RESUMO
As the Brønsted acid sites in the 8-membered ring (8-MR) of mordenite (MOR) are reported to be the active center for dimethyl ether (DME) carbonylation reaction, it is of great importance to selectively increase the Brønsted acid amount in the 8-MR. Herein, a series of Fe-HMOR was prepared through one-pot hydrothermal synthesis by adding the EDTA-Fe complex into the gel. By combining XRD, FTIR, UV-Vis, Raman and XPS, it was found that the Fe atoms selectively substituted for the Al atoms in the 12-MR channels because of the large size of the EDTA-Fe complex. The NH3-TPD and Py-IR results showed that with the increase in Fe addition from Fe/Si = 0 to 0.02, the Brønsted acid sites derived from Si-OH-Al in the 8-MR first increased and then decreased, with the maximum at Fe/Si = 0.01. The Fe-modified MOR with Fe/Si = 0.01 showed the highest activity in DME carbonylation, which was three times that of HMOR. The TG/DTG results indicated that the carbon deposition and heavy coke formation in the spent Fe-HMOR catalysts were inhibited due to Fe addition. This work provides a practical way to design a catalyst with enhanced catalytic performance.
RESUMO
Nanoscale zero-valent iron (nZVI) has attracted considerable attention for its potential to sequestrate and immobilize heavy metals such as Cr(VI) from an aqueous solution. However, nZVI can be easily oxidized and agglomerate, which strongly affects the removal efficiency. In this study, graphene-based nZVI (nZVI/rGO) composites coupled with ultrasonic (US) pretreatment were studied to solve the above problems and conduct the experiments of Cr(VI) removal from an aqueous solution. SEM-EDS, BET, XRD, and XPS were performed to analyze the morphology and structures of the composites. The findings showed that the removal efficiency of Cr(VI) in 30 min was increased from 45.84% on nZVI to 78.01% on nZVI/rGO and the removal process performed coupled with ultrasonic pretreatment could greatly shorten the reaction time to 15 min. Influencing factors such as the initial pH, temperature, initial Cr(VI) concentration, and co-existing anions were studied. The results showed that the initial pH was a principal factor. The presence of HPO42-, NO3-, and Cl- had a strong inhibitory effect on this process, while the presence of SO42- promoted the reactivity of nZVI/rGO. Combined with the above results, the process of Cr(VI) removal in US-nZVI/rGO system consisted of two phases: (1) The initial stage is dominated by solution reaction. Cr(VI) was reduced in the solution by Fe2+ caused by ultrasonic cavitation. (2) In the following processes, adsorption, reduction, and coprecipitation coexisted. The addition of rGO enhanced electron transportability weakened the influence of passivation layers and improved the dispersion of nZVI particles. Ultrasonic cavitation caused pores and corrosion at the passivation layers and fresh Fe0 core was exposed, which improved the reactivity of the composites.
