Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials
description
Transcript of Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials
![Page 1: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/1.jpg)
Multi-Scale Simulations of the Growth and Assembly of Colloidal
Nanoscale MaterialsKristen A. Fichthorn
Department of Chemical EngineeringDepartment of PhysicsPenn State University
DE-FG0207ER46414
![Page 2: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/2.jpg)
Complex Nanostructures in Colloidal Crystal Growth: How Do They Form?
Ostwald Ripening
Cluster-ClusterAggregation
OrientedAttachment
How Does OA Happen?
![Page 3: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/3.jpg)
Complex Nanostructures in Colloidal Crystal Growth: Oriented AttachmentOriented Attachment of TiO2:Intrinsic Crystal Forces
Oriented Attachment andthe Mesocrystal State:The Role of Solvent
R. Penn and J. Banfield, Geochim.Cosmochim. Acta 63, 1549 (1999).
M. Alimohammadi and K. Fichthorn, Nano Lett. 9, 4198 (2009).
V. Yuwano, N. Burrows, J. Soltis, and R. Penn, JACS 132, 2163 (2010).
![Page 4: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/4.jpg)
Complex Nanostructures in Colloidal Crystal Growth: Capping Agents
Y. Sun, B. Mayers, T. Herricks, andY. Xia, Nano Lett. 3, 955 (2003).
![Page 5: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/5.jpg)
Polyol ProcessSolvent: Ethylene GlycolSalt: AgNO3
“Stabilizer”: PVP
What Happensin the Pot?B. Wiley,…Y. Xia, Chem. Eur. J. 11, 454 (2005).
“One-Pot” Solution-Phase Synthesis of Nanostructured Metal Materials
N,N-DMF ReductionSolvent: N,N-DMF
Salt: AgNO3
“Stabilizer”: PVP
All Kinds ofNano-Shapes
Heat at ~400 K
![Page 6: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/6.jpg)
B. Wiley,…Y. Xia, Chem. Eur. J. 11, 454 (2005).
Reductionof Ag Nucleation
Growth
Nanostructure Formation:General Aspects
Determined bySalt and…Solvent or PVP? Probably Determined
by PVP…
SeedFormation
![Page 7: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/7.jpg)
Does PVP Prefer Ag(100) Over Ag(111)?
Nanowires from Multiply-Twinned DecahedralSeeds
Nanocubes from Single-Crystal Cubo-OctahedralSeeds
One Possible Role of PVP: Surface-Sensitive Binding
G. Grochola, I. Snook, and S. Russo, J. Chem. Phys. 127, 194707 (2007).
Y. Sun, B. Mayers, T. Herricks, and Y. Xia, Nano Lett. 3, 955 (2003).
![Page 8: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/8.jpg)
Interaction of PVP with Ag(100) and Ag(111):First-Principles Challenges
Direct Bonding +van der Waals (vdW)
vdW
Historically DFT Described Direct Bonds,Including vdW Interactions is New… S. Grimme, J. Comput. Chem. 27, 1787 (2006).M. Dion,…, D. C. Langreth, B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004).A. Tkatchenko and M. Scheffler, Phys. Rev. Lett. 102, 073005 (2009).K. Lee, …, D. C. Langreth, B. I. Lundqvist, Phys. Rev. B 82, 081101 (2010).
L. Delle Site, K. Kremer, Int. J. Quant. Chem. 101, 733 (2005).
nCoarse-Grained
Model
![Page 9: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/9.jpg)
Interaction of PVP with Ag(100) and Ag(111): VASP 5.2.11
• (4×4×14) Super Cell• Slab: 6 layers• Vacuum: 8 layers
• PAW-PBE (GGA) ± DFT-D2 ± TS*• Assess the Influence of
vdW Interactions• Cut-off: 29.4 Ry• k-points: (4×4×1)• Ab-initio Molecular Dynamics• Static Total-Energy Calculations
*Implemented in VASP by Wissam Al-Saidi
![Page 10: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/10.jpg)
van der Waals Interactions in DFT: How Do We Describe Ag??
aS. Grimme, J. Comput. Chem. 27, 1787 (2006).bA. Tkatchenko and M. Scheffler, Phys. Rev. Lett. 102, 073005 (2009) .cE. Zaremba and W. Kohn, Phys. Rev. B 13, 2279 (1976).dS. Eichenlaub, C. Chan, and S. P. Beaudoin, J. Coll. Int. Sci. 248, 389 (2002).eA. Khein, D. J. Singh, and C. J. Umrigar, Phys. Rev. B 51, 4105, (1995).fH. Li, et al., Phys. Rev. B 43, 7305 (1991).gF. R. De Boer, et al., Cohesion in Metals, Amsterdam, (1988).hM. Chelvayohan and C.H.B. Mee, J. Phys. C: Solid State Phys.15, 2305 (1982).
