Adsorption of ethylenediamine on Cu surfaces: attributes of a successful capping molecule using first-principles calculations
Abstract
The shape-controlled synthesis of Cu nanocrystals can benefit a wide range of applications, though challenges exist in achieving high and selective yields to a particular shape. Capping agents play a pivotal role in controlling shape, but their exact role remains ambiguous. In this study, the adsorption of ethylenediamine (EDA) on Cu(100) and Cu(111) was investigated with quantum density functional theory (DFT) to reveal the complex roles of EDA in promoting penta-twinned Cu nanowire growth. We find EDA has stronger binding on Cu(100) than on Cu(111), which agrees the general expectation that penta-twinned Cu nanowires express facets with stronger capping-molecule binding. Despite this stronger binding, ab initio thermodynamics reveals the surface energy of EDA-covered Cu(111) is lower than that EDA-covered Cu(100) at all solution-phase EDA chemical potentials, so there is no thermodynamic driving force for penta-twinned nanowires. We also investigated the capability of EDA to protect Cu surfaces from oxidation in water by quantifying energy barriers for a water molecule to diffuse through EDA layers on Cu(100) and Cu(111). The energy barrier on Cu(100) is significantly lower, which supports observations of faster oxidation of Cu(100) in electrochemical experiments. Thus, we elucidate another possible function of a capping agent – to enablemore »
- Publication Date:
- Research Org.:
- Pennsylvania State Univ., University Park, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF); USDOE
- OSTI Identifier:
- 1849766
- Alternate Identifier(s):
- OSTI ID: 1811585
- Grant/Contract Number:
- FG02-07ER46414; DGE-1449785
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 31; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
Citation Formats
Chen, Zihao, and Fichthorn, Kristen A. Adsorption of ethylenediamine on Cu surfaces: attributes of a successful capping molecule using first-principles calculations. United States: N. p., 2021.
Web. doi:10.1039/d1nr03173b.
Chen, Zihao, & Fichthorn, Kristen A. Adsorption of ethylenediamine on Cu surfaces: attributes of a successful capping molecule using first-principles calculations. United States. https://doi.org/10.1039/d1nr03173b
Chen, Zihao, and Fichthorn, Kristen A. Tue .
"Adsorption of ethylenediamine on Cu surfaces: attributes of a successful capping molecule using first-principles calculations". United States. https://doi.org/10.1039/d1nr03173b. https://www.osti.gov/servlets/purl/1849766.
@article{osti_1849766,
title = {Adsorption of ethylenediamine on Cu surfaces: attributes of a successful capping molecule using first-principles calculations},
author = {Chen, Zihao and Fichthorn, Kristen A.},
abstractNote = {The shape-controlled synthesis of Cu nanocrystals can benefit a wide range of applications, though challenges exist in achieving high and selective yields to a particular shape. Capping agents play a pivotal role in controlling shape, but their exact role remains ambiguous. In this study, the adsorption of ethylenediamine (EDA) on Cu(100) and Cu(111) was investigated with quantum density functional theory (DFT) to reveal the complex roles of EDA in promoting penta-twinned Cu nanowire growth. We find EDA has stronger binding on Cu(100) than on Cu(111), which agrees the general expectation that penta-twinned Cu nanowires express facets with stronger capping-molecule binding. Despite this stronger binding, ab initio thermodynamics reveals the surface energy of EDA-covered Cu(111) is lower than that EDA-covered Cu(100) at all solution-phase EDA chemical potentials, so there is no thermodynamic driving force for penta-twinned nanowires. We also investigated the capability of EDA to protect Cu surfaces from oxidation in water by quantifying energy barriers for a water molecule to diffuse through EDA layers on Cu(100) and Cu(111). The energy barrier on Cu(100) is significantly lower, which supports observations of faster oxidation of Cu(100) in electrochemical experiments. Thus, we elucidate another possible function of a capping agent – to enable selective oxidation of crystal facets. This finding adds to the general understanding of successful attributes of capping agents for shape-selective nanocrystal growth.},
doi = {10.1039/d1nr03173b},
journal = {Nanoscale},
number = 31,
volume = 13,
place = {United States},
year = {Tue Jul 27 00:00:00 EDT 2021},
month = {Tue Jul 27 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Adsorption of Amine Compounds on the Au(111) Surface: A Density Functional Study
journal, August 2007
- Hoft, Rainer C.; Ford, Michael J.; McDonagh, Andrew M.
