Effect of sulfate addition on the performance of Co/Al2O3 catalysts in catalytic dehydrogenation of propane

The effect of sulfate species in propane dehydrogenation over Co/Al₂O₃ catalysts was studied. On the one hand, the interaction between SO₄²⁻ and cobalt species leads to better dispersed cobalt oxide and restrains the reduction to metallic Co species, thereby inhibiting cracking reaction. On the other hand, the initial C–H bond activation and scission are facilitated on the electron-deficient cobalt and sulfate sites, resulting in dramatically improved dehydrogenation performance. XPS, MS and XRD results show that the reduction of sulfate species to SO₂ and consequently the loss of active cobalt species contribute to the irreversible deactivation of catalyst.     

Fischer–Tropsch synthesis using Co/SiO2 catalysts prepared from mixed precursors and addition effect of noble metals

Fischer–Tropsch synthesis in Co/SiO₂ catalysts, which were prepared by mixed impregnation of cobalt (II) nitrate and cobalt (II) acetate, was studied under mild reaction conditions (Total pressure=1 MPa, H₂/CO=2, T=513 K). X-ray diffraction indicated that highly dispersed cobalt metal was the main active sites on the catalyst prepared by the same method. It was considered that the metallic crystallines, which were readily reduced from cobalt nitrate, promoted the reduction of Co²⁺ to metallic a state in cobalt acetate by H₂ spillover mechanism during the catalyst reduction process. The reduced cobalt, from cobalt acetate, was highly dispersed one and remarkably enhanced the catalytic activity. The addition of a small amount of Ru to this type of catalyst remarkably increased the catalytic activity and the reduction degree. Its turn over frequency (TOF) increased but the selectivity of CH₄ was unchanged. However, when Pt or Pd were added into catalysts, they exhibited a higher selectivity of CH₄. Although Pt and Pd hardly exerted an effect on cobalt reduction degree, they promoted cobalt dispersion and decreased the value of TOF. Characterization of these bimetallic catalysts suggested that a different contact between Co and Ru, Pt or Pd existed. Ru was enriched on the metallic cobalt surface but, Pt or Pd dispersed well in the form of Pt–Co or Pd–Co alloy.     

X-Ray photoelectron spectroscopy reference data for identification of the C3N4 phase in carbon–nitrogen films

The β-C₃N₄ phase should have a tetrahedral (sp³-bonded) structure resulting in C1s and N1s XPS peaks with only one feature at a position defined by the electronegativity of four CN bonds. In this work we determined the binding energy of the C1s and N1s XPS peaks in melamine (C₃N₆H₆). In this compound the carbon atoms have four bonds with nitrogen atoms (double and two single); the nitrogen atoms have two chemical states: CNC and CNH₂. Since the total number of chemical bonds in this compound is the same as in the hypothetical β-C₃N₄ compound, this compound is more suitable as a C1s XPS reference for the β-C₃N₄ phase. The binding energy of the C1s and N1s XPS peaks in melamine was determined to be equal to 287.9 and 399.1 eV, respectively. The binding energies were determined relative to the C1s XPS peak for carbon contamination (adventitious carbon).     

Co/Al2O3 catalysts promoted with noble metals for production of hydrogen by methane steam reforming

The effect of noble metal addition on the catalytic properties of Co/Al₂O₃ was evaluated for the steam reforming of methane. Co/Al₂O₃ catalysts were prepared with addition of different noble metals (Pt, Pd, Ru and Ir 0.3 wt.%) by a wetness impregnation method and characterized by UV–vis spectroscopy, temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) of the reduced catalysts. The UV–vis spectra of the samples indicate that, most likely, large amounts of the supported cobalt form Co species in which cobalt is in octahedral and tetrahedral symmetries. No peaks assigned to cobalt species from aluminate were found for the promoted and unpromoted cobalt catalysts. TPO analyses showed that the addition of the noble metals on the Co/Al₂O₃ catalyst leads to a more stable metallic state and less susceptible to the deactivation process during the reforming reaction. The Co/Al₂O₃ promoted with Pt showed higher stability and selectivity for H₂production during the methane steam reforming.     

