Chemical Vapor Impregnation Research Articles

Controlling palladium particle size and dispersion as a function of loading by chemical vapour impregnation: an investigation using propane total oxidation as a model reaction

Chemical vapour impregnation gives a high level of control over palladium nanoparticle size and dispersion regardless of metal weight loading, with catalyst activity per active site being identical.

Zn Loading Effects on the Selectivity of PdZn Catalysts for CO2 Hydrogenation to Methanol

PdZn/TiO2 catalysts have been investigated for the hydrogenation of CO2 to methanol. Varying the ratio of Pd and Zn using TiO2 as a support has a dramatic effect on catalytic performance. Chemical vapour impregnation was used to produce PdZn alloys on TiO2 and X-ray diffraction, X-ray photoelectron spectroscopy, and scanning transmission electron microscopy revealed changes in the structure at varying total PdZn molar ratios. Compared to monometallic Pd/TiO2, introducing a low loading of Zn drastically changes product selectivity. When Pd is alloyed with Zn above a total Zn/Pd = 1 molar ratio, methanol selectivity is improved. Therefore, for enhanced methanol productivity, it is crucial for the Zn loading to be higher than that required for the stoichiometric formation of the 1:1 β-PdZn alloy.Graphical

Tension–tension fatigue behavior and residual strength evolution of SiC/(PyC/SiC)2/SiC minicomposites prepared by CVI+MI and CVI+PIP processes

The residual tensile strength (RTS) evolution of SiC/(PyC/SiC)2/SiC samples, prepared by chemical vapor impregnation (CVI) combined with either melting reaction sintering (MI) or polymer impregnation and pyrolysis (PIP), was investigated after 106 cycles as the pre-fatigue stress increased. The fatigue limits of the two tested specimen types, CVI + MI and CVI + PIP, were 760 and 660 MPa, respectively, corresponding to 95% and 75% of the tensile strength, respectively. Although the RTS of the two specimen types first increased and then decreased, it was interesting that after pre-fatigue, the maximum RTS of the CVI + PIP-prepared sample at 680 MPa, was 16 MPa higher than that of the CVI + MI-prepared sample at 590 MPa. The nanoindentation results indicate that the matrix prepared by CVI could protect the fiber from heavy damage in subsequent preparation, and the matrix modulus and hardness were higher in samples prepared by PIP than those prepared by MI. According to the microstructure observations and hysteresis characteristics, it was concluded that the differences mainly came from the internal stress state, matrix, and fiber properties.

Combination of Cu/ZnO Methanol Synthesis Catalysts and ZSM-5 Zeolites to Produce Oxygenates from CO2 and H2

Cu/ZnO methanol catalysts were deposited over several ZSM-5 acid zeolites to directly synthesise oxygenates (methanol and dimethyl ether) from a CO2/H2 feed. Catalysts were prepared by two different preparation methodologies: chemical vapour impregnation (CZZ-CVI) and oxalate gel precipitation (CZZ-OG). Chemical vapour impregnation led to Cu/ZnO being deposited on the zeolite surface, whilst oxalate gel precipitation led to the formation of Cu/ZnO agglomerates. For both sets of catalysts a higher concentration of mild and strong acid sites were produced, compared to the parent ZSM-5 zeolites, and CZZ-CVI had a higher concentration of acid sites compared to CZZ-OG. Nevertheless, CZZ-OG shows considerably higher oxygenate productivity, 1322 mmol Kgcat−1 h−1, compared to 192 mmol Kgcat−1 h−1 over CZZ-CVI (ZSM-5(50), 250 ℃, 20 bar, CO2/H2 = 1/3, 30 ml min−1), which could be assigned to a combination of smaller particle size and enhanced methanol mass transfer within the zeolites.

