Olefin selective carbon-supported K-Fe-Mn CO hydrogenation catalysts: A kinetic,calorimetric, chemisorption,infrared and Mössbauer spectroscopic investigation

Carbon-supported Fe, Fe-Mn, and K-Fe-Mn catalysts derived from stoichiometric mixed-metal carbonyl clusters were pretreated at either 473 K or 673 K in hydrogen. Chemisorption and kinetic measurements were conducted following these pretreatments. The iron remained highly dispersed at all times except after high temperature reductions when potassium was present. The single promotion by either Mn or K increases the olefin/paraffin ratio, while the doubly promoted catalyst gave very high selectivities for light olefins. Isothermal, integral heats of adsorption of CO were determined at 300 K, and they increased from 15 kcal/mole for Fe₃/C to nearly 17 kcal/mole for both the singly promoted Fe₂Mn/C and KFe₃/C catalysts to 21 kcal/mole for the doubly promoted KFe₂Mn/C sample. A model of the decomposition of these carbonyl clusters is proposed based on calorimetric, Mössbauer effect spectroscopic and diffuse reflectance Fourier transform infrared spectroscopic studies. The state of the MnO_x and K phases on the iron surface, as well as the Fe crystallite size, appears to play a dominant role in determining the catalytic behavior.     

Use of catalytic reactions to probe Mg-Al mixed oxide surfaces

The atmospheric hydroformylations of ethylene and propylene were investigated over SiO₂-supported Rh₄(CO)₁₂, Co₂(CO)₈, Rh₂Co₂(CO)₁₂ and RhCo₃(CO)₁₂-derived catalysts. The bimetal cluster-derived catalysts showed excellent activities for the formation of oxygenates. In situ IR study on partially dehydroxylated SiO₂-supported RhCo₃(CO)₁₂ suggested that the bimetal cluster framework may be preserved after decarbonylation under H₂ at 623 K and may be recarbonylated at room temperature. A strong physisorption of RhCo₃ (CO)₁₂ on SiO₂ is proposed, due to a nucleophilic attack of surface oxygen on the Co atoms, which promotes a metal-support interaction and thus stabilizes the bimetal cluster framework. A subcarbonyl bimetal cluster is thought to be the actual catalytic species on the surface.     

CO hydrogenation towards higher alcohols catalysed on SiO2-grafted and zeolite-entrapped Ru,Co and RuCo bimetallic clusters: Their EXAFS and FTIR characterization and catalytic performances

Some Ru and Co carbonyl clusters in zeolite pores such as Ru₃(CO)₁₂/NaY, [HRu₆(CO)₁₈]^–/NaY, [Ru₆(CO)₁₈]^2–/NaX, Co₄(CO)₁₂/NaY and Co₆(CO)₁₆/NaY were prepared by the ship-in-bottle technique, and characterized by FTIR and EXAFS. The RuCo bimetallic carbonyl cluster was prepared by reductive carbonylation of the oxidized RuCo/NaY, which provides the proposed assignment to [HRUCo₃(CO)₁₂]/NaY. The tailored Ru, RuCo and Co catalysts were prepared by H₂ reduction from the precursors, e.g. Ru, RuCo bimetallic and Co carbonyl clusters impregnated on SiO₂ and entrapped in NaY and NaX zeolites. The RuCo bimetallic carbonyl cluster-derived catalysts showed substantially higher activities and selectivities for oxygenates such as C₁–C₅ alcohols in CO hydrogenation (CO/H₂ = 0.33-1.0, 5 bar, 519–543 K). By contrast, hydrocarbons such as methane were preferentially obtained on the catalysts prepared from Ru₆, Ru₃ and Co₄ carbonyl clusters and provided lower CO conversion and poor selectivities for oxygenates. The RuCo bimetals are proposed to be associated with the selective formation of higher alcohols in CO hydrogenation.     

SiO2‐supported bimetallic Rh–Co catalysts derived from [Rh(CO)2Cl]2 and cobalt carbonyls

According to the results of IR characterization and catalytic study in ethylene hydroformylation, bimetallic Rh–Co catalysts can be efficiently prepared from [Rh(CO)₂Cl]₂ and cobalt carbonyls by co‐impregnation on SiO₂. The reaction of Co₂(CO)₈ with [Rh(CO)₂Cl]₂ (Rh : Co = 1 : 3 atomic ratio) gives rapidly RhCo₃(CO)₁₂ on the surface of SiO₂. Although Co₄(CO)₁₂ is not reactive with [Rh(CO)₂Cl]₂ on SiO₂ to form directly RhCo₃(CO)₁₂, an equivalent bimetallic catalyst can be easily obtained from ([Rh(CO)₂Cl]₂ + Co₄(CO)₁₂)/SiO₂ or its derivative (Rh⁺ + Co²⁺)/SiO₂ (Rh : Co = 1 : 3 atomic ratio) under reducing conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ship-in-Bottle synthesis of Pt9-Pt15 carbonyl clusters inside NaY and NaX zeolites,in-situ FTIR and EXAFS characterization and the catalytic behaviors in13CO exchange reaction and NO reduction by CO

