Available Projects for Master Students

Currently the following calls for MSc projects are open. If you are interested submit your request via the online form linked to here First please consult our page information for students.

 

Supervisor(s): Matteo Monai, Helen King (Geosciences)
Title: Can magnetic manipulation of FeS growth change its catalytic properties?
Description: The need for alternative feedstocks to conventional fossil fuels have put the development of carbon capture, storage and, in particular, utilisation technologies firmly on the scientific and political agenda. Although the catalytic potential of Fe-S nanoparticles is clear from their electronic make-up, production of iron sulphides is complicated and time consuming. However, iron sulphides have surface specific magnetic properties that may influence their behaviour. As surface reactivity is a key parameter for the nucleation and growth of minerals, this means that we may be able to manipulate these phenomena using magnetic fields to optimise iron sulphide growth for catalysis. In this multi-disciplinary project, the group of Helen King from the Department of Geosciences is starting to grow Fe-sulphides in the presence of different magnetic field strengths, while the MSc student in the ICC group will then examine whether this treatment can change the catalytic projects of the FeS particles.

 

Supervisor(s): Kordula Schnabl, Florian Zand
Title: Chitosan Depolymerization – Synthesis of Sustainable Coating Precursors
Description: Nowadays coating materials are still largely based on fossil-based feedstocks and their application often goes along with the use of organic solvents. [1,2] Chitosan-based coatings are a viable option to produce sustainable coating materials, however their weak solubility in water is limiting their industrial application. [3] In this project, we aim to increase the water solubility by depolymerizing the polymer into oligomers with the help of supported bimetallic catalysts which already was successfully shown for lignin. [4] For this, a set of catalysts will be synthesized and characterized with techniques such as electron microscopy and x-ray diffraction. Furthermore, the chitosan polymer and the obtained product solution will be analyzed on its degree of depolymerization with e.g. infrared spectroscopy, thermogravimetric analysis, and asymmetric-flow field flow fractioning. With this the student will get a valuable insight into the fields of synthesis, characterization and catalysis. Via the following approach we aim to optimize both the catalyst material as well as the conditions for the depolymerization of chitosan polymer. By this we offer a pathway for renewable alternatives in order to replace current fossil-derived materials.
References:
[1] Inamuddin I., Thomas S., Kumar Mishra R., Sustainable Polymer Composites and Nanocomposites, Springer, 2019.
[2] Helanto K., Maitikainen L., Talja R., Bio-based polymers for sustainable packaging and biobarriers: A critical review, BioRes. 14(2), 4902-4951, 2019.
[3] Rinaudo M., Chitin and chitosan: Properties and applications, Prog. Polym. Sci. 31 603-632, 2006.
[4] Zhang J., Cai, Y., Lu, G., Cai, C., Facile and selective hydrogenolysis of β-O-4 linkages in lignin catalyzed by Pd–Ni bimetallic nanoparticles supported on ZrO, Green Chemistry, 18, 6229-6235, 2016.

 

Supervisor(s): Sebastian Rejman, Ina Vollmer
Title: Understanding the Effect of Acidity and Pore Structure in Catalytic Cracking of Polyolefins
Description:The majority of the plastic waste produced worldwide ends up either in a landfill, or is incinerated. Only 12% is recycled, and with current mechanical recycling technology, the resulting recycled plastic is often of significantly lower quality than the original virgin material. Chemical recycling is an emerging technology that aims at converting plastic waste back into chemical building blocks that can be then converted into a variety of products using existing chemical infrastructure. Some approaches are already applied commercially: Pyrolysis of polyolefins yields a mixture of liquid hydrocarbons that can be fed into a steam cracker.1 Using a catalyst in this process allows to lower the energy requirements of the process, and can shift the product distribution towards more valuable products like aromatics.2 Many catalyst properties influence the reaction, e.g. Lewis and Brønsted acidity, pore structure and metal loading. In order to design novel catalyst for polyolefin cracking, the role of these effects must be understood. The goal of this thesis is to understand how acidity or pore structure of the catalyst affects activity and selectivity of the reaction, building upon prior research in our group.
Requirements: Initial experience with programming (e.g. Python or Matlab), interest in catalysis and polymer chemistry.
Earliest possible start: November 2022
References:
1. Vollmer, I. et al. Beyond Mechanical Recycling: Giving New Life to Plastic Waste. Angew. Chemie – Int. Ed. 59, 15402–15423 (2020).
2. Vollmer, I., Jenks, M. J. F., González, R. M., Meirer, F. & Weckhuysen, B. M. Plastic Waste Conversion over a Refinery Waste Catalyst. Angew. Chemie Int. Ed. 60, 16101 (2021).