CO2 Hydrogenation to CH3OH over PdZn Catalysts, with Reduced CH4 Production

AbstractMetallic Pd, under CO2 hydrogenation conditions (>175 °C, 20 bar in this work), promotes CO formation via the reverse water gas shift (RWGS) reaction. Pd‐based catalysts can show high selectivity to methanol when alloyed with Zn, and PdZn alloy catalysts are commonly reported as a stable alternative to Cu‐based catalysts for the CO2 hydrogenation to methanol. The production of CH4 is sometimes reported as a minor by‐product, but nevertheless this can be a major detriment for an industrial process, because methane builds up in the recycle loop, and hence would have to be purged periodically. Thus, it is extremely important to reduce methane production for future green methanol synthesis processes. In this work we have investigated TiO2 as a support for such catalysts, with Pd, or PdZn deposited by chemical vapour impregnation (CVI). Although titania‐supported PdZn materials show excellent performance, with high selectivity to CH3OH+CO, they suffer from methane formation (>0.01 %). However, when ZnTiO3 is used instead as a support medium for the PdZn alloy, methane production is greatly suppressed. The site for methane production appears to be the TiO2, which reduces methanol to methane at anion vacancy sites.

Partial oxidation of methane with hydrogen peroxide over Fe-ZSM-5 catalyst

The effect of the catalyst preparation method on the catalytic activity of Fe-ZSM-5 for the partial oxidation of methane with H2O2 in an aqueous phase was examined. UV–vis spectroscopy and FT-IR spectroscopy after NO adsorption were used to characterize the prepared catalysts. Various preparation methods, including wet impregnation, solid-state ion-exchange, chemical vapor impregnation, hydrothermal synthesis, and aqueous phase ion-exchange were compared. Among them, the aqueous phase ion-exchange method demonstrated the best results in producing isolated or oligonuclear extra-framework Fe species, which showed the highest catalytic activity. On the other hand, bulk iron oxides did not decompose H2O2 nor did they activate methane. The total product yield and the amount of H2O2 consumed increased with increasing Fe content in the case of the Fe-ZSM-5 catalyst prepared using an ion-exchange method. However, the fraction of less active Fe species, such as iron oxide clusters and larger iron oxide aggregates on the external crystal surface, increased with the Fe content, resulting in a decrease in the total product yield per Fe content and the amount of H2O2 consumed per Fe content.

Influence of the Preparation Method of Ag-K/CeO2-ZrO2-Al2O3 Catalysts on Their Structure and Activity for the Simultaneous Removal of Soot and NOx

Ag/CeO2-ZrO2-Al2O3, a known catalyst for the simultaneous removal of NOx and soot, was modified by the addition of K, and was prepared using various techniques: wet impregnation, incipient wetness, and chemical vapor impregnation at different temperatures. The effect of the preparation method on catalyst activity was studied. It was found that catalysts prepared via wet impregnation, incipient wetness, and chemical vapor impregnation at 80 °C were able to utilize in situ formed N2O at low temperatures, to simultaneously remove NOx and soot. The difference in preparation method affected the catalyst’s ability to produce and use N2O as an oxidant for soot. The temperature at which chemical vapor impregnation was performed greatly influenced the catalyst’s ability to oxidize soot. The introduction of K to the Ag/CeO2-ZrO2-Al2O3 vastly improved the soot oxidation activity, particularly for the catalyst prepared via wet impregnation. However, the incorporation of K had an adverse effect on the reduction of NOx.

Investigating the Influence of Fe Speciation on N2O Decomposition Over Fe\u2013ZSM-5 Catalysts

