Formation of Gold Nanorods by Seeded Growth: Mechanisms and

Subscriber access provided by Kaohsiung Medical University

Article

Formation of Gold Nanorods by Seeded Growth: Mechanisms and Modeling Advait Chhatre, Rochish Thaokar, and Anurag Mehra Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01387 • Publication Date (Web): 04 May 2018 Downloaded from http://pubs.acs.org on May 5, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Formation of Gold Nanorods by Seeded Growth: Mechanisms and Modeling ∗

Advait Chhatre, Rochish Thaokar, and Anurag Mehra

Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai, India

E-mail: [email protected] Phone: +91 (22) 2576 7217. Fax: +91 (22) 2572 6895

Abstract Seeded growth is one of the most successful and well-studied methods of making nanorods of FCC metals such as Ag, Au, Pt, etc. In this method separately prepared tiny metal seeds (typically smaller than 10 nm) are added to a growth solution containing metal precursor, a weak reducing agent such as ascorbic acid, and a capping agent. The mechanisms that lead to specic shape selection and growth of nanoparticles, in this method, are poorly understood. We propose a mechanism of nanorod growth based on the physical phenomenon of twinning and develop a population balance based model. Briey, on mixing with growth solution, the seeds start growing isotropically, during which some of the seeds undergo twinning and transform their growth habit to form nanorod nuclei. The nanorod nuclei grow along one dimension to form nanorods, and a mixture of nanorods and nanospheres is obtained after a short aging time (typically 25

the yield of nanorods

(RY ) depicts power law kind of trend with respect to yield parameter and scales as (from Figure 12). Let us write it as

YP as

RY ∝ Y P α .

Y P 0.8

From Equation 27, we can observe that

itself scales as square of width of nucleation window. Therefore, the nanorod yield scales

RY ∝

law for

RY

N˙ gs,mean NT 0

α

(nw2 − nw1 )2α

i.e., the power law index for

(nw2 − nw1 )

in scaling

is twice of that for the other terms in yield parameter. This indicates that the

stimuli that can alter the width of nucleation window are expected to have an accelerated impact on the yield of nanorods.

Conclusion Based on physical phenomena of twinning we have proposed a mechanism for the formation of gold nanorods in a seeded growth protocol. We have used the framework of population balance equations for simulating the proposed mechanism.

The only adjustable inputs to

our model are the rate constant for surface reaction and the product of solvation equilibrium constants of Au(I) complex and ascorbic acid.

Simulations capture the salient feature of

one-dimensional growth along with the kinetics of nanorod and nanosphere growth.

The

trends in the experimental data, such as inverse proportionality between the aspect ratio of nanorods and amount of seeds, the negative linear relation between the aspect ratio and size of seeds, and sigmoidal evolution pattern are replicated in the simulations. The model also has the capability of predicting the yield of nanorods.

Simulations also reveal that

growth of nanospheres competes with the nucleation of nanorods, and thus decides the yield of nanorods in the system. The model is quite general that it can be applied to simulate nanorod formation of any material that has FCC crystal structure.

31

ACS Paragon Plus Environment

Further, the model

Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 40

can also be extended to include more shapes such as triangular plates, hexagonal plates, etc.

by dening corresponding nucleation zones, nucleation rates and growth rates.

This

model therefore can serve as an excellent tool for scale-up of the nanorod synthesis using seed-mediated growth approach.

Acknowledgement This study was supported by a research grant titled Engineering Aspects of Ultrane Particle Technology, made available under the Intensication of Research in High Priority Areas (IRHPA) scheme of the Department of Science and Technology, Government of India, New Delhi. Authors thank Utsab Mukherjee for his help in debugging the solver for population balance equations using the high-resolution algorithm.

Supporting Information Available SI-1: Chemicals and Experimental Methods, SI-2: Number density of seeds, SI-3: Correlation between dimensions of nanorod seeds and nanospheres, SI-4: High resolution algorithm for solving PBEs, SI-5: Algorithm followed for simulating the model, SI-6: TEM micrographs for seed concentration study

This material is available free of charge via the Internet at

http://pubs.acs.org/.