 

Supervisor(s): Caroline Versluis, Eelco T.C. Vogt, Bert M. Weckhuysen
Title: Studying the Formation and Identification of Coke Species on Fluid Catalytic Cracking Catalyst Particles using Model Reactions
Description: Although the fluid catalytic cracking (FCC) process is being practiced for over 80 years to convert crude oil into usable products, there is still a lot to learn about the mechanism behind the catalytic cracking, both to tune the selectivity between fuels and chemicals and also to be able to effectively use different feedstocks (i.e., biomass and plastic waste) in future refinery processes. It is generally accepted that catalytic cracking involves the formation of carbenium ions and that several acid catalyzed reaction pathways can occur (in parallel), which leads to the formation of the products.[1] An inevitable by-product of the cracking reactions is carbon deposition (coke formation), which deactivates the FCC catalyst particles by clogging the pores and blocking the active sites. In addition, additive aromatic coke from the feed, coke formed during incomplete stripping and coke from dehydrogenation reactions on poisoning metals (e.g. Ni and V) also accumulate on the catalyst particles. All these different coke deposits might cause different deactivation mechanisms and vary in chemical nature.[2]
In this research project, the student will use an extensive set of model FCC catalyst particles with varying composition and deactivation mechanisms (metal deactivation or steam deactivation) in model reactions to study the formation and identification of coke species on these different catalyst particles using different techniques (e.g. UV-Vis spectroscopy, FTIR, CFM), with a focus on Time-Gated Raman. [3,4]
References:
[1] E.T.C Vogt & B.M. Weckhuysen, Chem. Soc. Rev., 2015, 44, 7342
[2] M. Veselý et al., ChemCatChem, 2021, 13, 2494-2507
[3] J. Ruiz-Martínez et al., APPL CATAL A-GEN, 2012, 419-420, 84-94
[4] S. Verkleij et al., ChemCatChem, 2019, 11, 4788-4796

 

Supervisor(s): Bettina Baumgartner, Matteo Monai
Title: Characterization of Pt nanoparticle facets via the Pt-CO bond using infrared spectroscopy
Description: Supported metal nanoparticles are an integral class of heterogenous catalysts and are used for instance from food preparation to bulk and specialty chemical synthesis or emission control. Besides the used metal, the size of the nanoparticle and in particular the ratio of the different facets exposed to the reaction are essential for the catalytic performance. Although being largely applied and studied in depth, the characterization and quantification of the facets of a nanoparticle relies mainly on imaging or tomographic techniques, which require high-end equipment (e.g. high-resolution transmission electron microscopes) and data analysis is time consuming and intricate.
We want to investigate if infrared spectroscopy can be used to probe the facet ratios in Pt nanoparticles of different shapes e.g. cubes, stars etc. Infrared spectroscopy is the Swiss Army knife for the characterization of catalytic processes: It allows for fast and simply identification and quantification of reaction intermediates or characterization of the catalyst itself. When combined with CO adsorption, very characteristic Pt0–CO bands are found in the IR spectrum. The Pt-CO bond strength is influenced by the surroundings of the Pt atom at which the CO adsorbs and directs the position and intensity of the Pt0–CO(ads) IR bands. This bands have been shown to be a measure of the Pt nanoparticle coordination, Pt nanoparticle growth, and CO coverage.1–5Furthermore, studies on flat Pt surfaces with different crystallographic facets, e.g. (100) or (111), indicate that different facets can be distinguished in their Pt0–CO(ads) band positions.
In this project, differently shaped Pt nanoparticles shall be synthesized using reported colloidal synthesis methods and will be exposed to CO during in situ IR spectroscopy. The obtained Pt0–CO(ads) bands will be analyzed and will be set in relations to the Pt nanoparticle’s shape.
References:
[1] Lentz, C., Jand, S. P., Melke, J., Roth, C., et al. DRIFTS study of CO adsorption on Pt nanoparticles supported by DFT calculations. J. Mol. Catal. A Chem. 426, 1–9 (2017).
[2] Garnier, A., Sall, S., Garin, F., Chetcuti, M. J., et al. Site effects in the adsorption of carbon monoxide on real 1.8 nm Pt nanoparticles: An Infrared investigation in time and temperature. J. Mol. Catal. A Chem. 373, 127–134 (2013).
[3] Avanesian, T., Dai, S., Kale, M. J., Graham, G. W., et al. Quantitative and Atomic-Scale View of CO-Induced Pt Nanoparticle Surface Reconstruction at Saturation Coverage via DFT Calculations Coupled with in Situ TEM and IR. J. Am. Chem. Soc. 139, 4551–4558 (2017).
[4] Kale, M. J. & Christopher, P. Utilizing Quantitative in Situ FTIR Spectroscopy To Identify Well-Coordinated Pt Atoms as the Active Site for CO Oxidation on Al2O3-Supported Pt Catalysts. ACS Catal. 6, 5599–5609 (2016).
[5] Haselmann, G. M., Baumgartner, B., Wang, J., Wieland, K., et al. In Situ Pt Photodeposition and Methanol Photooxidation on Pt/TiO2: Pt-Loading-Dependent Photocatalytic Reaction Pathways Studied by Liquid-Phase Infrared Spectroscopy. ACS Catal. 10, 2964–2977 (2020).