Study on a cobalt silica catalyst during reduction and Fischer–Tropsch reaction: In situ EXAFS compared to XPS and XRD

The reduction of a 25 wt% Co/SiO₂ catalyst for the hydrocarbon synthesis has been followed by several techniques: XRD, TPR, XPS and in situ EXAFS. Before reduction the cobalt is present as a Co₃O₄ spinel phase. A two-step reduction of Co₃O₄ to CoO and then to Co° is observed by EXAFS. This is consistent with XPS (surface) and TPR or XRD (bulk) studies. During CO/H₂ reaction, cobalt is always in the metallic state (EXAFS). The coordination number of cobalt has been determined at each reduction step and during CO hydrogenation reaction.     

Methanol oxidation over model cobalt catalysts: Influence of the cobalt oxidation state on the reactivity

X-ray photoelectron and absorption spectroscopies (XPS and XAS) combined with on-line mass spectrometry were applied under working catalytic conditions to investigate methanol oxidation on cobalt. Two cobalt oxidation states (Co₃O₄ and CoO) were prepared and investigated as regards their influence on the catalytic activity and selectivity. In addition adsorbed species were monitored in the transition of the catalyst from a non-active state, to an active one. It is shown that the surface oxidation state of cobalt is readily adapted to the oxygen chemical potential in the CH₃OH/O₂ reaction mixture. In particular, even in oxygen-rich mixtures the Co₃O₄ surface is partially reduced, with the extent of surface reduction following the methanol concentration. The reaction selectivity depends on the cobalt oxidation state, with the more reduced samples favouring the partial oxidation of methanol to formaldehyde. In the absence of oxygen, methanol effectively reduces cobalt to the metallic state, also promoting H₂ and CO production. Direct evidence of methoxy and formate species adsorbed on the surface upon reaction was found by analysing the O 1s and C 1s photoelectron spectra. However, the surface coverage of those species was not proportional to the catalytic activity, indicating that they might also act as reaction inhibitors.     

Study of the deactivation mechanism of Al2O3-supported cobalt Fischer-Tropsch catalysts

The influence of water on alumina-supported cobalt catalysts has been studied. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing different concentrations of water vapour. Supporting model studies were carried out using H₂O/H₂ feeds in conjunction with XPS and gravimetry. Rapid deactivation occurs on Re-promoted CO/Al₂O₃ catalysts when H₂/CO/H₂O feeds are used, whereas unpromoted CO/Al₂O₃ shows more stable activity. The results from the gravimetric studies suggest that only a small fraction of the bulk cobalt metal initially present reoxidizes to cobalt oxide during reaction. However, the XPS results indicate significant reoxidation of surface cobalt atoms or highly dispersed cobalt phases, which is likely to be the cause of the observed deactivation. Rhenium is shown to have a marked effect on the extent of reoxidation of alumina-supported cobalt catalysts.     

Photokatalytische Bildung von Wasserstoff aus Thiolen in Gegenwart von Vitamin B12-Modellverbindungen mit Azid als photochemischem Opferliganden

Photocatalytic Hydrogen Formation from Thioles in the Presence of Vitamin-B₁₂ Model Complexes with Azide as Photochemical Sacrificial Ligand The photolysis of [N₃Co(chelat)B] complexes ( 1–3 ) (chelat = dimethylglyoxime, dmg; N,N′-o-phynylenebis(salicylidenimine), salphen; N,N′-ethylene-bis(salicylidenimine), salen; B = pyridine) leads by homolytic cleavage of the Co–N₃ bond to both coordinatively unsaturated cobalt(II) chelates [Co(chelat)B] and N₃ ligand radicals that undergo fast decay to dinitrogen. The photolysis of the cobalt (III) complexes 1–3 in the presence of thiophenole and other thioles proceeds catalytically and yields the corresponding disulphides and dihydrogen. The mechanism of this photocatalytic generation of dihydrogen is due to the catalytic activity of the coordinatively unsaturated cobalt(II) species formed photochemically. A photocatalytic cycle is proposed describing the generation of hydrogen. Possible photochemical and thermal steps of that cycle are discussed.     

