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

UNIVERSITY OF SASKATCHEWAN

Saskatoon, Saskatchewan, Canada. www.usask.ca

Modified Biopolymer Adsorbents for Environmental Remediation

March 22, 2018 Saskatoon, SK.

SustainTech 2018

Lee D. Wilson Department of Chemistry lee.wilson@usask.ca

Wilson Research Group

Overview

• Background
• Overview of “polysaccharide

materials” & selected studies

Part 1. Conventional cross-linked cyclodextrin biopolymers Part 2. Responsive & hierarchical functional materials

Future Work & Conclusions

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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).

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http://www.unesco.org

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

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http://www.unesco.org

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

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 = occupied 1- = unoccupied KAds

Molecular Sponges: Tunable Materials by Design

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. Polyfunctional Carbohydrate Bifunctional Linker Molecular Sponge Crosslinked Framework

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Mohamed et al., Carbohydrate Research, 2011, 346, 219-229

Molecular Sponge Materials

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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 environmental contaminants from water Adsorption Desorption

Beyond Molecular Sponge Materials: Biopolymers from Alternative Sources

CASE STUDIES (1-3)

Highlights and Case Studies in Environmental Remediation Agriculture & Bioresources Energy: Oil-Water Separation Mining & Minerals Biotechnology & Chemical Separations Smart & Dual-Function Materials

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CASE STUDY #1

Remediation of Pesticides and Petrochemicals

Application of Cross-Linked Biopolymers

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Grand Challenges Canada

Mohamed et al. Adsorption, 2016, DOI 10.1007/s10450-016-9796-7 Mohamed et al. Chemosphere 2015, 136, 252–258

Adsorptive Removal of Pesticides

Biofuels Processing

SREDA Finalist for “Best Project” Award in 2017

Scheme 1: Water-ethanol separation of biofuel

• mixtures. publication:

Dehabadi & Wilson, Energy Fuels 2016, 30, 5684−5692. Energy & Fuels, 2015, 29, 6512-6521.

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OH ( )n O Z=0 R OH ( )n O Z=-2 R OH ( )n O R OH O ( )n OH O ( )n R R OH O (

n

) Z=-4

R OH O R OH R R OH OH O O O ( ( ( (

n n n n

) ) ) ) Z=-6

Tar Sands and Naphthenic Acids (NAs)

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.

• Phys. Chem. Chem. Phys. 2010, 13, 1112-1122.

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Mass Spectrometry Results: Molecular Selectivity

• Rev. Environ. Health 2014, 29, 5-8.

Commercial Commercial Industrial

HDI-1 NAs CDI-1

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Modified Chitosan via Cross-linking for OSPW

RSC Adv., 2015, 5, 82065–82077 (Chitosan) Carbohydrate Polymers, 2016, 136, 329-340 (Cellulose) S1: 2-hexydecanoic acid

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Surface vs. Micropore Sites: molecular sieving effects

Molecular imprinting via cross-linking with IF values ca. 43- to 83-fold

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Mohamed, Udoetok, et al. RSC Adv., 2015, 5, 82065–82077 “Pillared” Biopolymers

Molecular Selective Fractionation of Mixtures

S1 S2 S3 RSC Adv., 2015, 5, 82065–82077 Udoetok, et al. Carbohydrate Polymers, 2016, 136, 329-340

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CASE STUDY #2

Remediation of Fertilizer Nutrients & Minerals

Application of Cross-Linked Biopolymers

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DEPARTMENT OF CHEMISTRY

Adsorbents for the removal of fertilizer run-off?

• Algal blooms due to

build up of N- and P-

• 15,000 km2 in 2007

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Modified Chitosan for Urea Capture

Wilson & Xue,

• J. Appl. Polym. Sci.