- The Journal of Physical Chemistry C, Vol. 111, Issue 37
The Growth Mechanism of Copper Nanowires and Their Properties in Flexible, Transparent Conducting Films
journal, June 2010
- Rathmell, Aaron R.; Bergin, Stephen M.; Hua, Yi-Lei
- Advanced Materials, Vol. 22, Issue 32
Quantitative Analysis of the Role Played by Poly(vinylpyrrolidone) in Seed-Mediated Growth of Ag Nanocrystals
journal, January 2012
- Xia, Xiaohu; Zeng, Jie; Oetjen, L. Kyle
- Journal of the American Chemical Society, Vol. 134, Issue 3
Theoretical Description of the Role of Halides, Silver, and Surfactants on the Structure of Gold Nanorods
journal, January 2014
- Almora-Barrios, Neyvis; Novell-Leruth, Gerard; Whiting, Peter
- Nano Letters, Vol. 14, Issue 2
Density-Functional Theory with Screened van der Waals Interactions for the Modeling of Hybrid Inorganic-Organic Systems
journal, April 2012
- Ruiz, Victor G.; Liu, Wei; Zojer, Egbert
- Physical Review Letters, Vol. 108, Issue 14
How Copper Nanowires Grow and How To Control Their Properties
journal, February 2016
- Ye, Shengrong; Stewart, Ian E.; Chen, Zuofeng
- Accounts of Chemical Research, Vol. 49, Issue 3
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Single-Crystal Electrochemistry Reveals Why Metal Nanowires Grow
journal, October 2018
- Kim, Myung Jun; Alvarez, Samuel; Chen, Zihao
- Journal of the American Chemical Society, Vol. 140, Issue 44
The Synthesis and Coating of Long, Thin Copper Nanowires to Make Flexible, Transparent Conducting Films on Plastic Substrates
journal, September 2011
- Rathmell, Aaron R.; Wiley, Benjamin J.
- Advanced Materials, Vol. 23, Issue 41
Adsorption of Polyvinylpyrrolidone on Ag Surfaces: Insight into a Structure-Directing Agent
journal, January 2012
- Al-Saidi, W. A.; Feng, Haijun; Fichthorn, Kristen A.
- Nano Letters, Vol. 12, Issue 2
How Structure-Directing Agents Control Nanocrystal Shape: Polyvinylpyrrolidone-Mediated Growth of Ag Nanocubes
journal, October 2015
- Qi, Xin; Balankura, Tonnam; Zhou, Ya
- Nano Letters, Vol. 15, Issue 11
Deciphering Ligands’ Interaction with Cu and Cu 2 O Nanocrystal Surfaces by NMR Solution Tools
journal, November 2014
- Glaria, Arnaud; Cure, Jérémy; Piettre, Kilian
- Chemistry - A European Journal, Vol. 21, Issue 3
Synthesis and Electrical Characterization of Silver Nanobeams
journal, October 2006
- Wiley, Benjamin J.; Wang, Zenghui; Wei, Jiang
- Nano Letters, Vol. 6, Issue 10
Shape-Controlled Synthesis of Copper Nanocrystals in an Aqueous Solution with Glucose as a Reducing Agent and Hexadecylamine as a Capping Agent
journal, September 2011
- Jin, Mingshang; He, Guannan; Zhang, Hui
- Angewandte Chemie International Edition, Vol. 50, Issue 45, p. 10560-10564
Noncovalent Self-Assembled Monolayers on Graphene as a Highly Stable Platform for Molecular Tunnel Junctions
journal, November 2015
- Song, Peng; Sangeeth, C. S. Suchand; Thompson, Damien
- Advanced Materials, Vol. 28, Issue 4
Engineering Selectivity in Heterogeneous Catalysis: Ag Nanowires as Selective Ethylene Epoxidation Catalysts
journal, August 2008
- Christopher, Phillip; Linic, Suljo
- Journal of the American Chemical Society, Vol. 130, Issue 34
Platinum-Alloy Cathode Catalyst Degradation in Proton Exchange Membrane Fuel Cells: Nanometer-Scale Compositional and Morphological Changes
journal, January 2010
- Chen, Shuo; Gasteiger, Hubert A.; Hayakawa, Katsuichiro
- Journal of The Electrochemical Society, Vol. 157, Issue 1
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Why Citrate Shapes Tetrahedral and Octahedral Colloidal Platinum Nanoparticles in Water
journal, July 2018
- Gisbert-González, José M.; Feliu, Juan M.; Ferre-Vilaplana, Adolfo
- The Journal of Physical Chemistry C, Vol. 122, Issue 33
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Copper Nanowires as Conductive Ink for Low-Cost Draw-On Electronics
journal, July 2015
- Jason, Naveen Noah; Shen, Wei; Cheng, Wenlong
- ACS Applied Materials & Interfaces, Vol. 7, Issue 30
Comparison of the Binding of Polyvinylpyrrolidone and Polyethylene Oxide to Ag Surfaces: Elements of a Successful Structure-Directing Agent
journal, May 2013
- Zhou, Ya; Saidi, Wissam A.; Fichthorn, Kristen A.
