iron nanoparticle synthesis and immobilization -...

APPLIED CHEMICALS AND MATERIALS DIVISION

Lauren F. Greenlee

Hope A. Weinstein, Michael Voecks, Katie Estoque, Nikki S. Rentz,

Nicholas M. Bedford

Iron Nanoparticle Synthesis and

Immobilization

200 nm

Advances in Materials and Processes for Polymeric

Membrane Mediated Water Purification

Pacific Grove, CA

February 18, 2015


Research Motivation & Direction

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ENGINEERED NANOPARTICLE SYSTEMS

Research Motivation: Water & Energy

http://www.nrel.gov/http://www.chk.com/corporate-responsibility/ehs/environment/water/Pages/information.aspxhttp://voxglobal.com/2011/03/the-energy-water-nexus-an-emerging-risk/

NIST mission:To promote U.S. innovation and industrial competitiveness by advancing measurement science, standards, and technology in ways that enhance economic security and improve our quality of life.

FeNi nanoparticles

NP

http://www.nrel.gov/

http://www.chk.com/corporate-responsibility/ehs/environment/water/Pages/information.aspx

http://voxglobal.com/2011/03/the-energy-water-nexus-an-emerging-risk/


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Current Project Applications

Water Treatment: Heavy metals, textile dyes

Ammonia Synthesis: Fertilizer, fuel

Fuel Electrooxidation: Fuel cells

Need: Reactive/catalytic materials that are more efficient, selective, durable, and low-cost


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Why Nanoparticles?

Core/shell size, composition, atom-

scale/electronic structure

Shell thickness

Particle size

Surface lattice

structure

Core lattice structure

Spatial arrangement of atoms at surface

FeNiO O

Nanoparticle Properties: Enhanced Performance

% Fe, % Ni, % O

Key Features:• Structural disorder• Multi-metal combinations• Oxide/hydroxide phases• Surface functionalization• Nanoscale morphology / structure• Many catalytic surface sites


ENGINEERED NANOPARTICLE SYSTEMSCharacterization-Enabled Nanoparticle Design

Synthesis Performance

Characterization

Need: Nanoparticles designed for specific catalytic/reactive systems.

RepeatabilityControlOptimization

What are we making?

RepeatabilityTesting optimization

Does it work?

Atom-level structureIn situ/in operandoMulti-technique approach

How/why does it work?

Goal: Structure-function relationships to guide design

critical component of cycle

NPs


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Measurement Techniques for Nanoparticle Characterization

Microscopy: TEM, SEM, t-SEM

Powder X-Ray Diffraction

30 40 50 60 70 80 90

Unstabilized

0.0005 CMC

0.05 ATMP

0.5 ATMP

Inte

nsity (

arb

itra

ry u

nits)

2-Theta (deg.)

0.8 ATMP

Dynamic light scattering: Size, Zeta Potential

0

500

1000

1500

2000

2500

3000

3500

4000

-80

-60

-40

-20

0

20

2 4 6 8 10 12

Avera

ge S

ize (

nm

)

Ze

ta P

ote

ntia

l (mV

)pH

Synchrotron X-ray Techniques: In situ/ex situ Measurements for Atom-Level Structure

PdAu 1:3 PdAu 1:1

PdAu 2:1

IR/Raman/UV-vis Spectroscopy

in situ, in operando


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Catalyst Development: Reduction/Replacement of Precious Metals

Optimization of:StructureMetal combinationsMorphology

Chun et al. (2010) ES&T 44, 5079-5085.Alayoglu and Eichhorn (2008) JACS 130, 17479–17486.Zhang et al. (2010) Nano Lett. 10, 638-644.

