Heterogeneous catalysis plays a significant role in the chemical industry and the global economy. Most heterogeneous catalysts in the chemical industry and laboratory consist of supported metal nanoparticles, clusters and isolated (single) atoms. Understanding structure sensitivity and identifying the active site or sites are crucially essential for designing efficient catalysts. To determine the active sites of a catalyst for a particular chemical reaction, in-situ/operando spectroscopy, such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray absorption fine structure (XAFS) spectroscopy, is usually implemented as characterization tools. However, understanding the limitation of the characterization tools is crucial to eliminate misleading conclusions. Therefore, the main object of this work is not only to characterize the catalyst before and after the reaction but to investigate the reliability of the characterization tools as well as the stability of the metal clusters and single atoms during CO oxidation. There are four main findings that will be present in this work. First, a high-flux X-ray beam can induce structural change that leads to a reduction of the metal and agglomeration of metal clusters. This finding is very important since X-ray beam damage is uncommon for heterogeneous catalysis as for homogeneous catalysts and biological samples. In the study, the effect of high-flux X-ray on the Rh clusters and nanoparticles was highlighted along with providing mitigation strategies in order to reduce the damage caused by the high-flux X-ray beam. The second important finding is about the characterization of Rh clusters and nanoparticles during CO reduction treatment using DRIFTS. In this study, the integration of low-temperature CO oxidation kinetics as a characterization tool with DRIFTS, XAFS and scanning/transmission electron microscopy (STEM) was found to be necessary to improve the characterization of Rh single atoms. Implementing CO oxidation measurements at low temperatures can provide a rough estimation of the percentage of Rh single atoms. The third finding is related to the stability of Rh clusters upon exposure to CO, oxygen and CO oxidation at different temperatures. The study shows an unexpected dynamic structural change that the Rh cluster undergoes during exposure to oxygen even at room temperature in which the Rh clusters disperse to form Rh single atoms. This dispersion phenomenon was found to be size, gas environment and temperature dependent. For example, small clusters tend to disperse while large nanoparticles resist dispersion. additionally, increasing the temperature to ∼ 160 with CO and oxygen lead to an increase in the percentage of Rh single atoms. More importantly, the dispersed catalyst (Rh single atoms) exhibits higher CO oxidation activity than Rh nanoparticles by 350x. This finding can also be used for Rh single atoms synthesis for different oxide supports such as MgAl2O4, TiO2, and CeO2. Finally, the fourth finding is about investigating the CO oxidation kinetics and mechanism. The kinetics of Rh single atoms differ from Rh nanoparticles. Implementing in-situ spectroscopy helps to identify the resting state of the Rh complex during CO oxidation which is Rh(CO)2. By combining CO oxidation kinetics and in-situ spectroscopy, the plausible mechanism was suggested to be Eley-Rideal/Mars Van Krevelen mechanism. / Doctor of Philosophy / Heterogeneous catalysts are solid materials that scientists and chemical engineers use to convert undesirable raw reactants (liquid or gas) to other products (liquid or gas). One example of a heterogeneous catalyst is a catalytic converter used in most cars around the world. One goal of the catalytic converter is to convert CO (toxic gas) to CO2 (less toxic). The catalyst in a catalytic converter contains precious metals as nanoparticles such as Platinum (Pt), Palladium (Pd) and Rhodium (Rh) deposits on oxide supports (inert materials) such as Al2O3. These Pt, Pd and Rh nanoparticles help to accelerate the chemical reaction (e.g.CO oxidation) in which converting the toxic gas CO to CO2 at a relatively low temperature compared to if the reaction proceeds without those metal nanoparticles. In order to improve the performance of the catalyst, scientists and engineers implement characterization techniques to identify the active site based on the shape and size of the nanoparticles. One method to improve the catalyst performance is to decrease the particle size below 2 nm or even to reach isolated atoms. Unfortunately, synthesizing isolated (single) atoms supported on oxide support is very challenging. One main discovery presented in this work is that Rh single atoms can be synthesized using a simple but effective method. More importantly, Rh single atoms show higher performance than Rh nanoparticles by 350 times which helps to convert CO the toxic gas to CO2 at room temperature. This finding is important in which that the synthesis presented here can be used for different chemical reactions such as methane oxidation and methanol carbonylation.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/115082 |
| Date | 16 May 2023 |
| Creators | Albrahim, Malik Ali M. |
| Contributors | Chemical Engineering, Karim, Ayman M., Morris, John R., Deshmukh, Sanket A., Xin, Hongliang |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | English |
| Detected Language | English |
| Type | Dissertation |
| Format | ETD, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
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