References (1) Burrows, N. D.; Vartanian, A. M.; Abadeer, N. S.; Grzincic, E. M.; Jacob, L. M.; Lin, W.; Li, J.; Dennison, J. M.; Hinman, J. G.; Murphy, C. J. Anisotropic Nanoparticles and Anisotropic Surface Chemistry.

J. Phys. Chem. Lett.

2016, 7, 632641.

(2) Xia, Y.; Gilroy, K. D.; Peng, H.-C.; Xia, X. Seed-Mediated Growth of Colloidal Metal Nanocrystals.

Angew. Chem., Int. Ed.

2016, 56, 6095. 32


Page 33 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(3) Murphy, C. J.; Thompson, L. B.; Chernak, D. J.; Yang, J. A.; Sivapalan, S. T.; Boulos, S. P.; Huang, J.; Alkilany, A. M.; Sisco, P. N. Gold nanorod crystal growth: From seed-mediated synthesis to nanoscale sculpting.

Sci.

Curr. Opin. Colloid Interface

2011, 16, 128134.

(4) Murphy, C. J.; Thompson, L. B.; Alkilany, A. M.; Sisco, P. N.; Boulos, S. P.; Sivapalan, S. T.; Yang, J. A.; Chernak, D. J.; Huang, J. The many faces of gold nanorods.

J. Phys. Chem. Lett.

2010, 1, 28672875.

(5) Zhao, P.; Li, N.; Astruc, D. State of the art in gold nanoparticle synthesis.

Chem. Rev.

Coord.

2013, 257, 638665.

(6) Jones, M. R.; Osberg, K. D.; MacFarlane, R. J.; Langille, M. R.; Mirkin, C. A. Templated techniques for the synthesis and assembly of plasmonic nanostructures.

Rev. (Washington, DC, U. S.)

Chem.

2011, 111, 37363827, cited By 505.

(7) Sajanlal, P. R.; Sreeprasad, T. S.; Samal, A. K.; Pradeep, T. Anisotropic nanomaterials: structure, growth, assembly, and functions.

Nano Rev. Exp.

2011, 2, 20022727.

(8) Lakhani, P. M.; Rompicharla, S. V. K.; Ghosh, B.; Biswas, S. An overview of synthetic strategies and current applications of gold nanorods in cancer treatment.

ogy

Nanotechnol-

2015, 26, 432001143200117.

(9) Lohse, S. E.; Murphy, C. J. The quest for shape control: A history of gold nanorod synthesis.

Chem. Mater.

2013, 25, 12501261.

(10) Gupta, V. K. N.; Mehra, A.; Thaokar, R. Worm-like micelles as templates: Formation of anisotropic silver halide nanoparticles.

Colloids Surf., A

2012, 393, 73 80.

(11) Chhatre, A.; Duttagupta, S.; Thaokar, R.; Mehra, A. Mechanism of Nanorod Formation by Wormlike Micelle-Assisted Assembly of Nanospheres. 10531, PMID: 26348207.

33


Langmuir

2015,

31, 10524


Page 34 of 40

(12) Gupta, V. K. N.; Mehra, A.; Thaokar, R. A Robust worm-like micellar template based method for the synthesis of anisotropic nanoparticles.

Colloids Surf., A

2017, 531, 40

47.

(13) Gupta, V. K. N.; Mehra, A.; Thaokar, R. Self Assembly of Nickel Nanospheres into Nanoplates, Assisted by Hydrazine Hydrate.

J. Nanosci. Nanotechnol.

2017, 17, 5843

5851.

(14) Deshmukh, R.; Mehra, A.; Thaokar, R. Formation and shape-control of hierarchical cobalt nanostructures using quaternary ammonium salts in aqueous media.

Nanotechnol.

Beilstein J.