Palladium/Cobalt Coated on Multi‐Walled Carbon Nanotubes as an Electro‐catalyst for Oxygen Reduction Reaction in Passive Direct Methanol Fuel Cells

This work reports the synthesis of Pd‐based alloy electrocatalysts of Co supported on multi‐walled carbon nanotubes (MWCNTs) and their evaluation as cathode materials in a passive direct methanol fuel cell (PDMFC). The X‐ray diffraction (XRD) analysis showed well‐defined reflections corresponding to a face centered cubic phase of palladium. As compared to the Pd/MWCNT electrocatalyst, the bimetallic alloy electrocatalysts with the different Pd_xCo atomic ratios showed highly enhanced mass activity (MA) for the oxygen reduction reaction (ORR); however, the significant enhancement in the specific activity (SA) by a factor of about 1.2–5.6 for the ORR was found on the Pd_xCo alloy electrocatalysts in the presence and absence of methanol electrolyte solution. This enhancement SA in of the Pd‐based electrocatalysts was correlated to the changes in the lattice parameter and Pd_xCo surface composition. Surface area changes of Pd‐based electrocatalysts supported on MWCNT were evaluated using an accelerated durability test (ADT). The results obtained using the ADT were correlated to the performance of the Pd‐based electrocatalysts in the PDMFC. A better performance was obtained for the cell using Pd₃Co/MWCNT (2.53 mW cm^–2) compared to Pd/MWCNT (1.64 mW cm^–2) and Pt/C‐Electrochem (1.20 mW cm^–2) as cathode in the PDMFC. In the presence and absence of methanol the impedance Bode spectra showed one time constant that associated to follow a four electron pathway.     

Steam resistant CoLa-mordenite catalysts for the SCR of NOx with CH4

The stabilization of Co-mordenite catalysts through lanthanum exchange is reported here. The effect of exchange order and calcination conditions upon the reduction of NO_x to N₂ at 500 °C was tracked during 400 h on a stream containing NO_x, CH₄, O₂ and 10% H₂O. Both the fresh and used catalysts were characterized through TPR, Raman spectroscopy, FTIR spectroscopy using CO as probe molecule, and XPS. These techniques revealed that the CoLa-mordenite catalysts which were not affected by the severe hydrothermal treatment showed no sign of Co or La migration out of the exchange positions. Instead, those that rapidly deactivated showed the formation of cobalt oxides and, in some cases, the migration of the cations to other exchange positions. The presence of exchanged lanthanum seems to preserve the integrity of the zeolite structure preventing the migration of cobalt ions with the subsequent formation of cobalt oxides which favors the reaction of methane with O₂, thus decreasing N₂ production.     

Combined X-ray study of lithium (tin) cobalt oxide matrix negative electrodes for Li-ion batteries

The lithium insertion behaviours of the oxides Co₃O₄ and Co₂SnO₄ were studied using a range of electrochemical, spectroscopic and diffraction techniques. Co K-edge EXAFS studies on the Co₃O₄ oxide showed that the reversible lithium insertion is coupled with changes in cobalt oxidation state. On lithium insertion, Co₃O₄ is reduced to yield Co(II) and yields only metallic cobalt species on complete reduction. On lithium removal an oxide of Co is formed, which from coulometry should be CoO, however, EXAFS indicates the short range structure is quite different to that of the rocksalt CoO. The long range structure of the matrix is amorphous according to XRD. The EXAFS and XRD data also revealed that both the metallic and oxide phases were disordered, having low co-ordination numbers and large shell spacings, and that there was an initial reduction to CoO before full reduction to metallic Co. The electrochemical behaviour of Co₂SnO₄ cells was more reminiscent of that of SnO₂ than that of Co₃O₄, but did exhibit significant differences due to the presence of cobalt. EXAFS on Co₂SnO₄ cells revealed that Co is reduced to metallic cobalt on the initial discharge, but that it does not convert back to an oxide on cycling even though the electrochemical treatment was the same as for Co₃O₄. Together the EXAFS and Mössbauer data show that the Co and Sn are reduced concurrently, and that some of the Sn remains in the oxidised form. In summary, we have a surprising result in that the presence of the tin dramatically changes the redox behaviour of the cobalt. In a matrix derived from a cobalt oxide spinel, cobalt undergoes redox cycling, whereas in a matrix derived from a cobalt tin oxide spinel, the cobalt does not cycle whilst the tin does.     

