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Physics and Chemistry of Nanoclusters
Dr Lauro Oliver Paz-Borbón1
1Physics Institute National Autonomous University of Mexico (UNAM)
Seoul, South Korea 11th November 2016
THIS: Theory of Hetero- Interfaces and Surfaces Winter School
a little bit about me..
PhD in Chemistry University of Birmingham Birmingham, UKProf. Dr. Roy Johnston
Postdoc Fritz-Haber Institute Berlin Berlin, GermanyProf. Dr. Matthias Scheffler
Researcher Chalmers University of Technology Gothenburg, SwedenProf. Dr. Henrik Grönbeck
Postdoc King’s College London London, UKDr. Francesca Baletto
Assistant Professor Physics Institute, UNAM Mexico City, Mexico
Oliver Paz Borbón
Email: [email protected]
UNAM @ Mexico City
Course aims
“A bird’s eye view to nanoclusters!”
- History and background
- Physical and Chemical properties of nanoclusters
- Computational tools
Much of nanoscience and many nanotechnologies
are concerned with producing new
or enhanced materials.
https://t2.ftcdn.net/jpg/00/47/19/61/500_F_47196194_uaPhX5mywIr1GZtwAzsveCUtRHyFN1z8.jpg
Nature Nanotechnology 4, 538 (2009) www.nature.com/naturenanotechnology
Nanopapers
A nanometer is a unit of spatial measurement that is 10-9
meter, or one billionth of a meter.
Definitions
https://www.hdiac.org/sites/default/files/image_upload/CS_Figure1.png
Nanomaterial is an object that has at least one dimension in the nanometer scale approximately 1-100nm.
Nanomaterials classification
http://eng.thesaurus.rusnano.com/upload/iblock/dfc/nanomaterial1.jpg
Classification is based on the number of dimensions, which are not confined to the nanoscale range (<100 nm).
Historical Background
How it all started!
Richard P. Feynman, “There’s Plenty of Room at the Bottom” [1]
[1] Published on Caltech’s Engineering and Science Magazine (1960)
APS Meeting at Caltech, December 1959
Professor Norio Taniguchi (Tokyo University of Science) was the first one to use the term nanotechnology (1974)
K. Eric Drexler: Ph.D. work was the first doctoral degree on the topic of molecular nanotechnology.
Probe microscopy
In 1981, the Scanning Tunnelling Microscope (STM), was developed by Gerd Binning and Heinrich Rohrer, working at IBM Zurich.
Nobel in Physics (1986): Ruska, Binning and Rohrer
http://www.nobelprize.org/nobel_prizes/physics/laureates/1986/binnig-lecture.pdf
Si(111)- 7x7 surface reconstruction.
https://en.wikipedia.org/wiki/Scanning_tunneling_microscope
Au(100)
Carbon nanotube
Si(111)7x7
Pt @ HOPG
http://web.physik.uni-rostock.de/cluster/beams/forschung_en.htm
Probe microscopy
Fullerenes
http://www.wiley-vch.de/books/sample/3527331972_c01.pdf
The first fullerene molecule to be discovered, buckminsterfullerene (C60), was prepared in 1985 at Rice University via graphite vaporisation at low pressure (Harold Kroto, Nobel 1996)
Advances in interface and colloid science
Aqueous colloidal gold
Around 1850s, Michael Faraday discovered colloidal “ruby” gold while investigating the properties of light and matter.
Intense red colour is obtained for Au particles < 100 nm; or blue/purple for larger ones.
Advances in interface and colloid science
Lycurgus Cup (4th-century Roman glass cage cup)
M e d i e v a l a r t i s a n s w h e r e o n e o f t h e fi r s t nanotechnologists, as they made stained glass by mixing gold chloride into molten glass.
http://www.wiley-vch.de/books/sample/3527331972_c01.pdf
Key paper in (nano)cluster history! four distinct abundance maxima in their mass spectra of Na clustersat W = 2, 7, 19, and 38.
ISSPIC XVIII - International Symposium on Small Particles and Inorganic Clusters
Richard Smelley presents work on C60’s!
Gathers more than 200 scientist within the field!
vs.
icosahedral Au144(SR)60
Decahedral Au144(SR)60
state-of-the-art!
(Metal) Nanoclusters and nanoalloys
General properties
Nanoclusters
- Clusters can be defined as :
- Agglomerates of a few to millions of atoms or molecules.