2017, 8, 494505.

(15) Deshmukh, R.; Mehra, A.; Thaokar, R. Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions.

Nanopart. Res.

J.

2016, 19, 13.

(16) Hu, M.; Chen, J.; Li, Z.-Y.; Au, L.; Hartland, G. V.; Li, X.; Marquez, M.; Xia, Y. Gold nanostructures: tions.

Chem. Soc. Rev.

engineering their plasmonic properties for biomedical applica-

2006, 35, 1084.

(17) El-Sayed, M. A. Some interesting properties of metals conned in time and nanometer space of dierent shapes.

Acc. Chem. Res.

2001, 34, 257264.

(18) Dreaden, E. C.; Alkilany, A. M.; Huang, X.; Murphy, C. J.; El-Sayed, M. A. The golden age: Gold nanoparticles for biomedicine.

Chem. Soc. Rev.

2012, 41, 27402779.

(19) Murphy, C. J.; Sau, T. K.; Gole, A. M.; Orendor, C. J.; Gao, J.; Gou, L.; Hunyadi, S. E.; Li, T. Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications.

J. Phys. Chem. B

2005, 109, 1385713870.

(20) Daniel, M.-C.; Astruc, D. Gold Nanoparticles: Assembly, Supramolecular Chemistry,

34


Page 35 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Quantum-Size-Related Properties, and Applications Toward Biology, Catalysis, and Nanotechnology.

Chem. Rev. (Washington, DC, U. S.)

2004, 104, 293346.

(21) Pérez-Juste, J.; Pastoriza-Santos, I.; Liz-Marzán, L. M.; Mulvaney, P. Gold nanorods: Synthesis, characterization and applications.

Coord. Chem. Rev.

2005, 249, 18701901.

(22) Huang, X.; El-Sayed, I. H.; Qian, W.; El-Sayed, M. A. Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods.

Soc.

J. Am. Chem.

2006, 128, 21152120.

(23) Huang, X.; El-Sayed, I. H.; Qian, W.; El-Sayed, M. A. Cancer cells assemble and align gold nanorods conjugated to antibodies to produce highly enhanced, sharp, and polarized surface Raman spectra: A potential cancer diagnostic marker.

Nano Letters

2007, 7, 15911597. (24) Chithrani, B. D.; Ghazani, A. A.; Chan, W. C. W. Determining the size and shape dependence of gold nanoparticle uptake into mammalian cells.

Nano Letters

2006, 6,

662668.

(25) Xu, X.-H. N.; Brownlow, W. J.; Kyriacou, S. V.; Wan, Q.; Viola, J. J. Real-time probing of membrane transport in living microbial cells using single nanoparticle optics and living cell imaging.

Biochemistry

2004, 43, 1040010413.

(26) Nikoobakht, B.; Wang, J.; El-Sayed, M. A. Surface-enhanced Raman scattering of molecules adsorbed on gold nanorods: O-surface plasmon resonance condition.

Phys. Lett.

Chem.

2002, 366, 1723.

(27) Zijlstra, P.; Chon, J. W. M.; Gu, M. Five-dimensional optical recording mediated by surface plasmons in gold nanorods.

Nature

2009, 459, 410413.

(28) Murphy, C. J.; Gole, A. M.; Hunyadi, S. E.; Orendor, C. J. One-dimensional colloidal gold and silver nanostructures.

Inorg. Chem.

35

2006, 45, 75447554.



Page 36 of 40

(29) Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Shape-controlled synthesis of metal nanocrystals: Simple chemistry meets complex physics?

Angew. Chem., Int. Ed.

2009,

48, 60103. (30) Grzelczak, M.; Pérez-Juste, J.; Mulvaney, P.; Liz-Marzán, L. M. Shape control in gold nanoparticle synthesis.

Chem. Soc. Rev.

2008, 37, 17831791.

(31) Jana, N. R.; Wang, Z. L.; Sau, T. K.; Pal, T. Seed-mediated growth method to prepare cubic copper nanoparticles.

