Integration of graphene oxide in mixed-matrix

membranes: balancing membrane

performance with fouling resistance

Adam Inurria1, Pinar Cay Durgun2, Douglas Rice1, Mary Laura Lind2

François Perreault1

1School of Sustainable Engineering and the Built Environment2School for the Engineering of Matter, Transport and Energy

Ira A. Fulton Schools of Engineering

Arizona State University

Geim and Novoselov. Nature Mater. 20007

- Highest electron mobility

- Highest thermal conductivity

- High breaking strength

- High optical transparency

- Highest aspect ratio (2630 m2 g-1)

Andre Geim and

Konstantin Novoselov

2010 Nobel price in physics

Graphene-based materials

Perreault et al. Chem. Soc. Rev. 2015

▪ Contact-mediated antimicrobial activity

▪ Does not deplete over time

▪ Does not release toxic compound

Antimicrobial Properties of Graphene

Phospholipid

extraction

membrane

puncturing

oxidation of

cellular

components

O2

• Reduces permeate flux

• Reduces membrane selectivity

• Reduces membrane lifetime

• Up to 30% increase in operation

costs

Herzberg and Elimelech. 2007. J. Membr. Sci.

1 µm

Biofilm

Membrane

Membrane Biofouling

GO Mixed Matrix MembranesCtrl

Yin et al. Desalination 2016, Mi Science 2014

Embedding graphene oxide sheets into the active layer of RO membranes

can form nanochannels to enhance membrane performances.

Commercial Membranes

Estimate of new MMM

Hypothesis and objectives

Hypothesis: GO is a multifunctional nanomaterial that can

impart antifouling properties and improve the membrane

permselectivity

Objective 1: Characterize the antimicrobial, anti-adhesive, and

transport properties of GO mixed-matrix membranes of different

GO loadings.

Objective 2: Compare MMM with surface-functionalized

membranes.

Chng and Pumera Chem. Eur. J. 2013

Mi. Science 2014

Inurria et al, in preparation

Graphene Oxide

Acid Oxidizing Agent

ReducingAgent

Tung H2SO4 KMnO4 -

Tour 9:1 H2SO4: H3PO4 KMnO4 -

Staudenmaier 9:1 H2SO4: 90% HNO3 KClO3 -

Hofmann 9:1 H2SO4: 63% HNO3 KClO3 -

rGO H2SO4 KMnO4 Hydrazine

TourTung

StaudenmaierHofmann

graphite graphite oxide

ultrasonication

Graphene Oxide synthesis

St

graphene oxide

Salt rejecting range

TMCMPD

Polyamide

95oC

GO Mixed Matrix Membranes

Inurria et al. In preparation

Werber et al. Nature Materials 2015

GO is added to the monomer solution before interfacial

polymerization

Inurria et al. In preparation

GO-MMM permselectivity

0

2

4

6

8

10

TFN-22.5TFN-15 TFN-7.5

Wate

r pe

rmea

nce (

m s

-1 M

Pa

-1)

Salt p

erm

ean

e (

m s

-1)

TFC

*

75

80

85

90

95

100

Salt R

eje

ction

(%

)

Limited improvement in membrane performance, and

decreasing benefit as GO concentration increases

Inurria et al. In preparation

GO-MMM fouling with BSA-FITC

Membrane fouling by proteins is also reduced when more GO is

integrated into the MMM

0

15

30

45

60

75

90

b

c

b

TFN-22.5TFN-15TFN-7.5

Flu

ore

sce

nce

in

ten

sity (

a.u

.)

TFC

a Blank TFC

TFN-7.5 TFN-15 TFN-22.5

0

20

40

60

80

100

TFN-22.5TFN-15TFN-7.5

% o

f via

ble

cells

TFC

50 µm 50 µm 50 µm

TFC TFN-low GO TFC-high GO

Inurria et al. In preparation

GO-MMM biocidal properties

Increasing the concentration of GO in the

MMM increases the antimicrobial

properties of the membrane surface

Two approaches for GO-enabled TFC

Nanomaterials is integrated into the

polymer matrix

- Provide stronger binding

- Can affect transport properties

- Use more NMs

Nanomaterials is grafted on the

surface

- Use small amount of NMs

- Affect only surface properties

- Less stable

Surface functionalization Mixed-Matrix Membranes

0.0

0.5

1.0

1.5

2.0

GO-TFC

Wa

ter

Pe

rme

ab

ility

, A

(L

m-2h

-1 b

ar-

1)

Sa

lt P

erm

ea

bili

ty, B

(L

m-1h

-1)

Ctrl-TFC

A

B

Perreault et al., ES&T Lett. 2014

GO modification does not alter the membrane transport properties.

Membrane Transport Properties

0

20

40

60

80

100

120

GO-TFC

CF

U (

% o

f contr

ol)Ctrl-TFC

Perreault et al., ES&T Lett. 2014

Graphene oxide functionalized

membranes inactivate E. coli cells

attached to the membrane.

65% inactivation

after 1h of contact

*

Antimicrobial Properties

0

20

40

60

80

100

120

GO-TFC

CF

U (

% o

f co

ntr

ol)

Ctrl-TFC0

20

40

60

80

100

TFN-22.5TFN-15TFN-7.5

% o

f via

ble

cells

TFC

GO-MMM permselectivity

• At similar antimicrobial effect, GO-MMM does not provide

any improvement in membrane separation.

• GO-MMM uses more GO!

• GO-MMM cross-link the GO and reduce leaching.

Conclusions

• Antifouling properties increase with GO loading

• GO improves the membrane permeability at low

loadings

• GO may be more performant as an antifouling agent

than a permselectivity enhancer

• MMM and surface functionalization offer similar

nano-enabled performance

• Are they equal in sustainability?

Acknowledgements

Thank you!

Acknowledgements

Perreault et al. ES&T 2016

0

10

20

30

40

50

GO-TFC

Co

nta

ct

An

gle

()

Ctrl

The hydrated layer of more hydrophilic surfaces can

reduce the adhesion of foulants

*

Hydrophilic Surface Properties