Continuous Encodable Reshaping of Gold Nanocrystals through Facet Modulation

Lu, Fang; Zhang, Yugang; Zhang, Lihua; Su, Dong; Zhuang, Zechao; Liu, Mingzhao; Chen, Jingguang G.; Gang, Oleg

doi:10.1021/jacs.5c08014

Title: Continuous Encodable Reshaping of Gold Nanocrystals through Facet Modulation

Journal Article · Mon Jul 14 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5c08014 · OSTI ID:2574022

^[1]; Zhang, Yugang ^[1];

^[1]; Su, Dong ^[1];

^[2];

^[1]; Chen, Jingguang G. ^[3];

^[4]

Brookhaven National Laboratory (BNL), Upton, NY (United States)
Columbia University, New York City, NY (United States)
Columbia University, New York City, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Columbia University, New York City, NY (United States); Institute for Basic Science (IBS), Seoul (Korea, Republic of)

Shape control of nanocrystals (NCs) is crucial for tuning their assembly behavior and functional properties, yet the precise manipulation of facet composition remains challenging. Here, we present a nanocrystal reshaping strategy to control and modulate the facets of gold (Au) NCs. Our one-pot approach, conducted at room temperature, requires only initial Au NCs, Au³⁺ ions, and surfactants, distinguishing it from conventional reduction-mediated “etching-and-regrowth” methods. Detailed structural studies using electron microscopy, small-angle X-ray scattering (SAXS), and UV−vis spectroscopy reveal the surfactant-encoded pathway for NC transformation from shaped particles to spheres and then into various polyhedral shapes while preserving the individual particles' volume. The proposed reshaping mechanism involves the dissolution of surface Au atoms into Au⁺ complexes in the presence of Au³⁺ and surfactant, followed by surfactant-guided redeposition and formation of facets with different atomic planes. Using the ethanol oxidation reaction (EOR) as a probe, we observe a quasi-linear decrease in onset potential and an increase in activity with increasing {100} facet exposure. This work broadens synthetic strategies by offering precise NC reshaping and facet control.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Lab; Brookhaven National Laboratory; Brookhaven National Laboratory (BNL), Upton, NY (United States); Columbia Univ., New York, NY (United States)

Sponsoring Organization:: Brookhaven National Laboratory; Chemical Sciences, Geosciences, and Biosciences Division; Laboratory Directed Research and Development (LDRD); U.S. Department of Energy (DOE) Office of Science Facilities at Brookhaven National Laboratory; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0009476; SC0012704