TiO2 promoted Co/SiO2 catalysts for Fischer–Tropsch synthesis

The addition of small amount of TiO₂ to silica-supported cobalt catalysts significantly increasing the dispersion of cobalt and Co metallic surface area resulting in the remarkable enhancement of the Fisher–Tropsch synthesis (FTS) activity in the slurry-phase reaction. The addition of TiO₂ adjusted the interaction between cobalt and silica support quite well to realize the favorite dispersion and reduction degree of supported cobalt, leading to high catalytic activity in FTS. The properties of various catalysts were characterized by in-situ DRIFT, XRD, TPR, N₂ physisorption and H₂ chemisorption.     

Spectral,thermal stability and antibacterial studies of copper,nickel and cobalt complexes of N-methyl-N-phenyl dithiocarbamate

Copper(II), cobalt(II) and nickel(II) bis(N-methyl-N-phenyl dithiocarbamate) complexes having the general formula [M{S₂CN(MePh)}₂] (where M?=?Cu, Co and Ni) have been prepared and characterized by spectral and thermal analysis. The IR spectra suggest that coordination of dithiocarbamate (DTC) occurred through the two sulfur atoms in a symmetrical bidentate fashion. The electronic spectra, conductance measurement and magnetic moment analysis support the proposed geometry for the electronically dilute complexes. The results of the thermal analysis showed that after dehydration, a one-step decomposition pattern leading to the formation of respective metal sulfide as the end-product occurred. The results are consistent with the proposed composition of the complexes. The in vitro antibacterial activity of the complexes was investigated against strains of gram-negative Escherichia coli, Klebsiella oxytoea and Pseudomonas aureginosa, and gram-positive Bacillus cereus, Staphylococcus aureus and Protues mirabilis. The antibacterial activity of the complexes compared favorably with that of streptomycin and augmentine against S. aureus and B. cereus. The cobalt complex had the best antibacterial activity against the test compounds with inhibitory zone range of 11–14.5?mm.     

Characterization and photonic properties for the Pt-fullerene/TiO2 composites derived from titanium (IV) n-butoxide and C60

In this study, the structural variations, surface states, and mass transformations of fullerene [C₆₀] derivatives were investigated through the preparation of Pt-decorated oxidized fullerene and a Pt-fullerene/TiO₂ composite and comparison to an oxidized fullerene [C₆₀O]. These derivatives were synthesized with an improved oxidation method using m-chloroperbenzoic acid (MCPBA). Weak and strong peaks of metallic platinum and titanium dioxide, along with weak pristine fullerene [C₆₀] peaks, were observed in the XRD patterns for the Pt-fullerene and Pt-fullerene/TiO₂ composite. SEM micrographs for the metallic Pt-fullerene and Pt-fullerene/TiO₂ composite indicated that practically all the platinum and titanium dioxide that were introduced were located on the carbon cages and consequently, were dispersed into very small crystallites with growth of platinum metals and titanium dioxide. The EDX spectra of Pt-fullerene and Pt-fullerene/TiO₂ composite showed the presence of C, O, and Pt, with strong Ti peaks. From the MALDI-TOF mass spectra, the differences in the spectra for the three kinds of fullerene derivatives were due to oxidation including chemical bonding and interposing of metallic platinum and titanium dioxide in the fullerene [C₆₀] molecules. And, absorption property demonstrated by UV–vis diffuse reflectance method. From the photocatalytic results, the excellent activity of the Pt-fullerene/TiO₂ composites for organic dye and UV irradiation time could be attributed to the synergetic effects between photocatalysis of the supported TiO₂ and absorptivity of the platinum and fullerene.     