 

Supervisor(s): Joren Dorresteijn, Yaqi Wu 
Title: Understanding the working principle of a novel support for metallocene olefin polymerization catalyst for the production of high-impact polypropylene
Description: Polypropylene (PP) is one of the most important and widely used commodity polymers due to its heat resistance, tensile strength, processability, and low cost.1,2 However, application of PP is often limited by its poor impact resistance, in particular at low temperatures. One of the most promising strategies to increase impact resistance of PP is by introducing rubbery co-polymers consisting of ethylene and propylene blends into the isotactic PP matrix, which results in high-impact polypropylene (hiPP).3 Different strategies have been employed in the past for Ziegler-Natta catalysts for the production of hiPP, which comprises mainly of tuning the reactivity of the Titanium active site, porosity of the support or incorporation of nanoparticles into support matrix.3,4 However, metallocene-based olefin polymerization catalysts promise so far higher activity, control and better well-defined polymer properties, but have not been widely successfully used for the production of commercial hiPP, mainly due to it being relatively new technology and difficulty to immobilize the metallocene effectively on the support. For this project we are looking to employ a novel support in metallocene-based olefin polymerization catalysts for the production of hiPP. The student will utilize spray drying synthesis and use different spectroscopic (IR-spectroscopy, UV/VIS, DRIFTS) & microscopic (SEM & CFM) techniques for gaining more fundamental insight in the working principle of this novel support during polymerization.
References:
[1] Monai et al. Chem. Soc. Rev., 2021, 50, 11503.
[2] R. Mülhaupt, Macromol. Chem. Phys. 2013, 214, 159.
[3] Romina et al. Multimodal Polymers with Supported Catalysts, Springer, 2019.
[4] T. Vestberg et al. J. Polym. Sci. Part A Polym. Chem. 2013, 51, 2040.

 

Supervisor(s): Tom Smak, Ina Vollmer
Title: Catalyst Development for the Oxidation of Polyethylene to High Value Di-carboxylic Acids
Description: Plastic products have become an integral part of our daily lives and our extensive use of plastics has resulted in an enormous amount of plastic waste. Estimated is that only 2% of the produced plastics is recycled, while on the other hand 32% leaks into the environment with all its consequences.[1] To limit the environmental impact, the degree of recycling must be drastically increased. The currently applied recycling pathways for polyolefin (polyethylene (PE) and polypropylene (PP)) waste are mostly mechanical, but this is usually accompanied by degraded product properties. Therefore, it is of great importance that chemical recycling pathways are developed such that product properties can be retained.[2] However, competing with the cheap fossil based monomers is challenging. This problem could be circumvented by oxidation, where the economic value of the products could be increased. In a few literature precedents, it has been shown that PE can be upcycled to high value di-carboxylic acids such as succinic and adipic acid, which have a significantly higher value compared to mechanically recycled PE.[3,4]
This project will be about the development of a heterogeneous catalyst for the transformation of polyethylene to di-carboxylic acids. The student will learn how to synthesize, characterize and test different heterogeneous catalysts using a broad range of techniques. The goal of this project is to find out which parameters are important for the catalytic performance and how they influence the reaction. For example, specific parameters of interest are the metal, oxidation state and the support type and morphology. If time allows there are also options to use operando infrared spectroscopy to study how the catalysts influence the mechanism.
References:
[1] Ellen MacArthur Foundation, https://ellenmacarthurfoundation.org, accessed on 5-4-2022
[2] I. Vollmer, M.J.F. Jenks, M.C.P. Roelands, R.J. White, T. Harmelen, P. Wild, G.P. Laan, F. Meirer, J.T.F. Keurentjes and B.M. Weckhuysen, Angew. Chem. Int. Ed., 59, 15402-15423 , (2020).
[3] E. Bäckström, K. Odelius, M.A. Hakkarainen, Ind. Eng. Chem. Res, 56, 14814-14821, (2017).
[4] A. Pifer, A. Sen, Angew. Chem. Int. Ed., 37, 3306-3308, (1998).

