An Application of The Thermodynamic Approach to Explain the Shape Selection During Light-Induced Growth of Silver Nanoparticles
DOI:
https://doi.org/10.15330/pcss.27.1.20-26Keywords:
silver nanoparticles, light-induced synthesis, spectra, optical properties, photon energy, etching, surface energy, crystal growth, thermodynamics, solutionAbstract
Synthesis of silver nanoparticles of different shapes and sizes by the chemical reduction of Ag+ may be strongly influenced by the light irradiation. A key question is understanding the mechanism underlying the transformation of initial spherical seeds into prisms and decahedra under visible light. In this study, we summarize existing theories of light-induced nanoparticle growth and apply a thermodynamic approach to shape selection during the synthesis of silver nanoparticles. We propose a universal thermodynamic model that explains both the influence of light on the synthesis and transformation of silver nanoparticles in the presence of H2O2. This model accounts for the shift of the chemical potential relative to interfacial energies and the monoatomic step energies on the {111} facets. Our results demonstrate that the morphology of silver nanoparticles is determined primarily by photon energy rather than by the chemical nature of the reagents.
References
Y. Hang, A. Wanga, N. Wu, Plasmonic silver and gold nanoparticles: shape- and structure-modulated plasmonic functionality for point-of-caring sensing, bio-imaging and medical therapy, Chem. Soc. Rev., 53, 2932 (2024); https://doi.org/10.1039/D3CS00793F.
A. Loiseau, V. Asila, G. Boitel-Aullen, M. Lam, M. Salmain, S. Boujday, Silver-Based Plasmonic Nanoparticles for and Their Use in Biosensing, Biosensors (Basel), 9(2), 78 (2019); https://doi.org/10.3390/bios9020078.
T. Bruna, F. Maldonado-Bravo, P. Jara, N. Caro, Silver Nanoparticles and Their Antibacterial Applications, International Journal of Molecular Sciences, 22, 7202 (2021); https://doi.org/10.3390/ijms22137202.
D. Goyal, G. Kaur, R. Tewari, R. Kumar, Correlation of edge truncation with antibacterial activity of plate-like anisotropic silver nanoparticles. Environmental Science and Pollution Research, 24, 20429 (2017); https://doi.org/10.1007/s11356-017-9630-0.
J. Helmlinger, C. Sengstock, C. Groß-Heitfeld, C. Mayer, T. Schildhauer, M. Köller, M. Epple, Silver nanoparticles with different size and shape: equal cytotoxicity, but different antibacterial effects. RSC Advances, 6, 18490 (2016); https://doi.org/10.1039/C5RA27836H.
M. Guzman, J. Dille, S. Godet, Synthesis of silver nanoparticles by chemical reduction method and their antibacterial activity. International Journal of Chemical and Biomolecular Engineering, 2(3), 104 (2009).
Z. Zaheer, Biogenic synthesis, optical, catalytic, and in vitro antimicrobial potential of Ag-nanoparticles prepared using Palm date fruit extract, Journal of Photochemistry and Photobiology B: Biology, 178, 584 (2018); https://doi.org/10.1016/j.jphotobiol.2017.12.002.
K. Kelly, E. Coronado, L. Zhao, G. Schatz, The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment, J. Phys, Chem. B, 107, 668 (2003); https://doi.org/10.1021/jp026731y.
R. Jin, Y. Cao, C. Mirkin, K. Kelly, G. Schatz, J. Zheng, Photoinduced conversion of silver nanospheres to nanoprisms, Science, 294(5548), 1901 (2001); https://doi.org/10.1126/science.1066541.
L. Hirsch, R. Stafford, J. Bankson, S. Sershen, B. Rivera, R. Price, J Hazle, N. Halas, J. West, Nanoshell-mediated near-infrared thermal therapy of tumors under magnetic resonance guidance, Proc Natl Acad Sci U S A, 100(23), 13549 (2003); https://doi.org/10.1073/pnas.2232479100.
M. Langille, M. Personick, C. Mirkin, Plasmon-Mediated Syntheses of Metallic Nanostructures, Angewandte Chemie International Edition, 52(52), 13910 (2013); https://doi.org/10.1002/anie.201301875.
K. Stamplecoskie, J. Scaiano, Light Emitting Diode Irradiation Can Control the Morphology and Optical Properties of Silver Nanoparticles, J. Am. Chem. Soc., 132(6), 1825 (2010), https://doi.org/10.1021/ja910010b.
L.-C. Yang, Y.-S. Lai, C.-M. Tsai, Y.-T. Kong, C.-I. Lee, C.-L. Huang, One-Pot Synthesis of Monodispersed Silver Nanodecahedra with Optimal SERS Activities Using Seedless Photo-Assisted Citrate Reduction Method, J. Phys. Chem. C, 116(45), 24292 (2012); https://doi.org/10.1021/jp306308w.
C. Kittel, Introduction to Solid State Physics, 8th ed. (John Wiley & Sons, 2005).
Y. Xia, Y. Xiong, B. Lim, S. Skrabalak, Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics? Angewandte Chemie International Edition, 48(1), 60- (2008); https://doi.org/10.1002/anie.200802248.
J. Zhang, M. R. Langille, C. A. Mirkin, Photomediated Synthesis of Silver Triangular Bipyramids and Prisms: The Effect of pH and BSPP, J. Am. Chem. Soc., 132(35), 12502 (2010); https://doi.org/10.1021/ja106008b.
J. Zhang, M. R. Langille, C. A. Mirkin, Synthesis of Silver Nanorods by Low Energy Excitation of Spherical Plasmonic Seeds, Nano Lett., 11(6), 2495 (1011); https://doi.org/10.1021/nl2009789.
