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Rita Schwieters
Advised by
Dr. Chris Sorensen &
Grad Student Jeff Powell
INVESTIGATION OF
GOLD NANOPARTICLE
PROPERTIES
AU NANOPARTICLES
• An fcc cluster of gold atoms with long chain
molecules attached to surface gold atoms.
• They typically contain over 3,000 gold atoms, and
hundreds of ligands.[1]
• They do not have properties of gold atoms or of
macroscopic gold.
• They have some properties similar to large
molecules. This is attractive, because we already
have molecular theory.
• Typical models suggest the gold cores attract and
the ligands repel in such a way that we should
observe a familiar potential energy curve with
particle separation. (Potential Well)[2]
GOALS:
• The purpose of this research was to measure an Enthalpy of Dissolution
for 5nm AuNPs ligated with Dodecanethiol (DDT), and dissolved in a solution
of DDT & Toluene.
• From this the interparticle potential, melting point, and activity
coefficient for this system can be determined. Where the activity coefficient
is an indication of how far from ideal this system is.
• My work focused on the enthalpy of dissolution, and everything else was or
can be calculated from that.
• This is the first study on the enthalpy of dissolution of AuNPs, and should be
the beginning of a systematic investigation into how these properties are
effected by NP size, ligand, solvent, etc.
THEORY
• Start with Maxwell-Boltzmann statistics 𝑃 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝑒−
∆𝐻
𝑘𝑇
• Where ΔH is the enthalpy of dissolution or the energy required to dissolve.
• And probability dissolved is essentially the concentration.
• Beer-Lambert’s law allows a conversion between Absorbance (measured in the lab), and
concentration (variable needed for theory). 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
• Since I was looking for ΔH, I reworked the equations so that ΔH would be the slope of a line.
• Manipulating 𝑃 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝑒−
∆𝐻
𝑘𝑇 = Concentration
• To ln(Concentration) = -
∆𝐻
𝑘𝑇
+ ln(Constant)
• Plotting ln(Concentration) vs.
1000
𝑇
gives a slope of
∆𝐻
𝑘
in kJ.
• From this I can solve for ∆𝐻, the interparticle separation, the melting temperature, and the
activity coefficient.
METHODS
• To do this experiment samples of AuNPs were sythesized, and placed in small glass
ampules.
• Before each run I placed the samples in an ultrasonic bath to re-disperse the particles.
• The samples would then be placed in a home-made, thermally insulated, temperature
controlled centrifuge and left to sit for 15minutes. The small size of the samples and
thermal contact with the aluminum rotor allowed the temperature of the sample to
equilibrate quickly.
• I then spun at 3300g for 12min to get any precipitate out.
• Once the precipitate is spun out, I use a UV-Vis spectrophotometer to measure the
amount of light absorbed.
• Beer-Lambert converts that to concentration that I can plot as a function of temperature.
METHODS CONTINUED
• The samples I investigated were 5.2nm, 5.5nm, and 5.8nm diameter AuNPs .
• When I completed data collection, Transition Electron Microscope (TEM) pictures of the
particles were taken.
• These pictures were analyzed with a program, imagej, allowing me to analyze a large
number of particles.
• The resulting distribution was fit with a Gaussian to determine the average particle
diameter.
RESULTS
• TEM analysis showed the particles were slightly different in size: 5.2nm, 5.5nm, and
5.8nm. It also showed a somewhat large percent standard deviation despite the presence
of superlattices.
• Analysis of 354 particles over 5 different TEM pictures yields a particle diameter
distribution shown.
• This analysis gives the average
diameter 5.5nm, with a standard
deviation that’s 16% of the average.
That is higher than we’d like.
• Additional analysis shows less dispersity in localized groups.
RESULTS CONTINUED
• I collected data for three different samples of the same synthesis of AuNPs. I plotted the
data, and calculated the enthalpy of dissolution for each sample.
1130K1330K
1230K
WHAT THE RESULTS MEAN
• If those melting points seem high, that’s because they are.
• This is essentially a first order approximation to the enthalpy of dissolution which is used
to calculate Tmelt.
• Adjustments will need to be made that include interactions between the ligand chain and
the solvent which are currently not accounted for.
• However, we now have consistent and reproducible data leading to a the enthalpy of
dissolution, interparticle potential, and melting point of 5nm AuNPs ligated with
dodecanethiol and dissolved in a solution of toluene and excess DDT.
INTERESTING OBSERVATIONS
• Some of the samples weren’t completely stable.
• It could be an ethanol precipitation step causing destability if some ethanol is left in
solution.
• Brief boiling of these samples seems to stabilize them with an increase in solubility. We
have no idea how this works, and it did’t seem to work for one other system we attempted
to “rejuvenate.”
FUTURE WORK
• There is a lot of work to be done to understand how these NP solutions work.
• Investigation into rejuvenation process with this system.
• This work can be extended to a larger temperature range.
• Further studies should be done to test the effects of
• NP size
• Ligand
• Solvent
REFERENCES
• [1] Hao Yan, Solubility Phase Behavior of Gold Nanoparticles in Colloidal Solution,
Dissertation, 2009
• [2] B.L.V. Prasad, C.M. Sorensen, and Kenneth J. Klabunde, Gold nanoparticle
superlattices, Chemical Society Reviews, July 2008
ACKNOWLEDGMENTS
• This research was funded through an NSF grant PHYS-1461251
• I would also like to thank Kansas State University & the Physics
Department for hosting me this summer.
• Dr. Sorensen, Jeff Powell, and Jessica Changstrom for their many
efforts working with me on this project.
