Downloads

https://doi.org/10.53941/mi.2025.100017
He, J., Yu, H., & Xia, Y. Steady-State Synthesis of Colloidal Metal Nanocrystals. Materials and Interfaces. 2025, 2(2), 213–225. doi: https://doi.org/10.53941/mi.2025.100017
Volume 2, Issue 2, 2025
Copyright (c) 2025 by the authors.
Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

Despite remarkable progress, colloidal synthesis of metal nanocrystal is still far away from reaching the goal for robust, reproducible, and scalable production. Even with the adoption of seed-mediated growth, the synthesis can still be complicated by issues such as self-nucleation, galvanic replacement, stochastic symmetry reduction, and unwanted compositional variation. All these issues can be addressed by switching to steady-state synthesis characterized by a slow, constant, and tightly controlled reduction rate. Steady-state synthesis can be achieved by adding one reactant dropwise while using the other reactant in large excess, but this method is not suitable for scale-up production in a continuous flow reactor. There is a pressing need to develop alternative methods capable of establishing the steady-state kinetics characteristic of dropwise addition while introducing both reactants by one-shot injection. In this Perspective, we discuss a number of methods that allow for both one-shot injection and steady-state synthesis.

References

  1. Sun, S.; Murray, C.B.; Weller, D.; Folks, L.; Moser, A. Monodisperse FePt Nanoparticles and Ferromagnetic FePt Nanocrystal Superlattices. Science 2000, 287, 1989–1992. doi: 10.1126/science.287.5460.1989
  2. Jin, R.; Cao, Y.; Mirkin, C.A.; Kelly, K.L.; Schatz, G.C.; Zheng, J.G. Photoinduced Conversion of Silver Nanospheres to Nanoprisms. Science 2001, 294, 1901–1903. doi: 10.1126/science.1066541
  3. 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, 60–103. doi: 10.1002/anie.200802248
  4. Nguyen, Q.N.; Wang, C.; Shang, Y.; Janssen, A.; Xia, Y. Colloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry Breaking. Chem. Rev. 2023, 123, 3693–3760. doi: 10.1021/acs.chemrev.2c00468
  5. Quan, Z.; Wang, Y.; Fang, J. High-Index Faceted Noble Metal Nanocrystals. Acc. Chem. Res. 2013, 46, 191–202. doi: 10.1021/ar200293n
  6. Sherry, L.J.; Chang, S.-H.; Schatz, G.C.; Van Duyne, R.P.; Wiley, B.J.; Xia, Y. Localized Surface Plasmon Resonance Spectroscopy of Single Silver Nanocubes. Nano Lett. 2005, 5, 2034–2038. doi: 10.1021/nl0515753
  7. Bratlie, K.M.; Lee, H.; Komvopoulos, K.; Yang, P.; Somorjai, G.A. Platinum Nanoparticle Shape Effects on Benzene Hydrogenation Selectivity. Nano Lett. 2007, 7, 3097–3101. doi: 10.1021/nl0716000
  8. Guo, S.; Zhang, S.; Sun, S. Tuning Nanoparticle Catalysis for the Oxygen Reduction Reaction. Angew. Chem. Int. Ed. 2013, 52, 8526–8544. doi: 10.1002/anie.201207186
  9. Shi, Y.; Lyu, Z.; Zhao, M.; Chen, R.; Nguyen, Q.N.; Xia, Y. Noble-Metal Nanocrystals with Controlled Shapes for Catalytic and Electrocatalytic Applications. Chem. Rev. 2021, 121, 649–735. doi: 10.1021/acs.chemrev.0c00454
