Breaking the Rules of Classical Crystallization: An Unconventional Guide to Crystal Engineering

Abstract: Crystal engineering is a broad area of research that focuses on methods of designing and/or optimizing materials for diverse applications in fields spanning from energy to medicine. The ability to selectively control crystallization to achieve desired material properties requires detailed understandings of the thermodynamic and kinetic factors regulating crystal nucleation and growth. Combining this fundamental knowledge with innovative approaches to tailor crystal size, structure, and morphology can lead to the production of materials with superior properties beyond what is achievable by conventional routes. In this talk I will discuss two general mechanisms of crystal growth: (1) classical pathways involving growth by the addition of monomers (ions or molecules); and (2) nonclassical pathways, termed crystallization by particle attachment (CPA), involving the formation of metastable precursors that play a direct role in crystal nucleation and growth.^1-3 A ubiquitous approach in crystal engineering to selectively alter the rate(s) of anisotropic growth is through the use of modifiers, which are molecules (or macromolecules) that interact with specific crystal surfaces and mediate the attachment of growth units. In this talk, I will discuss how we are using organic and/or inorganic species that operate as either modifiers or structure-directing agents to tailor the properties of zeolites,^4,5 which are microporous aluminosilicates used in catalysis, adsorption, and ion-exchange processes. In order to elucidate the mechanisms of crystal growth, we developed a unique atomic force microscope (AFM) liquid cell that enables time-resolved imaging of surface growth under solvothermal conditions. I will show how in situ AFM has created new opportunities to probe complex pathways of nonclassical crystallization as part of our broader effort to develop new methods to tailor the physicochemical properties of crystalline materials for commercial applications in catalysis.⁶

1. De Yoreo et al.: “Crystallization by Particle Attachment in Synthetic, Biogenic, and Geologic Environments“ Science 349 (2015) aaa6760-1/9

2. Mallette, A.J., Seo, S., Rimer, J.D.: “Synthesis Strategies and Design Principles for Nanosized and Hierarchical Zeolites” Nature Synthesis 1 (2022), 521-534

3. Jain, R., Mallette, A.J., Rimer, J.D.: “Controlling Nucleation Pathways in Zeolite Crystallization: Seeding Conceptual Methodologies for Advanced Materials Design” J. Am. Chem. Soc. 143 (2021) 21446-21460

4. Parmar, D., Mallette, A.J., Yang, T., Zou, X., Rimer, J.D.: “Unique Role of GeO2 as a Noninvasive Promoter of Nano-sized Zeolite Crystals” Adv. Mater. 34 (2022) 2205885 (1-11)

5. Dai, H., Claret, J., Kunkes, E.L., Vattipalli, V., Linares, N., Huang, C., Fiji, M., Garcia-Martinez, J., Moini, A., Rimer, J.D.: “Accelerating the Crystallization of Zeolite SSZ-13 with Polyamines” Angew. Chem. Int. Ed. 61 (2022) e202117742 (1-6)

6. Dai, H., Shen, Y., Yang, T., Lee, C., Fu, D., Agarwal, A., Le, T.T., Tsapatsis, M., Palmer, J.C., Weckhuysen, B.M., Dauenhauer, P.J., Zou, X., Rimer, J.D.: “Finned Zeolite Catalysts“ Nat. Mater. 19 (2020) 1074-1080

Bio: Jeffrey Rimer is the Abraham E. Dukler Endowed Chair and Professor of Chemical Engineering at the University of Houston. Jeff received B.S. degrees in Chemical Engineering and Chemistry from Washington University in St. Louis and Allegheny College, respectively. He received his Ph.D. in Chemical Engineering from the University of Delaware and spent two years as a postdoctoral fellow at New York University prior to joining Houston in 2009. Jeff’s research in the area of crystal engineering focuses on the rational design of materials with specific applications in the synthesis of microporous catalysts and adsorbents, and the development of therapeutics to inhibit crystal formation in pathological diseases. Jeff has received numerous awards that include the NSF CAREER Award, the 2016 Owens Corning Early Career Award and 2017 FRI/John G. Kunesh Award from AIChE, and the inaugural 2016 Mellichamp Emerging Leader Lecturer at the University of California at Santa Barbara. In 2018 he received the Norman Hackerman Award in Chemical Research from The Welch Foundation, and in 2020 the Edith and Peter O’Donnell Award in Engineering from TAMEST. He has also been the recipient of the Excellence in Research and Scholarship Award from the University of Houston, and Teaching Excellence Awards at both the University and College level. Jeff was elected a Senior Member of the National Academy of Inventors. He is also a former chair of the Southwest Catalysis Society, an executive committee member for the American Associate for Crystal Growth and International Zeolite Association, and has chaired two Gordon Research Conferences on Crystal Growth & Assembly and Nanoporous Materials & Their Applications. Jeff is an Associate Editor of Crystal Growth & Design and also serves on the advisory boards for the AIChE Journal, Molecular Systems Design & Engineering, and Reaction Chemistry & Engineering.

All seminars are held on Wednesdays from 12:00 noon-1:00 p.m. in the Bowen Hall Auditorium Room 222. A light lunch is provided at 11:30 a.m. in the Bowen Hall Atrium immediately prior to the seminar.