Fe Fe

2 3 4 5 6 7 8 9 10

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

ATMP

HTPMP

DTPMP

Fe NPs

G(r

)

r (Å)

oxide

metal-metal

oxide

extended lattice structure, peak shifts suggest alloying/oxide

Our focus: Non-precious metal nanoparticles & ligand control of structure/morphology

HE-XRD

Fe-Pd Rh-Pt


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Aqueous Synthesis Method: Scalable & Adaptable

• Molar ratio of stabilizer:Fe• Fe concentration• Fe salt / oxidation state• Type of stabilizer

• Molar ratio of BH4:Fe• Rate of NaBH4 addition• Age of NaBH4

• Molar ratio of stabilizer:Ni• Molar ratio of Ni:Fe• Type of stabilizer• Rate of Ni/stabilizer

addition• Time between BH4 addition

and Ni/stabilizer addition


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Nanoparticle Immobilization

Goals:• Reactivity/performance enhancement• Control of location

100 nm

400 nm

10 mm

Fe NPs in PES pore wall

Carbon

FeNi NPs


Synthesis and Characterization of Iron-

Nanoparticle-Immobilized PES Membranes

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Nanoparticle Immobilization in Filtration Membranes

Surface Deposition

Incorporation into Polymer Matrix

Pore Deposition

Flexibility in material design: Nanoparticle synthesis Nanoparticle location Membrane pore

structure and material


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Iron NP Oxidation & Contaminant Degradation

Fe

OH*, H2O2, O2*-, Fe(IV)

H2 gas

+ H2O & O2

Pesticides & Herbicides

Heavy Metals

Cr6+As3+

Pb2+

IndustrialChemicals


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Synthesized Fe NPs

200 nm

Iron Metal

Magnetite/Maghemite(Fe3O4/g-Fe2O3)

(ATMP)


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Casting Solution Preparation & Membrane Casting

Polyethersulfone (PES)

0 - 2.0 % synthesized iron nanoparticles

0 – 2.0 wt % pore former:•Polyvinylpyrrolidone (PVP)

Solvent


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Parameters and Values Tested

Stabilizer (mol

stabilizer/mol Fe) Amino tris(methylene phosphonic

acid) (ATMP) (0.05 or 0.3)

Solvent Type dimethyl sulfoxide (DMSO)

dimethylacetamide (DMAC)

dimethylformamide (DMF)

Concentration of

nanoparticles in

casting solution

(g/L)

0, 1, 5, 10, 20


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Effect of Nanoparticles on Membrane Performance

Taurozzi, J.S. et al. (2011) Desalination 269, 111-119.Choi, J.-H. et al. (2006) Journal of Membrane Science 284, 406-415.

Taurozzi (2011) – C60 nps (139 nm) in 12% PSf by wet phase inversion

Choi (2006) – Carbon nanotubes in 15% PSf by wet phase inversion

In general, addition of nps causes:• Increase in viscosity• Increase then decrease in flux• Decrease then increase in solute rejection


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Viscosity: Increase with Nanoparticle Concentration

0

0.1

0.2

0.3

0.4

0.5

0 0.5 1 1.5 2 2.5

Vis

co

sity (

Pa

*s)

Nanoparticle Concentration (wt%)

NMP

DMAc

DMSO

DMF


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Effect of Nanoparticles on Membrane Thickness and Flux

All experiments run at 1 bar


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Polymer-Solvent Miscibility & Membrane Pore Structure

Lau W.W.Y. et al. (1991) Journal of Membrane Science 59, 219-227.

Polymer precipitation curvesPES solubility: DMAC > DMF > DMSO

Polymer + Solvent + NPs

Non-solvent (H2O)

DMAC: slow outflux of solvent = fast influx of non-solvent = delayed demixing, macrovoid formation & larger polymer precipitates/aggregates form

DMSO: fast outflux of solvent = slow influx of non-solvent = reduction in macrovoid formation, smaller polymer precipitates, cellular or nodular structures form

Flux decreases with increasing PES-solvent solubility


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Cross-Section Morphology

13.8 wt % PES

b ca

d e f

20 mm

20 mm

20 mm

20 mm 20 mm20 mm

13.8 wt % PES, 1 wt % Fe NPs

DMAC DMF DMSO

DMAC DMF DMSO


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Surface Morphology

b ca

d e f

400 nm400 nm

200 nm200 nm

2 mm

4 mm

13.8 wt % PES, 1 wt % Fe NPs

DMAC DMF DMSO

13.8 wt % PES

DMAC DMF DMSO


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Nanoparticles: Casting Solution Additive

Non-Solvent (e.g., butanol, water) Polymer (e.g., polyvinylpyrrolidone)

Li, Z and Jiang C. (2001) Journal of Applied Polymer Science 82, 283–291.M.-J. Han, S.-I: Nam (2002) Journal of Membrane Science 202, 55-61.