Supervisor(s): Bram Kappé
Title: 
Colloidal Ni nanoparticles on various supports as catalysts to study structure sensitivity in CO2 hydrogenation
Description:
 Most catalytic reactions are structure sensitive, which means that the surface atoms of a supported metal catalyst differ in activity. The specific activity of surface atoms depends nanoparticle shape, size and type of support. To study these effects monodisperse nanoparticles of several sizes are required. We have recently developed a novel size-tunable synthesis procedure for small, monodisperse colloidal Ni nanoparticles. In this project these Ni particles will be deposited on several different supports. The resulting catalysts will be tested for CO2 hydrogenation using operando IR, allowing simultaneous study of the activity and reaction mechanism. This will provide unique opportunity to systematically study the metal-support sites where the CO2 reaction is thought to take place. In this project, you will learn how to perform inert synthesis using a Schlenk line and glovebox, and become proficient in TEM, XRD and operando spectroscopy such as FT-IR.

Supervisor(s): Joyce Kromwijk
Title: 
Molybdenum versus Tungsten: who is the superior methane dehydroaromatization catalyst?
Description: Methane is an attractive source for producing valuable chemicals since it is a greenhouse gas that is  flared as a side-product of crude oil. In the so-called methane dehydroaromatization (MDA) reaction, methane is converted into aromatics such as benzene without the addition of oxidants. Molybdenum (Mo) supported on ZSM-5 is the most investigated catalyst for this reaction due to its exceptional performance with methane conversions of ~10%1. However, to make this reaction industrially applicable, catalysts should be developed further to obtain higher aromatic yields and stability. Due to the high temperatures that are required for MDA, coke formation (CH4 -> C + 2 H2) is thermodynamically favored and fast deactivation occurs. On top of that, the challenge of valorizing industrial methane streams are the gaseous impurities (e.g. steam and CO2) that are present in the feed. Mo/ZSM-5 might therefore not be the ideal candidate for industrial application: earlier experiments have shown that molybdenum is removed from the support in high concentrations of steam due to its volatile character. Tungsten (W) functionalized ZSM-5 is able to selectively convert methane into aromatics2, Our own experiments have also shown that over time the benzene yield for W/ZSM-5 is more stable compared to Mo/ZSM-5, which makes it a very interesting catalyst to study further. The performance of the catalyst is dependent on e.g. metal loading, preparation method, pretreatment and reaction conditions. Through varying these parameters, this project aims to get a better understanding of the structure-performance relation of W/ZSM-5 compared to the extensively studied Mo/ZSM-5 through a variety of techniques such as operando UV-Vis, solid-state NMR, XRD, NH3-TPD and Raman spectroscopy.


References:
[1] Vollmer, I.; Yarulina, I.; Kapteijn, F.; Gascon, J., ChemCatChem 2019, 11, 39–52.
[2] Weckhuysen, B. M.; Wang, D.; Rosynek, M. P.; Lunsford, J. H., J. Catal. 1998, 175 (2), 338–346.

 

Supervisor(s): Joren Dorresteijn, Kordula Schnabl
Title: 
Functionalized Chitosan Microspheres as a Organic Support for Sustainable Metallocene Olefin Polymerization Catalysts
Description: Polypropylene (PP) is one of the most important and widely used commodity polymers due to its heat resistance, tensile strength, processability, and low cost.1,2 However, application of PP is often limited by its poor impact resistance, in particular at low temperatures. One of the most promising strategies to increase impact resistance of PP is by introducing rubbery co-polymers consisting of ethylene and propylene blends into the isotactic PP matrix, which results in high-impact polypropylene (hiPP).3 A similar strategy can be employed by the incorporation of a different polymer phase into the PP matrix, chitosan. Chitosan is not only a sustainable alternative because it is derived from shrimp waste, but also shows potential as a polymerization catalyst support, since it contains surface groups that can anchor the active sites for metallocene polymerization catalysts and is fragile enough to break-up during polymerization.4 Therefore in this project the student will combine these synergistic properties of chitosan to create a sustainable polymerization catalyst.
The student will utilize the spray drying synthesis technique to create the chitosan microspheroidal support, heterogenize the support with anchoring of the active site and use different spectroscopic (IR-spectroscopy, UV/VIS, DRIFTS) & microscopic (SEM & CFM) techniques for gaining more fundamental insight in the working principle of this novel organic support during polymerization.
References:
[1] Monai et al. Chem. Soc. Rev.2021, 50, 11503.
[2] R. Mülhaupt, Macromol. Chem. Phys. 2013214, 159.
[3] Romina et al. Multimodal Polymers with Supported Catalysts, Springer, 2019.
[4] A. M. Eberhardt et al. Polym. Eng. Sci. 2001, 41, 946.