Advanced Environmentally Relevant Functionalized Membranes and - PowerPoint PPT Presentation

Advanced Environmentally Relevant Functionalized Membranes and Hybrid Technologies D. Bhattacharyya (DB), Professor, Chemical and Materials Engineering and Director Center of Membrane Sciences Students and Faculty Collaborators : Students: A. Saad, H. Wan, M. Detisch, S. Islam, R. Mills, F. Leniz, S. Schwab, R. J. Vogler, Faculty : L. Ormsbee (Civil Eng), Zach Hilt and Isabel Escobar (Chemical Eng),Todd Hastings (Electrical and Computer Eng), Yinan Wei (Biological Chemistry), University of Kentucky, Lexington, KY USA *email: db @uky.edu ; phone: 859-312-7790 ZOOM Webinar (for SG Mem) Wednesday, June 24, 8:30 pm (EST USA) 2020

Some Questions and possible answers • Can we use existing membranes to functionalize surface or pore? What benefits? • Membranes could be thin or many microns thick, symmetric to asymmetric pores, to spongy or fingerlike structure; Why waste pore space? • How about Adsorptive/ion exchange and recognition -based membranes with Responsive Properties • What can we learn from life sciences field ? Responsive to Biomimetic to Enzymes • Water virus (rotavirus in water) vs. corona virus (COVID-19 is about 125 nm) • Easy conversion from open structured water filtration membrane to air filtration membrane (what’s needed) Integrating knowledge from membrane, environmental, and biological chemistry field

Membrane Technology (Background) Dense Membranes Nanofiltration Ultrafiltration Microfiltration Reverse Osmosis(RO) (NF) (UF) (MF) Forward Osmosis (FO) Pervaporation(PV) Electrodialysis(ED) CDI, EDI, MD, SLM, etc. Advanced Functionalized Membranes: Responsive and Adsorptive Membranes, Catalytic-Nanoparticles, Bioinspired, GO-GQD How about extension to PPE Materials (such as Mask)?

Automated cross-flow NF and Functionalized MF membranes System (4 cross flow cells, one spiral module) with temperature control, etc.) 4

Fast throughput Membrane Solute PERMEABILITY ANALYSIS 5

Hybrid Water Treatment/Reuse Scenarios for Power Plant FGD Water and Converting Retentate to solids (joint work with Southern Company, Birmingham, AL) TDS Positively Iron (Fe/Fe x O y ) FGD water Retentate Se<10ppb charged NF Functionalized (1) for Selective PVDF Membrane TDS (Ca 2+ , Mg 2+ , Sep Na + , Cl - , SO 4 2- ) (A) (B) and lselenate Permeate with High Pressure RO Recycle to FGD unit low Ca 2+ , Mg 2+ ) (C) Positively-charged FGD water Crystallizer, Retentate NF (2) Spray Drying TDS (Ca 2+ , Mg 2+ , (D) Na + , Cl - , SO 4 2- ) (B) and selenate Need Total Iron (Fe/Fe x O y ) Functionalized Permeate Recycle to Solution PVDF Membrane FGD unit (A)

Functionalization of Porous membranes with Polyelectrolytes/Polypeptides (metal capture to adsorptive to reactive membranes) Helix Note: conformation change (helix-coil) + + ++ + Ultra high capacity metal + + Porin Channels + + capture + + + + + + + + Random Chain + + + + Electrostatically Bound + + + Ion Exchange LBL assembly in pores Me 2+ Me 2+ Me 2+ Me 2+ 2+ Me Me 2+ Chelation Stacked Membranes Nanoparticle Learning from life sciences field

pH responsive flux for Full-scale PVDF400HE- PAA Membranes (Sepro/Solecta, Oceanside, CA) Pure water permeability, Pure water flux, J w (L/m 2 (A) (B) 700 1400 pH 3.0 PAA 3.0 3.0 600 1200 A (L/m 2 h bar) 500 1000 Compact state 400 800 h) 5.5 5.5 300 600 5.5 Na + - OOC 7.3 COO - Na + 200 400 COO - Na + 7.3 Na + - OOC Na + - OOC COO - Na + 100 200 Na + - OOC COO - Na + Δ P=0.48 bar Ionized state 0 0 0 5 10 15 20 25 30 0 1 2 3 4 5 6 7 8 9 10 Time (min) pH M. Gui, L. Ormsbee and D. Bhattacharyya. Special issue honoring Enrico Drioli, I&EC Res. May, 2013 J. Membrane science (2015)

Converting commercial 0.1 micron PVDF MF membrane pores to Nanochannel Membranes: Selective small molecule Separations ≈ 1.2 x 0.7 nm Can we make nanochannel Membranes from commercial PVDF to remove low MW organics but not salts!! Hernandez, Cassandra Porter, Zhang, Wei, Bhattacharyya, RSC Advances ( 2017) Functionalizing Solecta PVDF MF membranes with precise channels to remove low MW valuable organics

High value metal recovery and toxic Metal Sorption by Thiol Functionalized Membrane Pores Membrane Adsorption Bed >> conventional ion exchange ; Joint work with Chevron • No pore diffusion issues • Convective flow • High dynamic capacity • > 90% sorption site utilization 30

Hybrid Treatment of Industrial Process Water containing toxic Metal Sulfide Nanoparticles and dissolved Hg by MF-UF-Thiol Functionalized Membrane Extremely high efficiency With thiol funcionalized PVDF membranes We have also demonstrated Very high efficiency Silver Recovery from water 36