- The Journal of Physical Chemistry C, Vol. 117, Issue 21
Explicit Detection of the Mechanism of Platinum Nanoparticle Shape Control by Polyvinylpyrrolidone
journal, March 2016
- Ye, Jin-Yu; Attard, Gary A.; Brew, Ashley
- The Journal of Physical Chemistry C, Vol. 120, Issue 14
Binding of Polyvinylpyrrolidone to Ag Surfaces: Insight into a Structure-Directing Agent from Dispersion-Corrected Density Functional Theory
journal, January 2013
- Saidi, Wissam A.; Feng, Haijun; Fichthorn, Kristen A.
- The Journal of Physical Chemistry C, Vol. 117, Issue 2
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals
journal, October 2016
- Balankura, Tonnam; Qi, Xin; Zhou, Ya
- The Journal of Chemical Physics, Vol. 145, Issue 14
Isotropic Iodide Adsorption Causes Anisotropic Growth of Copper Microplates
journal, December 2020
- Kim, Myung Jun; Cruz, Mutya A.; Chen, Zihao
- Chemistry of Materials, Vol. 33, Issue 3
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Theory of the thermodynamic influence of solution-phase additives in shape-controlled nanocrystal synthesis
journal, January 2017
- Qi, Xin; Fichthorn, Kristen A.
- Nanoscale, Vol. 9, Issue 40
High-precision sampling for Brillouin-zone integration in metals
journal, August 1989
- Methfessel, M.; Paxton, A. T.
- Physical Review B, Vol. 40, Issue 6
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts
journal, February 2015
- Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders
- Angewandte Chemie International Edition, Vol. 54, Issue 17
Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products
journal, June 2015
- Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh
- Journal of the American Chemical Society, Vol. 137, Issue 25
Scalable Coating and Properties of Transparent, Flexible, Silver Nanowire Electrodes
journal, March 2010
- Hu, Liangbing; Kim, Han Sun; Lee, Jung-Yong
- ACS Nano, Vol. 4, Issue 5, p. 2955-2963
Synthesis of Citrate-Coated Penta-twinned Palladium Nanorods and Ultrathin Nanowires with a Tunable Aspect Ratio
journal, October 2020
- Mastronardi, Valentina; Udayan, Gayatri; Cibecchini, Giulia
- ACS Applied Materials & Interfaces, Vol. 12, Issue 44
Accurate and efficient algorithm for Bader charge integration
journal, February 2011
- Yu, Min; Trinkle, Dallas R.
- The Journal of Chemical Physics, Vol. 134, Issue 6
Shape-Dependent Hydrogen-Storage Properties in Pd Nanocrystals: Which Does Hydrogen Prefer, Octahedron (111) or Cube (100)?
journal, July 2014
- Li, Guangqin; Kobayashi, Hirokazu; Dekura, Shun
- Journal of the American Chemical Society, Vol. 136, Issue 29
Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008
- Xia, Younan; Xiong, Yujie; Lim, Byungkwon
- Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
Oriented attachment mechanism of triangular Ag nanoplates: a molecular dynamics study
journal, January 2020
- Balankura, Tonnam; Yan, Tianyu; Jahanmahin, Omid
- Nanoscale Advances, Vol. 2, Issue 6
Interaction of Alkylamines with Cu Surfaces: A Metal–Organic Many-Body Force Field
journal, September 2017
- Liu, Shih-Hsien; Fichthorn, Kristen A.
- The Journal of Physical Chemistry C, Vol. 121, Issue 40
Continuous Patterning of Copper Nanowire-Based Transparent Conducting Electrodes for Use in Flexible Electronic Applications
journal, July 2016
- Zhong, Zhaoyang; Lee, Hyungjin; Kang, Dongwoo
- ACS Nano, Vol. 10, Issue 8
Self-assembled monolayer structures of hexadecylamine on Cu surfaces: density-functional theory
journal, January 2016
- Liu, Shih-Hsien; Balankura, Tonnam; Fichthorn, Kristen A.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 48
Modulating the Growth Rate, Aspect Ratio, and Yield of Copper Nanowires with Alkylamines
journal, March 2018
- Kim, Myung Jun; Alvarez, Samuel; Yan, Tianyu
- Chemistry of Materials, Vol. 30, Issue 8
Cu( ii )–alkyl amine complex mediated hydrothermal synthesis of Cu nanowires: exploring the dual role of alkyl amines
journal, January 2014
- Ravi Kumar, D. V.; Kim, Inhyuk; Zhong, Zhaoyang
- Phys. Chem. Chem. Phys., Vol. 16, Issue 40
3D self-assembly of aluminium nanoparticles for plasmon-enhanced solar desalination
journal, April 2016
- Zhou, Lin; Tan, Yingling; Wang, Jingyang
- Nature Photonics, Vol. 10, Issue 6
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Successive Deposition of Silver on Silver Nanoplates: Lateral versus Vertical Growth
journal, October 2010
- Zeng, Jie; Xia, Xiaohu; Rycenga, Matthew
- Angewandte Chemie International Edition, Vol. 50, Issue 1
Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces
journal, November 2016
- Qi, Xin; Zhou, Ya; Fichthorn, Kristen A.
