Platinum supported on highly-dispersed ceria on activated carbon for the total oxidation of VOCs

Catalysts consisting in platinum supported on cerium oxide highly dispersed on activated carbon, with a Pt loading of 1 wt.% and ceria loadings of 5, 10 and 20 wt.% have been prepared by impregnation method and characterized by several techniques (N2 adsorption at 77 K, ICP, XRD, H2-TPR and XPS). Their catalytic behavior has been evaluated in the total oxidation of ethanol and toluene after reduction at 473 K. The obtained results show that the prepared catalysts have better performances than platinum supported on bulk CeO2. The best catalytic performance was obtained for 10 wt.% ceria loading, likely due to an optimum synergistic interaction between highly dispersed cerium oxide and platinum particles. Pt-10Ce/C achieves total conversion of ethanol and toluene to CO2 at 433 K and 453 K, respectively, and shows no deactivation during a test for 100 h. Under humid conditions (relative humidity, RH, of 40 and 80%), the activity was only slightly influenced due to the hydrophobic character of the activated carbon support, which prevents the adsorption of water.

Effect of preparation method of palygorskite-supported Fe and Ni catalysts on catalytic cracking of biomass tar

In this study, the effect of catalyst preparation and additive precursors on the catalytic decomposition of biomass using palygorskite-supported Fe and Ni catalysts was investigated. The catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is concluded that the most active additive precursor was Fe(NO3)3·9H2O. As for the catalyst preparation method, co-precipitation had superiority over incipient wetness impregnation at low Fe loadings.

Infrared study of the adsorption of formic acid on silica-supported copper and oxidised copper catalysts

Infrared spectra are reported of formic acid adsorbed at 300 K on a reduced copper catalyst (Cu/SiO2) and a copper surface which had been oxidised by exposure to nitrous oxide. Formic acid was weakly adsorbed on the silica support. Ligation of formic acid to the copper surface occurred only on the reduced catalyst. Dissociative adsorption resulted in the formation of unidentate formate on the oxidised catalyst. The presence of reduced copper metal instigated a rapid reorientation to a bidentate formate species.

Carbon dioxide reforming of methane to produce synthesis gas over metal-supported catalysts: State of the art

Carbon dioxide reforming of methane produces synthesis gas with a low hydrogen to carbon monoxide ratio, which is desirable for many industrial synthesis processes. This reaction also has very important environmental implications since both methane and carbon dioxide contribute to the greenhouse effect. Converting these gases into a valuable feedstock may significantly reduce the atmospheric emissions of CO2 and CH4. In this paper, we present a comprehensive review on the thermodynamics, catalyst selection and activity, reaction mechanism, and kinetics of this important reaction. Recently, research has centered on the development of catalysts and the feasible applications of this reaction in industry. Group VIII metals supported on oxides are found to be effective for this reason. However, carbon deposition causing catalyst deactivation is the major problem inhibiting the industrial application of the CO2/CH4 reaction. Ni-based catalysts impregnated on certain supports show carbon-free operation and thus attract much attention. To develop an effective catalyst for CO2 reforming of CH4 and accelerate the commercial application of the reaction, the following are identified to be the most important areas for future work: (1) selection of metal and support and studying the effect of their interaction on catalyst activity; (2) the effect of different promoter on catalyst activity; (3) the reaction mechanism and kinetics; and (4) pilot reactor performance and scale-up operation.

Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Catalytic role of pre-adsorbed CO in platinum-based catalysts : the reduction of SO 2 by CO on Pt l Au m (CO) n

Using density functional theory, we have investigated the catalytic properties of bimetallic complex catalysts PtlAum(CO)n (l + m = 2, n = 1–3) in the reduction of SO2 by CO. Due to the strong coupling between the C-2p and metal 5d orbitals, pre-adsorption of CO molecules on the PtlAum is found to be very effective in not only reducing the activation energy, but also preventing poisoning by sulfur. As result of the coupling, the metal 5d band is broadened and down-shifted, and charge is transferred from the CO molecules to the PtlAum. As SO2 is adsorbed on the catalyst, partial charge moves to the anti-σ bonding orbitals between S and O in SO2, weakening the S–O bond strength. This effect is enhanced by pre-adsorbing up to three CO molecules, therefore the S–O bonds become vulnerable. Our results revealed the mechanism of the excellent catalytic properties of the bimetallic complex catalysts.