BA AB
ABdampvdW R
CfE
,6
6)]1(exp[1
1),()(
0
0
AB
AB
RfRABABdamp d
RRf
PBE DFT-D2a TS+ZKb+c ExperimentC6
(J nm6 mol-1) --- 24.67 6.89 6.25d
R0(Å) --- 1.64 1.34 ---aAg (Å) 4.16 4.15 4.02 4.07e
D12 Ag(100) (%) -2.05 1.3 -1.75 ±1.5f,g
D12 Ag(111) (%) -0.3 1.61 -0.32 0.5 ± 0.8h
![Page 11: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/11.jpg)
Binding Conformations:No vdW Interactions
Experimental IR and XPS:PVP Binds to Ag via the O and/or N Atom.
Ag(100)
TopHollow
BridgeAg(111)
Topfcc
Hollowhcp
Hollow
Bridge
Trial & Error:Bonding with O Atom Down
F. Bonet et al., Bull. Mater. Sci. 23, 165 (2000).Z. Zhang et al., J. Solid State Chem. 121, 105 (1996).H. H. Huang et al., Langmuir 12, 909 (1996).
![Page 12: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/12.jpg)
Binding Energies: No vdW Interactions
Adsorption site Ethane 2-Pyrrolidone(100) Hollow 0.0 0.19(100) Bridge 0.0 0.22
(100) Top - 0.21(111) fcc Hollow 0.0 0.19(111) hcp Hollow - 0.16
(111) Bridge - 0.20(111) Top - 0.26
Bond Strength (eV)
Predominantly vdW
Ag(100)
TopHollow
Bridge
Ag(111)
Topfcc
Hollowhcp
Hollow
Bridge
Preference for Ag(111): Contrary to Expectations
) ( surfacemoleculesurfacemoleculebind EEEE
Ethane Binds:X.-L. Zhou and J. M. White, J. Phys. Chem. 96, 7703 (1992).
![Page 13: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/13.jpg)
)( surfacemoleculesurfacemoleculebind EEEE
vdW Interactions Support Structure-Directing Hypothesis
Site PBE PBEDFT-D2
PBETS+ZK
(100) Hollow 0.19 1.05 0.59(100) Bridge 0.22 1.34 0.77
(100) Top 0.21 1.05 0.60(111) fcc 0.19 0.61 0.58(111) hcp 0.16 0.80 0.58
(111) Bridge 0.20 0.70 0.62(111) Top 0.26 0.79 0.64
Bond Strength (eV)
Why Such Big Differences Between Methods??
![Page 14: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/14.jpg)
DFT-D2: Ag(100) Reconstructs
eV 27.0 )100(
D EEE hexhex
Ag(100) Reconstruction has not been Observed Experimentally…
![Page 15: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/15.jpg)
TS+ZK:2-Pyrrolidone on Ag(100)
HollowEbind = 0.59
Bridge Ebind = 0.77
Top Ebind = 0.60
Hollow || Ebind = 0.77Bridge ||
Ebind = 0.81
Top ||Ebind = 0.78
Lots of Options!Binding via O and N
F. Bonet et al., Bull. Mater. Sci. 23 (2000).Z. Zhang et al., J. Solid State Chem. 121 (1996).H. H. Huang et al., Langmuir 12 (1996).
