Resume of Dr.

Nancy Artioli Lecture

Catalyst Surface Modification by Ion-Beam Sputtering

Phsyico Chemical Analysis Assignment

Prepared by
Nagina Belali
NPM # 260120177001

Pajajaran University
Faculty of Pharmacy
 Catalyst Surface Modification by Ion-Beam Sputtering
By
Dr. Nancy Artioli
Lecturer in Chemical Engineering
Queensland University Belfast

Different kinds of researchs are being organised in different themes, at Queensland University
among which are seven popular themes;

 Sustainable Energy Research Centre

 Advanced Materials and Nanotechnology
 Green and Sustainable Chemistry
 Multi-phase Flows, Reactors and Process intensificaion
 Organic Synthesis and Chemical Biology
 Sensors
 Theoretical and Applied Catalysis

The last mentioned research group that includes “Theoretical and Applied Catalysis” is the
research field of Dr. Nancy Artioli in today lecture. Queensland University has collaboration
with different companies and it includes integrated into the School of Chemistry and Chem
Engineering, opportuinities for internships, Opportuinities for PhD and Masters projects,
Bridging the gap between Academia and Industry and enabling rapid knowledge transfer.

The main topic of todays lecture was “Catalyst Surface Modificaiton by Ion-Beam Sputtering”,
first of all we will explain what is Ion Beam Engineering, Interface science is at the forefront
in the development of new materials for advanced technological applications. Method for
effective and controlled surface modification of several catalytic materials is with help of ion
beam sputtering. A wide variety of gas phase ions with kinetic energies from 1-107 eV
increasingly are being used for the growth and modification of state-of-the-art material
interfaces. Ions can be used to deposit thin films; expose fresh interfaces by sputtering; grow
mixed interface layers from ions, ambient neutrals, and/or surface atoms; modify the phases
of interfaces and interface structures. The kinetic energy or collision energy required for ion
implantation and ion sputtering is very low. According to the reference given, Hyperthermal
and low energy ions deposit their kinetic energy solely into the surface without affecting the
bulk region. This energy deposition causes sputtering of surface atoms as ions. Modification
of a target material by accelerating ions towards it’s surface and the effect depends on the
ion parameters and the nature of the target material.

The aim for Heterogeneous Catalysis are;

 Fragment and disperse metal in the form of nanoparticles with welldefined

characteristics
 Producing a very high density of metal nanoparticles (1 – 5 nm) with highly active
catalyst activity
 Assessing noble metal substitution

It has different applications such as;

 Three Way Catalyst for gasoline engines, Noble metal + Alkaline earth metal on an
oxide support, that can convert dangerous species such as CO, HC, Nox to less harmful
species such as O2, CO2, H2O, N2
 Diesel Oxidatiton Catalyst for Diesel engine:
Nobel metal on an oxide support

Aim of Presented Study:

In particular, surface properties strongly influence catalysis which is essentially a surface

phenomenon. One of the novel applications of ion beam irradiation includes the modification
of the catalytic activity of solid catalysts. In the work presented by Dr. Nancy, the effect of ion
irradiation on the catalytic properties of Ce0.7Zr0.3O2 and the supported noble metal catalyst
Pt/Ce0.7Zr0.3O2, which plays an important role in automotive exhaust control applications,
among others. The effect on the catalytic properties is discussed from Temperature
Programmed Oxidation (TPO) and Reduction (TPR) measurement, together with the results
of microstructural (TEM) and IR spectrometric analyses.

Experimental Method:

The source used for ion was kaufman type, and a mono-energetic beam with a range of 0.15
– 1.5 keV and ion beam current of 2 – 30 mA, were used. The ion source fed by N2 gas and the
ions present in the beam were N and + (20%) N2+ (80%). Materials being used for the
experiment were 1% w/w Pt/ Al2O3, 1% w/w Al2O3, Ce0.7Zr0.3O2 and Pt/Ce0.7Zr0.3O2 .

Simulation of Ion Sputtering by SRIM:

Stopping and range of ions (10ev – 2 GeV/amu) into Matter using a quantum mechanical
treatment of ion (mobile atom) – atom (target) collisions. At high ion energy the atoms
(recoils) are remixed in a larger volume and at a low energy values the remixing happens
closer to the surface.
Preferential sputtering:

Atoms sputtered from a multi component material have a different relative percentage of
atoms respect to those of initial composition. At energy of 1.5kev 77.8% of atoms sputtered
are oxygen, thus suface after treatment has low oxygen content that actually makes catalyst
more active and thats what is being wanted to achieve.

