This paper describes a study of the nature and the accessibility of the acid sites in micromesoporous mordenite zeolites obtained by desilication and dealumination and analysis of their activity and selectivity in the hydroisomerization of n-hexane. Alkaline−acid, acid−alkaline−acid, and fluorination−alkaline−acid postsynthesis treatments were employed for the preparation of micromesoporous mordenites. The FTIR spectra of adsorbed d 3 -acetonitrille, 27 Al MAS NMR, HR-TEM, and N 2 adsorption were used for quantitative analysis of the Brønsted and Lewis sites, the coordination of Al atoms, and the textural properties. The alkaline treatment causes desilication, preferably occurring along the crystal defects and resulting in the formation of a secondary mesoporous structure characterized by 5−20 nm cavities and the formation of extraframework (Al Ex ) species and terminal Si−OH groups. The Al Ex species formed by hydrolysis of perturbed or dislodged framework Al easily restrict part of the pseudomonodimensional channel structure of mordenite. The subsequent removal of Al Ex by mild acid leaching or simultaneous removal of Si and Al atoms by desilication of fluorinated zeolite result in a micromesoporous structure with a large number of unrestricted channel openings and lead to a large increase in the accessibility of OH groups for n-hexane. Thus, the sequential leaching treatments enable the formation of active acid sites in an environment of nonrestricted microporous channels with simultaneous enhancement of accessibility of the active sites and molecular transport. It is shown that the micromesoporous structure with high concentration of Brønsted sites of enhanced accessibility directs the hydroisomerization reaction toward high yields of branched isomers and shortening of the main 12-ring channels and that the larger numbers of channel openings result in an increase in selectivity, limiting nonselective subsequent cracking reactions.
This paper reports the results of an international interlaboratory study led by the National Institute of Standards and Technology (NIST) on the measurement of high-pressure surface excess methane adsorption isotherms on NIST Reference Material RM 8850 (Zeolite Y), at 25 °C up to 7.5 MPa. Twenty laboratories participated in the study and contributed over one-hundred adsorption isotherms of methane on Zeolite Y. From these data, an empirical reference equation was determined, along with a 95% uncertainty interval (Uk=2). By requiring participants to replicate a high-pressure reference isotherm for carbon dioxide adsorption on NIST Reference Material RM 8852 (ZSM-5), this interlaboratory study also demonstrated the usefulness of reference isotherms in evaluating the performance of high-pressure adsorption experiments.
This article presents an investigation of the sensing properties of chemiresistors based on Cu 2 O/CuO core−shell nanowires containing p−p′ heterojunctions. The nanowires were synthesized by a conventional hydrothermal method and used for the detection of ethanol and nitrogen dioxide, reducing and oxidizing agents, respectively. To unravel the chemical processes connected with gas detection, an in situ approach was applied. This approach was based on near-ambient pressure X-ray photoelectron spectroscopy combined with simultaneous monitoring of sensor responses. The in situ measurements were performed during exposure to the analytes at a total pressure of 0.05−1.05 mbar and 450 K and were correlated with chemiresistor response measurements carried out at a standard pressure and under an ambient atmosphere. The study revealed that heterojunction treatment with ethanol vapors, accompanied by partial reduction of the nanowires, is the key step to obtaining chemiresistors with good sensing performance. While the untreated heterojunctions exhibited poor n-type sensing responses, the treated ones showed significantly improved p-type responses. The treated sensors were characterized by a stable baseline, high reversibility, detection limits estimated as 50 ppm for ethanol and 100 ppb for nitrogen dioxide, and with response times in tens of seconds. In all cases, we propose a band scheme of Cu 2 O/CuO heterojunctions and a gas-sensing mechanism.
Cerium oxide nanoparticles (CeNPs) possess multiple redox enzyme mimetic activities to scavenge reactive oxygen species (ROS) as potential biomedicine. These enzymatic activities of CeNPs are closely related to their surface...
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