![Page 16: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/16.jpg)
KTkTEPP
400 );/exp(139)111(
)100( D
PVP ~139 Times More Likely to Bind toAg(100) “Sides” than Ag(111) “Ends”
![Page 17: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/17.jpg)
TS+ZK EnergiesTS+ZK Geometries
PBE Energies TS+ZK Geometries D
Site Ebind EPauli+Edirect bond EvdW(100) Hollow || 0.78 0.36 0.42(100) Bridge || 0.81 0.32 0.48
(100) Top || 0.77 0.30 0.47(111) Top ┴ 0.64 0.12 0.51
(111) Bridge ┴ 0.62 0.09 0.53(111) Bridge || 0.63 -0.19 0.82
TS+ZK Method: Break-Downof Binding Energy
bonddirectPaulivdWbind EEEE
![Page 18: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/18.jpg)
TS+ZK EnergiesTS+ZK Geometries
PBE Energies TS+ZK Geometries D
Site Ebind EPauli+Edirect bond EvdW(100) Hollow || 0.78 0.36 0.42(100) Bridge || 0.81 0.32 0.48
(100) Top || 0.77 0.30 0.47(111) Top ┴ 0.64 0.12 0.51
(111) Bridge ┴ 0.62 0.09 0.53(111) Bridge || 0.63 -0.19 0.82
TS+ZK Method: Break-Downof Binding Energy
bonddirectPaulivdWbind EEEE
Ag(100): vdW and Direct Bonding Synergize
![Page 19: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/19.jpg)
TS+ZK EnergiesTS+ZK Geometries
PBE Energies TS+ZK Geometries D
Site Ebind EPauli+Edirect bond EvdW(100) Hollow || 0.78 0.36 0.42(100) Bridge || 0.81 0.32 0.48
(100) Top|| 0.77 0.30 0.47(111) Top ┴ 0.64 0.12 0.51
(111) Bridge ┴ 0.62 0.09 0.53(111) Bridge || 0.63 -0.19 0.82
TS+ZK Method: Break-Downof Binding Energy
bonddirectPaulivdWbind EEEE
Ag(111): vdW is the Dominant Attractive ForceSometimes the only Attractive Force
![Page 20: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/20.jpg)
• We Observed Stronger Binding to Ag(100) when we Include vdW As Inferred by Experiment
Conclusions• We Studied Surface-Sensitivity of PVP Binding to Ag(111) and Ag(100)
• DFT-D2 Reconstructs Ag(100)
• Ag(100) Preference from Synergy Between vdW Attraction and Direct Bonding
![Page 21: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/21.jpg)
Oriented Attachment in Crystal Growth:Role of Intrinsic Crystal Forces
See Also:M. Niederberger and H. Cölfen, Phys. Chem. Chem. Phys. 8, 3271 (2006). Q. Zhang, S. Liu, and S. Yu, J. Mater. Chem. 19, 191 (2009).
HRTEM: Oriented Attachment of TiO2 NanoparticlesR. Penn and J. Banfield, Geochim. Cosmochim.Acta 63, 1549 (1999).
![Page 22: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/22.jpg)
Dipole-Dipole Interactions May Assemble Nanoparticles
T. Zhang, N. Kotov, and S. Glotzer, Nano Lett. 7, 1670 (2007).
Z. Tang and N. Kotov, Adv. Mater. 17, 951 (2005); Z. Tang, N. Kotov, M. Giersig, Science 297, 237 (2002).
CdTe Nanoparticle Chains
+ - + -
![Page 23: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/23.jpg)
Two WulffNanocrystals
(001) TruncatedNanocrystals
(112) TruncatedNanocrystals
i
iiq r=35 D
=0
=250 D
=75 D
TiO2 (Anatase) NanocrystalsMatsui-Akaogi Force FieldMol. Sim. 6, 239, 1991.*
![Page 24: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/24.jpg)
Aggregation of Wulff Nanocrystals
![Page 25: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/25.jpg)
Nanocrystal Aggregation:The Hinge Mechanism
Initial Contact of Edges:The “Hinge” Rotation About the “Hinge”
![Page 26: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/26.jpg)
Nanocrystal Aggregation:Driven by Electrostatic Forces
M. Alimohammadi and K. Fichthorn, Nano Lett. 9, 4198 (2009).
![Page 27: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/27.jpg)
Nanocrystal Aggregation: Driven by Multipoles from Under-CoordinatedSurface Atoms
M. Alimohammadi and K. Fichthorn, Nano Lett. 9, 4198 (2009).
![Page 28: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/28.jpg)
HRTEM Image Showing Oriented Attachment of 5 TiO2 NanoparticlesR. Penn and J. Banfield, Geochim. Cosmochim. Acta 63, 1549 (1999).
