Photocatalysts Based on Graphite-like Carbon Nitride with a Low Content of Rhodium and Palladium for Hydrogen Production under Visible Light.

In this study, we proposed photocatalysts based on graphite-like carbon nitride with a low content (0.01-0.5 wt.%) of noble metals (Pd, Rh) for hydrogen evolution under visible light irradiation. As precursors of rhodium and palladium, labile aqua and nitrato complexes [Rh2(H2O)8(µ-OH)2](NO3)4∙4H2O and (Et4N)2[Pd(NO3)4], respectively, were proposed. To obtain metallic particles, reduction was carried out in H2 at 400 °C. The synthesized photocatalysts were studied using X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectroscopy and high-resolution transmission electron microscopy. The activity of the photocatalysts was tested in the hydrogen evolution from aqueous and aqueous alkaline solutions of TEOA under visible light with a wavelength of 428 nm. It was shown that the activity for the 0.01-0.5% Rh/g-C3N4 series is higher than in the case of the 0.01-0.5% Pd/g-C3N4 photocatalysts. The 0.5% Rh/g-C3N4 sample showed the highest activity per gram of catalyst, equal to 3.9 mmol gcat-1 h-1, whereas the most efficient use of the metal particles was found over the 0.1% Rh/g-C3N4 photocatalyst, with the activity of 2.4 mol per gram of Rh per hour. The data obtained are of interest and can serve for further research in the field of photocatalytic hydrogen evolution using noble metals as cocatalysts.

Insights into the Contribution of Oxidation-Reduction Pretreatment for Mn0.2Zr0.8O2-δ Catalyst of CO Oxidation Reaction.

A Mn0.2Zr0.8O2-δ mixed oxide catalyst was synthesized via the co-precipitation method and studied in a CO oxidation reaction after different redox pretreatments. The surface and structural properties of the catalyst were studied before and after the pretreatment using XRD, XANES, XPS, and TEM techniques. Operando XRD was used to monitor the changes in the crystal structure under pretreatment and reaction conditions. The catalytic properties were found to depend on the activation procedure: reducing the CO atmosphere at 400-600 °C and the reaction mixture (O2 excess) or oxidative O2 atmosphere at 250-400 °C. A maximum catalytic effect characterized by decreasing T50 from 193 to 171 °C was observed after a reduction at 400 °C and further oxidation in the CO/O2 reaction mixture was observed at 250 °C. Operando XRD showed a reversible reduction-oxidation of Mn cations in the volume of Mn0.2Zr0.8O2-δ solid solution. XPS and TEM detected the segregation of manganese cations on the surface of the mixed oxide. TEM showed that Mn-rich regions have a structure of MnO2. The pretreatment caused the partial decomposition of the Mn0.2Zr0.8O2-δ solid solution and the formation of surface Mn-rich areas that are active in catalytic CO oxidation. In this work it was shown that the introduction of oxidation-reduction pretreatment cycles leads to an increase in catalytic activity due to changes in the origin of active states.

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.

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.

Self-sustained oscillations in oxidation of methane over palladium: Experimental study and mathematical modeling.

An experimental study of the catalytic oxidation of methane over Pd foil in a flow reactor revealed that regular temporal oscillations in the reaction rate can arise at atmospheric pressure under methane-rich conditions. CO, CO2, H2, and H2O were detected as products. The oscillations of partial pressures of products and reactants in the gas phase were accompanied by oscillations of the catalyst temperature. According to an operando x-ray diffraction and mass-spectrometry study, the oscillations originate due to spontaneous oxidation and reduction of palladium; the high active catalyst surface is represented by metallic palladium, and the transition to the low-active state is accompanied by the formation of the PdO phase. In addition, it was detected that carbon dissolves in near-surface layers of palladium to form the PdCx phase. To describe the oscillations in the oxidation of methane, a 17-step reaction mechanism and a corresponding kinetic model were developed. The mechanism considers direct dissociative adsorption of methane and oxygen, pyrolytic activation of methane, oxidation and reduction of palladium, and direct formation and desorption of CO, CO2, H2, and H2O. Numerical solutions from the mathematical model of the continuously stirred-tank reactor qualitatively reproduce experimentally observed oscillatory dynamics. We have also developed a model, which considers the reversible diffusion of adsorbed oxygen and carbon atoms into the Pd bulk that allows us to explain the long induction period preceding the appearance of the oscillations. Mathematical modeling shows that the concentrations of dissolved oxygen and carbon atoms also oscillate under reaction conditions.

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).

Promoting effect of Zn in high-loading Zn/Ni-SiO2 catalysts for selective hydrogen evolution from methylcyclohexane.