- Can be made of one single atom (or molecule) or two or more different species.
Ru3Sn3 Pt49Au49Pt2
Roy Johnston, Dalton Trans. , 2003, 4193
Nanoclusters
- Clusters can be studied in:
- Gas-phase (“free-cluster”) - Supported on a substrate (such as silica, TiO2 and MgO) or in an inert
matrix. - Passivated by ligands (the cluster surface is stabilised by surfactant
molecules)
Pt6@CeO2(111)Pt6
gas-phase
lateral view top view Au102(para- mercaptobenzoic acid)44.
http://www.pnas.org/content/105/27/9157.figures-only
- Have different segregation mixing patterns, i.e. the chemical ordering between the two metals.
- Segregation dependance on bond strength, surface energy, overall cluster size, charge transfer, strength of binding to ligands/substrate, specific electronic effects, etc..
- Bimetallic clusters can:
Nanoclusters
Julius Jellinek, Faraday Discuss., 2008, 138, 11–35
Nanoclusters
HRTEM image of Ni-Pt nanoparticle (ca. 3nm)
HRTEM Pd-Au @ C film
(ca. 8 nm)
http://phys.org/news/2012-02-world-smallest-atomic-valentine.htmlhttp://physics.utsa.edu/Faculty/Yacaman/Yacaman.html
- Present a wide variety of structures: varying from non-crystalline (e.g. decahedral, icosahedral), to crystalline arrangements (e.g. fcc-type bulk-like fragments).
- Due to their size, clusters can:
gas-phase Pt-Pd
FCC-like
gas-phase Pt-Pd
Decahedral
Nanoclusters
http://www.nanoalloy.eu/attachments/article/114/Structure_Ferrando_1.pdf
Nanoclusters
It is difficult to unambiguously define a cluster as being small, medium or large in size!
http://w0.rz-berlin.mpg.de/imprs-cs/download/2012clusterchem.pdf
- Present physico-chemical properties which make them differ from bulk metals.
- Successive fragmentation of a macroscopic piece of a bulk metal will induce a transition to a microscopic insulating particle.
Nanoclusters
http://www.chm.bris.ac.uk/webprojects2002/etan/Webpages/theory.htm
- Due to their size, (metal) clusters can:
- Emergence of new properties e.g.: magnetic, optical / luminescence, chemical / catalytic
- Effects at the (sub)nano-scale quantum confinement large surface/volume ratio, structural changes
- Have a large number of atoms occupying surface sites, where the morphology of the cluster is essential in determining their catalytic properties, with many reactions taking place on nanoparticle surface
Nanoclusters
- Due to their size, (metal) clusters:
Nanoclusters
- For a fixed size, clusters can display:- A wide variety of structural isomers!
- They refer to different structures, having different energies, for a given size (and same chemical for bimetallic clusters).
Pt6@MgO(100) Global minima
0.0 eV
Pt6@MgO(100) 0.5 eV
higher in energy!
Nanoclusters
- For a fixed size, clusters can (also) display:- The existence of homotops in bimetallic nanoalloys (e.g. Pd-Pt, Pd-
Au, Ag-Pt,Ag-Au)
- This leads to different cluster geometrical structures, compositions, structures, geometries!
Study of 40-atom Pt–Au clusters using a combined empirical potential-density
functional approach
Dung T. Tran, Roy L. Johnston
Published 9 March 2011.DOI: 10.1098/rspa.
2010.0562
Overall technological applications…
Heterogenous Catalysis
Nanoclusters applicationsNovel metal nanocatalysts for emission control systems (gasoline and diesel).
Three-way catalysts
Improved oxygen reduction reaction at at hydrogen fuel cell cathode using novel metal nanocatalyst
Nanomaterials applications
https://4wheelonlineblog.files.wordpress.com/2014/11/mirai2.jpg
• Future transportation applications
• Nanobiosystems, medical, health applications
Researchers have developed an imaging technology (PET-MRI) to measure the amount of an antibody-nanoparticle complex that accumulates specifically in atherosclerotic plaque to monitor the development of plaque as well as its disappearance following treatment.