The influence of Fe speciation on the decomposition rates of N2O over Fe–ZSM-5 catalysts prepared by Chemical Vapour Impregnation were investigated. Various weight loadings of Fe–ZSM-5 catalysts were prepared from the parent zeolite H-ZSM-5 with a Si:Al ratio of 23 or 30. The effect of Si:Al ratio and Fe weight loading was initially investigated before focussing on a single weight loading and the effects of acid washing on catalyst activity and iron speciation. UV/Vis spectroscopy, surface area analysis, XPS and ICP-OES of the acid washed catalysts indicated a reduction of ca. 60% of Fe loading when compared to the parent catalyst with a 0.4 wt% Fe loading. The TOF of N2O decomposition at 600 °C improved to 3.99 × 103 s−1 over the acid washed catalyst which had a weight loading of 0.16%, in contrast, the parent catalyst had a TOF of 1.60 × 103 s−1. Propane was added to the gas stream to act as a reductant and remove any inhibiting oxygen species that remain on the surface of the catalyst. Comparison of catalysts with relatively high and low Fe loadings achieved comparable levels of N2O decomposition when propane is present. When only N2O is present, low metal loading Fe–ZSM-5 catalysts are not capable of achieving high conversions due to the low proximity of active framework Fe3+ ions and extra-framework ɑ-Fe species, which limits oxygen desorption. Acid washing extracts Fe from these active sites and deposits it on the surface of the catalyst as FexOy, leading to a drop in activity. The Fe species present in the catalyst were identified using UV/Vis spectroscopy and speculate on the active species. We consider high loadings of Fe do not lead to an active catalyst when propane is present due to the formation of FexOy nanoparticles and clusters during catalyst preparation. These are inactive species which lead to a decrease in overall efficiency of the Fe ions and consequentially a lower TOF.

Hydrogenation of CO2 to Dimethyl Ether over Brønsted Acidic PdZn Catalysts

Eschewing the common trend toward use of catalysts composed of Cu, it is reported that PdZn alloys are active for CO2 hydrogenation to oxygenates. It is shown that enhanced CO2 conversion is achievable through the introduction of Bronsted acid sites, which promote dehydration of methanol to dimethyl ether. We report that deposition of PdZn alloy nanoparticles onto the solid acid ZSM-5, via chemical vapor impregnation affords catalysts for the direct hydrogenation of CO2 to DME. This catalyst shows dual functionality; catalyzing both CO2 hydrogenation to methanol and its dehydration to dimethyl in a single catalyst bed, at temperatures of >270 °C. A physically mixed bed comprising 5% Pd 15% Zn/TiO2 and H-ZSM-5 shows a comparably high performance, affording a dimethyl ether synthesis rate of 546 mmol kgcat–1 h–1 at a reaction temperature of 270 °C.

The Role of Copper Speciation in the Low Temperature Oxidative Upgrading of Short Chain Alkanes over Cu/ZSM-5 Catalysts.

Partial oxidative upgrading of C1 -C3 alkanes over Cu/ZSM-5 catalysts prepared by chemical vapour impregnation (CVI) has been studied. The undoped ZSM-5 support is itself able to catalyse selective oxidations, for example, methane to methanol, using mild reaction conditions and the green oxidant H2 O2 . Addition of Cu suppresses secondary oxidation reactions, affording methanol selectivities of up to 97 %. Characterisation studies attribute this ability to population of specific Cu sites below the level of total exchange (Cu/Al<0.5). These species also show activity for radical-based methane oxidation, with productivities exceeding those of the parent zeolite supports. When tested for ethane and propane oxidation reactions, comparable trends are observed.

Solvent Free Synthesis of PdZn/TiO2 Catalysts for the Hydrogenation of CO2 to Methanol

Catalytic upgrading of CO2 to value-added chemicals is an important challenge within the chemical sciences. Of particular interest are catalysts which are both active and selective for the hydrogenation of CO2 to methanol. PdZn alloy nanoparticles supported on TiO2 via a solvent-free chemical vapour impregnation method are shown to be effective for this reaction. This synthesis technique is shown to minimise surface contaminants, which are detrimental to catalyst activity. The effect of reductive heat treatments on both structural properties of PdZn/TiO2 catalysts and rates of catalytic CO2 hydrogenation are investigated. PdZn nanoparticles formed upon reduction showed high stability towards particle sintering at high reduction temperature with average diameter of 3–6 nm to give 1710 mmol kg−1 h of methanol. Reductive treatment at high temperature results in the formation of ZnTiO3 as well as PdZn, and gives the highest methanol yield.

PdZn catalysts for CO2 hydrogenation to methanol using chemical vapour impregnation (CVI).

