Synthesis and characterization of aluminium containing CIT-1 and their structure–property relationship to hydrocarbon trap performance

Abstract

The present work focuses on the synthesis of Al-CIT-1 by various post-modification procedures of B-CIT-1 and their structure–property relation to hydrocarbon trap performance. Al substitution in B-CIT-1 was carried out by three different post-modification procedures, viz., direct exchange (Al-CIT-1_DEX), insertion (Al-CIT-1_INS), and impregnation (Al-CIT-1_IMP), and characterized in detail by various physico-chemical techniques such as XRD, N 2 adsorption, SEM, NH 3-TPD, XPS, and solid state 27Al and 29Si MAS NMR. The Al-CIT-1 samples were tested for their adsorption–desorption characteristics of toluene, and 2,2,4-trimethylpentane (2,2,4-TMP) to understand the Al distribution in CIT-1 as well as the efficacy of these materials as hydrocarbon traps. The Al distribution in Al-CIT-1 plays a critical role in the adsorption–desorption characteristics of toluene and 2,2,4-TMP. Al-CIT-1 with high relative proportion of framework Al and less extraframework Al (Al-CIT-1_DEX) showed maximum toluene and 2,2,4-TMP adsorption capacity. The presence of finely distributed extraframework Al 2O 3 species in Al-CIT-1_INS modify the pores and causes a slow release of toluene during desorption. Al-CIT-1_IMP with less Al content and acidity showed the lowest toluene desorption temperature. Large amount of surface Al species hinder a relatively bulky molecule 2,2,4-TMP to access the available active sites of tetrahedral Al and the associated Brϕnsted sites in the zeolite, and as a result, Al-CIT-1_INS showed hardly any adsorption towards 2,2,4-TMP. Thus, by varying the post-modification method and treatment condition, it is possible to tune the performance of Al incorporated CIT-1 as a useful material for hydrocarbon trap.