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<span style="font-size:12.0pt; font-family:"Times New Roman",serif"><img width="600" height="171" id="x_Picture_x0020_3" alt="Dissertation Defense Announcement at the Cullen College of Engineering" style="width:6.25in; height:1.7812in" data-outlook-trace="F:1|T:1" src="cid:image005.jpg@01D845D5.17B10F60"></span><span style="font-size:12.0pt; font-family:"Times New Roman",serif"></span></p>
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<b><span style="font-size:16.0pt; font-family:"Times New Roman",serif; color:red; text-transform:uppercase">Biomimetic Active Sites in Metal-Organic Framework Catalysts for Hydrocarbon Transformations</span></b></p>
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<b><span style="font-size:13.5pt; font-family:"Times New Roman",serif">Jacklyn Hall</span></b><span style="font-size:13.5pt; font-family:"Times New Roman",serif"></span></p>
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<span style="font-family:"Times New Roman",serif">April 11, 2022; 12:00-2:00 PM (CST)<br>
Location: AERB 320</span></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>
Praveen Bollini, Ph.D.</span></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 Harold, Ph.D. <b>| </b>Jeffrey Rimer, Ph.D. <b>|</b> Devin Shaffer, Ph.D.
<b>|</b> Hsu Chiang, Ph.D.</span><span style="font-size:10.5pt; font-family:"Times New Roman",serif"></span></p>
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<b><span style="font-size:12.0pt; font-family:"Times New Roman",serif; color:#C8102E">Abstract</span></b><span style="font-size:12.0pt; font-family:"Times New Roman",serif; color:#C8102E"></span></p>
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<span style="font-size:12.0pt; font-family:"Times New Roman",serif"> Metal-organic frameworks (MOFs) are a class of crystalline materials featuring uniform distributions of inorganic nodes interconnected within well-defined organic porous environments. For
applications in catalysis, the homogeneity of active centers attainable within MOFs enables achieving a level of clarity into structure-catalytic property relationships and reaction mechanisms beyond which can be realized in synthetic catalysts delimited by
a high degree of heterogeneity in active site speciation ¨C a feature of particular importance in the development of biomimetic catalysts. Herein, we demonstrate MIL-100 (MIL =
<i>Materials of Institut Lavoisier</i>), a prototypical MOF featuring mixed-valent trinuclear metal nodes [M<sup>2+</sup>(M<sup>3+</sup>)<sub>2</sub>O], features an active site pool which is uniform in structure and catalytic performance.
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<span style="font-size:12.0pt; font-family:"Times New Roman",serif"> A combination of in-situ infrared spectroscopic characterization and probe molecule adsorption experiments with H<sub>2</sub>O, NO, and CO evidence the accessibility of the near theoretical
density of coordinatively unsaturated divalent and trivalent open-metal sites within the Cr- and Fe-analogues of MIL-100 through facile thermal activation protocols (¡Ü 523 K, inert or vacuum). Furthermore, we demonstrate the activated catalysts effectuate
the gas-phase stoichiometric oxidation of CH<sub>4</sub> with N<sub>2</sub>O to partial oxygenates (methanol and acetaldehyde) through the involvement of every potentially available M<sup>2+</sup> open-metal site. Carbon monoxide is applied as a reductant
to further elucidate reaction steps that mediate redox turnovers with N<sub>2</sub>O over MIL-100. Transient, steady-state, and isotopic kinetic analyses provide novel insight into levers for tuning the kinetic relevance of specific reduction and oxidation
elementary reaction steps through second-sphere coordination effects and identity of the active metal.</span></p>
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<span style="font-size:12.0pt; font-family:"Times New Roman",serif"><img width="600" height="82" id="x_Picture_x0020_4" alt="Engineered For What's Next" style="width:6.25in; height:.8541in" data-outlook-trace="F:1|T:1" src="cid:image006.jpg@01D845D5.17B10F60"></span><span style="font-size:12.0pt; font-family:"Times New Roman",serif"></span></p>
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