The catalytic oxidation of toluene has been investigated using a series of Pt/SBA-15 and Pt/SiO 2 catalysts, and the Pt/SBA-15 catalyst exhibits significantly higher catalytic activity for the oxidation of toluene than the Pt/SiO 2 catalysts. The SBA-15-supported Pt nanoparticles possess the ability to strongly dissociate toluene to benzene, hydrocarbon fragments (CH x ), and H 2 at low temperatures, but the Pt/SiO 2 catalysts are nonreactive toward the decomposition of toluene. The products resulting from the dissociation of toluene were easily oxidized by oxygen, thereby positively affecting the conversion rate of toluene oxidation on Pt/ SBA-15. Temperature-programmed desorption measurements clearly indicate that the dissociation reaction mainly consists of breakage of the C−C bonds between the phenyl and methyl groups. Combined density functional theory (DFT) calculations and DRIFT spectroscopy are carried out to investigate the stretching frequency of CO adsorbed on the defect sites of various Pt clusters, suggesting that the subnanosized Pt particles (icosahedron cluster) and/or Pt single atom may be formed in the structure of SBA-15. Pt sites associated with low coordination and subnanoscale Pt particles and/or single Pt atoms in the SBA-15 support can facilitate toluene adsorption and induce strong dissociation.
In this paper, we have shown that Cu/TiO(2) catalysts are highly active in CO oxidation. For instance, a 3.4% Cu/TiO(2) catalyst exhibits a higher turnover rate for the effective removal of CO in air than 3-5% Pt/TiO(2) and 20% Cu/ZnO/Al(2)O(3) catalysts. A small amount of Cu(+) species is formed during the calcination treatment at 225 °C, which is the main active phase for the CO oxidation. However, it is proposed that some highly dispersed CuO can also form in the TiO(2) lattice during the calcination treatment. Furthermore, a strong electron interaction between Cu(2+) in highly dispersed CuO and Ti(3+) on rutile TiO(2) (Cu(2+)+Ti(3+)→Cu(+)+Ti(4+)) has been shown to occur. Overall, the reduction of Cu(+) is a major factor that contributes to the reaction rate of the CO oxidation.
SBA-15 functionalized with carboxylic acid groups has been used to synthesize Cu nanoparticles 2–6 nm in average size with 7.6–25.2 wt % Cu. In this study, the formation mechanism and characterization of Cu nanoparticles at various Cu concentrations are described. For samples with 7.6 and 11.9 wt % Cu, linear [Cuδ+···Oδ−···Cuδ+] n chains generated through calcination are possibly located inside the SBA-15 channels. When the concentration of Cu is increased to 18.3 wt %, the Cu2(OH)3NO3 species becomes the dominant intermediate before bulky CuO is formed. It is found that the average 2-nm Cu particles provided a significantly higher turnover rate for water–gas shift (WGS) reaction than did higher Cu contents on SBA-15. We propose that the highly dispersed Cu particles or isolated Cu atoms on Cu/SBA-15 catalysts can serve as major active sites for the WGS reaction. The 7.6 and 11.9 wt % Cu/SBA-15 catalysts provide abundant sites on highly dispersed Cu particles or isolated Cu atoms, which lead to a highly efficient WGS reaction.
Mesoporous SBA-15 silica materials functionalized with and without carboxylic acid groups were used to effectively control the morphology of Pt crystals, and the materials thus obtained were applied to methanol oxidation reactions. The Pt particles aggregated to form long spheroids inside the channels in pure SBA-15. When carboxylic acid groups were utilized, the SBA-15(-COOH) material facilitated the formation of higher Pt surface area, smaller Pt nanoparticles and nearly spherical shape due to the strong interaction between Pt(4+) ions and carboxylic acid on SBA-15. The Pt(4+) ions on the SBA-15(-COOH) material can be directly transformed to reduced Pt particles during calcination. The methanol oxidation activity on a Pt surface is strongly dependent on the shape of Pt particles. The near-spherical Pt nanoparticles on the SBA-15(-COOH) exhibited higher catalytic activity during methanol oxidation than Pt catalysts on unmodified SBA-15. The near-spherical Pt particles on the SBA-15(-COOH) contained large numbers of terrace sites on their surfaces, which led to high efficiency during methanol oxidation.
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