Nanomaterials applications
http://www.nano.gov/you/nanotechnology-benefits
https://csb.mgh.harvard.edu/nahrendorfhttp://pubs.acs.org/doi/pdf/10.1021/nn500962q
Past, current and future research on (metal) nanoclusters
- Cluster reactivity at the nanoscale
Activity increases with decreasing size, with most active Au particles reported to have a few nm in diameter
Haruta et al. J. Catal. 115 (1989) 301http://www.fhi-berlin.mpg.de/acnew/department/pages/teaching/pages/teaching__wintersemester__2006_2007/fielicke_clusterchemistry_020207.pdf
Nanoclusters reactivity and catalisis
- Cluster reactivity at the nanoscaleExcellent (nano)-catalyst due to their high surface to volume ratio!
http://www.fhi-berlin.mpg.de/acnew/department/pages/teaching/pages/teaching__wintersemester__2006_2007/fielicke_clusterchemistry_020207.pdf
Nanoclusters reactivity and catalisis
Nanoclusters reactivity and catalisis
Model reaction CO + O2 —> CO2
examined by gas phase ion
chemistry and mass spectrometry techniques
[EXP 1998] [EXP/THEO 2003]
Nanoclusters reactivity and catalisis
[THEO 2012] [EXP/THEO 2014]
Nanoclusters reactivity and catalisis
[EXP/THEO 2016][EXP/THEO 2015]
Nanoclusters reactivity and catalisis
[EXP/THEO 2013][THEO 2016]
Experimental preparationtechniques and characterization
Manufactur ing a t the nanoscale is known as nanomanufacturing.
http://www.nature.com/nrn/journal/v7/n1/images/nrn1827-i1.jpg
Nanomaterials fabrication
“Bottom up” “Top down”
Laser ablationExperimental background
https://en.wikipedia.org/wiki/Physical_vapor_deposition
A small metal target (plate or rod) of bulk material is evaporated by laser ablation.
lnf-wiki.eecs.umich.edu/wiki/images/c/ce/Sputter_Deposition.png
white disk Al2O3
squared substrate SrTiO3
650 °C
plasma explosion
https://en.wikipedia.org/wiki/Pulsed_laser_deposition
Physical vapour deposition (PVD)
https://en.wikipedia.org/wiki/Physical_vapor_deposition
1. Vaporization of the material from a solid source. 2. Transportation of the vapor in vacuum to the substrate surface3. Condensation onto the substrate
Sputting target: Al, Cu, Cr, ZnO, Al2O3,
In2O3, Ti, I, W, Y
lnf-wiki.eecs.umich.edu/wiki/images/c/ce/Sputter_Deposition.png
Au atoms adsorbed on the MgO surface
http://journals.aps.org/prl/pdf/10.1103/PhysRevLett.96.146804http://www.sigmaaldrich.com/materials-science/material-science-products.html?TablePage=108832720
Experimental background
Sol-Gel Method
Is a method for producing solid materials from small molecules. Typical precursors are metal alkoxides and metal chlorides.
white disk Al2O3
squared substrate SrTiO3
650 °C
plasma explosion
https://en.wikipedia.org/wiki/Sol-gel
Involves the conversion of
monomers into a colloidal solution (sol) that acts as the precursor for
an integrated network (gel)
http://www.photokatalyse.fraunhofer.de/en/Kompetenzen/Schicht_Prozessentwicklung/Sol-Gel-Lacktechnik.html
Experimental background
650 °C
A solution of Ag+ or Au3+ ions is prepared separately.
http://onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.2000.tb01566.x/epdf
The Ag+ or Au3+ precursors are AgNO3
and HAuCl4.3H2O
A suitable ligand for the formation of metal ion complexes is introduced.
Mono dispersed Particles from Solution:
http://education.mrsec.wisc.edu/277.htm
TEM image
Chloroauric acidsilver nitrate
Experimental background
Nanomaterials characterisation
State-of-the-art characterisation of nanoclusters involve a number of experimentaltechniques:
X-ray analysis
Electron microscopy
Scanning probe microscopy
Vibrational spectrometry
Auger-electron microscopy
Mass spectrometry
Optical techniques …
Nanomaterials characterisation:
X-ray diffraction (XRD)
3-D X-ray diffraction image of a truncated octahedra nanoparticle with 200nm diameter
http://phys.org/news/2015-02-x-ray-pulses-uncover-free-nanoparticles.html
X-ray photoemission spectra (XPS)
Phys. Chem. Chem. Phys.,2014, 16, 26645
SLAC - USA
Nanomaterials fabrication
Miguel Yacaman, UTSA, personal communication
(HR) TEM (Transmission Electron Microscopy)
SEM (Scanning Electron Microscopy)
http://www.microscopy.ethz.ch/catalysis.htm
SEM images of Pt particles on alumina.
