Preparation of a mesoporous ceria–zirconia supported Ni–Fe catalyst for the high temperature water–gas shift reaction

A Ni–Fe/ceria–zirconia catalyst with ordered mesostructure was prepared by the hard-template method employing mesoporous silica (KIT-6) as a template to impart its highly ordered structure to the ceria–zirconia mixed oxide support. Catalytic activities of the Ni–Fe/CeO₂–ZrO₂ catalyst for the water–gas shift reaction were superior to those of a commercial Fe–Cr-based catalyst. The ordered structure of Ni–Fe/CeO₂–ZrO₂ catalyst became more stable compared to one prepared without zirconia due to structural stabilization of the mixed oxide by added zirconia in the framework. Alloying of Ni and Fe and enhanced mobility of lattice oxygen in the oxide support may promote its catalytic activity and selectivity for the water–gas shift reaction.     

W-promoted Co–Mo–K/γ–Al2O3 catalysts for water–gas shift reaction

The effects of incorporating tungsten into the traditional Co–Mo–K/γ–Al₂O₃ catalysts on the catalytic performances for water–gas shift reaction were investigated. Activity tests showed that W-promoted Co–Mo–K/γ–Al₂O₃ catalysts exhibited higher activity than W-free Co–Mo–K/γ–Al₂O₃ catalyst. Raman and H₂-TPR studies indicated that part of the octahedrally coordinated Mo–O species on Co–Mo–K catalysts transformed into tetrahedrally coordinated Mo–O species in the presence of W promoter.     

Effect of structural and acidity/basicity changes of CuO–CeO2 catalysts on their activity for water–gas shift reaction

The objective of this work was to investigate the influence of CuO loading and catalyst pretreatment procedure to derive an optimal CuO–CeO₂ catalyst for the water–gas shift reaction (WGS), and to study in detail structure– and surface acidity–activity relationships. Catalyst samples prepared by coprecipitation and a 10, 15 and 20 mol% CuO content were examined by XRD, BET and TPR/TPD analyses and subjected to pulse WGS activity tests in the temperature range of 180–400 °C. Strong structure–activity dependence in the WGS reaction was observed for all catalyst samples. It was established that increasing CuO content has a positive effect on H₂ production during the WGS reaction, due to favored CeO₂ reduction. Increasing calcination temperature on the other hand reduces the BET surface area, induced by CuO sintering and agglomeration of CeO₂ particles, resulting in a negative effect on H₂ production. Distinctive WGS activity dependence on surface acidity was observed and investigated.     

Synergistic Effect in Selective Reduction of NO by Alkanes over Mechanically Mixed Oxide Catalysts

The process of selective catalytic reduction of nitrogen oxides by propane in the presence of O₂, as well as in the presence or absence of CO, was studied over series of commercial oxide catalysts used in petrochemical processes. For the first time synergistic effect was observed for catalytic systems consisting of mechanical mixtures of Cu–Zn–Ni–Al (catalyst I) + Fe–Cr (catalyst II) and Cu–Zn–Ni–Al (catalyst I) + Ni–Cr (catalyst III). The activity of these mixtures in nitrogen oxides reduction by propane was greater than that of individual components in each case. The worked-out catalytical systems showed high effectivity in the process of simultaneous removal of several toxic components: NO _x , CO, hydrocarbons – from model gas mixtures, as well as from real exhausts of automotive transport.     