Simulation vs. Experiment: Still Have a Way to Go
Aqueous EnvironmentHour (or longer) Times
Vacuum EnvironmentNanosecond Times
![Page 29: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/29.jpg)
Nanocrystal Aggregation is Driven by Local Interactions.
We Should Re-Think the Dipole Idea…
Conclusions
P. Schapotschnikow et al., Nano Lett. 10, 3966 (2010).
Also found this for capped and uncapped PbSe…
![Page 30: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/30.jpg)
1D Nanostructures form via Mesocrystals and Oriented Attachment
M. Giersig, I. Pastoriza-Santos, L. Liz-Marzan,J. Mater. Chem. 14, 607 (2004).
Ag Nanowires
V. Yuwano, …, and R. Penn,JACS 132, 2163 (2010).
Goethite Nanowires
![Page 31: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/31.jpg)
Solvent Ordering and Solvation Forces
Solvent Density Profile
Solvent ordering around solvophilic nanoparticlesY. Qin and K. A. Fichthorn, J. Chem. Phys. 119, 9745 (2003).Y. Qin and K. A. Fichthorn, Phys. Rev. E 73, 020401 (2006).
![Page 32: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/32.jpg)
MD: Aggregation of a Small, Isotropic*Crystal with a Larger, Anisotropic Crystal
*Relatively
RectangularCuboid
SquarePlate
2
1
32
1
● Generic Anisotropic fcc Nanoparticles● Solvophilic Nanoparticles● Strong vdW Attraction (Ag)● Isotropic Organic Solvent
![Page 33: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/33.jpg)
Aggregation of Small and Large Nanocrystals: Mesocrystal States
Mesocrystal State 1One Solvent Layer
Mesocrystal State 1One Solvent Layer
Mesocrystal State 2Two Solvent Layers
![Page 34: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/34.jpg)
Mesocrystal States: Free-Energy Minima
Escape-Time Distribution
Aggregation Probability
kTGeR
eRtf/
Rt
~
)(D
RA eP 1)(
Aggregation of Small and Large Nanocrystals: Mesocrystal States
Mesocrystal State 1One Solvent Layer
Mesocrystal State 1One Solvent Layer
Mesocrystal State 2Two Solvent Layers
![Page 35: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/35.jpg)
Aggregation:Fastest at End of RectangleSlowest on Face of SquareEven on SidesMesocrystal State 1
Most FrequentMesocrystal State 2Occurs on SquareMesocrystal State 3
DissociationNot Typically FrequentDissociation
Nanocrystal Encounters:Frequency of Outcomes
3
1
2
1
2
Aggregation is the Most FrequentOn the Smallest Facets,Perpetuating 1D Growth
![Page 36: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/36.jpg)
Disruption Solvent Ordering at EdgesLeads to Fast Aggregation on Small Facets
Square Plate
Rectangle
7.26.66.05.44.84.23.63.02.41.81.20.60
r/rb
Rectangle
![Page 37: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/37.jpg)
Conclusions
Solvent Ordering Around Nanocrystal SurfacesPromotes Growth of 1D Nanostructures
Leads to Mesocrystal States
Faster Aggregation on Smaller Facets
![Page 38: Multi-Scale Simulations of the Growth and Assembly of Colloidal Nanoscale Materials](https://reader030.fdocuments.us/reader030/viewer/2022033104/56813f07550346895da98bd9/html5/thumbnails/38.jpg)
Collaborators
FundingNSF DMR-1006452, NIRT CCR-0303976, CBET-0730987DOE DE-FG0207ER46414ACS, EPA, NCSA
Mozhgan AlimohammadiHaijun FengAzar ShahrazJin Pyo HongDr. Ya ZhouDr. Yangzheng Lin
AlumsDr. Yong QinDr. Rajesh SathiyanarayananDr. Leonidas Gergidis
Fritz Haber InstituteAlexander TkatchenkoVictor Gonzalo Ruiz LopezMatthias Scheffler
Univ. of PittsburghDr. Wissam Al-Saidi