  10. Rathmell, A.R.; Bergin, S.M.; Hua, Y.; Li, Z.; Wiley, B.J. The Growth Mechanism of Copper Nanowires and Their Properties in Flexible, Transparent Conducting Films. Adv. Mater. 2010, 22, 3558–3563. doi: 10.1002/adma.201000775
  11. Li, M.; Zhao, Z.; Cheng, T.; Fortunelli, A.; Chen, C.-Y.; Yu, R.; Zhang, Q.; Gu, L.; Merinov, B.V.; Lin, Z.; et al. Ultrafine Jagged Platinum Nanowires Enable Ultrahigh Mass Activity for the Oxygen Reduction Reaction. Science 2016, 354, 1414–1419. doi: 10.1126/science.aaf9050
  12. Burda, C.; Chen, X.; Narayanan, R.; El-Sayed, M.A. Chemistry and Properties of Nanocrystals of Different Shapes. Chem. Rev. 2005, 105, 1025–1102. doi: 10.1021/cr030063a
  13. 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. Chem. Rev. 2011, 111, 3736–3827. doi: 10.1021/cr1004452
  14. Wang, Y.; Black, K.C.L.; Luehmann, H.; Li, W.; Zhang, Y.; Cai, X.; Wan, D.; Liu, S.-Y.; Li, M.; Kim, P.; et al. Comparison Study of Gold Nanohexapods, Nanorods, and Nanocages for Photothermal Cancer Treatment. ACS Nano 2013, 7, 2068–2077. doi: 10.1021/nn304332s
  15. Linic, S.; Christopher, P.; Ingram, D.B. Plasmonic-Metal Nanostructures for Efficient Conversion of Solar to Chemical Energy. Nat. Mater. 2011, 10, 911–921. doi: 10.1038/nmat3151
  16. Lee, I.; Delbecq, F.; Morales, R.; Albiter, M.A.; Zaera, F. Tuning Selectivity in Catalysis by Controlling Particle Shape. Nat. Mater. 2009, 8, 132–138. doi: 10.1038/nmat2371
  17. Reske, R.; Mistry, H.; Behafarid, F.; Roldan Cuenya, B.; Strasser, P. Particle Size Effects in the Catalytic Electroreduction of CO2 on Cu Nanoparticles. J. Am. Chem. Soc. 2014, 136, 6978–6986. doi: 10.1021/ja500328k
  18. Singh, A.R.; Rohr, B.A.; Schwalbe, J.A.; Cargnello, M.; Chan, K.; Jaramillo, T.F.; Chorkendorff, I.; Nørskov, J.K. Electrochemical Ammonia Synthesis—The Selectivity Challenge. ACS Catal. 2017, 7, 706–709. doi: 10.1021/acscatal.6b03035
  19. Kang, Y.; Li, M.; Cai, Y.; Cargnello, M.; Diaz, R.E.; Gordon, T.R.; Wieder, N.L.; Adzic, R.R.; Gorte, R.J.; Stach, E.A.; et al. Heterogeneous Catalysts Need Not Be so “Heterogeneous”: Monodisperse Pt Nanocrystals by Combining Shape-Controlled Synthesis and Purification by Colloidal Recrystallization. J. Am. Chem. Soc. 2013, 135, 2741–2747. doi: 10.1021/ja3116839
  20. Kline, T.R.; Paxton, W.F.; Mallouk, T.E.; Sen, A. Catalytic Nanomotors: Remote-Controlled Autonomous Movement of Striped Metallic Nanorods. Angew. Chem. Int. Ed. 2005, 44, 744–746. doi: 10.1002/anie.200461890
  21. Choi, S.-I.; Xie, S.; Shao, M.; Odell, J.H.; Lu, N.; Peng, H.-C.; Protsailo, L.; Guerrero, S.; Park, J.; Xia, X.; et al. Synthesis and Characterization of 9 nm Pt–Ni Octahedra with a Record High Activity of 3.3 A/mgPt for the Oxygen Reduction Reaction. Nano Lett. 2013, 13, 3420–3425. doi: 10.1021/nl401881z
  22. Zhang, J.; Yang, H.; Fang, J.; Zou, S. Synthesis and Oxygen Reduction Activity of Shape-Controlled Pt3Ni Nanopolyhedra. Nano Lett. 2010, 10, 638–644. doi: 10.1021/nl903717z
