Annual Progress Report for renewal of Next Generation Scholarship for 2012

PROCESS FOR SUBMISSION 1. Student completes the relevant sections and submits to Supervisor. 2. Supervisor completes relevant section and submits to HOD who then submits to the Executive Dean. 3. The renewal applications must be submitted from the Deans Office to Ms Dudu Mbatha at the Postgraduate Funding Section (rdmbatha@uj.ac.za; 011-559 4016) Please ensure that sufficient detail is provided in the report as a selection panel will determine whether it is approved or not.

Due Date: Level

11 November, 2011
2nd year Masters 2nd or 3rd year Doctoral
X

Please tick as appropriate

Masters entering Doctoral

1. Details of Scholarship holder

Name (title, initials, surname) Identification Number Faculty Race Home Tel No. Cell No. Student No.
NGS Renewal Application Mr NC Antonels 8311075181084 Science Coloured 0835632597 201070676 1

Citizenship Departmen t Gender Fax e-mail address

South African Chemistry Male

nathan@metacatalysis. co.za

Are you legally disabled? If so, please specify the nature of your disability

No

2. Project Summary
Short Project Title Descriptive Project Title Discipline Supervisor Co-Supervisor Project Duration (Please indicate start and anticipated end month and year)
Dendrimer encapsulated nanoparticles and their applications.

The size controlled preparation of ruthenium nanoparticles by dendrimer templated synthesis and evaluation as catalysts. Chemistry Assoc. Prof. R Meijboom Dr A Muller
1 February 2010 31 December 2012

3. Details of Research
3.1. Progress Report
Provide a detailed summary of the progress thus far including milestones achieved or any setbacks experienced. The main objective of my project is to prepare ruthenium nanoparticles using dendrimers as templates to control the size of the nanoparticles and form nanoparticles with a narrow size distribution. Generation four, five and six poly(amidoamine) amine dendrimers were used as the dendrimer template in preparation of the ruthenium nanoparticles producing nanoparticles of increasing size respectively. The initial plan of this research was to evaluate these nanoparticles in the reduction of p-nitrophenol as an easy benchmark reaction to correlate nanoparticle size to activity. The idea is to create a size correlated catalytic activity profile such that nanoparticle size can be estimated by observing their activity in the pnitrophenol reduction reaction. One of the setbacks experienced while doing these reactions was not seeing the expected trend when varying catalytic conditions but this was rectified by changing the reaction conditions. This led us to conclude after consulting existing literature that for the p-nitrophenol reduction, not all metals show the same activity and are condition sensitive, hence fitting in with the requirement to create separate catalytic activity profiles for each metal you want to investigate. The secondary objective of the p-nitrophenol reduction study is to help prove that the reaction follows a Langmuir-Hinshelwood reaction mechanism during catalysis which requires that both substrate and reactant are adsorbed onto the catalyst surface before the catalytic reaction takes place. This behaviour was noted as an increase the substrate leads to a decrease in catalytic rate by blocking adsorption sites for the reducing agent therefore both substrate and reactant must be adsorbed on the catalyst surface. The reduction of p-nitrophenol using this particular ruthenium catalyst has not been demonstrated and published in literature providing good opportunity for publication upon finalising all the results. The second part of my research was initially intended to focus on the evaluation of NGS Renewal Application 2