- The Journal of Chemical Physics, Vol. 145, Issue 19
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Solvent Effects on Molecular Adsorption on Ag Surfaces: Polyvinylpyrrolidone Oligomers
journal, May 2018
- Balankura, Tonnam; Qi, Xin; Fichthorn, Kristen A.
- The Journal of Physical Chemistry C, Vol. 122, Issue 26
Theoretical Perspectives on the Influence of Solution-Phase Additives in Shape-Controlled Nanocrystal Synthesis
journal, April 2018
- Qi, Xin; Balankura, Tonnam; Fichthorn, Kristen A.
- The Journal of Physical Chemistry C, Vol. 122, Issue 33
Copper Nanocrystal Plane Effect on Stereoselectivity of Catalytic Deoxygenation of Aromatic Epoxides
journal, March 2015
- Xiao, Bin; Niu, Zhiqiang; Wang, Yang-Gang
- Journal of the American Chemical Society, Vol. 137, Issue 11
Seed-Mediated Growth of Colloidal Metal Nanocrystals
journal, December 2016
- Xia, Younan; Gilroy, Kyle D.; Peng, Hsin-Chieh
- Angewandte Chemie International Edition, Vol. 56, Issue 1
Surface science of shape-selective metal nanocrystal synthesis from first-principles: Growth of Cu nanowires and nanocubes
journal, March 2020
- Fichthorn, Kristen A.; Chen, Zihao
- Journal of Vacuum Science & Technology A, Vol. 38, Issue 2
Materials for Hydrogen Storage: Past, Present, and Future
journal, January 2011
- Jena, Puru
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 3
Shape-controlled synthesis of silver nanoparticles: Ab initio study of preferential surface coordination with citric acid
journal, June 2008
- Kilin, Dmitri S.; Prezhdo, Oleg V.; Xia, Younan
- Chemical Physics Letters, Vol. 458, Issue 1-3
Ethylenediamine Promotes Cu Nanowire Growth by Inhibiting Oxidation of Cu(111)
journal, December 2016
- Kim, Myung Jun; Flowers, Patrick F.; Stewart, Ian E.
- Journal of the American Chemical Society, Vol. 139, Issue 1
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Facile synthesis of oleylamine-capped silver nanowires and their application in transparent conductive electrodes
journal, January 2015
- Zhu, Jun; Xu, Xiufang; Liu, Jinglei
- RSC Advances, Vol. 5, Issue 90
Improved grid-based algorithm for Bader charge allocation
journal, January 2007
- Sanville, Edward; Kenny, Steven D.; Smith, Roger
- Journal of Computational Chemistry, Vol. 28, Issue 5
Understanding the Solution-Phase Growth of Cu and Ag Nanowires and Nanocubes from First Principles
journal, April 2021
- Fichthorn, Kristen A.; Chen, Zihao; Chen, Zhifeng
- Langmuir, Vol. 37, Issue 15
Synthesis of colloidal metal and metal alloy nanoparticles for electrochemical energy applications
journal, January 2013
- You, Hongjun; Yang, Shengchun; Ding, Bingjun
- Chem. Soc. Rev., Vol. 42, Issue 7
Synthesis of Silver Nanostructures with Controlled Shapes and Properties
journal, October 2007
- Wiley, Benjamin; Sun, Yugang; Xia, Younan
- Accounts of Chemical Research, Vol. 40, Issue 10
Shape-Controlled Synthesis of Metal Nanostructures The Case of Silver
journal, January 2005
- Wiley, Benjamin; Sun, Yugang; Mayers, Brian
- Chemistry - A European Journal, Vol. 11, Issue 2, p. 454-463
Molecular phenomena in colloidal nanostructure synthesis
journal, December 2013
- Fichthorn, Kristen A.
- Molecular Simulation, Vol. 40, Issue 1-3
Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy
journal, January 2013
- Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos
- The Journal of Physical Chemistry C, Vol. 117, Issue 4
Surface Capping Agents and Their Roles in Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals
journal, June 2020
- Yang, Tung‐Han; Shi, Yifeng; Janssen, Annemieke
- Angewandte Chemie International Edition, Vol. 59, Issue 36