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<b><span style="font-size:16.0pt;font-family:"Times New Roman",serif;color:red;text-transform:uppercase">Low Temperature NO<i><sub>x</sub></i> Trapping in Pd-exchanged SSZ-13 Zeolite Passive NO<i><sub>x
</sub></i>Adsorbers: </span></b><o:p></o:p></p>
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<b><span style="font-size:16.0pt;font-family:"Times New Roman",serif;color:red;text-transform:uppercase">Density Functional Theory Simulations, Transient Microkinetic Modeling and Bond Analysis</span></b><o:p></o:p></p>
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<span style="font-size:12.0pt;font-family:"Times New Roman",serif;text-transform:uppercase"> </span><o:p></o:p></p>
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<b><span style="font-size:13.5pt;font-family:"Times New Roman",serif">Bhuiyan Md. Rahman</span></b><o:p></o:p></p>
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<span style="font-family:"Times New Roman",serif">July 25, 2022; 2:00 PM – 4:00 PM (CST)</span><o:p></o:p></p>
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<span style="font-family:"Times New Roman",serif"><br>
<b>Room:</b> Chemical Engineering Conference Room</span><o:p></o:p></p>
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<b><span style="font-size:12.0pt;font-family:"Times New Roman",serif;color:black">MS Teams Meeting ID</span></b><span style="font-size:12.0pt;font-family:"Times New Roman",serif;color:black">: </span><span style="font-size:10.5pt;font-family:"Times New Roman",serif;color:#252424"> </span><span style="font-size:12.0pt;font-family:"Times New Roman",serif;color:#252424">256
743 304 035, </span><b><span style="font-size:10.5pt;font-family:"Times New Roman",serif;color:#252424">Passcode</span></b><span style="font-size:10.5pt;font-family:"Times New Roman",serif;color:#252424">:
</span><span style="font-size:12.0pt;font-family:"Times New Roman",serif;color:#252424">ExXaJQ</span><o:p></o:p></p>
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<b><span style="font-family:"Times New Roman",serif">Committee Chair:</span></b><span style="font-family:"Times New Roman",serif"><br>
Lars C Grabow, Ph.D.</span><o:p></o:p></p>
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<b><span style="font-family:"Times New Roman",serif">Committee Members:</span></b><span style="font-size:10.0pt;font-family:"Times New Roman",serif"><br>
Michael P Harold, Ph.D. <b>| </b>Jeffrey D. Rimer, Ph.D. <b>|</b> Saurabh Bhandari, Ph.D.
<b>|</b> Thomas P Senftle, PhD.</span><o:p></o:p></p>
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<p class="MsoNormal" style="mso-margin-top-alt:auto;mso-margin-bottom-alt:auto"><b><span style="font-size:12.0pt;font-family:"Times New Roman",serif;color:#C8102E">Abstract</span></b><o:p></o:p></p>
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<span style="font-family:"Times New Roman",serif;color:black">Lean-burn designs of higher fuel-efficient diesel engines have resulted in exhaust emissions at considerably lower temperatures. However, leading emission control technologies available to abate
NO<i><sub>x</sub></i>,<sub> </sub>CO and hydrocarbon emission levels function at temperatures typically above 200
</span><span style="font-family:Symbol;color:black">°</span><span style="font-family:"Times New Roman",serif;color:black">C. Passive NO<i><sub>x</sub></i> adsorbers (PNA), using 1% Pd-exchanged SSZ-13 with CHA framework, have shown great promise in trapping
NO<i><sub>x</sub></i> at temperatures below 150 </span><span style="font-family:Symbol;color:black">°</span><span style="font-family:"Times New Roman",serif;color:black">C and releasing them above 200
</span><span style="font-family:Symbol;color:black">°</span><span style="font-family:"Times New Roman",serif;color:black">C. With the help of density functional theory (DFT) simulations, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements
combined with microkinetic modeling of simulated temperature programmed desorption (TPD), we have investigated the nature of relevant active sites. A transient microkinetic model developed primarily under dry conditions identified the dominant reaction pathways
responsible for the cycling between Pd<sup>II</sup> and Pd<sup>I</sup> stabilized by its high NO binding energy. A second monolithic kinetic model was developed under wet conditions as a predictive tool to simulate NO<i><sub>x</sub></i> uptake. NO uptake in
the presence of the reductant CO is enhanced accompanied by CO<sub>2</sub> formation. The increased NO uptake is consistent with the strongly exothermic nature of CO oxidation and lower activation barrier.</span><o:p></o:p></p>
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<span style="font-family:"Times New Roman",serif;color:black">Density functional theory (DFT) simulations are susceptible to the choice of exchange-correlation (XC) functional and improper selection of the functional can lead to fallacious conclusions. One
such example where the choice of XC functional can potentially alter qualitative conclusions is NO binding on Pd-exchanged SSZ-13 zeolites, which is relevant for passive NO<i><sub>x
</sub></i>adsorption. We have investigated the binding properties predicted by different XC functionals on various possible active sites on Pd-exchanged SSZ-13, spanning multiple levels of theory. The accuracy of XC functionals was assessed by comparison to
reliable measurements of relevant properties, including the gas phase reaction enthalpy of CO oxidation by NO<sub>2</sub>, gas phase frequencies of CO and NO, ionization energy of Pd, and reported frequencies of Z<sub>2</sub>Pd<sup>II</sup>(NO) and ZH(CO)
sites. To analyze bonding properties at the electronic structure level, we employed electron density difference and crystal orbital Hamilton population (COHP) analyses. The benchmark results indicate that the hybrid meta-GGA functional TPSSh most reliably
predicts different properties investigated, whereas the GGA BEEF-vdW also performs adequately in describing relevant frequencies.</span><span style="font-size:12.0pt;line-height:150%;font-family:"Times New Roman",serif">
</span><o:p></o:p></p>
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<p class="MsoNormal"><span style="font-size:12.0pt;font-family:"Times New Roman",serif"><img width="600" height="82" style="width:6.25in;height:.8541in" id="Picture_x0020_4" src="cid:image002.jpg@01D89B51.F4A59C20" alt="Engineered For What's Next"></span><o:p></o:p></p>
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