & Wilson, Carbohydrate Polymers , 2016 , 135(1), 180-186 Chitosan Low CL High CL High CL/ Cu(II) One-pot Method 26

Modified Biopolymer Beads JAPS , 2015 , 132, 42949-42958 Phase inversion method & tandem cross-linking Key Finding: Cross-linking alters the HLB of bead surface 27

Tunable Biopolymer Beads for Phosphate Removal Hydrophilic vs . Lipophile linkers 28 J. Applied Polym. Sci ., 2015 , 132, 42949-42958

Phosphate Removal & Bead Regeneration J. Applied Polym. Sci ., 2015 , 132, 42949-42958 29 DEPARTMENT OF CHEMISTRY

Structure & Function [ Editor’s Choice ] J. Colloid & Interface Sci ., 2017 , 485, 201 – 212 Key Results: EPI differs from GLU beads based on HLB and P i EPI GLU uptake profiles 30

Advanced Water Treatment: Iron Oxide Composites Cellulose supported Goethite Core-Shell & Multi-Core for Arsenic Removal Systems Kong & Wilson, Carbohydrate Polymers , 2017 , in press . Adv Colloid Interface Sci 201 – 202, 2013 , 68 – 93 31 Kong & Wilson, ACS Nano , 2018 , manuscript in preparation

Application of Cross-Linked Biopolymers Smart and Advanced Materials: Responsive & Multi-Functional CASE STUDY #3 32

Chitosan: Design of a Marine “ Responsive Biomaterial ” 2013 U of S “ Innovator ” Series (Feb. 8, 2013) www.usask.ca 33 DEPARTMENT OF CHEMISTRY

Chitosan-PAA Polymers PAA J. Colloid Interface Sci. 2012 , 388 , 225-234. 34

Chitosan “ Smart Materials ” Chitosan-PAA Copolymers Adsorption Sorbent Sorbent Low  High  pH < pK a pH > pK a J. Colloid Interface Sci. 2012 , (PAA) (PAA) 387 , 250-261. J. Colloid Interface Sci. 2012 , 388 , 225-234. Desorption 35 DEPARTMENT OF CHEMISTRY

Grafted & Supported Chitosan Polymer Brushes ACS Applied Mat. Interfaces , 2016 , 8 (8), 5595 – 5607 36

Enhanced Sorption Properties & Responsive Behviour Before After ACS Applied Mat. Interfaces , 2016 , 8 (8), 5595 – 5607 37

Switchable Starch Particles: Carriers with “on - off” Properties Karoyo, Dehabadi, & Wilson ACS Sustainable Chemistry & Engineering , 2018 , in press. 38

Smart Polymer-based Chlorophenol Removal Karoyo, Wilson, & Yang, Environ. Sci. Technol . , 2018 , manuscript in preparation . 39

Can Biopolymer Supports Actas Hierarchical Functional Materials? Can we develop a device address the removal of PFCs and chlorinated organics in aquatic environments without the challenging waste disposal issues? Two-step Process for Chlorophenols Catalytic Adsorption Breakdown Journal of Molecular Catalysis B: CO 2 + H 2 O Enzymatic 2013 , 87, 105-112 + chloride 40

Single- and Dual-Function Materials Karoyo, Wilson, & Yang, ES&T , 2018 , in preparation . 41

Multi-Functional Biopolymers & Processes Coagulation-Flocculation Water Treatment Self-assembly + Adsorption  phase separation Bhalkaran & Wilson, Int. J. Mol. Sci . 2016 , in press 42 Agbovi & Wilson. Carbohydrate Polymers . 2018 , 189, 360−370. .

Conclusions & Future Work  Further research is underway to design advanced materials with increased sorption capacity, molecular recognition/ responsiveness for a variety of technology applications  Collaborative technology development with industry, government, & stakeholders 43

Acknowledgements  University of Saskatchewan  Government of Saskatchewan  Environment & Climate Change Canada and NRCan

Contact Information Lee D. Wilson Department of Chemistry Canada lee.wilson@usask.ca UNIVERSITY OF SASKATCHEWAN Saskatoon, Saskatchewan, Canada. www.usask.ca

Composite Materials Iron Oxide Adsorbents  = +  = - Surface charge of SF at low and high pH Coord. Chem. Rev ., 315, 2016 , 90 – 111