Manjesh Kumar

A Facile Strategy To Design Zeolite L Crystals with Tunable Morphology and Surface Architecture

Tailoring the anisotropic growth rates of materials to achieve desired structural outcomes is a pervasive challenge in synthetic crystallization. Here we discuss a method to selectively control the growth of zeolite crystals, which are used extensively in a wide range of industrial applications. This facile method cooperatively tunes crystal properties, such as morphology and surface architecture, through the use of inexpensive, commercially available chemicals with specificity for binding to crystallographic surfaces and mediating anisotropic growth. We examined over 30 molecules as potential zeolite growth modifiers (ZGMs) of zeolite L (LTL type) crystallization. ZGM efficacy was quantified through a combination of macroscopic (bulk) and microscopic (surface) investigations that identified modifiers capable of dramatically altering the cylindrical morphology of LTL crystals. We demonstrate an ability to tailor properties critical to zeolite performance, such as external porous surface area, crystal shape, and pore length, which can enhance sorbate accessibility to LTL pores, tune the supramolecular organization of guest-host composites, and minimize the diffusion path length, respectively. We report that a synergistic combination of ZGMs and the judicious adjustment of synthesis parameters produce LTL crystals with unique surface features, and a range of length-to-diameter aspect ratios spanning 3 orders of magnitude. A systematic examination of different ZGM structures and molecular compositions (i.e., hydrophobicity and binding moieties) reveal interesting physicochemical properties governing their efficacy and specificity. Results of this study suggest this versatile strategy may prove applicable for a host of framework types to produce unrivaled materials that have eluded more conventional techniques.

SSZ-13 Crystallization by Particle Attachment and Deterministic Pathways to Crystal Size Control

Many synthetic and natural crystalline materials are either known or postulated to grow via nonclassical pathways involving the initial self-assembly of precursors that serve as putative growth units for crystallization. Elucidating the pathway(s) by which precursors attach to crystal surfaces and structurally rearrange (postattachment) to incorporate into the underlying crystalline lattice is an active and expanding area of research comprising many unanswered fundamental questions. Here, we examine the crystallization of SSZ-13, which is an aluminosilicate zeolite that possesses exceptional physicochemical properties for applications in separations and catalysis (e.g., methanol upgrading to chemicals and the environmental remediation of NO(x)). We show that SSZ-13 grows by two concerted mechanisms: nonclassical growth involving the attachment of amorphous aluminosilicate particles to crystal surfaces and classical layer-by-layer growth via the incorporation of molecules to advancing steps on the crystal surface. A facile, commercially viable method of tailoring SSZ-13 crystal size and morphology is introduced wherein growth modifiers are used to mediate precursor aggregation and attachment to crystal surfaces. We demonstrate that small quantities of polymers can be used to tune crystal size over 3 orders of magnitude (0.1-20 μm), alter crystal shape, and introduce mesoporosity. Given the ubiquitous presence of amorphous precursors in a wide variety of microporous crystals, insight of the SSZ-13 growth mechanism may prove to be broadly applicable to other materials. Moreover, the ability to selectively tailor the physical properties of SSZ-13 crystals through molecular design offers new routes to optimize their performance in a wide range of commercial applications.

Tailoring the physicochemical properties of zeolite catalysts

The physicochemical properties of zeolite catalysts, such as crystal topology, composition, size, and morphology, can have a marked effect on their performance for a broad range of reactions, notably in catalyst activity, hydrothermal stability, shape selectivity, and/or lifetime. There are relatively few zeolite framework types employed as commercial catalysts. Contributing factors include the high cost of synthesis and the difficulty of tailoring crystal nucleation and growth to achieve the desired properties. There is an increasing amount of structure performance data in the literature and patents that can be used to guide the identification of effective zeolite “formulations”; however, the challenges for realizing these materials are generally twofold: (i) growth mechanisms are not well understood, which often prohibits the control of zeolite crystallization, and (ii) the impracticality of most design schemes hinders their economic feasibility and their potential for facile implementation. These aspects are often overlooked in the design of zeolite catalysts, yet they are essential for any plans aimed at eventual commercialization. In this review, we summarize our recent findings in the area of zeolite synthesis and characterization, focusing specifically on practical routes to control zeolite crystallization in the absence of costly organics, tailoring crystal habit through the use of versatile and recyclable zeolite growth modifiers, and pioneering techniques in zeolite surface science as a platform to expand our knowledge of crystal growth mechanisms. These concerted efforts in rational design bridge fundamental and applied research towards the development of zeolites with improved catalytic performance.

Nanoscale Control of Homoepitaxial Growth on a Two-Dimensional Zeolite

Nanoscale crystal growth control is crucial for tailoring two-dimensional (2D) zeolites (crystallites with thickness less than two unit cells) and thicker zeolite nanosheets for applications in separation membranes and as hierarchical catalysts. However, methods to control zeolite crystal growth with nanometer precision are still in their infancy. Herein, we report solution-based growth conditions leading to anisotropic epitaxial growth of 2D zeolites with rates as low as few nanometers per day. Contributions from misoriented surface nucleation and rotational intergrowths are eliminated. Growth monitoring at the single-unit-cell level reveals novel nanoscale crystal-growth phenomena associated with the lateral size and surface curvature of 2D zeolites.