Molecular Modification of Zeolites with Cold Atmospheric-Pressure Plasma Jet: A Green and Facile Strategy

Widespread applications of zeolites demand the optimization of crystal size and morphology. Crystal growth modifiers (CGMs) have been proved effective for zeolite rational design, but the additional chemicals raise environmental and safety concerns. Herein, the industry-ready technique of cold atmospheric-pressure plasma jet (CAPPJ) was employed to induce reactive plasma species as green and eco-friendly CGMs. The synthesis mixtures of three aluminosilicate zeolites with assorted Si/Al ratios (SAR), channel dimensionalities, and pore apertures (i.e., MFI, LTA, and LTL framework types) were first subjected to Ar-CAPPJ treatment for up to 30 min during the aging period. Apparent size and shape modifications were successfully achieved for the resulting crystals with the emergence of rounded surfaces implying surface roughening at the molecular level. For the silicoaluminophosphate SAPO-34 (CHA type), the introduction of plasma CGMs was found to propel a phase transformation, promoting the crystallization of SAPO-18 (AEI type) impurity with reduced framework density. Experimental observations seem to suggest that the classical model of CGMs attaching to selected crystal surfaces is less likely to happen. Whereas, the investigation of zeolite L dispersions revealed enhanced concentrations and altered physicochemical properties of soluble species and amorphous precursors, alluding to the potential functional mechanism (s) of plasma CGMs. As a plausible technique to generate green and versatile CGMs, the impacts of CAPPJ on zeolite crystallization are systematically investigated for the first time, promoting the understanding of classical and nonclassical crystallization phenomena during zeolite synthesis.