The formation of PdZn bimetallic alloys on ZnO, TiO2 and Al2O3 supports was investigated, together with the effect of alloy formation on the CO2 hydrogenation reaction. The chemical vapour impregnation (CVI) method produced PdZn nanoparticles with diameters of 3-6 nm. X-ray photoelectron spectroscopy and X-ray diffraction revealed the changes in the structure of the PdZn alloy that help stabilise formate intermediates during methanol synthesis. PdZn supported on TiO2 exhibits high methanol productivity of 1730 mmol kgcat-1 h-1 that is associated with the high dispersion of the supported PdZn alloy.

Continuous selective oxidation of methane to methanol over Cu- and Fe-modified ZSM-5 catalysts in a flow reactor

The selective oxidation of methane to methanol is a key challenge in catalysis. Iron and copper modified ZSM-5 catalysts are shown to be effective for this reaction using H2O2 as the oxidant under continuous flow operation. Co-impregnation of ZSM-5 with Fe and Cu by chemical vapour impregnation yielded catalysts that showed high selectivity to methanol (>92% selectivity, 0.5% conversion), as the only product in the liquid phase. The catalysts investigated did not deactivate during continuous reaction, and methanol selectivity remained high. The effect of reaction pressure, temperature, hydrogen peroxide concentration and catalyst mass were investigated. An increase in any of these led to increased methane conversion, with high methanol selectivity (≥73%) maintained throughout. Catalysts were characterised using DR-FTIR, DR-UV-Vis and 27Al MAS-NMR spectroscopy.

Well-controlled metal co-catalysts synthesised by chemical vapour impregnation for photocatalytic hydrogen production and water purification.

As co-catalyst materials, metal nanoparticles (NPs) play crucial roles in heterogeneous photocatalysis. The photocatalytic performance strongly relies on the physical properties (i.e., composition, microstructure, and surface impurities) of the metal NPs. Here we report a convenient chemical vapour impregnation (CVI) approach for the deposition of monometallic-, alloyed, and core-shell structured metal co-catalysts onto the TiO2 photocatalyst. The as-synthesised metal NPs are highly dispersed on the support and show narrow size distributions, which suit photocatalysis applications. More importantly, the surfaces of the as-synthesised metal NPs are free of protecting ligands, enabling the photocatalysts to be ready to use without further treatment. The effect of the metal identity, the alloy chemical composition, and the microstructure on the photocatalytic performance has been investigated for hydrogen production and phenol decomposition. Whilst the photocatalytic H2 production performance can be greatly enhanced by using the core-shell structured co-catalyst (Pdshell-Aucore and Ptshell-Aucore), the Ptshell-Aucore modified TiO2 yields enhanced quantum efficiency but a reduced effective decomposition of phenol to CO2 compared to that of the monometallic counterparts. We consider the CVI approach provides a feasible and elegant process for the decoration of photocatalyst materials.

Light alkane oxidation using catalysts prepared by chemical vapour impregnation: tuning alcohol selectivity through catalyst pre-treatment

Heat treating Fe/ZSM-5 under hydrogen leads to high dispersion of Fe species and higher alcohol selectivity in the oxidation of alkanes, as compared to oxygen treated catalysts.

High Activity Redox Catalysts Synthesized by Chemical Vapor Impregnation

The use of precious metals in heterogeneous catalysis relies on the preparation of small nanoparticles that are stable under reaction conditions. To date, most conventional routes used to prepare noble metal nanoparticles have drawbacks related to surface contamination, particle agglomeration, and reproducibility restraints. We have prepared titania-supported palladium (Pd) and platinum (Pt) catalysts using a simplified vapor deposition technique termed chemical vapor impregnation (CVI) that can be performed in any standard chemical laboratory. These materials, composed of nanoparticles typically below 3 nm in size, show remarkable activity under mild conditions for oxidation and hydrogenation reactions of industrial importance. We demonstrate the preparation of bimetallic Pd-Pt homogeneous alloy nanoparticles by this new CVI method, which show synergistic effects in toluene oxidation. The versatility of our CVI methodology to be able to tailor the composition and morphology of supported nanoparticles in an easily accessible and scalable manner is further demonstrated by the synthesis of Pdshell-Aucore nanoparticles using CVI deposition of Pd onto preformed Au nanoparticles supported on titania (prepared by sol immobilization) in addition to the presence of monometallic Au and Pd nanoparticles.