Effects of ZnO Contained in Supported Cu-Based Catalysts on Their Activities for Several Reactions

The specific activity of Cu-based catalyst supported on Al₂O₃, ZrO₂ or SiO₂ for methanol synthesis and reverse water–gas shift reactions was improved by the addition of ZnO to the catalyst. On the other hand, the specific activity of the supported Cu-based catalyst for methanol steam reforming and water–gas shift reactions was not improved by the addition of ZnO to the catalyst.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Effects of Pretreatments of Cu/ZnO-Based Catalysts on Their Activities for the Water–Gas Shift Reaction

The effects of the pretreatments of Cu/ZnO-based catalysts prepared by a coprecipitation method on their activities for the water–gas shift reaction at 523K were investigated. The activity of a Cu/ZnO/ZrO₂/Al₂O₃ catalyst for the water–gas shift reaction was less affected by calcination at temperatures ranging from 673-973K and by H₂ treatment at 573 or 723K than that of a Cu/ZnO/Al₂O₃ catalyst. The catalyst activity could be correlated mainly to the Cu surface area of the catalyst.     

Mesoporous Cu–Mn Hopcalite catalyst and its performance in low temperature ethylene combustion in a carbon dioxide stream

Complete combustion of trace amounts of ethylene in food grade CO₂ over a Cu–Mn Hopcalite catalyst has been investigated. A mesoporous structure is identified in the catalyst. Low temperature calcined samples are found to be more active than the high temperature calcined ones. The presence of Cu²⁺ and Mn³⁺ is essential for the high activity of the catalyst. The Cu–Mn catalyst without a third component deactivates quickly in the reaction stream. However, doping with Al or Mg individually and with Ni–Al or Mg–Al simultaneously increases the lifetime. In situ DRIFTS measurements provide evidence that hydroxyl groups form and adsorb on Mn species. With the doping of Al, Mg and Ni ions, the amount of hydroxyl groups adsorbed reduces and the stability improves. Doping with Al and Mg simultaneously gives the best stability. A synergetic effect between CuO and amorphous Cu–Mn oxide phases is also confirmed.     

Effective MgO surface doping of Cu/Zn/Al oxides as water–gas shift catalysts

Trace amounts of MgO were doped on Cu/ZnO/Al₂O₃ catalysts with the Cu/Zn/Al molar ratio of 45/45/10 and tested for the water–gas shift (WGS) reaction. A mixture of Zn(Cu)–Al hydrotalcite (HT) and Cu/Zn aurichalcite was prepared by co-precipitation (cp) of the metal nitrates and calcined at 300 °C to form the catalyst precursor. When the precursor was dispersed in an aqueous solution of Mg(II) nitrate, HT was reconstituted by the “memory effect.” During this procedure, the catalyst particle surface was modified by MgO-doping, leading to a high sustainability. Contrarily, cp-Mg/Cu/Zn/Al prepared by Mg²⁺, Cu²⁺, Zn²⁺ and Al³⁺ co-precipitation as a control exhibited high activity but low sustainability. Mg²⁺ ions were enriched in the surface layer of m-Mg–Cu/Zn/Al, whereas Mg²⁺ ions were homogeneously distributed throughout the particles of cp-Mg/Cu/Zn/Al. CuO particles were significantly sintered on the m-catalyst during the dispersion, whereas CuO particles were highly dispersed on the cp-catalyst. However, the m-catalyst was more sustainable against sintering than the cp-catalyst. Judging from TOF, the surface doping of MgO more efficiently enhanced an intrinsic activity of the m-catalyst than the cp-catalyst. Trace amounts of MgO on the catalyst surface were enough to enhance both activity and sustainability of the m-catalyst by accelerating the reduction–oxidation between Cu⁰ and Cu⁺ and by suppressing Cu⁰ (or Cu⁺) oxidation to Cu²⁺.     

Deposition and characteristics of iron–silicon thin film catalyst for CNT growth

Fe–Si catalyst thin films for the growth of carbon nanotubes were prepared using co-sputter deposition. As-deposited Fe–Si films consist of different amounts of α-Fe and amorphous Si. The amount depends on the Si concentration in the film. Hydrogen plasma etched Fe–Si films become particles having different sizes. The particle size is also dependent on the Si concentration. Correlation among the Si concentration, the particle size, and the growth rate of carbon nanotube was made. Optimal growth of carbon nanotubes at 370 °C was obtained at an average particle size of 45 nm or a Si concentration of 21%.     