  23. Xie, M.; Shen, M.; Chen, R.; Xia, Y. Development of Highly-Active Catalysts toward Oxygen Reduction by Controlling the Shape and Composition of Pt–Ni Nanocrystals. ACS Appl. Mater. Interfaces 2023, 15, 49146–49153. doi: 10.1021/acsami.3c10514
  24. Xia, Y.; Gilroy, K.D.; Peng, H.-C.; Xia, X. Seed-Mediated Growth of Colloidal Metal Nanocrystals. Angew. Chem. Int. Ed. 2017, 56, 60–95. doi: 10.1002/anie.201604731
  25. Zhang, H.; Li, W.; Jin, M.; Zeng, J.; Yu, T.; Yang, D.; Xia, Y. Controlling the Morphology of Rhodium Nanocrystals by Manipulating the Growth Kinetics with a Syringe Pump. Nano Lett. 2011, 11, 898–903. doi: 10.1021/nl104347j
  26. Peng, H.-C.; Park, J.; Zhang, L.; Xia, Y. Toward a Quantitative Understanding of Symmetry Reduction Involved in the Seed-Mediated Growth of Pd Nanocrystals. J. Am. Chem. Soc. 2015, 137, 6643–6652. doi: 10.1021/jacs.5b03040
  27. Wang, C.; Huang, Z.; Ding, Y.; Xie, M.; Chi, M.; Xia, Y. Facet-Controlled Synthesis of Platinum-Group-Metal Quaternary Alloys: The Case of Nanocubes and {100} Facets. J. Am. Chem. Soc. 2023, 145, 2553–2560. doi: 10.1021/jacs.2c12368
  28. Wang, C.; He, J.; Xia, Y. Controlling the Composition and Elemental Distribution of Bi- and Multi-Metallic Nanocrystals via Dropwise Addition. Nat. Synth. 2024, 3, 1076–1082. doi: 10.1038/s44160-024-00600-x
  29. Niu, G.; Ruditskiy, A.; Vara, M.; Xia, Y. Toward Continuous and Scalable Production of Colloidal Nanocrystals by Switching from Batch to Droplet Reactors. Chem. Soc. Rev. 2015, 44, 5806–5820. doi: 10.1039/C5CS00049A
  30. Zhou, M.; Wang, H.; Vara, M.; Hood, Z.D.; Luo, M.; Yang, T.-H.; Bao, S.; Chi, M.; Xiao, P.; Zhang, Y.; et al. Quantitative Analysis of the Reduction Kinetics Responsible for the One-Pot Synthesis of Pd–Pt Bimetallic Nanocrystals with Different Structures. J. Am. Chem. Soc. 2016, 138, 12263–12270. doi: 10.1021/jacs.6b07213
  31. Luty-Błocho, M.; Pacławski, K.; Wojnicki, M.; Fitzner, K. The Kinetics of Redox Reaction of Gold(III) Chloride Complex Ions with L-Ascorbic Acid. Inorg. Chim. Acta 2013, 395, 189–196. doi: 10.1016/j.ica.2012.10.031
  32. Corbett, J.F. Pseudo First-Order Kinetics. J. Chem. Educ. 1972, 49, 663. doi: 10.1021/ed049p663
  33. Yang, T.-H.; Gilroy, K.D.; Xia, Y. Reduction Rate as a Quantitative Knob for Achieving Deterministic Synthesis of Colloidal Metal Nanocrystals. Chem. Sci. 2017, 8, 6730–6749. doi: 10.1039/C7SC02833D
  34. Smith, J.H.; Luo, Q.; Millheim, S.L.; Millstone, J.E. Decoupling Intrinsic Metal Ion Reduction Rates from Structural Outcomes in Multimetallic Nanoparticles. J. Am. Chem. Soc. 2024, 146, 34822–34832. doi: 10.1021/jacs.4c13826
  35. Rodrigues, T.S.; Zhao, M.; Yang, T.-H.; Gilroy, K.D.; da Silva, A.G.M.; Camargo, P.H.C.; Xia, Y. Synthesis of Colloidal Metal Nanocrystals: A Comprehensive Review on the Reductants. Chem. Eur. J. 2018, 24, 16944–16963. doi: 10.1002/chem.201802194