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

0 0.2 0.4 0.6 0.8 1

Vis

cosi

ty (

Pa.s

)

Relative Content Value (-)

1-Butanol

Water

15 wt % PES/NMP

Non-Solvent:• Closer to solubility limit• Increase in viscosity• Decrease in flux• Moves to polymer-lean phase in phase

inversion

Polymer:• Suppression of macrovoids• Increase in viscosity• Increase then decrease in flux• Stays entangled with membrane

polymer in phase inversion

Thermodynamics:Enhanced demixingdue to lower stability (solubility)

Kinetics:Delayed demixingdue to rheology / diffusion


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Thermodynamics vs. Kinetics: Solvent Dependence

0

0.1

0.2

0.3

0.4

0.5

0 1 2 3

Vis

cosity (

Pa*s

)

Nanoparticle Concentration (wt%)

NMP

DMAc

DMSO

DMF

Thermodynamics dominating? Increase in flux with NP additionIncrease in viscosity with NP concentration

Kinetics dominating?Decrease in flux with NP concentrationIncrease in viscosity with NP concentration


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Nanoparticle-Polymer Interactions in Solution

• Polymer functional groups• Stabilizer/pore former• Nanoparticle concentration• Polymer concentration• Ex situ vs. in situ NP synthesis

Polymer conformation & dynamics changes due to NPs


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Nanoparticle Location During Phase Inversion

100 nm

500 nm

3 mm


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Iron Nanoparticle Oxidation in PS Membrane

Oxidation on a gold QCM crystal surface

Oxidation on pores of PES membrane

400 nm 400 nm

200 nm 200 nm


Controlling Fe Nanoparticle Oxidation

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Bimetallic nanoparticles: Ni:Fe ratio

Greenlee, L.F. et al. (2012) Environmental Science & Technology 46, 12913.

0.5 mmol Ni:mol Fe 5 mmol Ni:mol Fe

100 mmol Ni:mol Fe 1000 mmol Ni:mol Fe


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Iron NP oxidation in water: Quartz crystal microbalance measurements

Greenlee, L.F. et al. (2012) Environmental Science & Technology 46, 12913.


Water Treatment with FeNi Nanoparticles

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FeNi Nanoparticles: Orange G dye removal from water

Textile Industry: 2nd largest water contributor to water contamination• Dyes• Metals

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 20 40 60 80

Co

nce

ntr

atio

n (

g/L)

Time (min)

100 mg/L

75 mg/L

50 mg/L

25 mg/L

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 20 40 60 80

Co

nce

ntr

atio

n (

g/L)

Time (min)

100 mg/L

50 mg/L

1:1 Ni:Fe, core-shell 1:1 Ni:Fe, alloy

1 g/L

•CHED: Undergraduate Research Posters•Hall C - Colorado Convention Center

•12:00pm - 2:00pm Mon, Mar 23Environmental Chemistry


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Conclusions & Future Work

Future Work: Optimization of FeNi nanoparticles for dye removal• Characterization of NPs• FeNi immobilization in membranes

• NP concentration• Polymer type and concentration

• Membrane characterization• Flux• Viscosity• Neutron scattering / SAXS experiments / microscopy• Orange G dye removal

Conclusions:• Viscosity, flux, and microscopy data can be used to understand nanoparticles

as a membrane additive• Iron nanoparticle oxidation can be controlled through addition of a second

metal (e.g., nickel)• FeNi nanoparticle structure affects Orange G dye removal


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Thank You! Questions?

Contact Information:Lauren [email protected]

AcknowledgementsProf. Andrew Herring & lab members, Colorado School of MinesProf. Matthew Liberatore & lab members, Colorado School of MinesNIST TEM – Roy Geiss, Alex Curtin, Ann Debay, Taylor WoehlNIST XRD – Justin ShawCU TEM – Tom GiddingsNIST/Argonne HE-XRD: Nicholas Bedford

mailto:[email protected]


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Stabilizers used during NP synthesis

Amino tri(methylene phosphonicacid) (ATMP)Carboxymethyl cellulose

Diethylenetriamine penta(methylene phosphonic acid) (DTPMP)


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Effect of stabilizer properties on Fe NP oxidation in water

200 nm

DTPMP prevents Fe NP oxidation in flowing water.