QUESTIONS?

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Final Presentation

  • 1. Rita Schwieters Advised by Dr. Chris Sorensen & Grad Student Jeff Powell INVESTIGATION OF GOLD NANOPARTICLE PROPERTIES
  • 2. AU NANOPARTICLES • An fcc cluster of gold atoms with long chain molecules attached to surface gold atoms. • They typically contain over 3,000 gold atoms, and hundreds of ligands.[1] • They do not have properties of gold atoms or of macroscopic gold. • They have some properties similar to large molecules. This is attractive, because we already have molecular theory. • Typical models suggest the gold cores attract and the ligands repel in such a way that we should observe a familiar potential energy curve with particle separation. (Potential Well)[2]
  • 3. GOALS: • The purpose of this research was to measure an Enthalpy of Dissolution for 5nm AuNPs ligated with Dodecanethiol (DDT), and dissolved in a solution of DDT & Toluene. • From this the interparticle potential, melting point, and activity coefficient for this system can be determined. Where the activity coefficient is an indication of how far from ideal this system is. • My work focused on the enthalpy of dissolution, and everything else was or can be calculated from that. • This is the first study on the enthalpy of dissolution of AuNPs, and should be the beginning of a systematic investigation into how these properties are effected by NP size, ligand, solvent, etc.
  • 4. THEORY • Start with Maxwell-Boltzmann statistics 𝑃 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝑒− ∆𝐻 𝑘𝑇 • Where ΔH is the enthalpy of dissolution or the energy required to dissolve. • And probability dissolved is essentially the concentration. • Beer-Lambert’s law allows a conversion between Absorbance (measured in the lab), and concentration (variable needed for theory). 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 • Since I was looking for ΔH, I reworked the equations so that ΔH would be the slope of a line. • Manipulating 𝑃 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∗ 𝑒− ∆𝐻 𝑘𝑇 = Concentration • To ln(Concentration) = - ∆𝐻 𝑘𝑇 + ln(Constant) • Plotting ln(Concentration) vs. 1000 𝑇 gives a slope of ∆𝐻 𝑘 in kJ. • From this I can solve for ∆𝐻, the interparticle separation, the melting temperature, and the activity coefficient.
  • 5. METHODS • To do this experiment samples of AuNPs were sythesized, and placed in small glass ampules. • Before each run I placed the samples in an ultrasonic bath to re-disperse the particles. • The samples would then be placed in a home-made, thermally insulated, temperature controlled centrifuge and left to sit for 15minutes. The small size of the samples and thermal contact with the aluminum rotor allowed the temperature of the sample to equilibrate quickly. • I then spun at 3300g for 12min to get any precipitate out. • Once the precipitate is spun out, I use a UV-Vis spectrophotometer to measure the amount of light absorbed. • Beer-Lambert converts that to concentration that I can plot as a function of temperature.
  • 6. METHODS CONTINUED • The samples I investigated were 5.2nm, 5.5nm, and 5.8nm diameter AuNPs . • When I completed data collection, Transition Electron Microscope (TEM) pictures of the particles were taken. • These pictures were analyzed with a program, imagej, allowing me to analyze a large number of particles. • The resulting distribution was fit with a Gaussian to determine the average particle diameter.
  • 7. RESULTS • TEM analysis showed the particles were slightly different in size: 5.2nm, 5.5nm, and 5.8nm. It also showed a somewhat large percent standard deviation despite the presence of superlattices. • Analysis of 354 particles over 5 different TEM pictures yields a particle diameter distribution shown. • This analysis gives the average diameter 5.5nm, with a standard deviation that’s 16% of the average. That is higher than we’d like.
  • 8. • Additional analysis shows less dispersity in localized groups.
  • 9. RESULTS CONTINUED • I collected data for three different samples of the same synthesis of AuNPs. I plotted the data, and calculated the enthalpy of dissolution for each sample. 1130K1330K 1230K
  • 10. WHAT THE RESULTS MEAN • If those melting points seem high, that’s because they are. • This is essentially a first order approximation to the enthalpy of dissolution which is used to calculate Tmelt. • Adjustments will need to be made that include interactions between the ligand chain and the solvent which are currently not accounted for. • However, we now have consistent and reproducible data leading to a the enthalpy of dissolution, interparticle potential, and melting point of 5nm AuNPs ligated with dodecanethiol and dissolved in a solution of toluene and excess DDT.
  • 11. INTERESTING OBSERVATIONS • Some of the samples weren’t completely stable. • It could be an ethanol precipitation step causing destability if some ethanol is left in solution. • Brief boiling of these samples seems to stabilize them with an increase in solubility. We have no idea how this works, and it did’t seem to work for one other system we attempted to “rejuvenate.”
  • 12. FUTURE WORK • There is a lot of work to be done to understand how these NP solutions work. • Investigation into rejuvenation process with this system. • This work can be extended to a larger temperature range. • Further studies should be done to test the effects of • NP size • Ligand • Solvent
  • 13. REFERENCES • [1] Hao Yan, Solubility Phase Behavior of Gold Nanoparticles in Colloidal Solution, Dissertation, 2009 • [2] B.L.V. Prasad, C.M. Sorensen, and Kenneth J. Klabunde, Gold nanoparticle superlattices, Chemical Society Reviews, July 2008
  • 14. ACKNOWLEDGMENTS • This research was funded through an NSF grant PHYS-1461251 • I would also like to thank Kansas State University & the Physics Department for hosting me this summer. • Dr. Sorensen, Jeff Powell, and Jessica Changstrom for their many efforts working with me on this project.