OSTI ID:: 2574022

Report Number(s):: BNL-228494-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 29 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Metal Nanowire Networks: The Next Generation of Transparent Conductors Ye, Shengrong; Rathmell, Aaron R.; Chen, Zuofeng Advanced Materials, Vol. 26, Issue 39 https://doi.org/10.1002/adma.201402710	journal	September 2014
Nanocube Superlattices of Cesium Lead Bromide Perovskites and Pressure-Induced Phase Transformations at Atomic and Mesoscale Levels Nagaoka, Yasutaka; Hills-Kimball, Katie; Tan, Rui Advanced Materials, Vol. 29, Issue 18 https://doi.org/10.1002/adma.201606666	journal	March 2017
Seed-Mediated Growth of Colloidal Metal Nanocrystals Xia, Younan; Gilroy, Kyle D.; Peng, Hsin-Chieh Angewandte Chemie International Edition, Vol. 56, Issue 1 https://doi.org/10.1002/anie.201604731	journal	December 2016
Surface Capping Agents and Their Roles in Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals Yang, Tung‐Han; Shi, Yifeng; Janssen, Annemieke Angewandte Chemie International Edition, Vol. 59, Issue 36 https://doi.org/10.1002/anie.201911135	journal	June 2020
Seed-Mediated and Iodide-Assisted Synthesis of Gold Nanocrystals with Systematic Shape Evolution from Rhombic Dodecahedral to Octahedral Structures Chung, Pei-Ju; Lyu, Lian-Ming; Huang, Michael H. Chemistry - A European Journal, Vol. 17, Issue 35 https://doi.org/10.1002/chem.201101155	journal	July 2011
Shape Transformation via Etching and Regrowth: A Systematic Study of Pd Nanocrystals with Different Shapes and Twin Structures Lv, Tian; Liu, Maochang; Zhou, Siyu Chemistry – A European Journal, Vol. 29, Issue 48 https://doi.org/10.1002/chem.202301465	journal	August 2023
Spherical to truncated octahedral shape transformation of palladium nanocrystals driven by e-beam in aqueous solution Jiang, Yingying; Li, Xiao; Ma, Xiaoming Nano Research, Vol. 12, Issue 10 https://doi.org/10.1007/s12274-019-2498-1	journal	August 2019
Crystalline arrangements of microbubbles in monodisperse foams van der Net, Antje; Delaney, Gary W.; Drenckhan, Wiebke Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 309, Issue 1-3 https://doi.org/10.1016/j.colsurfa.2006.11.056	journal	November 2007
Electrochemical and in situ FTIR studies of ethanol adsorption and oxidation on gold single crystal electrodes in alkaline media Beyhan, Seden; Uosaki, Kohei; Feliu, Juan M. Journal of Electroanalytical Chemistry, Vol. 707 https://doi.org/10.1016/j.jelechem.2013.08.034	journal	October 2013
Polyol Synthesis of Pd Icosahedral Nanocrystals: Insights into the Growth Mechanism and Size Control Zhou, Siyu; Wang, Chenxiao; Xia, Younan Chemistry of Materials, Vol. 34, Issue 11 https://doi.org/10.1021/acs.chemmater.2c00397	journal	May 2022
Mechanistic Insights into Copper(I) and Copper(II) Cation Exchange Reactions in CdSe Nanoplatelets Banerjee, Progna; Filatov, Alexander S.; Zuo, Xiaobing Chemistry of Materials, Vol. 35, Issue 21 https://doi.org/10.1021/acs.chemmater.3c01130	journal	October 2023
Noble-Metal Nanocrystals with Controlled Shapes for Catalytic and Electrocatalytic Applications Shi, Yifeng; Lyu, Zhiheng; Zhao, Ming Chemical Reviews, Vol. 121, Issue 2 https://doi.org/10.1021/acs.chemrev.0c00454	journal	July 2020
Gold Nanomaterials at Work in Biomedicine Yang, Xuan; Yang, Miaoxin; Pang, Bo Chemical Reviews, Vol. 115, Issue 19 https://doi.org/10.1021/acs.chemrev.5b00193	journal	April 2015
The Many “Facets” of Halide Ions in the Chemistry of Colloidal Inorganic Nanocrystals Ghosh, Sandeep; Manna, Liberato Chemical Reviews, Vol. 118, Issue 16 https://doi.org/10.1021/acs.chemrev.8b00158	journal	July 2018
Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties Shamsi, Javad; Urban, Alexander S.; Imran, Muhammad Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00644	journal	February 2019
Systematic Shape Evolution of Gold Nanocrystals Achieved through Adjustment in the Amount of HAuCl₄ Solution Used Kuo, Bing-Hong; Hsia, Chi-Fu; Chen, Tzu-Ning The Journal of Physical Chemistry C, Vol. 122, Issue 43 https://doi.org/10.1021/acs.jpcc.8b08479	journal	October 2018
Digestive Ripening: A Fine Chemical Machining Process on the Nanoscale Shimpi, Jayesh R.; Sidhaye, Deepti S.; Prasad, Bhagavatula L. V. Langmuir, Vol. 33, Issue 38 https://doi.org/10.1021/acs.langmuir.7b00193	journal	June 2017
Shape Evolution of Metal Nanoparticles in Water Vapor Environment Zhu, Beien; Xu, Zhen; Wang, Chunlei Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.6b00254	journal	March 2016
