Broadening the Action Spectrum of TiO₂-Based Photocatalysts to Visible Region by Substituting Platinum with Copper

In this study, TiO2-based photocatalysts modified with Pt and Cu/CuOx were synthesized and studied in the photocatalytic reduction of CO2. The morphology and chemical states of synthesized photocatalysts were studied using UV-Vis diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. A series of light-emitting diodes (LEDs) with maximum intensity in the range of 365–450 nm was used to determine the action spectrum of photocatalysts. It is shown for, the first time, that the pre-calcination of TiO2 at 700 °C and the use of Cu/CuOx instead of Pt allow one to design a highly efficient photocatalyst for CO2 transformation shifting the working range to the visible light (425 nm). Cu/CuOx/TiO2 (calcined at 700 °C) shows a rate of CH4 formation of 1.2 ± 0.1 µmol h−1 g−1 and an overall CO2 reduction rate of 11 ± 1 µmol h−1 g−1 (at 425 nm)

The Origin of the Size Effect in the Oxidation of CO on Supported Palladium Nanoparticles

Two Pd/TiO2 catalysts with mean particle sizes of 1 and 3 nm were prepared and tested in the low-temperature oxidation of CO. It was found that the first catalyst with higher dispersion is more active. Turnover frequencies varied for these catalysts by almost six times. In contrast, the apparent activation energy of the oxidation of CO on the catalyst with smaller Pd nanoparticles was estimated at 76 kJ/mol, and for the catalyst with larger Pd nanoparticles at 58 kJ/mol. According to in situ XANES studies, the particle size effect originates from the oxidation of small palladium nanoparticles under reaction conditions, whereas larger nanoparticles are stable and consist of palladium atoms mainly in the metallic state. Palladium oxide is more active in the low-temperature oxidation of CO than metallic palladium. This means that the origin of size-dependent activity of Pd nanoparticles in the low-temperature oxidation of CO is associated with the change in the chemical composition of nanoparticles that leads to a change in the reaction mechanism and, as a result, in their activity

Highly Active CuFeAl-containing Catalysts for Selective Hydrogenation of Furfural to Furfuryl Alcohol

CuFe-containing catalysts with different copper oxide content were prepared by fusion of metal salts. The obtained catalyst showed high activity in the hydrogenation of furfural to furfuryl alcohol (FA) in the batch reactor in the presence of isopropanol as a solvent at a temperature of 100 °C and a hydrogen pressure of 6.0 MPa. The yield of FA and furfural conversion are 97% and 98%, respectively. In the solvent-free reaction in the flow-type reactor; the most active catalyst Cu20Fe66Al14 leads to the 96% formation of FA with 100% conversion of furfural at liquid hourly space velocity (LHSV) = 1 h−1; 160 °C and a hydrogen pressure of 5.0 MPa during 30 h. According to the X-ray diffraction (XRD) method, the active component of the spent and fresh Cu20Fe66Al14 catalyst is the same and is represented by metallic copper and Fe3O4-type spinel. Using different methods, the formation of active sites was investigated

Efficient Photocatalytic Hydrogen Production over NiS-Modified Cadmium and Manganese Sulfide Solid Solutions

In this work, new photocatalysts based on Cd1−xMnxS sulfide solid solutions were synthesized by varying the fraction of MnS (x = 0.4, 0.6, and 0.8) and the hydrothermal treatment temperature (T = 100, 120, 140, and 160 °C). The active samples were modified with Pt and NiS co-catalysts. Characterization was performed using various methods, including XRD, XPS, HR TEM, and UV-vis spectroscopy. The photocatalytic activity was tested in hydrogen evolution from aqueous solutions of Na2S/Na2SO3 and glucose under visible light (425 nm). When studying the process of hydrogen evolution using an equimolar mixture of Na2S/Na2SO3 as a sacrificial agent, the photocatalysts Cd0.5Mn0.5S/Mn(OH)2 (T = 120 °C) and Cd0.4Mn0.6S (T = 160 °C) demonstrated the highest activity among the non-modified solid solutions. The deposition of NiS co-catalyst led to a significant increase in activity. The best activity in the case of the modified samples was shown by 0.5 wt.% NiS/Cd0.5Mn0.5S (T = 120 °C) at the extraordinary level of 34.2 mmol g−1 h−1 (AQE 14.4%) for the Na2S/Na2SO3 solution and 4.6 mmol g−1 h−1 (AQE 2.9%) for the glucose solution. The nickel-containing samples possessed a high stability in solutions of both sodium sulfide/sulfite and glucose. Thus, nickel sulfide is considered an alternative to depositing precious metals, which is attractive from an economic point of view. It worth noting that the process of photocatalytic hydrogen evolution from sugar solutions by adding samples based on Cd1−xMnxS has not been studied before