Polymer supported metal complexes as catalysts for oxidation of thiosalts by molecular oxygen IV. Quaternised poly(4-vinyl pyridine) complexes with Cu2+ as template

Copper(II) complexes of quaternised poly(4-vinylpyridine) (PVP) of different degrees of quaternisation and copper content have been prepared by crosslinking the polymer with 1,2-dibromoethane in the presence of Cu2+ ion as template. The stability constant of the PVP---Cu(II) complexes is found to increase with the degree of crosslinking quaternisation of the resin, but the rate at which Cu2+ is adsorbed by the resin decreases. An optimum combination of both stability and rate can be achieved with a moderate degree (31%) of crosslinking. A kinetic study reveals that quaternisation increases significantly the catalytic activity of the complex for the oxidation of S2O2−3 by O2 compared with PVP----Cu(II) without quaternisation, but it deactivates the complex for the oxidation of both S3O2−6 and S4O2−6. The batch reactor oxidation kinetics at pH 2.16, where the rate is observed to be maximum, is well explained by the Langmuir—Hinshelwood model assuming the coordination of both O2 and thioanion to Cu(II) as a precursor to the oxidation reaction.

Single atom (Pd/Pt) supported on graphitic carbon nitride as efficient photocatalyst for visible-light reduction of carbon dioxide

Reducing carbon dioxide (CO2) to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single palladium/platinum (Pd/Pt) atoms supported on graphitic carbon nitride (g-C3N4), i.e. Pd/g-C3N4 and Pt/g-C3N4, acting as photocatalysts for CO2 reduction were investigated by density function theory (DFT) calcu-lations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, depositing atom catalysts on g-C3N4 significantly enhances the visible light absorption, rendering them ideal for visible light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.

Synergitic Promotion of Electrooxidation of Methanol of Carbon-Supported PT-SN Catalysts

Electrooxidation of methanol in sulphuric acid on carbon-supported electrodes containing Pt-Sn bimetal catalysts prepared by an in-situ route is reported, The catalysts have been characterized employing chemical analyses, XRD, and XANES data in conjunction with electrochemistry. This study suggests that the Sn content in Pt-Sn bimetals produces: (i) a charge transfer from Sn to Pt and (ii) an increase in the coverage of adsorbed methanolic residues with the Sn content. From the electrode-kinetics data, it is inferred that while the electrodes of (3:3) Pt-Sn/C catalyst involve a 2-electron rate-limiting step akin to Pt/C electrodes, it is shifted to only 1-electron on (3:2) Pt-Sn/C, (3:3) Pt-Sn/C, and (3:4) Pt-Sn/C electrodes.

Oxidation and decomposition of NH3 over combustion synthesized Al2O3 and CeO2 supported Pt, Pd and Ag catalysts

The catalytic oxidation and decomposition of NH3 have been carried out over combustion synthesized Al2O3 and CeO2 supported Pt, Pd and Ag catalysts using temperature programmed reaction (TPR) technique in a packed bed tubular reactor. Metals are ionically dispersed over CeO2 and fine metal particles are found on Al2O3. NH3 oxidation occurs over 1% Pt/Al2O3, 1% Pd/Al2O3 and 1% Ag/Al2O3 at 175, 270 and 350 C respectively producing N-2, NO, N2O and H2O, whereas 1% Pt/CeO2, 1% Pd/CeO2 and 1% Ag/CeO2 give N-2 along with NO, N2O and H2O at 200, 225 and 250degreesC respectively. N-2 predominates over other nitrogen-containing products during the reaction on all catalysts. At less O-2 concentration, N-2 and H2O are the only products obtained during NH3 Oxidation. NH3 decomposition over all the catalysts occurs above 450degreesC.

New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate Is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 degrees C with Pt-CeO(2) catalyst and at 50 degrees C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Gasoline-range hydrocarbon synthesis over cobalt-based Fischer-Tropsch catalysts supported onSiO2/HZSM-5

Two types of SiO2 with different mesopore size and HZSM-5 zeolite were used to prepare hybrid supported cobalt-based catalysts. The textual and structural properties of the catalysts were studied using N-2 physisorption, X-ray diffraction (XRD), and H-2 temperature-programmed reduction (TPR) techniques. Fischer-Tropsch synthesis (FTS) performances of the catalysts were carried out in a fixed-bed reactor. The combination effects of the meso- and micropores of the supports as well as the interaction between supports and cobalt particles on FTS activity are discussed. The results indicate that the catalyst supported on the tailor-made SiO2 and HZSM-5 hybrid maintained both meso- and micropore pores during the preparation process without HZSM-5 particles agglomerating. The mesopores provided quick mass transfer channels, while the micropores contributed to high metal dispersion and accelerated hydrocracking/hydroisomerization reaction rate. High CO conversion of 83.9% and selectivity to gasoline-range hydrocarbons (C-5-C-12) of 55%, including more than 10% isoparaffins, were achieved simultaneously on this type of catalyst.