Converting lower value MF membranes to high value temperature responsive separations PNIPAm (Poly(N-isopropylacrylamide) Functionalized Responsive Membranes and hydrogels for temperature swing perfluoro- organics Sorption/desorption (Emerging Pollutants in water) PFOA: Why not carbon Adsorption? High T regeneration and Corrosive gas potential Saad, A., Mills, R., Wan, H., Mottaleb, MA., Ormsbee, L., & Bhattacharyya, D. J. Membrane Science (January 2020) US Patent Pending, 2020, Bhattacharyya, Saad, et al

Temperature Responsive Polymer Sorption/desorption applications T < LCST T > LCST PNIPAm • LCST behavior • Controllable LCST value • Controlled flux • Gating character • Conformational changes Hydrophilic functional group of PNIPAm Hydrophobic functional group of PNIPAm Hydrophobic contaminant (PFOA, PFOS) Water

pNIPAM Hydrogel-Based PFOA Adsorption/Desorption 60 Desorption Adsorption PSO Desorption Model PSO Adsorption Model 50 PFOA Adsorbed (mg/g) 40 50 PFOA Adsorbed Adsorption Desorption 30 (mg/g) 20 0 0 20 40 60 80 100 Time (minutes) 10 0 Time (hrs) 0 5 10 15 20 25 30 Adsorption and desorption kinetics of PFOA onto PNIPAm hydrogels (15wt% NIPAm, 3 mol% BIS crosslinker, 2 mol% APS) in water.

PFOA sorption-desorption from water over multiple cycles: Temp Responsive PVDF membranes Pressure= 3.5 bar Sorption Desorption Above below LCST LCST Membrane Water Permeability

One can use MF membrane pores to synthesize highly controlled size Nanoparticles or directly use it for catalysis 1 1 Direct Synthesis of catalytic nanoparticles in [Biphenyl]/[Biphenyl] max 0.9 0.9 0.8 0.8 membranes (Take advantage of MF pores) [PCB]/[PCB] 0 0.7 0.7 0.6 0.6 0.5 0.5 Reduction (NaBH 4 0.4 0.4 or polyphenols) 0.3 0.3 Fe 2 Na + COO - 2-Chlorobiphenyl + 0.2 0.2 -COONa Fe 2+ PA PA Biphenyl 0.1 0.1 -COOH COO - Carbon balance A A 0 0 0 10 20 30 40 50 60 Polyacrylic acid (PAA) Residence Time (s) Fe/Pd Fe 0 Functionalized Membrane H 2 O 2 /Persulfate Fe 2+ Fe 0 Fe x O y Mass (Fe)=6.1 mg Oxidation (size: 80 nm, ρ m =58.5 potentials: Model compounds OH•: 2.7 V g/L), Pressure varied Iron Oxide (Fe x O y ) SO 4- •: 2.6 V PCB TCE between 5 and 11 bar. s Reductive pathway Oxidative pathway Membrane external Fe 2+ area: 13.2 cm 2 . Pd e - H 2 O loading: 0.9 wt% 0f Fe, H 2 O 2 [PCB] 0 = 31 µM, Fe 2 O 3 Fe 3 O 4 pH=7.5-8.0 Fe 0 H 2 OH• RCl Pd 0 L-Fe 2+ /Fe 3+ H* RH + Cl - 16 Gui, Bhattacharyya, et al, JMS (2015); Hernandez, Orsmbee, Wang, Bhattacharyya, ACS journal on Sustainable Chemistry and Engineering (2016); Wan, et al, JMS (2020)

Functionalized Membranes/enzymes/biomolecules to Corona Virus PPE and surface disinfection approaches

Is it possible make dilute hydrogen peroxide directly in a membrane mat Or even in a porous sponge (we just need small amount sugar and an inexpensive Enzyme?) GOX enzyme Fe(II, III) or in LbL assembly Glucose oxidase enzyme Iron Oxide Nanoparticles Stacked-Nanocomposite Hybrid Membranes Lewis, Datta, Gui, Huggins, Daunert, Bachas, Bhattacharyya. PNAS (2011) In situ generation of H 2 O 2 (LbL assembly of Glucose oxidase enzyme) to oxidize pollutants or detoxify a surface by hydroxy radicals

Binding between CoV spike protein to human cellular receptor ACE2. (Ref: Vaduganathan, M., et al, Renin–Angiotensin– Aldosterone System Inhibitors in Patients with Covid-19. New England Journal of Medicine, 2020.

Our Lab data: 0.1 micron pore PVDF 400 membrane Air Flow=37,000 LMH/bar Functionalized Membrane Mask Approach Water Flow = 417 LMH/bar Membrane functionalized outer layer inner layer enzyme/antibody For a mask: 100 liter/hr air flow even at 0.1 bar Air virus in droplets 0.5-2 µm Air enzyme Ex enzyme Subtilisin is a virus in aerosols deactivated virus 120-130 nm protease (a protein-digesting enzyme) Other approaches include very thin surface coating of 2D thin layer of GO Or lignin-sulfonate based materials on existing mask

Acknowledgement  NIH-NIEHS –SRC program  NSF- EPSCoR program; NSF-EAGER  NSF RAPID (Corona Virus Mask and Enclosed space air filtration)  Southern Co.  Chevron Corp  Dr. Scott Lewis, Dr. S. Hernandez, Dr. V. Smuleac, Doug Davenport, Dr. Xiao, Dr. Gui, Dr. Colburn, Dr. Sikdar (US EPA), Ben Weaver, Solecta Membranes, Dr. Evan Hatakyama, Chevron co. NIH-NIEHS-SRC