Selectivity Control of CO₂ Reduction over Pt/g-C₃N₄ Photocatalysts under Visible Light

Photocatalysts based on g-C3N4 have been investigated in the CO2 reduction reaction under visible light irradiation (λ = 397, 427, 452 nm). Photocatalysts were prepared by melamine calcination at 500–600 °C with further platinum deposition (0.1–1.0 wt.%). The effect of the preparation conditions of g-C3N4 and the method of platinum deposition on the physicochemical properties and activity of photocatalysts was studied. The photocatalysts were investigated by X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, X-ray diffraction, high resolution transmission electron microscopy, UV-Vis spectroscopy, and low temperature nitrogen adsorption techniques. It has been found that the efficiency of CO2 reduction is governed by the surface area of g-C3N4 and the presence of platinum in the metallic state, while the optimal content of platinum is 0.5 wt. %. The highest rate of CO2 reduction achieved over Pt/g-C3N4 photocatalyst is 13.2 µmol h−1 g−1 (397 nm), which exceeds the activity of pristine g-C3N4 by 7 times. The most active photocatalysts was prepared by calcining melamine in air at 600 °C, followed by modification with platinum (0.5 wt.%)

Hydroprocessing of Maya vacuum residue using a NiMo catalyst supported on Cr-doped alumina

6 figures, 7 tables.-- © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/Mesoporous alumina was doped with Cr using a co-precipitation method to prepare a support for hydrocracking catalysts. Ni and Mo were then impregnated on Cr-doped mesoporous alumina (NiMo/Al2O3-Cr). Catalytic activity was tested in hydrodeasphaltenisation (HDA), hydrodesulfurisation (HDS) and hydrodemetallisation (HDM) of Maya vacuum residue in a batch reactor and compared with NiMo supported on mesoporous alumina not doped with Cr (NiMo/Al2O3). Following activation and initial carbon deposition, experiments involving contact of the catalysts with fresh feed were performed. Greater HDA extent and maltene to asphaltene ratios were obtained with NiMo/Al2O3-Cr than NiMo/Al2O3 despite a larger amount of coke deposits. Significant activity of both NiMo/Al2O3-Cr and NiMo/Al2O3 towards HDS and HDM were also observed. Alumina textural properties remained relatively unaffected by the co-precipitation of Cr. X-ray photoelectron spectroscopy (XPS) showed that the catalysts contained Cr3+ and after reduction all Ni was present in metallic state at least in the near-surface region, while Mo6+ was reduced to Mo4+ and Moδ+ (0 ≤ δ ≤ 3) to a larger extent in NiMo/Al2O3-Cr. Lower reduction temperatures in the presence of Cr were determined, suggesting a larger number of metal sites available in reduced form at operating conditions. It was found that Cr aided metal dispersion in catalyst synthesis and coke dispersion during reaction. Spent catalysts showed reductions in surface area and pore volume. However, while spent NiMo/Al2O3 catalysts had a decrease in average pore diameter (APD), NiMo/Al2O3-Cr maintained the fresh material APD, which may explain the sustained catalytic activity.H.P. thanks the support of CONACYT Mexico for the award of her PhD grant. Founding from Skolkovo Foundation and BP through UNIHEAT Project is gratefully acknowledged.Peer reviewe

Influence of Thermal Activation of Titania on Photoreactivity of Pt/TiO2 in Hydrogen Production

