Ultrafast laser synthesis of nanoporous zeolite A

Abstract

Zeolites are microporous aluminosilicate self-assembled nanocrystals. Zeolite A is the first commercially synthesized zeolite, which has cubic unit cell that consist of alumina and silica tetrahedra together with the extraframework cations like Na+, K+, Ca2+. Zeolite A has been widely studied zeolite in the literature owing to the properties like high porosity, high surface area (∼ 600 m2/g), and high chemical and thermal stability, and high ion exchange capacity. All of these properties make Zeolite A used in various industrial applications like CO2 adsorption, wastewater treatments, biosensor applications, etc. Although zeolites have a wide range of industrial uses, they have still been extensively investigated in academia as well. Accordingly, various zeolite synthesis methods have been developed, but all have limitations. While conventional hydrothermal synthesis offers benefits such as high-quality discrete crystals, ease of use, safety, and industrial scalability, it lacks precise control over nucleation and growth. A method that combines these advantages with the ability to produce defect-free crystals using low-energy photons within a short reaction time has not been developed yet. To address this, we introduce a new method for synthesizing zeolites (TPA-silicalite-1, zeolite Y, zeolite A, and hierarchical ZSM-5) using ultrafast laser energy deposition. In this approach, energy is deposited on a timescale comparable to the polymerization reactions that drive crystal formation. In this thesis study, we further investigate the ultrafast laser pulses on the synthesis mechanism and crystalline structure of nanoporous zeolite A. Utilizing a femtosecond laser at 1040 nm wavelength, we achieved controlled energy deposition in the precursor suspension, accelerating the reaction via multiphoton absorption and laser-induced flows for nearly uniform-sized zeolite A crystals (∼260 nm). Through the controlled deposition of energy, this method achieves rapid crystallization of Zeolite A with high crystallinity (90-100%) and a narrower particle size distribution compared to the crystals synthesized via the conventional hydrothermal method. Comprehensive characterizations, including Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDXS), X-Ray Diffraction (XRD), High Resolution Transmission Electron Microscopy (HRTEM), Selected Area Electron Diffraction (SAED), Thermo-gravimetric Analysis (TGA), Brauener-Emmet-Teller (BET), and Fourier Transformed Infrared (FTIR) Spectroscopy, revealed that the laser-synthesized zeolites exhibit structural integrity and quality comparable to conventionally synthesized counterparts. Moreover, CO2 adsorption capacity analysis was carried out to evaluate the gas capture performance and practical applicability of Zeolite A synthesized via the ultrafast laser synthesis method. The ultrafast laser synthesis method was successfully repeated over 80 times to enable various characterizations. This novel technique offers a rapid and alternative approach to synthesizing zeolites with precise control over structural and functional properties.