Structure and electrochemical behaviors of a series of Co-B alloys

A series of Co_xB (x = 1, 2, 3) alloys were prepared by arc melting, the phase structure of the alloys were characterized by X-ray diffraction (XRD). The electrochemical experimental results demonstrated that the Co_xB (x = 1, 2, 3) series alloys showed excellent cycling stability, the capacity retention was 94.2%, 93.6% and 93.8% in the 100th cycle, respectively, as the cobalt content decreased. The CoB alloy electrode showed very good electrochemical reversibility in cyclic voltammetry (CV) curves, the oxidation and reduction peaks resembled the pure cobalt element powder electrode. The electrode mechanism was discussed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), using pure CoB alloy cast electrode. From the SEM, after first and second cycle, the surface became porous and pulverous; also, the oxidation state of Co changed through XPS, after second cycle, the Co of 0 oxidation state could not be found on the surface. Based on the experiment, a proper mechanism was proposed: on this condition, the discharge capacity may due to the Co(OH)₂/Co reaction, which happened on the porous surface as the boron dissolved when the cycle increased.     

The catalytic removal of CO and NO over Co-Pt(Pd, Rh)/γ-Al2O3 catalysts and their structural characterizations

A series of Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts were prepared by successive wetness impregnation. The catalytic activities for CO oxidation, NO decomposition and NO selective catalytic reduction (SCR) by C₂H₄ over the samples calcined at 500°C and reduced at 450°C were determined. The activities of the samples calcined at 750°C and reduced at 450°C for NO selective catalytic reduction (SCR) by C₂H₄ were also determined. All the samples were characterized by XRD, XPS, XANES, EXAFS, TPR, TPO and TPD techniques. The results of activity measurements show that the presence of noble metals greatly enhances the activity of Co/γ-Al₂O₃ for CO or C₂H₄ oxidation. For NO decomposition, the H₂-reduced Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts exhibit very high activities during the initial period of catalytic reaction, but with the increase of reaction time, the activities decrease obviously because of the oxidation of surface cobalt phase. For NO selective reduction by C₂H₄, the reduced samples are oxidized more quickly by the excess oxygen in reaction gas. The oxidized samples possess very low activities for NO selective reduction. The results of XRD, XPS and EXAFS indicate that all the cobalt in Co-Pt(Pd, Rh)/γ-Al₂O₃ has been reduced to zero valence during reduction by H₂ at 450°C, but in Co/γ-Al₂O₃ only a part of the cobalt has been reduced to zero valence, the rest exists as CoAl₂O₄-like spinel which is difficult to reduce. For the samples calcined at 750°C, the cobalt exists as CoAl₂O₄ which cannot be reduced by H₂ at 450°C and possesses better activities for NO selective reduction. The results of XANES spectra show that the cobalt in Co/γ- Al₂O₃ has lower coordination symmetry than that in Co-Pt(Pd, Rh)/γ-Al₂O₃. This difference mainly results from the distorting tetrahedrally- coordinated Co²⁺ ions which have lower coordination symmetry than Co⁰ in the catalysts. The coordination number for the Co-Co shell from EXAFS has shown that the cobalt phase is highly dispersed on Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts. The TPR results indicate that the addition of noble metals to Co/γ- Al₂O₃ makes the TPR peaks shift to lower temperatures, which implies the spillover of hydrogen species from noble metals to cobalt oxides. The oxygen spillover from noble metals to cobalt is also inferred from the shift of TPO peaks to lower temperatures and the increased amount of desorbed oxygen from TPD. For CO oxidation, the Co⁰ is the main active phase. For NO decomposition and selective reduction, Co⁰ is also catalytically active, but it can be oxidized into Co₃O₄ by oxygen at high reaction temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Efficient solar-light-driven photoelectrochemical water oxidation of one-step in-situ synthesized Co-doped g-C3N4 nanolayers