ruthenium nanoparticles as catalysts in the Fischer-Tropsch synthesis. The focus was changed to the evaluation of ruthenium nanoparticles as hydrogenation catalysts. Toluene hydrogenation was the test reaction and this work was conducted in Germany at the University of Erlangen. The catalytic system utilised is novel and is referred as a nano-SILP (nanoparticles in supported ionic liquid phase) catalyst. The catalytic system consists of nanoparticles extracted from the dendrimers after encapsulation. The extracted nanoparticles are characterised using transmission electron miscroscopy (TEM) to calculate the size distribution of the nanoparticles. The nanoparticles have a well-defined narrow size distribution before and after extraction. The extracted nanoparticles are then suspended in an ionic liquid and this mixture supported on a solid support such as silica. Ionic liquids have various properties that are advantageous such as their low vapour pressure and stability at high temperatures. In conventional biphasic systems where ionic liquids are utilised, there is a relatively small surface area at the interface between the ionic liquid containing the catalyst and the phase containing the substrates. The advantages of a nano-SILP system is the stabilisation of the nanoparticles by the ionic liquid and the increase in surface area of the ionic liquid once distributed across the solid support surface. Catalytic evaluation of this nano-SILP for the hydrogenation of toluene using a fixed bed reactor showed deactivation of the catalyst with time, an undesirable result. The problem of deactivation was solved by incorporating an activation step for the catalyst. Therefore, prior to each reaction the catalyst is pre-treated with hydrogen gas at an elevated temperature. The activated nanoSILP catalysts showed a steady state conversion over four days which is indicative of a stable catalyst. The conversion of toluene was however low and an increase in the amount of ruthenium could help solve this. Selectivity to the partially hydrogenated cycloalkenes was favoured. An analogous catalyst without ionic liquid was prepared and compared to the nano-SILP catalyst. The selectivity for partially hydrogenated products decreased therefore the ionic liquid affects the selectivity in a positive way as the partially hydrogenated products are desirable. The study will be extended to use of solid supports with more regular, ordered mesoporous structures such as the mesoporous silica support, SBA-15. The uniform structure of this material might affect the selectivity obtained during catalysis as well. Further catalytic evaluation of the nano-SILP catalyst in the toluene hydrogenation reaction will be conducted using a batch reactor instead of the fixed bed reactor as we do not have the latter facilities at our institute. The second type of catalyst to be prepared is the referred to as a supported ionic liquid phase (SILP) catalyst and consists of a transition metal complex dissolved in an ionic liquid and dispersed over a suitable support such as amorphous silica 60. The use of mesoporous silica SBA-15 will be investigated as well. The advantages of a SILP system is similar to that of a nano-SILP in that the catalyst is well dispersed in a stabilising ionic liquid and spread across the support to increase the surface area of the catalytic mixture. The SILP catalysts will be characterised using TEM, Scanning Electron Microscopy (SEM) and Brunauer-EmmettTeller (BET) analyses. This will give information of the surface area, porosity and overall catalyst morphology. These catalysts in addition to the nano-SILP catalysts will be evaluated in the hydroformylation of select olefins. This research will commence in February 2012 and continue through the first semester. The two review publications referred to in the previous report was returned for revision upon submission and the corrections are currently being made. Submission of these reviews is due in November 2011. In addition, I am currently working on compiling my data obtained for the catalytic reduction of p-nitrophenol using dendrimer encapsulated ruthenium nanoparticles in the form of a publication.

4. Research Outputs
(Please add boxes if required)

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4.1. Publications
Name of first author (title, initials, surname) Name of coauthor(s) (title, initials, surname) Title of chapter in book, conference paper/ poster, research article Date submitted (month & year) Type of publication (i.e. book, chapter in book, conference paper/poster, research article) Name of Book, Conference, Journal
Mr NC Antonels

Prof J.R. Moss and Dr G.S. Smith

Hydroformylation activity of multinuclear rhodium complexes coordinated to dendritic iminopyridyl and iminophosphine scaffolds. Submitted June 2010 and Accepted October 2010 Research Article

STATUS

Published

Journal of Organometallic Chemistry, 2011, 696, 10, 20032007.

Name of first author (title, initials, surname) Name of coauthor(s) (title, initials, surname) Title of chapter in book, conference paper/ poster, research article Date submitted (month & year) Type of publication (i.e. book, chapter in book, conference paper/poster, research article) Name of Book, Conference, Journal Name of first author (title, initials, surname)
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Mr P Govendor

Mr N.C. Antonels, Mr J. Mattsson, Miss A.K. Renfrew, Prof P.J. Dyson, Prof J.R. Moss, Dr B. Therrien, and Dr G.S. Smith. Anticancer activity of multinuclear arene ruthenium complexes coordinated to dendritic polypyridyl scaffolds.

Submitted April 2009 and Accepted June 2009 Research Article

STATUS

Published

Journal of Organometallic Chemistry, 2009, 694, 21, 34703476.

Mr NC Antonels

Name of coauthor(s) (title, initials, surname) Title of chapter in book, conference paper/ poster, research article Date submitted (month & year) Type of publication (i.e. book, chapter in book, conference paper/poster, research article) Name of Book, Conference, Journal Name of first author (title, initials, surname) Name of coauthor(s) (title, initials, surname) Title of chapter in book, conference paper/ poster, research article Date submitted (month & year) Type of publication (i.e. book, chapter in book, conference paper/poster, research article) Name of Book, Conference, Journal

Dr B. Therrien, Prof J.R. Moss and Dr G.S. Smith

Rhodium(I) iminophosphine poly(propyleneimine) dendrimers: Synthesis, characterization and molecular structure of a mononuclear analogue. Submitted February 2009 and Accepted May 2009 Research Article

STATUS

Published

Inorganic Chemistry Communications, 2009, 12, 8, 716-719.

