ABSTRACT
Silver catalysts supported on ceria-zirconia (CZ) mechanically mixed oxide were synthesized by wet impregnation and chelating methods. Nominal loadings of 5 wt.% of Ag was deposited on the CZ support. These catalysts were tested for the CO2 hydrogenation reaction to methanol with feed gas composition of CO2-H2 = 3:1 at 250 °C, 20 bar total pressure and GHSV of 1800 h-1. The calcined and reduced catalysts were characterized using XRD, BET, TPR, SEM-EDS, XPS and FTIR-DRIFTs techniques. Finely deposited silver crystallites sized in the range of 20-50 nm were observed through SEM and HR-TEM analysis. TPR and XRD studies demonstrated the presence of Ag2O and metallic silver (Ag0) on CZ support. About 10% of CO formation was observed on chelating catalyst (5Ag/CZ CHE). However, only, 5% CO was observed on impregnated (5Ag/CZ IMP) catalyst. The greater CO formation was associated with ease reduction of Ag2O to metallic silver in 5Ag/CZ CHE catalyst. Further, 70% of methanol selectivity was observed on 5Ag/CZ IMP due to the presence of Ag2O on CZ. FTIR-DRIFTs results revealed the methanol formation via formate intermediates and CO formation via RWGS reaction on the studied catalysts.
ABSTRACT
A comparative study is presented of the hydrolytic and thermal stability of 24 different kinds of monolayers on Si(111), Si(100), SiC, SiN, SiO2, CrN, ITO, PAO, Au, and stainless steel surfaces. These surfaces were modified utilizing appropriate organic compounds having a constant alkyl chain length (C18), but with different surface-reactive groups, such as 1-octadecene, 1-octadecyne, 1-octadecyltrichlorosilane, 1-octadecanethiol, 1-octadecylamine and 1-octadecylphosphonic acid. The hydrolytic stability of obtained monolayers was systematically investigated in triplicate in constantly flowing aqueous media at room temperature in acidic (pH 3), basic (pH 11), phosphate buffer saline (PBS) and deionized water (neutral conditions), for a period of 1 day, 7 days, and 30 days, yielding 1152 data points for the hydrolytic stability. The hydrolytic stability was monitored by static contact angle measurements and X-ray photoelectron spectroscopy (XPS). The covalently bound alkyne monolayers on Si(111), Si(100), and SiC were shown to be among the most stable monolayers under acidic and neutral conditions. Additionally, the thermal stability of 14 different monolayers was studied in vacuum using XPS at elevated temperatures (25-600 °C). Similar to the hydrolytic stability, the covalently bound both alkyne and alkene monolayers on Si(111), Si(100) and SiC started to degrade from temperatures above 260 °C, whereas on oxide surfaces (e.g., PAO) phosphonate monolayers even displayed thermal stability up to â¼500 °C.