A series of Pt/TiO2 photocatalysts was prepared by impregnation of fresh and thermal-activated titania (commercial Evonik Aeroxide P25 TiO2) with an aqueous solution of H2PtCl6 followed by reduction in an aqueous solution of NaBH4. The thermal activation was performed by annealing in air. The photocatalytic activity of the Pt/TiO2 catalysts was measured for the hydrogen production from a mixture of glycerol under UV radiation. It was found that the activation at 300–600 °C provides an increase in the photoreactivity of resulting Pt/TiO2 photocatalysts in the production of hydrogen while its structural and textural properties do not change. This effect is due to formation of cationic vacancies that limits fast electron–hole recombination

CuFeAl Nanocomposite Catalysts for Coal Combustion in Fluidized Bed

A method of oil-drop granulation was suggested for the preparation of spherical CuFeAl nanocomposite catalysts. The catalysts were characterized by a set of physicochemical methods (X-ray diffraction, temperature-programmed reduction by H2, low-temperature nitrogen adsorption, crushing strength) and tested in the oxidation of CO and burning of brown coal in a fluidized bed. It was found that the catalysts have high mechanical strength (16.2 MPa), and their catalytic properties in the oxidation of CO are comparable to the characteristics of industrial Cr-containing catalysts. It was shown that the addition of pseudoboehmite at the stage of drop formation contributes to the production of uniform spherical high-strength granules and facilitates the stabilization of the phase state of the active component. The use of CuFeAl nanocomposite catalysts for the burning of brown coal provides a low emission of CO (600 ppm) and NOx (220 ppm) and a high degree of coal burnout (95%), which are close to those of the industrial Cr-containing catalysts (emission of CO is 700 ppm, NOx—230 ppm, and degree of coal burnout is 95%)

Copper-Modified Titania-Based Photocatalysts for the Efficient Hydrogen Production under UV and Visible Light from Aqueous Solutions of Glycerol

In this study, we have proposed titania-based photocatalysts modified with copper compounds for hydrogen evolution. Thermal pre-treatment of commercial TiO2 Degussa P25 (DTiO2) and Hombifine N (HTiO2) in the range from 600 to 800 °C was carried out followed by the deposition of copper oxides (1–10 wt. % of Cu). The morphology and chemical state of synthesized photocatalysts were studied using X-ray diffraction, UV–Vis diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and XANES/EXAFS X-ray absorption spectroscopy. Photocatalytic activity was tested in the hydrogen evolution from aqueous solutions of glycerol under ultraviolet (λ = 381 nm) and visible (λ = 427 nm) light. The photocatalysts 2% CuOx/DTiO2 T750 and 5% CuOx/DTiO2 T700 showed the highest activity under UV irradiation (λ = 380 nm), with the rate of H2 evolution at the level of 2.5 mmol (H2) g−1 h−1. Under the visible light irradiation (λ = 427 nm), the highest activity of 0.6 mmol (H2) g−1 h−1 was achieved with the 5% CuOx/DTiO2 T700 photocatalyst. The activity of these photocatalysts is 50% higher than that of the platinized 1% Pt/DTiO2 sample. Thus, it was shown for the first time that a simple heat treatment of a commercial titanium dioxide in combination with a deposition of non-noble metal particles led to a significant increase in the activity of photocatalysts and made it possible to obtain materials that were active in hydrogen production under visible light irradiation

Atomic Structure of Pd-, Pt-, and PdPt-Based Catalysts of Total Oxidation of Methane: In Situ EXAFS Study

In this study, 3%Pd/Al2O3, 3%Pt/Al2O3 and bimetallic (1%Pd + 2%Pt)/Al2O3 catalysts were examined in the total oxidation of methane in a temperature range of 150–400 °C. The evolution of the active component under the reaction conditions was studied by transmission electron microscopy and in situ extended X-ray absorption fine structure (EXAFS) spectroscopy. It was found that the platinum and bimetallic palladium-platinum catalysts are more stable against sintering than the palladium catalysts. For all the catalysts, the active component forms a “core-shell” structure in which the metallic core is covered by an oxide shell. The “core-shell” structure for the platinum and bimetallic palladium-platinum catalysts is stable in the temperature range of 150–400 °C. However, in the case of the palladium catalysts the metallic core undergoes the reversible oxidation at temperatures above 300 °C and reduced to the metallic state with the decrease in the reaction temperature. The scheme of the active component evolution during the oxidation of methane is proposed and discussed