The dehydrogenation of methylcyclohexane to toluene was investigated over high-loading monometallic Ni-SiO2 and bimetallic Zn/Ni-SiO2 catalysts. The catalysts were prepared by the impregnation coupled with the advantageous heterophase sol-gel technique. Their performance was tested in a fixed-bed flow reactor at 250-350 °C, 0.1 MPa pressure, equimolar ratio H2/Ar (24 nL h-1 in total), and a methylcyclohexane feed rate of 12 mL h-1. Information regarding the structure of Ni-Zn catalysts was obtained by N2 and CO adsorption, temperature-programmed reduction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, in situ X-ray diffraction, and in situ X-ray absorption spectroscopy. The results have shown that the addition of zinc leads to the hindrance of Ni reducibility along with weakening the Ni interaction with the silica matrix. This behavior particularly indicated the formation of solid oxide nickel-zinc solutions. The catalytic properties of Zn-modified catalysts in the dehydrogenation of methylcyclohexane appeared significantly superior to their Ni-Cu counterparts. For example, the selectivity of Zn/Ni-SiO2 catalysts toward toluene formation increased markedly with a decrease in the Ni : Zn mass ratio, achieving 97% at 350 °C over the sample with Ni : Zn = 80 : 20. This is attributed to the promoting geometric and electronic effects arising from the formation of bimetallic Ni-Zn solid solutions. Moreover, a deeper reduction of zinc and a more efficient formation of solid bimetallic solutions are observed after the catalytic tests.

Low Temperature Multilayer Adsorption of Methanol and Ethanol on Platinum.

Adsorption of methanol and ethanol on the clean Pt (111) surface was studied at temperatures between 80 and 130 K using polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS). It was shown that adsorption of methanol at 80 K leads to the formation of amorphous solid methanol, and fast crystallization of the amorphous phase occurs upon warming at 100 K. Vapor deposition of methanol at 100 K directly leads to the formation of well-crystallized layers of solid methanol. According to PM-IRRAS, these crystalline layers consist of chains of hydrogen-bonded methanol molecules lying in a plane oriented close to the normal to the platinum surface. Adsorbed methanol is removed completely from platinum after heating to 120 K. Vapor deposition of ethanol at 80 K also leads to the formation of amorphous solid ethanol. However, subsequent warming does not lead to ordering of the adsorption layers, and at 130 K, ethanol is also completely desorbed.

In Situ Study of Reduction of MnxCo3-xO4 Mixed Oxides: The Role of Manganese Content.

A series of Mn-Co mixed oxides with a gradual variation of the Mn/Co molar ratio were prepared by coprecipitation of cobalt and manganese nitrates. The structure, chemistry, and reducibility of the oxides were studied by X-ray diffraction (XRD), X-ray absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR). It was found that at concentrations of Mn below 37 atom %, a solid solution with a cubic spinel structure is formed. At concentrations above 63 atom %, a solid solution is formed on the basis of a tetragonal spinel, while at concentrations in a range of 37-63 atom %, a two-phase system, which contains tetragonal and cubic oxides, is formed. To elucidate the reduction route of mixed oxides, two approaches were used. The first was based on a gradual change in the chemical composition of Mn-Co oxides, illustrating slow changes in the TPR profiles. The second approach consisted in a combination of in situ XRD and pseudo-in situ XPS techniques, which made it possible to directly determine the structure and chemistry of the oxides under reductive conditions. It was shown that the reduction of Mn-Co mixed oxides proceeds via two stages. During the first stage, (Mn, Co)3O4 is reduced to (Mn, Co)O. During the second stage, the solid solution (Mn, Co)O is transformed into metallic cobalt and MnO. The introduction of manganese cations into the structure of cobalt oxide leads to a decrease in the rate of both reduction stages. However, the influence of additional cations on the second reduction stage is more noticeable. This is due to crystallographic peculiarities of the compounds: the conversion from the initial oxide (Mn, Co)3O4 into the intermediate oxide (Mn, Co)O requires only a small displacement of cations, whereas the formation of metallic cobalt from (Mn, Co)O requires a rearrangement of the entire structure.

The Formation of Mn-Ce Oxide Catalysts for CO Oxidation by Oxalate Route: The Role of Manganese Content.

The Mn-Ce oxide catalysts active in the oxidation of CO were studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), transition electron microscopy (TEM), energy dispersive X-Ray (EDX), and a differential dissolution technique. The Mn-Ce catalysts were prepared by thermal decomposition of oxalates by varying the Mn:Ce ratio. The nanocrystalline oxides with a fluorite structure and particle sizes of 4-6 nm were formed. The introduction of manganese led to a reduction of the oxide particle size, a decrease in the surface area, and the formation of a MnyCe1-yO2-δ solid solution. An increase in the manganese content resulted in the formation of manganese oxides such as Mn2O3, Mn3O4, and Mn5O8. The catalytic activity as a function of the manganese content had a volcano-like shape. The best catalytic performance was exhibited by the catalyst containing ca. 50 at.% Mn due to the high specific surface area, the formation of the solid solution, and the maximum content of the solid solution.