Changes in the chemical composition of V2O5-loaded CVC-TiO2 materials with calcination temperatures for NH3-SCR of NOx

In this study, the aim was to evaluate the effect of calcinations temperature on the catalytic activity and chemical composition of V2O5/TiO2. We prepared V2O5-loaded CVC-TiO2 catalysts by a combination of chemical vapor condensation (CVC) and impregnation method at different calcination temperatures. These catalysts were analyzed for their ability to catalyze NH3-based selective catalytic reduction of NOx. Compared with V2O5 loaded P25-TiO2 (commercial). V2O5/CVC-TiO2 catalysts calcined above 200 °C exhibited better performance towards NOx conversion than that by a commercial catalyst prepared using P25-TiO2 (calcined at 500 °C). In addition, the NOx conversion rate obtained with the sample calcined at 500 °C gave the best result (90 %) at a reaction temperature of 200 °C. From the XPS results, we observed that the V4+/5+ ratio was well balanced when the V2O5 loaded CVC-TiO2 sample was calcined at 500 oC.

Investigation of thermal expansion of 3D-stitched C–SiC composites

Carbon fiber reinforced silicon carbide (C–SiC) composites are promising materials for a severe thermo-erosive environment. 3D-stitched C–SiC composites were fabricated using liquid silicon infiltration. The infiltration was carried out at 1450–1650 °C for 10–120 min in vacuum. Coefficient of thermal expansion (CTE) of the composites was determined in in-plane and through-thickness directions in the temperature range from room temperature to 1050 °C. The in-plane CTE varies in the range (0.5–2) × 10 −6/°C, while that in the through-thickness direction, it varies in the range (1.5–4) × 10 −6/°C. The effect of siliconization conditions is higher in the through-thickness direction than in the in-plane direction. The CTE values are lower than the values reported for chemical vapor impregnation based 3D C–SiC composites. An extensive microstructure study was also carried out to understand the thermal expansion behavior of the composites. It was found out that CTE behavior is closely related to the composition of the composite which in turn depends upon siliconization conditions. The best conditions were 1650 °C and 120 min.

Deposition of Ruthenium Nanoparticles on Carbon Aerogels for High Energy Density Supercapacitor Electrodes

The preparation and characterization of high surface area ruthenium/carbon aerogel composite electrodes for use in electrochemical capacitors is reported. These new materials have been prepared by the chemical vapor impregnation of ruthenium into carbon aerogels to produce a uniform distribution of adherent ≈20 Å nanoparticles on the aerogel surface. The electrochemically oxidized ruthenium particles contribute a pseudocapacitance to the electrode and dramatically improve the energy storage characteristics of the aerogel. These composites have demonstrated specific capacitances in excess of 200 F/g, in comparison to 95 F/g for the untreated aerogel.

PREPARATION OF SIC-WHISKER REINFORCED CVD-SIC

The paper describes an experimental study on the preparation ofSiC-whisker reinforced Sic-composites by Chemical Vapour Deposition (CVD) and Chemical Vapour Impregnation (CVI) with trichloromethylsilane as volatile Sic-precursor. The experimental procedure is described in terms of deposition temperature, total pressure, carrier gas composition and content of the MTS (H CSiC1)-precursor in the gas phase. The results are discussed in terms of weight gain, change in porosity and pore size distribution. Scanning electron micrographs are presented for the description of the morphology of the deposits. Tentative values on the mechanical properties of selected samples are given as room temperature flexural strength data. The process parameters to achieve whisker reinforced all SiCcomposites with about 25 vol-% remaining total porosity are described in detail.