Remote detection NMR imaging of chemical reactions and adsorption phenomena

Abstract

<div lang="en" class="abs"><p class="abs_header">Abstract</p><p>The subject of this thesis is the characterization of chemical reactions and adsorption by means of remote detection (RD) method of nuclear magnetic resonance (NMR). The thesis consists of three related topics: In the first one, novel RD NMR based methods for characterizing chemical reactions were presented. In the second topic RD NMR methods were used to study the performance of new kind of microfluidic reactors. The third project concentrated on the development of a novel way to quantify the adsorption of flowing gas mixtures in porous materials. Even though all the topics cover quite different areas of research, they have few common nominators: remote detection NMR, microfluidics and method development.</p><p>Microfluidic devices are of interest for many areas of science (such as molecular biology, disease diagnosis, chemistry) as they offer great promises for future technologies. Small dimensions enable, among many other things, the benefits of small sample volumes, large surface to volume ratio, efficient heat exchange and precise control of flow features and chemical reactions. The efficient evolution of microfluidic processes requires also the development of new innovative ways to characterize the performance of microfluidic devices. In this work, remote detection NMR is utilized for the purpose. RD is a method where the encoding and detection of information are separated physically. In many cases, the encoding and detection are performed with two separate RF coils while a fluid is passing through the studied system.</p><p>In the first part of the thesis work, we introduced the concept of remote detection exchange (RD-EXSY) NMR spectroscopy. We demonstrated that the RD-EXSY method can provide unique chemical information. Furthermore, the time-of-flight (TOF) information, which is a natural side product of the experimental setup used, can be converted into indirect spatial information, showing the active reaction regions in a microfluidic device. Additionally, we demonstrated that by applying the principles of Hadamard spectroscopy in the encoding of the indirect spectral dimension we were able to produce with high efficiency RD-EXSY TOF images with direct spatial information. This allows even more accurate characterization of the active regions.</p><p>The second topic concentrates on the development of microfluidc hydrogenation reactors. In the project atomic layer depositon (ALD) method was used for the first time to deposit both catalyst nanoparticles and support material on the surface of wall-coated microreactors. As a model reaction continuous flow propene hydrogenation into propane was studied by means of remote detection NMR. Reaction yield, mass transport phenomena and the activity of the catalyst surface were determined from the RD NMR data.</p><p>Thirdly we presented a novel method for gas adsorption measurements in porous materials using RD TOF NMR. Traditional adsorption measurements are carried out at static conditions for a single gas component, as multi-component adsorption measurements are challenging and time-consuming. We investigated adsorption of continuously flowing propane and propene gases as well as their mixture in packed beds of mesoporous materials. The unique time-of-flight information obtained using the RD NMR method was utilized in the determination of flow velocity, which was then converted into amount of adsorbed gas.</p></div>