Curr. Sci.

2000, 79, 1367.

(32) Jana, N. R.; Gearheart, L.; Murphy, C. J. Seed-Mediated Growth Approach for ShapeControlled Synthesis of Spheroidal and Rod-like Gold Nanoparticles Using a Surfactant Template.

Adv. Mater. (Weinheim, Ger.)

2001, 13, 13891393.

(33) Johnson, C. J.; Dujardin, E.; Davis, S. A.; Murphy, C. J.; Mann, S. Growth and form of gold nanorods prepared by seed-mediated, surfactant-directed synthesis.

Chem.

J. Mater.

2002, 12, 17651770.

(34) Nikoobakht, B.; El-Sayed, M. A. Evidence for bilayer assembly of cationic surfactants on the surface of gold nanorods.

Langmuir

2001, 17, 63686374.

(35) Henkel, A.; Schubert, O.; Plech, A.; Sönnichsen, C. Growth kinetic of a rod-shaped metal nanocrystal.

J. Phys. Chem. C

2009, 113, 1039010394.

(36) Wang, Y.-y.; Li, B.-x.; Vdovic, S.; Wang, X.-f.; Xia, A.-d. Kinetic simulation of gold nanorod growth in solution based on optical spectra.

Chin. J. Chem. Phys.

2012, 25,

135141.

(37) Takenaka, Y.; Kitahata, H. Analysis of the growth process of gold nanorods with timeresolved observation.

Phys. Rev. E

2009, 80, 02060110206014.

(38) Thomas, N.; Ethayaraja, M. An analytical solution to the kinetics of growth of gold nanorods.

RSC Adv.

2016, 6, 3002830036. 36


Page 37 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(39) Barnard, A. S.; Curtiss, L. A. Modeling the preferred shape, orientation and aspect ratio of gold nanorods.

J. Mater. Chem.

2007, 17, 33153323.

(40) Grochola, G.; Snook, I. K.; Russo, S. P. Computational modeling of nanorod growth.

J. Chem. Phys.

2007, 127, 194707119470713.

(41) Meena, S. K.; Sulpizi, M. Understanding the microscopic origin of gold nanoparticle anisotropic growth from molecular dynamics simulations.

Langmuir

2013, 29, 14954

14961.

(42) Meena, S. K.; Celiksoy, S.; Schäfer, P.; Henkel, A.; Sönnichsen, C.; Sulpizi, M. The role of halide ions in the anisotropic growth of gold nanoparticles: a microscopic, atomistic perspective.

Phys. Chem. Chem. Phys.

2016, 18, 1324613254.

(43) Busbee, B. D.; Obare, S. O.; Murphy, C. J. An improved synthesis of high-aspect-ratio gold nanorods.

Adv. Mater. (Weinheim, Ger.)

2003, 15, 414416.

(44) Nikoobakht, B.; El-Sayed, M. A. Preparation and growth mechanism of gold nanorods (NRs) using seed-mediated growth method.

Chem. Mater.

2003, 15, 19571962.

(45) Ha, T. H.; Koo, H.-J.; Chung, B. H. Shape-controlled syntheses of gold nanoprisms and nanorods inuenced by specic adsorption of halide ions.

J. Phys. Chem. C

2007, 111,

11231130.

(46) Gao, J.; Bender, C. M.; Murphy, C. J. Dependence of the Gold Nanorod Aspect Ratio on the Nature of the Directing Surfactant in Aqueous Solution.

Langmuir

2003,

19,

90659070.

(47) Pérez-Juste, J.; Liz-Marzán, L. M.; Carnie, S.; Chan, D. Y. C.; Mulvaney, P. Electriceld-directed growth of gold nanorods in aqueous surfactant solutions.

Mater.

2004, 14, 571579.

37


Adv. Funct.


Page 38 of 40

(48) Personick, M. L.; Mirkin, C. A. Making sense of the mayhem behind shape control in the synthesis of gold nanoparticles.