Cobalt-doped g-C₃N₄ (Co-g-CN) nanolayers were prepared by a single-step thermal treatment with urea and cobalt nitrate. Different amounts of cobalt nitrate were tested to optimize the amount of cobalt dopant in the g-C₃N₄ (g-CN) matrix. Several characterization methods were used to explore the structural and optical properties along with the photoelectrochemical (PEC) performance. X-ray diffraction and Fourier transform infrared studies confirmed that g-CN nanolayers were successfully doped with cobalt without disturbing the basic 2-D structure and tris-triazine units of g-CN. Furthermore, microscopy images demonstrated that the cobalt effectively transformed the short nanosheets into long nanolayers. The cobalt-doping enhanced the visible absorption of g-CN and tuned the bandgap from 2.71 to 2.62 eV. An X-ray photoelectron spectroscopy (XPS) investigation discovered that cobalt entered into the g-CN network as Co²⁺ ions. XPS valence band spectra gave information on the modification in the valence and conduction band edge potentials due to cobalt doping. The photoluminescence intensity from the Co-g-CN samples was lesser than that from g-CN nanosheets, and the PEC activity of the Co-g-CN nanolayers was greater than that of as-prepared g-CN nanosheets. Co-g-CN samples prepared with 15 mg of cobalt nitrate hexahydrate showed a PEC performance of 3.2522 mA/cm², which was greater than that of g-CN nanosheets (1.9246 mA/cm²). The better PEC performance was ascribed to the synergistic consequence of the higher visible absorption obtained by tuning the bandgap and the host–guest interactions between cobalt and g-CN.     

Ozone Decomposition over Cobalt Supported on Olive Stones Activated Carbon: Effect of Preparation Method on Catalyst Activity

Aqueous ozone decomposition was studied over highly dispersed cobalt nanoparticles supported on olive stones activated carbon (AC) prepared by: wetness impregnation (Co/AC_w) and incipient wetness impregnation (Co/AC_iw) with respect to pore volume. Nitrogen adsorption-desorption at 77K, SEM, XRD and XPS analyses were used to characterize the catalysts. Analyses results show that Co/AC_w was more uniformly dispersed on the AC than Co/AC_iw. The effect of the presence of tert-butanol as radical scavenger was also studied. Higher catalytic activity was measured for Co/AC_w than Co/AC_iw. Ozone decomposition extent goes to 99% in only 3 min in the presence of Co/AC_w compared to 60% and 58% using Co/AC_iw catalyst and AC, respectively.     

Chemical bonding in carbon nitride films studied by X-ray spectroscopies

Carbon nitride films are deposited using dc magnetron sputtering in a N₂ discharge. The nature of chemical bonding of the films is investigated using X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure, and X-ray emission spectroscopy. X-Ray photoelectron spectroscopy spectra show that N1s binding states depend on substrate temperature, in which two pronounced peaks can be observed. The near edge X-ray absorption fine structure at C1s and N1s exhibits a similar absorption profile in the π* resonance region, but the σ* resonance is sharper in the N1s spectra. Resonant N K-emission spectra show a strong dependence on excitation photo energies. Compared XPS N1s spectra with recent theoretical calculations by Johansson and Stafstrom, two main nitrogen sites are assigned in which N bound to sp³ hybridized C and sp² hybridized C, respectively. The correlation of X-ray photoelectron, X-ray absorption, and X-ray emission spectra for N in carbon nitride films is also discussed.     

CO oxidation in the presence of hydrogen on Au/TiO2 catalyst: an FTIR–MS study

A new and simple method for obtaining highly dispersed Co/ZrO₂ catalyst is described. The presence of ethylenediamine during the preparation of Co/ZrO₂ was studied and compared with a reference catalyst conventionally prepared. Addition of an aqueous solution of ethylenediamine to a cobalt nitrate solution had a dramatic effect on the catalytic performance of the catalyst as compared with a reference catalyst. This promotional effect was explained in terms of higher cobalt dispersion in the catalysts using ethylenediamine. The reason why ethylenediamine improves dispersion of the cobalt species was explained in terms of the size of the stable complex ions which could be formed in situ during impregnation. The best catalytic results were also explained in terms of Co-support interaction since new cobalt species were reducible at lower temperatures.