<html><head></head><body style="word-wrap: break-word; -webkit-nbsp-mode: space; -webkit-line-break: after-white-space; color: rgb(0, 0, 0); font-size: 14px; font-family: Calibri, sans-serif; "><div><br></div><span id="OLK_SRC_BODY_SECTION"><div xmlns:v="urn:schemas-microsoft-com:vml" xmlns:o="urn:schemas-microsoft-com:office:office" xmlns:w="urn:schemas-microsoft-com:office:word" xmlns:m="http://schemas.microsoft.com/office/2004/12/omml" xmlns="http://www.w3.org/TR/REC-html40"><div lang="EN-US" link="blue" vlink="purple"><div class="WordSection1"><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;margin-bottom:6.0pt;text-align:center;line-height:18.0pt"><a name="_Toc434675189"><b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">PhD DEFENSE STUDENT: </span></b></a><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">Manjesh Kumar</span><span style="font-family: 'Times New Roman', serif; color: black; "><o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;margin-bottom:6.0pt;text-align:center;line-height:18.0pt"><b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">DATE: </span></b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">Monday, August 1, 2016</span><span style="font-family: 'Times New Roman', serif; color: black; "><o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;margin-bottom:6.0pt;text-align:center;line-height:18.0pt"><b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">TIME: </span></b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">4:00 PM</span><span style="font-family: 'Times New Roman', serif; color: black; "><o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;margin-bottom:6.0pt;text-align:center;line-height:18.0pt"><b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">PLACE: </span></b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">Chemical Engineering Conference Room</span><span style="font-family: 'Times New Roman', serif; color: black; "><o:p></o:p></span></p><p class="MsoNormal" align="center" style="mso-margin-top-alt:auto;margin-bottom:6.0pt;text-align:center;line-height:18.0pt"><b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">DISSERTATION CHAIR: </span></b><span style="font-size: 14pt; font-family: 'Times New Roman', serif; color: black; ">Dr. Jeffrey Rimer</span><span style="color:black"><o:p></o:p></span></p><div style="margin-bottom:10.0pt"><div class="MsoNormal" align="center" style="margin-bottom:0in;margin-bottom:.0001pt;text-align:center"><b><span style="font-size:14.0pt;line-height:115%;color:black"><hr size="2" width="100%" align="center"></span></b></div></div><p class="doctitle0" align="center" style="text-align:center"><b><span style="font-size:14.0pt;color:black;mso-fareast-language:ZH-CN">TITLE:</span></b><b><span style="font-size:10.5pt;color:black"><o:p></o:p></span></b></p><p class="DocTitle"><span style="font-size:14.0pt">Rational Design of Nanoporous Zeolite Material through Molecular Design and Mechanistic Study of Nucleation and Growth<o:p></o:p></span></p><p class="DocTitle"><span style="font-size:14.0pt"><o:p> </o:p></span></p><p class="MsoNormal" style="margin-bottom:0in;margin-bottom:.0001pt;text-align:justify;text-indent:.5in;line-height:200%"><span style="font-size: 12pt; line-height: 200%; font-family: 'Times New Roman', serif; ">Microporous zeolites have garnered much attention due to the growing opportunities for their use in a wide range of applications spanning energy to medicine. Despite their
extensive use in commercial processes, an understanding of their growth mechanism(s) remains elusive. The rational design of zeolite materials calls for more versatile synthetic approaches capable of
<i>a priori</i> tailoring crystal properties, such as crystal size, morphology, and surface architecture. This class of porous materials, which are heavily utilized as catalysts for the production of fuel and chemicals, are often synthesized with undesirable
properties, thus presenting an opportunity to explore the impact of crystal engineering on catalyst performance (i.e., activity and selectivity). This dissertation focusses on the design and characterization of zeolites that commonly exhibit severe mass transport
limitations due to their suboptimal crystal habit. <o:p></o:p></span></p><p class="MsoNormal" style="margin-bottom:0in;margin-bottom:.0001pt;text-align:justify;text-indent:.5in;line-height:200%"><span style="font-size: 12pt; line-height: 200%; font-family: 'Times New Roman', serif; ">To this end, we have taken a multifaceted approach of first developing a deeper understanding of zeolite crystallization, which in turn can be used to develop generalized
design platforms for controlling physicochemical properties of crystals with varying topology. Here we will present mechanistic studies of zeolite frameworks LTL, CHA, MFI, and LTA. Using a variety of techniques, we examined the time-resolved transformation
of bulk amorphous precursors in LTL and CHA synthesis to their crystalline phase.
<i>Ex situ</i> techniques such as static light scattering (SLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and XRD) were used to establish the direct role of initial precursor during crystal growth, which occurs via a process
generally referred to as crystallization by particle attachment (or CPA). To this end, we developed more sensitive characterization tools to track the extent of crystallization (compared to XRD); however, these techniques have the inherent drawback of being
invasive during sample analysis or preparation. To avoid this problem, we studied MFI and LTA crystallization using non-invasive
<i>in-situ </i>atomic force microscope (AFM). We used this state-of-the-art tool to monitor the growth of zeolite surfaces by nonclassical mechanisms (e.g., nanoparticle attachment) under solvothermal conditions. From time-resolved AFM images we established
that growth pathways can switch between classical and nonclassical routes depending upon the physicochemical conditions of growth solution, such as the selection of organic structure-directing agent (OSDA), synthesis temperature, and supersaturation. These
studies provide the direct evidence for tailoring the growth mechanisms of zeolite crystallization.
<o:p></o:p></span></p><p class="MsoNormal" style="margin-bottom:0in;margin-bottom:.0001pt;text-align:justify;text-indent:.5in;line-height:200%"><span style="font-size: 12pt; line-height: 200%; font-family: 'Times New Roman', serif; ">In the light of dual growth mechanism, we will discuss our studies of zeolite crystallization in the presence of zeolite growth modifiers (ZGMs), which are molecules that
selectively bind to specific surfaces of zeolite crystals and mediate anisotropic growth rates and/or control aggregation of bulk precursors. We systematically examined a library of modifiers ranging in their structure and functional moieties to assess the
physicochemical properties that regulate their efficacy and specificity. We demonstrate that the judicious selection of ZGMs can markedly alter zeolite crystal morphology and size for LTL and SSZ-13 (often modifying size over 3 orders of magnitude). These
studies revealed that ZGM hydrophobicity and the spatial sequencing of binding moieties are effective molecular descriptors of its efficacy. Moreover, polymers proved to be more effective modifiers than their corresponding monomers. In addition, we established
the synergistic effect of binary modifier combinations, which yield unprecedented control of crystal size. Collectively, these studies seek to establish general heuristics for designing zeolites with tailored properties. This facile, economical method is unmatched
in its ability to tune SSZ-13 and LTL crystal size. Given the fact that modifiers are inexpensive and recoverable (post-synthesis), this practical approach to crystal engineering has the potential to be more broadly applicable to a wider range of zeolite framework
types. <o:p></o:p></span></p><p class="MsoNormal" style="line-height:200%"><span style="font-size: 12pt; line-height: 200%; font-family: 'Times New Roman', serif; "><o:p> </o:p></span></p><p class="MsoNormal" style="line-height:200%"><span style="font-size: 12pt; line-height: 200%; font-family: 'Times New Roman', serif; "><o:p> </o:p></span></p><p class="MsoNormal" style="line-height:200%"><span style="font-size: 12pt; line-height: 200%; font-family: 'Times New Roman', serif; "><o:p> </o:p></span></p></div></div></div></span><style><!--
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