Thermal behaviour of Cu–Mg–Mn and Ni–Mg–Mn layered double hydroxides and characterization of formed oxides

Thermal behaviour of synthetic Cu–Mg–Mn and Ni–Mg–Mn layered double hydroxides (LDHs) with M^II/Mg/Mn molar ratio of 1:1:1 was studied in the temperature range 200–1100 °C by thermal analysis (TG/DTA/EGA), powder X-ray diffraction (XRD), Raman spectroscopy, and voltammetry of microparticles. Powder XRD patterns of prepared LDHs showed characteristic hydrotalcite-like phases, but further phases were indirectly found as admixtures. The Cu–Mg–Mn precipitate was decomposed at temperatures up to ca. 200 °C to form an XRD-amorphous mixture of oxides. The crystallization of CuO (tenorite) and a spinel type mixed oxide of varying composition Cu_xMg_yMn_zO₄ with Mn⁴⁺ was detected at 300–500 °C. At high temperatures (900–1000 °C), tenorite disappeared and a consecutive crystallization of 2CuO·MgO (gueggonite) was observed. The high-temperature transformation of oxide phases led to a formation of Cu^I oxides accompanied by oxygen evolution. The DTA curve of Ni–Mg–Mn sample exhibited two endothermic effects characteristic for hydrotalcite-like compounds. The first one with minimum at 190 °C can be ascribed to a loss of interlayer water, the second one with minimum at 305 °C to the sample decomposition. Heating of the Ni–Mg–Mn sample at 300 °C led to the onset of crystallization of oxide phases identified as Ni_xMg_yMn_zO₄ spinel, (Ni,Mg)O oxide containing Mn⁴⁺ cations, and easily reducible XRD-amorphous species, probably free Mn^III,IV oxides. At 600 °C (Raman spectroscopy) and 700 °C (XRD), the (Ni,Mg)₆MnO₈ oxide with murdochite structure together with spinel phase were detected. Only spinel and (Ni,Mg)O were found after heating at 900 °C and higher temperatures. Temperature-programmed reduction (TPR) profiles of calcined Cu–Mg–Mn samples exhibited a single reduction peak with maximum around 250 °C. The highest H₂ consumption was observed for the sample calcined at 800 °C. The reduction of Ni–Mg–Mn samples proceeded by a more complex way and the TPR profiles reflected the phase composition changing depending on the calcination temperature.     

Molybdenum carbide catalysts for water–gas shift

Molybdenum carbide (Mo₂C) was demonstrated to be highly active for the water–gas shift of a synthetic steam reformer exhaust stream. This catalyst was more active than a commercial Cu–Zn–Al shift catalyst under the conditions employed (220–295°C and atmospheric pressure). In addition, Mo₂C did not catalyze the methanation reaction. There was no apparent deactivation or modification of the structure during 48 h on‐stream. The results suggest that high surface area carbides are promising candidates for development as commercial water–gas shift catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Selective CO-Oxidation over Ru-Based Catalysts in H2-Rich Gas for Fuel Cell Applications

Ru-based catalysts supported on A zeolites and alumina were synthesised, characterised (XRD, SEM-EDS, TPR) and tested under realistic conditions for the preferential oxidation of CO (CO-PROX) from the hydrogen-rich gas streams produced by fossil fuels reforming. Comparative tests with a commercial catalyst were also carried out with special attention to the detection of possible side reactions (i.e. methanation and return water gas shift). The 0.5%Ru–Al₂O₃ catalyst resulted the most active, the most selective and the least prone to side reactions; methanation, in particular, was found to occur only when the catalyst is oxidised because of occasional exposure to O₂-rich streams.     