2013, 128, 667-675. Cu(II) imbibed copolymers Chi-Glu copolymers

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Low Low + Cu (II) High

Sorption of Urea: Role of Cross-linking & Cu (II)

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. Urea Uptake

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“One-Pot” Urea Uptake Kinetics

Chitosan Low CL High CL High CL/ Cu(II)

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Xue & Wilson, Carbohydrate Polymers, 2016, 135(1), 180-186 One-pot Method

Modified Biopolymer Beads

JAPS, 2015, 132, 42949-42958

Phase inversion method & tandem cross-linking Key Finding: Cross-linking alters the HLB of bead surface

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Tunable Biopolymer Beads for Phosphate Removal

• J. Applied Polym. Sci., 2015, 132, 42949-42958

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Hydrophilic vs. Lipophile linkers

Phosphate Removal & Bead Regeneration

DEPARTMENT OF CHEMISTRY

• J. Applied Polym. Sci., 2015, 132, 42949-42958

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Structure & Function

• J. Colloid & Interface Sci., 2017, 485, 201–212

Key Results: EPI differs from GLU beads based

• n HLB and Pi

uptake profiles EPI GLU [Editor’s Choice]

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Advanced Water Treatment: Iron Oxide Composites

Kong & Wilson, Carbohydrate Polymers, 2017, in press. Adv Colloid Interface Sci 201–202, 2013, 68–93 Kong & Wilson, ACS Nano, 2018, manuscript in preparation

Core-Shell & Multi-Core Systems Cellulose supported Goethite for Arsenic Removal

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CASE STUDY #3

Smart and Advanced Materials: Responsive & Multi-Functional

Application of Cross-Linked Biopolymers

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Chitosan: Design of a Marine “Responsive Biomaterial”

DEPARTMENT OF CHEMISTRY

2013 U of S “Innovator” Series (Feb. 8, 2013) www.usask.ca

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Chitosan-PAA Polymers

PAA

• J. Colloid Interface Sci. 2012, 388, 225-234.

DEPARTMENT OF CHEMISTRY

pH < pKa (PAA) pH > pKa (PAA) Adsorption Desorption

Chitosan “Smart Materials”

• J. Colloid Interface Sci. 2012,

387, 250-261.

• J. Colloid Interface Sci. 2012,

388, 225-234.

Sorbent Sorbent Low  High  Chitosan-PAA Copolymers

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Grafted & Supported Chitosan Polymer Brushes

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ACS Applied Mat. Interfaces, 2016, 8 (8), 5595–5607

Enhanced Sorption Properties & Responsive Behviour

Before After ACS Applied Mat. Interfaces, 2016, 8 (8), 5595–5607

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Switchable Starch Particles: Carriers with “on-off” Properties

Karoyo, Dehabadi, & Wilson ACS Sustainable Chemistry & Engineering, 2018, in press.

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Smart Polymer-based Chlorophenol Removal

Karoyo, Wilson, & Yang, Environ. Sci. Technol. , 2018, manuscript in preparation.

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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 Adsorption Catalytic Breakdown CO2 + H2O + chloride Journal of Molecular Catalysis B: Enzymatic 2013, 87, 105-112

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Single- and Dual-Function Materials

Karoyo, Wilson, & Yang, ES&T, 2018, in preparation.

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Multi-Functional Biopolymers & Processes

Coagulation-Flocculation Water Treatment Self-assembly + Adsorption  phase separation

Bhalkaran & Wilson, Int. J. Mol. Sci. 2016, in press Agbovi & Wilson. Carbohydrate Polymers. 2018, 189, 360−370. .

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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

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Acknowledgements

University of Saskatchewan Government of Saskatchewan Environment & Climate Change

Canada and NRCan

UNIVERSITY OF SASKATCHEWAN

Saskatoon, Saskatchewan, Canada. www.usask.ca

Lee D. Wilson Department of Chemistry Canada lee.wilson@usask.ca

Contact Information

Surface charge of SF at low and high pH

Iron Oxide Adsorbents

• Coord. Chem. Rev., 315, 2016, 90–111

= + = -

Composite Materials