Solvation Structure of Methanol-in-Salt Electrolyte Revealed by Small-Angle X-ray Scattering and Simulations Lyu, Xingyi; Wang, Haimeng; Liu, Xinyi ACS Nano, Vol. 18, Issue 9 https://doi.org/10.1021/acsnano.3c10469	journal	February 2024
Site-Selective Deposition of Silica Nanoframes and Nanocages onto Faceted Gold Nanostructures Using a Primer-free Tetraethyl Orthosilicate Synthesis Nieukirk, Brendan D.; Tang, Runze; Hughes, Robert A. ACS Nano, Vol. 18, Issue 29 https://doi.org/10.1021/acsnano.4c05258	journal	July 2024
Localized Surface Plasmon Resonance Sensors Mayer, Kathryn M.; Hafner, Jason H. Chemical Reviews, Vol. 111, Issue 6 https://doi.org/10.1021/cr100313v	journal	June 2011
Polyhedral Gold Nanocrystals with O h Symmetry: From Octahedra to Cubes Seo, Daeha; Park, Ji Chan; Song, Hyunjoon Journal of the American Chemical Society, Vol. 128, Issue 46 https://doi.org/10.1021/ja062892u	journal	November 2006
Truncated Ditetragonal Gold Prisms as Nanofacet Activators of Catalytic Platinum Lu, Fang; Zhang, Yu; Zhang, Lihua Journal of the American Chemical Society, Vol. 133, Issue 45, p. 18074-18077 https://doi.org/10.1021/ja207848e	journal	November 2011
Transformation of Pd Nanocubes into Octahedra with Controlled Sizes by Maneuvering the Rates of Etching and Regrowth Liu, Maochang; Zheng, Yiqun; Zhang, Lei Journal of the American Chemical Society, Vol. 135, Issue 32, p. 11752-11755 https://doi.org/10.1021/ja406344j	journal	July 2013
Making Sense of the Mayhem behind Shape Control in the Synthesis of Gold Nanoparticles Personick, Michelle L.; Mirkin, Chad A. Journal of the American Chemical Society, Vol. 135, Issue 49 https://doi.org/10.1021/ja408645b	journal	November 2013
Universal Noble Metal Nanoparticle Seeds Realized Through Iterative Reductive Growth and Oxidative Dissolution Reactions O’Brien, Matthew N.; Jones, Matthew R.; Brown, Keith A. Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja503509k	journal	May 2014
Selective Synthesis of Single-Crystalline Rhombic Dodecahedral, Octahedral, and Cubic Gold Nanocrystals Niu, Wenxin; Zheng, Shanliang; Wang, Dawei Journal of the American Chemical Society, Vol. 131, Issue 2, p. 697-703 https://doi.org/10.1021/ja804115r	journal	January 2009
Dynamic Transformation of High-Architectural Nanocrystal Superlattices upon Solvent Molecule Exposure Nagaoka, Yasutaka; Schneider, Jeremy; Jin, Na Journal of the American Chemical Society, Vol. 146, Issue 19 https://doi.org/10.1021/jacs.3c14603	journal	May 2024
Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh Journal of the American Chemical Society, Vol. 137, Issue 25 https://doi.org/10.1021/jacs.5b04641	journal	June 2015
Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution Lu, Fang; Zhang, Yu; Liu, Shizhong Journal of the American Chemical Society, Vol. 139, Issue 21 https://doi.org/10.1021/jacs.7b01735	journal	May 2017
Formation of Long-Range-Ordered Nanocrystal Superlattices on Silicon Nitride Substrates Lin, X. M.; Jaeger, H. M.; Sorensen, C. M. The Journal of Physical Chemistry B, Vol. 105, Issue 17 https://doi.org/10.1021/jp0102062	journal	May 2001
Spatially-Directed Oxidation of Gold Nanoparticles by Au(III)−CTAB Complexes Rodríguez-Fernández, Jessica; Pérez-Juste, Jorge; Mulvaney, Paul The Journal of Physical Chemistry B, Vol. 109, Issue 30 https://doi.org/10.1021/jp052516g	journal	August 2005
Seed-Mediated Synthesis of Gold Nanocrystals with Systematic Shape Evolution from Cubic to Trisoctahedral and Rhombic Dodecahedral Structures Wu, Hsin-Lun; Kuo, Chun-Hong; Huang, Michael H. Langmuir, Vol. 26, Issue 14 https://doi.org/10.1021/la1015065	journal	July 2010
Ultrasmooth, Highly Spherical Monocrystalline Gold Particles for Precision Plasmonics Lee, You-Jin; Schade, Nicholas B.; Sun, Li ACS Nano, Vol. 7, Issue 12 https://doi.org/10.1021/nn404765w	journal	November 2013
Glycerol Electrooxidation over Precision-Synthesized Gold Nanocrystals with Different Surface Facets Mou, Hansen; Lu, Fang; Zhuang, Zechao Precision Chemistry, Vol. 2, Issue 3 https://doi.org/10.1021/prechem.3c00105	journal	January 2024
Self-assembly of uniform polyhedral silver nanocrystals into densest packings and exotic superlattices Henzie, Joel; Grünwald, Michael; Widmer-Cooper, Asaph Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3178	journal	November 2011
