Spectroscopy in Thermal decomposition of copper (II)

acetylacetonate in supercriticalcarbon dioxide: In situ

observation via UV–vis spectroscopy

Yoda, S.; Takebayashi, Y.; Sue, K.; Furuya, T.; Otake, K. Thermal Decomposition of Copper (II)
Acetylacetonate in Supercritical Carbon Dioxide: In Situ Observation via UV–Vis Spectroscopy. The Journal
of Supercritical Fluids 2017, 123, 82–91.
Organometallics are precursors to
nanomaterials
Organometallic complexes can be dissolved in supercritical CO2
◦ scCO2 can reach areas that other solutions cannot due to its lack of surface tension
◦ Useful for depositing organometallic precursors for nanomaterials in machinery

Process for nanomaterial formation from organometallic complex involves decomposition

◦ Decomposition of copper (II) acetylacetonate in scCO2 is observed due to thermal and solvent effects
Decomposition of Cu(II)(acac)2
Copper (II) acetylacetate (Cu(II)(acac)2) decomposes in a supercritical carbon dioxide (sCO2)
solution when exposed to heat
◦ Products formed: Cu(acac) and acac

Use UV-VIS spectroscopy to observe the rate of decay

Copper (II) acetylacetonate Acetylacetone

Use of UV-VIS Spectroscopy
Observe the spectra of Cu(acac)2 and acac
Observe the relative concentrations of the
compounds over time
Determine the rate of decomposition of Cu(acac)2

UV spectrum of copper (II) acetylacetonate

(black) and acetylacetone (red).
Decomposition Spectra Over Time
Red line represents original recorded UV spectra
Black line represents result of curve fitting for original
spectra
Green line represents peak separation of UV spectra

UV spectra of decomposition solution

at t=0 minutes
Continued Decomposition Spectra Over
Time

t=3 minutes t=5 minutes t=10 minutes

Determination of Rate
Lambert-Beer’s Law: A = εcl
◦ A = absorbance at certain wavelength (nm)
◦ ε = extinction constant (constant)
◦ C = concentration of sample
◦ l = length of light travel (constant)

Absorption is directly proportional to concentration, allowing

the value be used for a first order kinetics reaction
◦ ln(At/ At=0) = –k1t
◦ A = absorbance (proportional to concentration)
◦ k1 = rate of reaction
◦ t = time
Natural log of ratio of absorbances
against time at 255 nm
(Cu(II)(acac)2 peak) and 453 K
Pressure Effects on Decomposition
Graph shows effects of different constant pressure on
the rate of reaction of the decomposition
◦ ○ = 15 MPa
◦ = 20 MPa
◦ □ = 25 MPa

Rate increases with increasing pressure

Natural log of ratio of absorbances against

time at 255 nm and 443 K
Density of Solvent and Temperature
Effects on Decomposition
Graph shows effects of different constant temperature
on the relationship between density and rate
◦ ◊ = 423 K
◦ = 433 K
◦ □ = 443 K
◦ ● = 453 K

Rate increases with increasing density

Rate increases with increasing temperature

Rate of reaction against density at 255 nm

and 443 K
UV-VIS spectroscopy can be used to study the
rate of decomposition of Cu(II)(acac)2
Variables have been observed to affect rate using UV-VIS
◦ Increasing density increases rate
◦ Increasing temperature increases rate
◦ Increasing pressure increases rate

Advances in this field of study may lead to better procedures of nanomaterial fabrication