Stabilizer size and chelator strength appear to affect NP oxidation in water.


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Size Control of Bimetallic FeNi Nanoparticles

200 nm

100 nm

0.05 mol ATMP:mol Fe

0.8 mol ATMP:mol Fe


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0

0.04

0.08

0.12

0.16

0.2

Vis

cosi

ty (

Pa*

s)Membranes: How do nanoparticles change casting solution properties?

Viscosity: Higher viscosity tends to slow kinetics of phase inversion due to slower diffusion of solvent and non-solvent; slower demixing = reduction in macrovoids

No Nanoparticles

1% 5% 15% 25%

15% PES in DMAC

1% Nanoparticles

1% 5% 15% 25%

EtOH Vol. %EtOH Vol. %


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Cloud point measurement: Thermodynamic stability & polymer solubility

0

5

10

15

20

25

30

35

No

n-S

olv

en

t A

dd

ed

(m

l)

No Nanoparticles

1% 5% 15% 25%

15% PES in DMAC

1% Nanoparticles

EtOH Vol. %

1% 5% 15% 25%

EtOH Vol. %

Cloud point: Thermodynamic stability of solution – lower stability of polymer-solvent solution = lower polymer solubility, increased outflux of solvent and decreased influx of non-solvent = reduction in macrovoid formation


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Membrane lifetime: PES with iron nanoparticles

PES

1 µm2 µm

400 nm

Before filtration After filtration

After filtration

Significant flux decline & surface

degradation

100 nm

Before filtration


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Advanced Photon Source, Argonne Nat’l Lab: A Synchrotron Facility

Stats:

• Circumference: 3,622 ft. (0.69 miles)

• 35 experimental sectors• >1000 bending magnets• Electron energy:

• Linear accelerator: 450 MeV

• Booster synchrotron: 7 GeV

• X-rays: 3 keV – 100 keV

e-

X-rays


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X-Ray Absorption Spectroscopy (XAS)

Information Obtained:Element-specific chemical state: Coordination #, oxidation state

X-Ray Absorption Near Edge Structure (XANES)

Extended X-Ray Absorption Fine Structure (EXAFS)

X-Ray Absorption Spectroscopy (XAS)

Single Scattering:Who is my neighbor?-Atomic pair distribution-Modeling of interatomic distances

Multiple Scattering:Who is my neighbor?-First coordination sphere

http://en.wikipedia.org/wiki/XANEShttp://www.esrf.eu/UsersAndScience/Publications/Highlights/2000/surfaces/SU7.html


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High Energy X-Ray Diffraction (HE-XRD)

Wavelength:HE-XRD: 0.1 AngstromsPowder XRD: 1.54 Angstroms (CuKa)

Information Obtained:Structure: Atom pair distances, measures over multiple coordination spheres, allows modeling on nm scale

30 40 50 60 70 80 90

Fe-Ni

Ni Only

Inte

nsity

2-Theta (deg.)

Fe Only

2 3 4 5 6 7 8 9 10

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

ATMP

HTPMP

DTPMP

Fe NPs

G(r

)

r (Å)

oxide

metal-metal

oxide

extended lattice structure, peak shifts suggest alloying/oxide

Powder XRD


ENGINEERED NANOPARTICLE SYSTEMSPDF Results for Peptide-Enabled Pd Nanoparticles

1 nm

Pd4 A6 A11

A6,11 C6 C11

C6,11 C6A11 A6C11

Clear sequence-dependence structural differences


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Viscosity: Effect of nanoparticles, pore former, and non-solvent

0

0.04

0.08

0.12

0.16

0.2

Vis

cosi

ty (

Pa*s

)

CMC

ATMP

No NPs

Higher viscosity tends to slow kinetics of phase inversion due to slower diffusion of solvent and non-solvent; slower demixing = reduction in macrovoids

15% PES 15% PES2% PVP

15% PES2% PVP5% EtOH

15% PES2% PVP25% EtOH

15% PES5% EtOH

15% PES25% EtOH


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Nanoparticle Catalysis

Lee and Sedlak. (2008) ES&T 42, 8528-8533.Chun et al. (2010) ES&T 44, 5079-5085.Alayoglu and Eichhorn (2008) JACS 130, 17479–17486.Sasaki et al. (2012) Nature Communications, 3, 1115.

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