Nano-optics from sensing to waveguiding Lal, Surbhi; Link, Stephan; Halas, Naomi J. Nature Photonics, Vol. 1, Issue 11 https://doi.org/10.1038/nphoton.2007.223	journal	November 2007
Octo-diamond crystal of nanoscale tetrahedra with interchanging chiral motifs Lu, Fang; Zhang, Yugang; Dwyer, Tobias Nature Materials, Vol. 24, Issue 5 https://doi.org/10.1038/s41563-025-02185-y	journal	March 2025
Evolution of gold nanoparticles through Catalan, Archimedean, and Platonic solids Kim, Do Youb; Im, Sang Hyuk; Park, O. Ok CrystEngComm, Vol. 12, Issue 1 https://doi.org/10.1039/B914353J	journal	January 2010
Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation Jin, Mingshang; Zhang, Hui; Xie, Zhaoxiong Energy Environ. Sci., Vol. 5, Issue 4 https://doi.org/10.1039/C2EE02866B	journal	January 2012
Electrocatalysis on gold Rodriguez, Paramaconi; Koper, Marc T. M. Phys. Chem. Chem. Phys., Vol. 16, Issue 27 https://doi.org/10.1039/C4CP00394B	journal	January 2014
Redox reaction induced Ostwald ripening for size- and shape-focusing of palladium nanocrystals Zhang, Zhaorui; Wang, Zhenni; He, Shengnan Chemical Science, Vol. 6, Issue 9 https://doi.org/10.1039/C5SC01787D	journal	January 2015
The role of halide ions in the anisotropic growth of gold nanoparticles: a microscopic, atomistic perspective Meena, Santosh Kumar; Celiksoy, Sirin; Schäfer, Philipp Physical Chemistry Chemical Physics, Vol. 18, Issue 19 https://doi.org/10.1039/C6CP01076H	journal	January 2016
Stepwise evolution of Au micro/nanocrystals from an octahedron into a truncated ditetragonal prism Qin, Yazhou; Pan, Wufan; Yu, Dongdong Chemical Communications, Vol. 54, Issue 27 https://doi.org/10.1039/C8CC00973B	journal	January 2018
Influence of morphology on the blinking mechanisms and the excitonic fine structure of single colloidal nanoplatelets Hu, Zhongjian; Singh, Ajay; Goupalov, Serguei V. Nanoscale, Vol. 10, Issue 48 https://doi.org/10.1039/C8NR06234J	journal	January 2018
Shape-controlled synthesis and self-assembly of highly uniform upconverting calcium fluoride nanocrystals Paik, Taejong; Greybush, Nicholas J.; Najmr, Stan Inorganic Chemistry Frontiers, Vol. 11, Issue 1 https://doi.org/10.1039/D3QI01864D	journal	January 2024
Reshaping and LSPR tuning of Au nanostars in the presence of CTAB Rodríguez-Lorenzo, Laura; Romo-Herrera, José M.; Pérez-Juste, Jorge Journal of Materials Chemistry, Vol. 21, Issue 31 https://doi.org/10.1039/c1jm10603a	journal	January 2011
Optical properties of rodlike and bipyramidal gold nanoparticles from three-dimensional computations Liu, Mingzhao; Guyot-Sionnest, Philippe; Lee, Tae-Woo Physical Review B, Vol. 76, Issue 23 https://doi.org/10.1103/PhysRevB.76.235428	journal	December 2007
Periodic lattices of arbitrary nano-objects: modeling and applications for self-assembled systems Yager, Kevin G.; Zhang, Yugang; Lu, Fang Journal of Applied Crystallography, Vol. 47, Issue 1 https://doi.org/10.1107/S160057671302832X	journal	December 2013
Quantitative 3D evolution of colloidal nanoparticle oxidation in solution Sun, Yugang; Zuo, Xiaobing; Sankaranarayanan, Subramanian K. R. S. Science, Vol. 356, Issue 6335 https://doi.org/10.1126/science.aaf6792	journal	April 2017
Adsorption and desorption behaviors of cetylpyridinium chloride on hydroxyapatite nanoparticles with different morphologies Okada, Masahiro; Hiramatsu, Daisuke; Okihara, Takumi Dental Materials Journal, Vol. 35, Issue 4 https://doi.org/10.4012/dmj.2015-420	journal	January 2016

Similar Records

Nucleation-mediated reshaping of facetted metallic nanocrystals: Breakdown of the classical free energy picture

Journal Article · Tue Feb 14 00:00:00 UTC 2023 · Journal of Chemical Physics · OSTI ID:1960543

Lai, King C.; Liu, Da-Jiang; Evans, James W.

Glycerol Electrooxidation over Precision-Synthesized Gold Nanocrystals with Different Surface Facets

Journal Article · Thu Jan 25 00:00:00 UTC 2024 · Precision Chemistry · OSTI ID:2282826

Mou, Hansen; Lu, Fang; Zhuang, Zechao; +5 more

Thermal Shape Stability of fcc Metal Nanocrystals Synthesized with Faceted Nonequilibrium Shapes

Journal Article · Mon Apr 22 00:00:00 UTC 2024 · Journal of Physical Chemistry. C · OSTI ID:2340127

Lai, King C.; Liu, Da-Jiang; Huang, Wenyu; +2 more

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical reactions
Gold
Nanoparticles
Surfactants
X-ray scattering

Title: Continuous Encodable Reshaping of Gold Nanocrystals through Facet Modulation

Citation Formats

References (51)

Similar Records

Related Subjects