[Pt₉(CO)₁₈]^2–/NaY (orange-brown, 2056 and 1798 cm^–1), [Pt₁₂(CO)₂₄]^2–/NaY (dark-green, 2080 and 1824 cm^–1 and [Pt₁₅(CO)₃₀]^2–/NaX (yellow-green, 2100 and 1865 cm^–1) were stoichiometrically synthesized by the reductive carbonylation of [Pt(NH₃)₄]²⁺/NaY, Pt²⁺/NaY and Pt²⁺/NaX, respectively. The IR bands characteristic of their linear carbonyls shift to higher frequencies whereas the bridging CO bands to lower frequencies, compared with those on the external zeolites and in solution. In-situ FTIR studies suggested that the subcarbonyl species such as PtO(CO) and Pt₃(CO)₃(₂ –CO)₃ are formed as the proposed intermediates towards [Pt₁₂(CO)₂₄]^2–/NaY in the reductive carbonylation of Pt²⁺/NaY.¹³CO exchange reaction preceded with the different intrazeolite Pt carbonyl species in the following order of activity at 298–343 K: Pt₃(CO)₃(₂ –CO)₃/NaY PtO(CO)/NaY>[Pt₉(CO)₁₈]^2–/NaY >[Pt₁₂(CO)₂₄]^2–/NaY. Pt-L₃-edge EXAFS measurment for these synthesized samples demonstrated that they are consistent with the Pt carbonyl clusters having trigonal prismatic Pt₉ and Pt₁₂ frameworks infered to a series of the Chini complexes such as [NEt₄]₂[Pt₃(CO)₆] _n ( _n = 3–5). The intrazeolite Pt₉ and Pt₁₂ carbonyl clusters exhibited higher cataytic activity in NO reduction by CO towards N₂ and N₂O at 473 K, compared with those on the conventional Pt/Al₂O₃ catalysts. The mechanism of intrazeolite Pt₉-Pt₁₅ carbonyl cluster formation are discussed in terms of the intrazeolite basicity and acidity.On leave from National Laboratory for Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 129 Street, China.     

Catalytic Oxidation of CO Gas over Nanocrystallite Cu x Mn1−x Fe2O4

The catalytic oxidation of CO over nanocrystallite Cu _x Mn_(1−x)Fe₂O₄ powders was studied using advanced quadruple mass gas analyzer system. The oxidation of CO to CO₂ was investigated as a function of reactants ratio and firing temperature of ferrite powders. The maximum CO conversion was observed for ferrite powders which have equal amount of Cu²⁺ and Mn²⁺ (Cu_0.5Mn_0.5Fe₂O₄). The high catalytic activity of Cu_0.5Mn_0.5Fe₂O₄ can be attributed to the changes of the valence state of catalytically active components of the ferrite powders. The firing temperature plays insignificant role in the catalytic activity of CO over nanocrystallite copper manganese ferrites. The mechanism of catalytic oxidation reactions was studied. It was found that the CO catalytic oxidation reactions on the surface of the Cu _x Mn_1−x Fe₂O₄ was done by the reduction of the ferrite by CO to the oxygen deficient lower oxide then re-oxidation of this phase to the saturated oxygen metal ferrite again.     

Effect of large cations (La and Ba) on the catalytic performance of Mn-substituted hexaaluminates for N2O decomposition

Mn-substituted La-hexaaluminate (LaMn_xAl_(12−x)O₁₉) and Ba-hexaaluminate (BaMn_xAl_(12−x)O₁₉) catalysts were prepared using the carbonates route and investigated for high-concentration of N₂O decomposition. It was for the first time found that the Ba-hexaaluminate exhibited higher activity than the La-hexaaluminate at a given Mn content, both of which were much more active than Mn/Al₂O₃ after being subjected to high-temperature (1400 °C) treatment. The catalytic activity varied with the Mn content and attained the best one at x = 1. X-ray diffraction (XRD) characterizations showed that a small amount of Mn (up to x = 1) promoted greatly the formation of phase-pure hexaaluminate, while excess Mn caused formation of catalytically inactive impurity phases, such as LaAlO₃, BaAl₂O₄, Mn₃O₄, and LaMnO₃, which covered partially the active sites and then led to a loss of the activity. UV–visible spectra showed that Mn²⁺ preferentially enter tetrahedral Al sites at a low Mn content (x = 0.5) for the La-hexaaluminate, which is quite different from the case of Ba-hexaaluminate where Mn³⁺ can substitute octahedral Al sites even at x = 0.5. Such a difference in the number of catalytically active Mn³⁺ sites in the octahedral position should be responsible for the higher activity of the Mn-substituted Ba-hexaaluminate.     