Coupling Hydrogenation of Guaiacol with In Situ Hydrogen Production by Glycerol Aqueous Reforming over Ni/Al2O3 and Ni-X/Al2O3 (X = Cu, Mo, P) Catalysts.

Biomass-derived liquids, such as bio-oil obtained by fast pyrolysis, can be a valuable source of fuels and chemicals. However, these liquids have high oxygen and water content, needing further upgrading typically involving hydrotreating using H2 at high pressure and temperature. The harsh reaction conditions and use of expensive H2 have hindered the progress of this technology and led to the search for alternative processes. In this work, hydrogenation in aqueous phase is investigated using in-situ produced hydrogen from reforming of glycerol, a low-value by-product from biodiesel production, over Ni-based catalysts. Guaiacol was selected as a bio-oil model compound and high conversion (95%) to phenol and aromatic ring hydrogenation products was obtained over Ni/γ-Al2O3 at 250 °C and 2-h reaction time. Seventy percent selectivity to cyclohexanol and cyclohexanone was achieved at this condition. Hydrogenation capacity of P and Mo modified Ni/γ-Al2O3 was inhibited because more hydrogen undergoes methanation, while Cu showed a good performance in suppressing methane formation. These results demonstrate the feasibility of coupling aqueous phase reforming of glycerol with bio-oil hydrogenation, enabling the reaction to be carried out at lower temperatures and pressures and without the need for molecular H2.

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%).

New titania-based photocatalysts for hydrogen production from aqueous-alcoholic solutions of methylene blue.

A series of CuO x -TiO2 photocatalysts were prepared using fresh and thermally activated Evonik Aeroxide P25 titanium dioxide. The photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, XANES, diffuse reflectance spectroscopy, and N2 adsorption technique. Photocatalytic activity of the samples was tested in hydrogen production from aqueous-alcoholic solutions of methylene blue under UV radiation (λ = 386 nm). It was found for the first time the synergistic effect of hydrogen production from two substrates-dye and ethanol. The maximum hydrogen production rate in the system water-ethanol-methylene blue was 1 µmol min-1, which is 25 times higher than a value measured in a 10% solution of ethanol in water. The thermal activation of titania also leads to a change in the rate of hydrogen production. The highest catalytic activity was observed for a CuO x -TiO2 photocatalyst based on titania thermally-activated at 600 °C in air. A mechanism of the photocatalytic reaction is discussed.

The Influence of Cu and Al Additives on Reduction of Iron(III) Oxide: In Situ XRD and XANES Study.

The reduction of Fe-based nanocomposite catalysts doped with Al and Cu has been studied using in situ X-ray diffraction (XRD), in situ X-ray absorption near-edge structure (XANES), and temperature-programmed reduction (TPR) techniques. The catalysts have been synthesized by melting of iron, aluminum, and copper salts. According to XRD, the catalysts consist mainly of Fe2O3 and Al2O3 phases. Alumina is in an amorphous state, whereas iron oxide forms nanoparticles with the protohematite structure. The Al3+ cations are partially dissolved in the Fe2O3 lattice. Due to strong alumina-iron oxide interaction, the specific surface area of the catalysts increases significantly. TPR and XANES data indicate that copper forms highly dispersed surface CuO nanoparticles and partially dissolves in iron oxide. It has been shown that the reduction of iron(III) oxide by CO proceeds via two routes: a direct two-stage reduction of iron(III) oxide to metal (Fe2O3 → Fe3O4 → Fe) or an indirect three-stage reduction with the formation of FeO intermediate phases (Fe2O3 → Fe3O4 → FeO → Fe). The introduction of Al into Fe2O3 leads to a decrease in the rate for all reduction steps. In addition, the introduction of Al stabilizes small Fe3O4 particles and prevents further sintering of the iron oxide. The mechanism of stabilization is associated with the formation of Fe3- xAl xO4 solid solution. The addition of copper to the Fe-Al catalyst leads to the formation of highly dispersed CuO particles on the catalyst surface and a mixed oxide with a spinel-type crystalline structure similar to that of CuFe2O4. The low-temperature reduction of Cu2+ to Cu0 accelerates the Fe2O3 → Fe3O4 and FeO → Fe transformations but does not affect the Fe3O4 → FeO/Fe stages. These changes in the reduction properties significantly affect the catalytic performance of the Fe-based nanocomposite catalysts in the low-temperature oxidation of CO.

Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

The self-sustained kinetic oscillations in the oxidation of CH4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO2, H2, and H2O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.