B. Pietrobon, V. Kitaev, Photochemical Synthesis of Monodisperse Size-Controlled Silver Decahedral Nanoparticles and Their Remarkable Optical Properties, Chem. Mater., 20(16), 5186 (2008); https://doi.org/10.1021/cm800926u.
B. Viswanath, P. Kundu, B. Mukherjee, N. Ravishankar, Predicting the Growth of Two-Dimensional Nanostructures, Nanotechnology, 19(19), 195603 (2008); https://doi.org/10.1088/0957-4484/19/19/195603.
B. Viswanath, P. Kundu, A. Halder, N. Ravishankar, Mechanistic Aspects of Shape Selection and Symmetry Breaking during Nanostructure Growth by Wet Chemical Methods, J. Phys. Chem. C, 113(39), 16866 (2009); https://doi.org/10.1021/jp903370f.
A. Korop, Y. Khalavka, International Conference Correlation Optics (SPIE Proceedings Chernivtsi, Ukraine, 2023), p. 129382I; https://doi.org/10.1117/12.3016087.
J. Cahn, Theory of Crystal Growth and Interface Motion in Crystalline Materials, Acta Metall, 8(8), 554 (1960); https://doi.org/10.1016/0001-6160(60)90110-3.
J. Cahn, W. Hillig, G. Sears, The molecular mechanism of solidification, Acta Metall, 12(12), 1421 (1964); https://doi.org/10.1016/0001-6160(64)90130-0.
W. Burton, N. Cabrera, F. Frank, The Growth of Crystals and the Equilibrium Structure of Their Surfaces, Phil. Trans. R. Soc. A, 243, 299 (1951); https://doi.org/10.1098/rsta.1951.0006.
Y. Khalavka, Metal and Semiconductor Heteronanostructures, Dissertation, Johannes Gutenberg-Universität Mainz, (2015).
X. Wu, P. Redmond, H. Liu, Y. Chen, M. Steigerwald, L. Brus, Photovoltage Mechanism for Room Light Conversion of Citrate Stabilized Silver Nanocrystal Seeds to Large Nanoprisms, J. Am. Chem. Soc., 130(29), 9500 (2008); https://doi.org/10.1021/ja8018669.
C. Xue, G. Métraux, J. Millstone, C. Mirkin, Mechanistic Study of Photomediated Triangular Silver Nanoprism Growth, J. Am. Chem. Soc., 130(26), 8337 (2008); https://doi.org/10.1021/ja8005258.
A. Ivanova-Tolpintseva, O. Tynkevych, A. Diaconu, A. Rotaru, Y. Khalavka, Synthesis and light-induced aggregation of benzoate-stabilized silver nanoparticles, Applied Nanoscience, 9, 709 (2019); https://doi.org/10.1007/s13204-018-0847-0.
X. Zheng, W. Xu, C. Corredor, S. Xu, J. An, B. Zhao, J. Lombardi, Laser-Induced Growth of Monodisperse Silver Nanoparticles with Tunable Surface Plasmon Resonance Properties and a Wavelength Self-Limiting Effect, J. Phys. Chem. C, 111(41), 14962 (2007); https://doi.org/10.1021/jp074583b.
B. Tang, S. Xu, J. An, B. Zhao, W. Xu, Photoinduced Shape Conversion and Reconstruction of Silver Nanoprisms, J. Phys. Chem. C, 113(17), 7025 (2009); https://doi.org/10.1021/jp810711a.
G. Lee, A. Minett, P. Innis, G. Wallace, A new twist: controlled shape-shifting of silver nanoparticles from prisms to discs, J. Mater. Chem., 19(44), 8294 (2009); https://doi.org/10.1039/B913811K.
D. He, S. Garg, T. Waite, H2O2-Mediated Oxidation of Zero-Valent Silver and Resultant Interactions among Silver Nanoparticles, Silver Ions, and Reactive Oxygen Species, Langmuir, 28, 10266 (2012); https://doi.org/10.1021/la300929g.
C. Ho, S. Yau, C. Lok, M. So, C. Che, Oxidative Dissolution of Silver Nanoparticles by Biologically Relevant Oxidants: A Kinetic and Mechanistic Study, Chem. Asian J., 5, 285 (2010); https://doi.org/10.1002/asia.200900387.
K. Li, Q. Wu, Y. Shan, S. Qiu, F. Cui, Y. Lin, Z. Chen, C. Guo, T. Zheng, Shape Transformation of Ag Nanospheres to Triangular Ag Nanoplates: Hydrogen Peroxide is a Magic Reagent, Integrated Ferroelectrics, 169(1), 22 (2016); http://dx.doi.org/10.1080/10584587.2016.1162594.
M. Tsuji, S. Gomi, Y. Maeda, M. Matsunaga, S. Hikino, K. Uto, T. Tsuji, H. Kawazumi, Rapid Transformation from Spherical Nanoparticles, Nanorods, Cubes, or Bipyramids to Triangular Prisms of Silver with PVP, Citrate, and H2O2, Langmuir, 28, 8845 (2012); https://doi.org/10.1021/la3001027.
Y. Khalavka, S. Harms, A. Henkel, M. Strozyk, R. Ahijado-Guzman, C. Sönnichsen, Synthesis of Au–CdS@CdSe Hybrid Nanoparticles with a Highly Reactive Gold Domain, Langmuir, 34(1), 187 (2018); https://doi.org/10.1021/acs.langmuir.7b02756.
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