J. Am. Chem. Soc.

2013, 135, 1823818247.

(49) Johnson, C. L.; Snoeck, E.; Ezcurdia, M.; Rodríguez-González, B.; Pastoriza-Santos, I.; Liz-Marzán, L. M.; H¸tch, M. J. Eects of elastic anisotropy on strain distributions in decahedral gold nanoparticles.

Nat. Mater.

2008, 7, 120124.

(50) Elechiguerra, J. L.; Reyes-Gasga, J.; Yacaman, M. J. The role of twinning in shape evolution of anisotropic noble metal nanostructures.

J. Mater. Chem.

2006, 16, 3906

3919.

(51) Liao, H.; Hafner, J. H. Monitoring gold nanorod synthesis on surfaces.

B

J. Phys. Chem.

2004, 108, 1927619280.

(52) Lim, B.; Jiang, M.; Tao, J.; Camargo, P. H. C.; Zhu, Y.; Xia, Y. Shape-Controlled Synthesis of Pd Nanocrystals in Aqueous Solutions.

Adv. Funct. Mater.

2009, 19, 189

200.

(53) Gole, A.; Murphy, C. J. Seed-mediated synthesis of gold nanorods: Role of the size and nature of the seed.

Chem. Mater.

2004, 16, 36333640.

(54) Jana, N. R.; Gearheart, L.; Murphy, C. J. Wet chemical synthesis of high aspect ratio cylindrical gold nanorods.

J. Phys. Chem. B

2001, 105, 40654067.

(55) Orendor, C. J.; Murphy, C. J. Quantitation of metal content in the silver-assisted growth of gold nanorods.

J. Phys. Chem. B

2006, 110, 39903994.

(56) Gunawan, R.; Fusman, I.; Braatz, R. D. High resolution algorithms for multidimensional population balance equations.

AIChE J.

2004, 50, 27382749.

(57) Otto, W. H.; Britten, D. J.; Larive, C. K. NMR diusion analysis of surfactant-humic substance interactions.

J. Colloid Interface Sci.

38

2003, 261, 508 513.


Page 39 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(58) Yu, C.; Irudayaraj, J. Quantitative evaluation of sensitivity and selectivity of multiplex

Biophys. J.

nanoSPR biosensor assays.

2007, 93, 36843692.

(59) Raoof, J.-B.; Ojani, R.; Beitollah, H. Electrocatalytic determination of ascorbic acid at chemically modied Carbon paste electrode with 2, 7-bis (Ferrocenyl ethynyl) uoren9-one.

Int. J. Electrochem. Sci.

2007, 2, 534548.

(60) Sau, T.; Murphy, C. Role of ions in the colloidal synthesis of gold nanowires.

Mag.

Philos.

2007, 87, 21432158.

(61) Edgar, J. A.; McDonagh, A. M.; Cortie, M. B. Formation of gold nanorods by a stochastic "popcorn" mechanism.

ACS Nano

2012, 6, 11161125.

(62) Bullen, C.; Zijlstra, P.; Bakker, E.; Gu, M.; Raston, C. Chemical kinetics of gold nanorod growth in aqueous CTAB solutions.

39

Cryst. Growth Des.


2011, 11, 33753380.


Graphical TOC Entry

For Table of Contents Use Only, Title: Formation of Gold Nanorods by Seeded Growth: Mechanisms and Modeling Authors: Advait Chhatre, Rochish Thaokar, and Anurag Mehra Synopsis: We propose a mechanism for the formation of gold nanorods by seeded growth. Five-fold twinning in FCC crystals and its occurrence over a specic size range are the central ideas in the mechanism. Apart from the ability to predict the evolution of the size of nanorods and nanospheres, it also provides valuable clues for predicting the yield of nanorods.

40


Page 40 of 40

Formation of Gold Nanorods by Seeded Growth: Mechanisms and

Recommend Documents