  36. Zhang, H.; Lu, Y.; Liu, H.; Fang, J. Controllable Synthesis of Three-Dimensional Branched Gold Nanocrystals Assisted by Cationic Surfactant Poly(Diallyldimethylammonium) Chloride in Acidic Aqueous Solution. RSC Adv. 2014, 4, 36757–36764. doi: 10.1039/C4RA07535H
  37. Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid. J. Am. Chem. Soc. 2008, 130, 5406–5407. doi: 10.1021/ja800656y
  38. Wilkins, P.C.; Johnson, M.D.; Holder, A.A.; Crans, D.C. Reduction of Vanadium(V) by L-Ascorbic Acid at Low and Neutral pH: Kinetic, Mechanistic, and Spectroscopic Characterization. Inorg. Chem. 2006, 45, 1471–1479. doi: 10.1021/ic050749g
  39. Yu, H.; He, J.; Li, K.K.; Huang, Q.; Ding, Y.; Xia, Y. Synthesis of Ag@Pd Nanocubes and Pd-Based Nanoframes via One-Shot Injection of a Halide-Free Precursor for Continuous Production in a Flow Reactor. Chem. Eur. J. 2025, 31, e202500201. doi: 10.1002/chem.202500201
  40. Fiévet, F.; Ammar-Merah, S.; Brayner, R.; Chau, F.; Giraud, M.; Mammeri, F.; Peron, J.; Piquemal, J.-Y.; Sicard, L.; Viau, G. The Polyol Process: A Unique Method for Easy Access to Metal Nanoparticles with Tailored Sizes, Shapes and Compositions. Chem. Soc. Rev. 2018, 47, 5187–5233. doi: 10.1039/C7CS00777A
  41. Sun, Y.; Xia, Y. Shape-Controlled Synthesis of gold and silver nanoparticles. Science 2002, 298, 2176–2179. doi: 10.1126/science.1077229
  42. Zhang, D.; Chen, Y.; Huang, Y.-S.; Huang, Q.; Kwan Li, K.; Xia, Y. Robust, Reproducible, and Scalable Synthesis of Silver Nanocubes. Chem. Eur. J. 2024, 30, e202400833. doi: 10.1002/chem.202400833
  43. Wiley, B.J.; Xiong, Y.; Li, Z.-Y.; Yin, Y.; Xia, Y. Right Bipyramids of Silver: A New Shape Derived from Single Twinned Seeds. Nano Lett. 2006, 6, 765–768. doi: 10.1021/nl060069q
  44. Wiley, B.J.; Sun, Y.; Xia, Y. Synthesis of Silver Nanostructures with Controlled Shapes and Properties. Acc. Chem. Res. 2007, 40, 1067–1076. doi: 10.1021/ar7000974
  45. Skrabalak, S.E.; Wiley, B.J.; Kim, M.; Formo, E.V.; Xia, Y. On the Polyol Synthesis of Silver Nanostructures: Glycolaldehyde as a Reducing Agent. Nano Lett. 2008, 8, 2077–2081. doi: 10.1021/nl800910d
  46. Sun, Y.; Gates, B.; Mayers, B.; Xia, Y. Crystalline Silver Nanowires by Soft Solution Processing. Nano Lett. 2002, 2, 165–168. doi: 10.1021/nl010093y
  47. Sun, Y.; Mayers, B.; Herricks, T.; Xia, Y. Polyol Synthesis of Uniform Silver Nanowires: A Plausible Growth Mechanism and the Supporting Evidence. Nano Lett. 2003, 3, 955–960. doi: 10.1021/nl034312m
  48. Korte, K.E.; Skrabalak, S.E.; Xia, Y. Rapid Synthesis of Silver Nanowires through a CuCl- or CuCl2-Mediated Polyol Process. J. Mater. Chem. 2008, 18, 437–441. doi: 10.1039/B714072J
  49. Chan, J.M.; Zhang, L.; Yuet, K.P.; Liao, G.; Rhee, J.-W.; Langer, R.; Farokhzad, O.C. PLGA–Lecithin–PEG Core–Shell Nanoparticles for Controlled Drug Delivery. Biomaterials 2009, 30, 1627–1634. doi: 10.1016/j.biomaterials.2008.12.013
  50. Fredenberg, S.; Wahlgren, M.; Reslow, M.; Axelsson, A. The Mechanisms of Drug Release in Poly(Lactic-Co-Glycolic Acid)-Based Drug Delivery Systems—A Review. Int. J. Pharm. 2011, 415, 34–52. doi: 10.1016/j.ijpharm.2011.05.049