High temperature SrCe0.9Eu0.1O3−δ proton conducting membrane reactor for H2 production using the water–gas shift reaction

The water–gas shift (WGS) reaction is used to shift the CO/H₂ ratio prior to Fischer–Tropsch synthesis and/or to increase H₂ yield. A WGS membrane reactor was developed using a mixed protonic–electronic conducting SrCe_0.9Eu_0.1O_3−δ membrane coated on a Ni–SrCeO_3−δ support. The membrane reactor overcomes the thermodynamic equilibrium limitations. A 46% increase in CO conversion and total H₂ yield was achieved at 900 °C under 3% CO and 6% H₂O, resulting in a 92% single pass H₂ production yield and 32% single pass yield of pure permeated H₂.     

Effects of Zn, Cu, and K Promoters on the Structure and on the Reduction, Carburization, and Catalytic Behavior of Iron-Based Fischer–Tropsch Synthesis Catalysts

Zn, K, and Cu effects on the structure and surface area and on the reduction, carburization, and catalytic behavior of Fe–Zn and Fe oxides used as precursors to Fischer–Tropsch synthesis (FTS) catalysts, were examined using X-ray diffraction, kinetic studies of their reactions with H₂ or CO, and FTS reaction rate measurements. Fe₂O₃ precursors initially reduce to Fe₃O₄ and then to metallic Fe (in H₂) or to a mixture of Fe_2.5C and Fe₃C (in CO). Zn, present as ZnFe₂O₄, increases the surface area of precipitated oxide precursors by inhibiting sintering during thermal treatment and during activation in H₂/CO reactant mixtures, leading to higher FTS rates than on ZnO-free precursors. ZnFe₂O₄ species do not reduce to active FTS structures, but lead instead to the loss of active components; as a result, maximum FTS rates are achieved at intermediate Zn/Fe atomic ratios. Cu increases the rate of Fe₂O₃ reduction to Fe₃O₄ by providing H₂ dissociation sites. Potassium increases CO activation rates and increases the rate of carburization of Fe₃O₄. In this manner, Cu and K promote the nucleation of oxygen-deficient FeO _x species involved as intermediate inorganic structures in reduction and carburization of Fe₂O₃ and decrease the ultimate size of the Fe oxide and carbide structures formed during activation in synthesis gas. As a result, Cu and K increase FTS rates on catalysts formed from Fe–Zn oxide precursors. Cu increases CH₄ and the paraffin content in FTS products, but the additional presence of K inhibits these effects. Potassium titrates residual acid and hydrogenation sites and increases the olefin content and molecular weight of FTS products. K increases the rate of secondary water–gas shift reactions, while Cu increases the relative rate of oxygen removal as CO₂ instead of water after CO is dissociated in FTS elementary steps. Through these two different mechanisms, K and Cu both increase CO₂ selectivities during FTS reactions on catalysts based on Fe–Zn oxide precursors.     

Relating catalyst structure and composition to the water–gas shift activity of Cu–Zn-based mixed-oxide catalysts

In order to investigate the effect of cerium oxide on Cu–Zn-based mixed-oxide catalysts four catalyst samples were characterized by means of XRD, in situ XANES and thermogravimetric analysis. The activity of the catalyst samples was tested for the forward water–gas shift reaction. Cerium oxide was found to increase the crystallinity of the ZnO phase indicating a segregation of the Cu and ZnO phases. The TOF of the water–gas shift reaction based on chemisorption data was found to be independent of composition and preparation conditions of the four catalyst samples. In contrast, the catalyst stability depends on composition and preparation conditions. Cerium oxide impregnated before calcination of the hydrotalcite-based Cu–Zn precursors leads to a more stable water–gas shift catalyst.     