Temperature Programmed Oxidation (TPO) and Temperature Programmed Reduction (TPR)

measurement:

The effect on the catalytic properties is discussed from Temperature Programmed Oxidation
(TPO) and Temperature Programmed Reduction (TPR) measurement. Both catalysts
Ce0.7Zr0.3O2 and Pt/Ce0.7Zr0.3O2 were studied with TPR and TPO before ionic Bombardment
and after ionic Bombardment. The graph presented for TPO as we observed showed the effect
of rising temperature with respect to time, about 2K/min and then constant for 2 hours at
823K, and then declining again. The composition of exhaust or flow compositio, n consisted
of CO 2000PPm, CH4 2000PPM, C3H6 2000PPM, C6H14 2000PPM, O2 10% (Complement ar).

The results acheived from TPO were shown in the graph, in which the T50 value was of
importance showed with a green line in the graph, T50 value shows the 50% conversion of
catalysts, and also the results show that bombarded catalyst had lower T50 values for all
components. Later the same experiment was done with Pt/Ce0.7Zr0.3O2 catalyst that had 1 %
of platinium and the results derived for this catalysts were much better then the last catalyst
for all of the gasses. So, if we summarize the results of TPO for both catalysts, the table
showed that when catalysts were bombardment the temperature for it becomes 20 – 40
degree less and when the same experiment is done in presence of platinium, results showed
the required temperature was much lower and in point of view of the research it was a great
acheivement. As it was a catalyst that was present in market and bought from there in the
present research it was modified to acheive better results that were obvious with use of
Platinium. The results acheived were for oxidation in the presence of mentioned gases.

Temperature Programmed Reduction TPR:

Vice versa to the last method, TPR was used to asses the different capacity of catalyst to reach
reduction. Temperature Programmed Reduction (TPR) measurement for both catalysts
Ce0.7Zr0.3O2 and Pt/Ce0.7Zr0.3O2 was performed before ionic Bombardment and after ionic
Bombardment. Flow composition consisted of hydrogen and argon, the process was like this
that the temperature was increased and then decreased in the presence of Argon and later
in the presence of H2 and reduction was performed. The results were reported in term of H2
consumption in function of temperature in graph for both catalysts. It was observed that
Ce0.7Zr0.3O2 catalyst treated with ion irradiation presents a remarkably higher reducibility
respect to the non bombarded catalyst. As a result, the peak of H2 consumption was measured
at 585 K, a temperature roughly 100 K lower than that reported for the correspondent
unmodified catalyst. In the presence of Pt, the reduction was achieved at lower temperature
(520 K) than on the bare support and the ion bombardment lead to a further decrement of
the temperature in correspondence of the maximum of the reduction peak to 340 K. And as
catalyst was more reducable so it has advantage of this that noble atom will not be displaced,
and was considered a big acheivement.

Effect of the ion bombardment:

This that what happened on the surface of catalyst after bombardment was then analyzed
and also confirmed by FTIR study. The evolution of surface hydroxyl species vibrational
modes ν(OH) was used as probe of the surface oxidation state.
In particular, the band assigned to the hydroxyl group coordinated to two cations in
prossimity of an oxygen vacancy (~3630 cm-1) was observed to increase in intensity with the
reduction temperature until 673 K and to be always more intense for the bombarded catalysts
respect to the correspondent untreated ones. The results were in line with HRTEM analysis
which revealed that the sample, after ion bombardment, is characterized by an uniform
distribution of nanoparticles on the catalytic surface, as well as by the formation of atom
vacancies and incomplete terraces. Both Ce0.7Zr0.3O2 and Pt/Ce0.7Zr0.3O2 after ion irradiaton
were more stable and resistant to aging respect to the non treated catalysts. Analogous
results have been obtained from the study of alternative catalytic systems such as Pd/Al2O3
treated with the same ion bombardment protocol, which provokes a remarkable change in
the particle morphology, as highlighted by both XPS and IR studies

Conclusion:

The study revealed from the results such as;

Formation of morphologic and structural defects (vacancies and terraces) on the surface upon
bombardment, creation of preferential absorption sites and routes for oxygen that increases
the oxygen activation and mobility. Modification of the localelectronic structure of the sites
the electrostatic charges that affect both metal and support. Also enhanced reducability that
was a goal was acheived after bombardment, enhanced catalytic activity of nanoscale
systemsm and Better graftting of metal particles that is better resistance to aging.