Mr NC Antonels

Assoc. Prof. R. Meijboom and Dr A Muller

Templated preparation of ruthenium nanoparticles and its evaluation as nano-SILP catalyst in hydrogenation.

November 2011 Poster

STATU S

Catalysis South Africa (CATSA), Johannesburg, 13-16 November 2011

4.2. Patents
Name of Inventor (title, initials, surname) Title of Patent Description of Patent Patent application
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date Patent granting date Local Application/ Registration Number International Application/ Registration Number Countries where submitted Countries where accepted

4.3. Products/Artefacts
Name (title, initials, surname) Description of Product/Artefact Impact of Product/Artefact Date of Production (month & year)

4.4. Other related Outputs

OTHER PRESENTATIONS

Templated preparation of ruthenium nanoparticles and its evaluation as nano-SILP catalyst in hydrogenation. Catalysis South Africa (CATSA), Johannesburg, 13-16 November 2011, (Poster Presentation).

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4.5. Links with and impact on Industry/Community

Report on any links with industry/community

The next phase of the project is concerned with the use of ruthenium nanoSILP catalyst in the hydroformylation. This is the conversion of alkenes into value added products such as aldehydes and with further hydrogenation, alcohols. The use of nano-SILP and SILP catalysts has not gained enough exposure here in South Africa and could help to further diversify the knowledge base in our country. The use of nano-SILP and SILP catalysts hold great potential in improving catalyst recyclability which holds great importance from an economic aspect as increased recycling leads to a decrease in money being spent on new catalysts.

4.6. Any other outputs resulting from the research

4.7

Science Awareness Activities

List all activities, including workshops, conferences and seminars organised in relation to this project
(Please add boxes if required one for each activity)

Nature of Activity Title of workshop/seminar Target group Impact and outputs

4.8 Conferences/Workshops
Conference attended/ Institution visited City and country Year attended Contribution made Impact of attendance
NGS Renewal Application University of Erlangen Erlangen, Germany 2011 Catalytic evaluation of nano-SILP catalyst in toluene hydrogenation Learnt how to prepare nano-SILP catalysts and some aspects 7

of how to conduct the catalytic reactions using a fixed bed reactor.

Conference attended/ Institution visited City and country Year attended Contribution made Impact of attendance

Catalysis South Africa (CATSA) Johannesburg, South Africa 2011 Poster Presentation Showcased my research on ruthenium nano-SILP catalysts used as a catalyst in toluene hydrogenation.

5. Statement by Scholarship-holder
Did you receive any other bursaries, scholarships, awards or emoluments? Please answer yes or no. If yes, please complete the columns below. Name of organisation NRF (Innovation) Period awarded ie from month/year to month/year January December 2011 yes

Amount R 90 000

Purpose of award eg tutorial duties PhD scholarship

University of Johannesburg (Student assistantship)

R 12 000

February November 2011

Demonstrating Duties

Does any support received to date bind you to a service contract. Please answer yes or no. If yes, please attach proof of deferment of duties. I certify that the information supplied in this application is correct and that, if my scholarship is renewed, I will abide by the terms and conditions in the agreement between me and the UJ. Signature of Applicant Date 04/11/11

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6. Supervisors report

Please complete this section and email to rdmbatha@uj.ac.za Should you have any queries, please contact Ms Mbatha on x4016.
CONFIDENTIAL STATEMENT BY APPLICANT'S SUPERVISOR NB: Complete in typescript please Please provide a detailed summary of the students progress to date.

Will applicant complete the Master's degree within the two year period (renewal of Master's scholarships only). Please indicate yes or no. Expected date of completion of the Master's degree (month and year) Will the Master's registration be upgraded to doctoral registration? Please indicate yes, no or uncertain Expected date of upgrading of Master's degree (if applicable). Kindly note that you are requested to advise the UJ as soon as upgrading has been approved. Expected date of completion of doctoral degree (renewal of doctoral scholarships) only).
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Please make a recommendation on the continuation of the applicant's scholarship. Give detailed reasons for your recommendation.

Name Department Supervisors Signature HOD Recommendation

Position

Dat e

HOD recommendation Executive Dean recommendation

Dat e

Executive Dean signature

Dat e

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FOR OFFICIAL PURPOSES ONLY

Date received by the Postgraduate Funding Support Section (Stamp)

Renewal granted Date Renewal/Reject ion letter prepared Date Letter signed by student Name Date renewal completed Month in which monthly payment will begin

Yes

No

Signatu re

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