Controlling the inhomogeneity of solid catalysts at the mesoscopic scale

High-performance catalysts are often composed of two or more active phases, which are believed to interact with each other at the mesoscopic scale structure. Unlike conventional powder catalysts flat surfaces is advantageous in that its surface structure can be precisely designed. We prepared precisely designed Sb2O4/VSbO4/Si catalysts containing Sb2O4 ribbons with finely controlled width and separation by electron lithography. We demonstrated that the acrolein generation rate on the catalysts was related to the width and separation of the Sb2O4 ribbons. This work shows the possibility to regulate catalyses by inhomogeneity of the surface structure at the mesoscopic level

Electrodeposition study on a single-crystal titanium dioxide electrode : platinum on a niobium-doped titanium dioxide(110) electrode

Pt was successfully electrodeposited on a Nb-doped TiO2(110) electrode from a solution of 1 mM K-2[PtCl4] and 50 mM H2SO4 using single-pulse chronoamperometry. The morphology of the deposited Pt nanoparticles was sensitive to the deposition potential and holding time. A novel method for the preparation of metal particles on a single-crystal TiO2 surface in a controlled manner has been proposed

Polarization-dependent Total Reflection Fluorescence X-ray Absorption Fine Structure (PTRF-XAFS) Studies on the Structure of a Pt Monolayer on Au(111) Prepared by the Surface-limited Redox Replacement Reaction

We studied the initial stage of a Pt monolayer produced by surface-limited redox replacement (SLRR) using polarization-dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS). Different from the widely accepted understanding that metallic monolayer islands are formed, our XAFS showed that the Pt monolayer, initially present on the Au(111) substrate, was mainly in the form of a planar [PtCl4]2− complex with its molecular plane parallel to Au(111). This result provides a new insight into the mechanism of SLRR

Silver-modulated SiO2-supported copper catalysts for selective hydrogenation of dimethyl oxalate to ethylene glycol

We present the application of a one-step urea-assisted gelation method to prepare a SiO2-supported bimetallic catalyst composed of copper (Cu) and silver (Ag). Results show the remarkably enhanced performance of the catalyst for selective hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG). Coupled with a series of characterization and kinetic studies, the improved activity is attributed to the formation of Cu nanoparticles containing Ag nanoclusters on the SiO2 surface. The coherent interactions between the Cu and Ag species help create the active Cu+/Cu-0 species in a suitable proportion and prevent the transmigration of bimetallic nanoparticles during the hydrogenation process. The optimized Cu-Ag/SiO2 catalyst with an Ag/Cu atomic ratio of 0.05 has a balanced Cu+/Cu-0 ratio and highly dispersed bimetal particles, which account for its high turnover frequency, EG selectivity of 97.0%, and excellent catalytic stability during the hydrogenation of DMO to EG for longer than 150 h

Fine tuning and orientation control of surface Cu complexes on TiO2(110) premodified with mercapto compounds: the effect of different mercapto group positions

Three-dimensional structures of vacuum-deposited Cu species formed on TiO2(110) surfaces premodified with three mercaptobenzoic acid (MBA) isomers were studied using polarization-dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS). We explored the possibility of fine tuning and orientation control of the surface Cu structures, including their coordination and configuration against the surface, according to the different mercapto group positions of the three MBA isomers (o(-), m(-), and p-MBA). Almost linear S-Cu-O (lattice O of TiO2) surface compounds were formed on the three MBA-modified TiO2(110) surfaces; however, the orientation of the Cu species on the o- and m-MBA-modified TiO2(110) surfaces (40-45 degrees inclined from the surface normal) was different from that on the p-MBA-modified TiO2(110) surface (60 degrees from the surface normal). This work suggests that the selection of a different MBA isomer for premodification of a single crystal TiO2(110) surface enables fine tuning and orientation control of surface Cu complexes

Elimination of Indoor Volatile Organic Compounds on Au/SBA-15 Catalysts: Insights into the Nature, Size, and Dispersion of the Active Sites and Reaction Mechanism

Peer reviewed: TrueFunder: Joint Usage/Research Program at the Institute of Catalysis, Hokkaido University, JapanGold catalysts, with different particle sizes ranging from 19 to 556 Å, and supported on SBA-15 mesoporous silica, were prepared by using deposition-precipitation, co-precipitation, and impregnation methods. All samples were characterised by TEM, EXAFS, XPS, XRD, CFR (Continuous Flow Reactor), and TPR. The sample which proved to have the highest activity was characterised by TAP (Temporal Analysis of Products) as well. XPS, wide-angle XRD, EXAFS, and H2-TPR measurements and data analysis confirmed that gold was present as Au0 only on all samples. The size of the Au nanoparticle was determined from TEM measurements and confirmed through wide-angle XRD measurements. EXAFS measurements showed that as the Au-Au coordination number decreased the Au-Au bond length decreased. TEM data analysis revealed a dispersion range from 58% (for the smallest particle size) to 2% (for the highest particle size). For Au particles’ sized lower that 60 Å, the Au dispersion was determined using a literature correlation between the dispersion and EXAFS Au-Au coordination number, and was in good agreement with the dispersion data obtained from TEM. The Au dispersion decreased as the particle size increased. CFR experiments validated the relationship between the size of the gold particles in a sample and the sample’s catalytic activity towards acetone oxidation. The lowest temperature for the acetone 100% conversion, i.e., 250 °C, was observed over the reduced catalyst sample with the smallest particle size. This sample not only showed the highest catalytic activity towards acetone conversion, but, at the same time, showed high reaction stability, as catalyst lifetime tests, performed for 25 h in a CFR at 270 °C for the as-synthesised sample, and at 220 °C for the reduced sample, have confirmed. TAP (Temporal Analysis of Products) measurements and data analysis confirmed a weak competitive adsorption of acetone and oxygen over the Au/SBA-15 sample. Based on TAP data, a combination of Eley–Rideal and Langmuir–Hinshelwood mechanisms for acetone complete oxidation was proposed.</jats:p