Polymer-stabilized Nickel Nanoparticle Catalysts

Olivier NguonUniversity of WaterlooGauthier LaboratoryMay 1, 2009

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Outline

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Overview

Utilization of metallic nanoparticles as high performance catalysts

Performance maximized by preventing aggregation with polymeric stabilizers

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NanoparticlesNanoparticles (10-9 m) New properties New applications

Size effect: High surface-to-volume ratio

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Catalysis

5A. I. Frenkel, C. W. Hills, R. G. Nuzzo, J. Phys. Chem. B (2001) 105: 51.

Increased surface area Increased density of reactive sites (kinks, edges: low coordination sites )

Increased activity, selectivity

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van der Waals Interactions

Attractive interactions

A: Effective Hamaker constant

a: Radius of the particles

H: Distance between particles

δ-δ+δ- δ+δ-δ+δ- δ+

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Steric Stabilization

Steric stabilization1:

Independent of electrolyte concentrationApplicable to polar and non-polar solventsReversible flocculation (non solvent/good solvent)

71. Napper (1983). “Polymeric Stabilization of Colloidal Dispersions”, p. 20. Academic Press, London.

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StabilizersSmall molecule surfactants: CTAB, SDS, etc.

Polymers: Homopolymers, telechelic polymers, block copolymers

Advantages of polymers:Increased colloidal stabilityProtection from oxidation“Polymeric field” (hydrophobic, electrostatic, acidic, etc.)

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Outline

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Nickel Nanoparticles

Supplied by Vale-Inco

Synthesized by gas condensation technique

Ni(CO)4 Ni + 4 CO

Control over size, composition (residual C,O)

10E. Kauffeldt, T. Kauffeldt, J. Nano. Res. (2006), 8: 477.

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Inco Nanoparticles – Size Distribution

Average particle size: 60 nm

Broad size distributionIP

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Hydrogenation Reactions

Adiponitrile: Precursor in nylon-6,6 synthesis

NCCN NH2NH2

Adiponitrile 1,6-HexamethylenediamineNi

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Hydrogenation Reactions (cont’d)

Mesityl oxide: Precursor for methyl isobutyl ketone (solvent)

W.K. O’Keefe, M. Jiang, F.T.T. Ng, G.L. Rempel, Chemical Engineering Science (2005), 60: 4131. 13

Mesityl oxide MIBK MIBC

CH3CH3

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Hydrogenation Reactions (cont’d)

Nickel particles (under N2)Addition of substrate (mesityl oxide) and particles to solvent (2-propanol)Sonication

Reaction: 200 psig, 50°C, 330 rpmConversion monitoring

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Outline

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Polymeric StabilizersTelechelic polymers:

PEO-diethylenetriaminePEO-bis-2-picolylaminePEO-COOH

Diblock copolymers:PS-block-PMMAPS-block-P2VP

Triblock copolymers:PEO-block-PS-block-PEOP2VP-block-PS-block-P2VP

HC CH2 CH2 CH CH2 HCH H

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Synthesis: Triblock Copolymer

Electron-transfer Initiator:

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Synthesis: Triblock Copolymer (cont’d)PS addition:

P2VP addition:

18Termination: HCl/MeOH

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Outline

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Nanoparticles Activity: AdiponitrileNanoparticles more than 3X more active than Raney nickelImportant variations among nanonickel samples

0.11 0.09 0.090.05 0.03 0.02 0.02 0.02 0.01 0.01 0.00

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Nanoparticles Activity: Mesityl Oxide

Increased activity

Solubilization of nickel oxide surface

Diethylenetriamine (DETA) treatment

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Inco 982174 – 97 m²/g

Activity variation for bare nanoparticles

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Inco 982174 (cont’d)

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Outline

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Conclusions

Different stabilizing polymers synthesized

Triblock copolymers work best

Protective effect from oxidation

Catalytic activity and colloidal stability of nanoparticles enhanced

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Applications

Mixed catalyst systems (Ni+Fe, Co)

Applications as efficient catalytic systems (fuel cells, specialty chemicals synthesis, etc.)

Tailoring of polymer structure and composition

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Acknowledgements

Supervisor: Prof. Mario Gauthier

Co-supervisor: Prof. Flora T.T. Ng

Vale - Inco: Vladimir PaserinSteve BaksaJun ShuNam Nguyen

Colleagues in the Gauthier and Duhamel Labs

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Thank You

Any questionsIPR 20

Size EffectSize decreases:

High surface-to-volume ratioQuantum effects

D.B. van Wyck, Anna CE Symposium, New Orleans, LA, 2004.29

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Size Dependence

M. Valden, X. Lai, D.W. Goddman, Science (1998), 281: 1647.

Increased activity with decreasing size

Maximum in activity can be observed

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London Interaction Energy

Hamaker constant for 60 nm particles: Ni = 22.10-20 JEthanol = 4.20 10-20 J

-4.0E-19

-3.5E-19

-3.0E-19

-2.5E-19

-2.0E-19

-1.5E-19

-1.0E-19

-5.0E-20

0.0E+000 20 40 60 80 100 120 140R (nm)

(J) IP

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Rate Constant Determination

Kinetics:SamplingGC analysis

0.00.10.20.30.40.50.60.70.80.91.0

0 0.5 1 1.5 2 2.5 3

Time (hour)

M] 0 y = -2.4599x + 0.0898

R2 = 0.9843

0 0.2 0.4 0.6 0.8 1 1.2

Time (hour)

Inco 982174 + 5% polymerIP

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Nanoparticles Activity: Adiponitrile (cont’d)

0.200.15 0.12 0.11 0.11 0.10 0.07 0.05 0.04 0.02

0.00.10.20.30.40.50.6

Quantu

mSphere

Inco 928

31Aldr

ich 827

o 11237

o 10877

Raney N

Inco 113

Inco 959

o 85109

Inco 730

Raney N

Inco 928

Rate of hydrogenation normalized per surface area

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Colloidal Stability in WaterInco 82325 (23 mg) in Water (10 mL) with Stabilizer

01020304050607080

0 5000 10000 15000 20000 25000 30000 35000

Time (s)

Water Ref

PEO 2k (123 mg)

MPEG2k-DETA (65 mg)

PVP 10k (62 mg)

MPEG2k-DETA (125 mg)

PVP 1.3M (65 mg)

PEI 60k (60 mg)

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Polymer Bridging Effect

Interactions of stabilizing polymer with two different particles

Significant at low polymer concentration

May induce catalyst flocculation

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Inco 85109 in Methanol

Polymer/Particles(mg/mg)

0 10 1 0.1 0.003

t = 0 min

t = 30 mint = 1 h

t = 2 h 30

t = 1 min

t = 2 h

t = 4 h

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372. Napper (1983). “Polymeric Stabilization of Colloidal Dispersions”, p. 16. Academic Press, London.

Polymer Effects

“Enormous complexity of the effects [of] polymer chains…”2

D.H. Napper

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Effect of Polymer Degree of Polymerization

H.Hirai. In “Tailored Metal Catalysts” (Ed. Y. Iwasawa). P.132, Reidel Publishing, Dordrecht (1986).

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Polymer-stabilized Nickel Nanoparticle Catalysts · Steric Stabilization Steric stabilization1:...

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