Iron–cobalt mixed oxide nanocatalysts: Heterogeneous peroxymonosulfate activation, cobalt leaching, and ferromagnetic properties for environmental applications

Sulfate radical-based advanced oxidation technologies (SR-AOTs) are attracting considerable attention due to the high oxidizing ability of SRs to degrade organic pollutants in aqueous environments. This study was carried out to respond to current concerns and challenges in SR-AOTs, including (i) need of heterogeneous activation of sulfate salts using transition metal oxides, (ii) nanoscaling of the metal oxide catalysts for high catalytic activity and promising properties with respect to leaching, and (iii) easy removal and recovery of the catalytic materials after their applications for water and wastewater treatments. In this study, we report a novel approach of using Fe–Co mixed oxide nanocatalysts for the heterogeneous activation of peroxymonosulfate (PMS) to generate SRs targeting the decomposition of 2,4-dichlorophenol, and especially focus on some synthesis parameters such as calcination temperature, Fe/Co contents, and TiO₂ support. The physicochemical properties of the catalysts were investigated using porosimetry, XRD, HR-TEM, H₂-TPR, and XPS. Ferromagnetic CoFe₂O₄ composites formed by thermal oxidation of a mixed phase of Fe and Co exhibited significant implications for the efficient and environmentally friendly activation of PMS, including (i) the cobalt species in CoFe₂O₄ are of Co(II), unlike Co₃O₄ showing some detrimental effects of Co(III) on the PMS activation, (ii) CoFe₂O₄ possesses suppressed Co leaching properties due to strong Fe–Co interactions (i.e. Fe–Co linkages), and (iii) Fe–Co catalysts in form of CoFe₂O₄ are easier to recover due to the unique ferromagnetic nature of CoFe₂O₄. In addition, the presence of Fe was found to be beneficial for enriching hydroxyl group content on the Fe–Co catalyst surface, which is believed to facilitate the formation of Co(II)-OH complexes that are vital for heterogeneous PMS activation.     

Electrodeposition of Ni, Fe and Ni–Fe alloys on a 316 stainless steel surface in a fluorborate bath

Electrodeposition processes of Ni, Fe and Ni–Fe alloys on 316 stainless steel surfaces in fluorborate baths were studied using conventional electrochemical techniques and atomic force microscopy. The results showed that these processes occurred under mass transfer control, associated with nucleation and growth process. Cathodic current–time transients indicated that the nucleation and growth of Ni–Fe alloy was different from that of the single metal (Ni or Fe). For one, two nucleation and growth processes occurred during Ni–Fe alloy codeposition. Also, there was a nucleation and growth process of Ni–Fe alloy on Ni–Fe clusters, due to a change of the Ni–Fe alloy composition and phase. Homogeneous Ni–Fe alloy deposits could be obtained by pulse potential plating. AFM images of Ni, Fe and Ni–Fe deposits prepared by pulse potential plating revealed the following results: (1) the growth rate of Ni nuclei was faster in parallel than in perpendicular to the 316 electrode surface; (2) for Fe nuclei, the preferential growth direction was perpendicular to the 316 electrode surface; and (3) for Ni–Fe nuclei, there was no preferential growth direction and uniformly hemispherical Ni–Fe clusters were obtained.     

Effect of preparation and reaction condition on the catalytic performance of Mo–V–Te–Nb catalysts for selective oxidation of propane to acrylic acid by high-throughput methodology

Combinatorial screening technique has been applied to investigate the catalytic activity and selectivity of quaternary Mo–V–Te–Nb mixed oxide catalysts treated with various chemicals during preparation for selective oxidation of propane to acrylic acid. The catalyst libraries were prepared by the slurry method and catalytic activities were examined in 32-channel high-throughput screening reactor system coupled with a mass spectrometer and/or gas chromatograph.The obtained results provided substantial evidence that the sample preparation condition would have strong effect on the catalytic performance for propane selective oxidation. Among screened samples, Mo–V–Te–Nb treated with HIO₃ solution presented a better performance. The reaction results of promising catalysts selected from the libraries were applied to further scale-up of the system and confirmed catalytic performance. Quantification of the result of Mo–V–Te–Nb treated with HIO₃ solution was realized by combination of GC and MS and relationship between the MS data and the GC results can be established.