Pt
4Pt5
HR-STEM
STM (Scanning Tunneling Microscopy)
Ag particle supported on ZnO Pt atoms supported on Al2O3
Pt7 on TiO2
Nat Nanotechnol. 2015 Jul;10(7):577-88. doi: 10.1038/nnano.2015.140.
Nanomaterials fabrication
Infrared spectroscopy (IR)
Exploits the fact that molecules absorb specific frequencies that are characteristic of their structure. These absorptions are resonant frequencies
http://onlinelibrary.wiley.com/doi/10.1002/chem.201304586/full
http://www.wag.caltech.edu/home/jang/genchem/infrared.htmhttp://fel.fhi-berlin.mpg.de/
Schematic view of the dual-target dual-laser ablation source for the production
of metal clusters +
mass selection
Computational tools for (metal) nanoclusters
Atomistic modelling can reduce the cost and accelerate the time scales of understanding and developing novel materials. http://www.icams.de/content/research/index.html
Computational Modelling
Computational Modelling
http://www.icmr.ucsb.edu/programs/summer-school-2013/LeSar%20UCSB%20Summer%20School.pdf
How do we create models?
Think before you compute!
Electronic Structure Methods
LDA Local Density Approx.
GGA Generalised Gradient Approx.
meta-GGA
hybrids
RPA
Density Laplacian
Exact exchange
Exact exchange + correlation
V xc
acc
urac
yan
d C
PU ti
me!
Density Functional Theory (DFT) is the current electronic structure workhorse via High-Performance Computing (HPC) calculations.
Quantum Chemistry (Hartree-Fock theory)
Single reference: Møller-Plesset (MP)
Conf. interaction (CI) Coupled cluster (CC)
…
Computational Materials Modeling
Density Functional Theory (DFT)
LDA GGA
Hybrids …
Tight binding …
Time dependent DFT … Interatomic potentials
Pair potentials (Lennard-Jones)
Morse potential Gupta many-body
…
Molecular Dynamics Classical
Born-Oppenheimer Car-Parinello
…
Computational Methodologies
*Does not include ALL techniques!
QM/MM methods Development of force fields
…
Global optimizations (genetic algorithm) + atomistic level potentials + DFT simulations of < 100 atom size gas-phase clusters - with Dr. Roy Johnston (UniBham) [1]
Other research lines @ IFUNAM
[1] Rossi, Ellaby, Paz-Borbón, Atanasov, Baletto, submitted J. Phys.: Condens. Matter (2016)
Atomistic (classical) Molecular Dynamics simulations of > 500 atom size supported clusters - with Dr. Francesca Baletto (KCL) [1]
Other research lines @ IFUNAM
LoDiS MD manual
Kevin Rossi, Francesca Baletto
⇤
Physics Department,
King’s College London, WC2R 2LS,
UK
[1] Rossi, Ellaby, Paz-Borbón, Atanasov, Baletto, submitted J. Phys.: Condens. Matter (2016)
+
metal
atom-atom
Metal atom-oxide
Main objetive
Andrés López BSc Thesis
c) Our own Basin Hopping-DFT (Python3.4 code + Quantum Espresso, eventually + LODIS-MD) implementation for global optimization of (oxide) supported metal clusters
[1] López-Martínez, Garzón, Grönbeck, Posada-Amarillas, Paz-Borbón, in preparation (2016)
Main objetive c) Our own Basin Hopping-DFT (Python3.4 code + Quantum Espresso, eventually + LODIS-MD) implementation for global optimization of (oxide) supported metal clusters
…@ γ-Al2O3 …@ TiO2
… open GitHub link for the community :D
Pt @ CeO2 (111) (PBE+U, Ueffec = 4.5 eV)
Dr Francesca Baletto (KCL)Dr Henrik Grönbeck (Chalmers)Dr Miguel José Yacaman (UTSA)
Project IA102716
SC16-1-IG-78 SC15-1-IG-82
Dr Carlos Villagomez (IFUNAM)Mr Andres Lopez (IFUNAM)
Dr Ignacio Garzón (IFUNAM)
Dr Alvaro Posada (UniSonora)
CPU-time (1,600,000 hrs)
AcknowledgementsCollaborators: Funding:
Dr Gabriela Diaz (IFUNAM)
Dr Aloysius Soon (Yonsei)