A highly active bimetallic supported Rh–Co hydroformylation catalyst prepared from RhCl3 and Co2(CO)8

The preparation of a highly active bimetallic SiO₂‐supported Rh–Co catalyst from RhCl₃ and Co₂(CO)₈ (Rh:Co= 1 : 3 atomic ratio) has been studied by IR spectroscopy and ethylene hydroformylation, etc. Two steps are involved in the preparative process: (1) surface‐mediated synthesis of Rh⁺(CO)₂/SiO₂ from calcined RhCl₃/SiO₂; (2) impregnation of Rh⁺(CO)₂/SiO₂ with a Co₂(CO)₈ solution followed by H₂ reduction at 623 K. The IR results of reductive carbonylation of calcined RhCl₃/SiO₂ have been compared to those of uncalcined RhCl₃/SiO₂ at 373 K. In situ IR observations, extraction results and elemental analysis suggest that approximately 50% of RhCl₃ are transformed to Rh₂O₃ on the SiO₂ surface and that calcined RhCl₃/SiO₂ is converted to a mixture of [Rh(CO)₂Cl]₂ and [Rh(CO)₂O₂ (O_s: surface oxygen) under CO at 373 K. When this SiO₂‐supported mixture was submitted to impregnation with a Co₂(CO)₈ solution at room temperature, IR study and elemental analysis show that [Rh(CO)₂Cl]₂ reacts easily with Co₂(CO)₈ on the surface to give RhCo₃(CO)₁₂, whereas [Rh(CO)₂O₂ does not react with Co₂(CO)₈. Catalytic study in steady‐state ethylene hydroformylation shows that a catalyst thus derived is more active than a catalyst derived from RhCo₃(CO)₁₂/SiO₂ and a catalyst derived by coimpregnation of [Rh(CO)₂Cl]₂ and Co₂(CO)₈ on SiO₂. This result suggests that the high rhodium dispersion of [Rh(CO)₂O₂ plays a crucial role in the formation of highly dispersed bimetallic Rh–Co sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

On the nature of catalyst promotion by manganese in CO hydrogenation to oxygenates over RhMn/NaY

CO hydrogenation over Mn promoted Rh/NaY catalysts was studied at 10 bar and 250°C. Significant selectivity to oxygenates, mainly ethanol and ethyl acetate, was obtained after neutralizing the protons that are formed during reduction of Rh ions. Layered bed experiments show that protons act as sites catalyzing secondary reactions. Protons also convert Mn(OH)₂ to Mn²⁺ ions; the catalysts with highest selectivity to oxygenates contain MnO particles and Rh clusters. The results suggest chemical interaction of adsorbates on Rh_n clusters with those on MnO.     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

EXAFS characterization and selective olefin hydroformylation on Rh4, Rh2Co2 and RhCo3 carbonyl clusters attached to tris-hydroxymethylphosphine-grafted silica

Rh_4-xCo_x(CO)₁₂ (x = 0, 2, 3) are attached by carbonyl substitution to THP (tris-hydroxymethylphospine)-grafted silica keeping their cluster frameworks. They have been characterized by Rh K-edge EXAFS (extended X-ray absorption fine structure) and Fourier transform IR spectroscopy. They exhibited high catalytic activity with > 98% selectivity in gas phase hydroformylation of ethene and propene to give aldehydes under mild conditions (40 kPa and 300–373 K).On leave from Research Center, Arakawa Chemical Industries, LTD, Tsurumi, Osaka 538, Japan.On leave from Department of Chemistry, National University of Literal, Santiago del Estero, 2829-3000, Santa Fe, Argentina.     

Observation of [Al(OH) n (H2O)6-n ] n (MoO4) in hydrotreating catalyst precursors by solid-state27 Al NMR

A previously unobserved octahedral²⁷Al MAS NMR resonance has been detected in rehydrated calcined Mo/Al₂O₃ hydrotreating catalyst precursors. This resonance is attributed to the presence of hydrated forms of aluminum molybdate such as [Al(OH) _n (H₂O)_6-n ] _n (MoO₄) (n = 1 or 2). The cross-polarization relaxation parameters, obtained from variable contact time experiments, yielded information on the relative sizes of the [Al(OH) _n (H₂O)_6-n ] _n (MoO₄) domains in the catalysts with different molybdenum loadings. Analysis of the²⁷A1 MAS NMR spectra of P-Mo(8)/Al₂O₃ and P-Mo(12)/Al₂O₃ (wt%P = 0.0–12.0) shows that a function of the phosphate in the 12 wt% Mo catalyst is to prevent the re-hydration of the molybdate phases on the calcined catalysts.     

In situ X-ray absorption spectroscopic study for the electrochemical delithiation of a cathode LiFe0.4Mn0.6PO4 material

The electronic and local atomic structural characterization of a promising cathode material, LiFe_0.4Mn_0.6PO₄, for a lithium rechargeable battery was performed by in situ X-ray absorption fine structure (XAFS) on both Mn and Fe K-edges. Upon delithiation, the X-ray absorption near edge structure (XANES) spectra analysis showed that the Fe²⁺/Fe³⁺ electrochemical reaction was two times faster than that of Mn²⁺/Mn³⁺. The Fe and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectra were effectively altered with different spectral behaviors for the local atomic structure near Fe and Mn during delithiation. Alternatively, the EXAFS spectra of LiFePO₄ changed significantly and those of LiMnPO₄ were constant through all delithiations for the corresponding reference materials of LiFePO₄ and LiMnPO₄. The present study with XAFS characterization demonstrates that initially delithiated Fe-rich domains at 3.5 V can promote more effective local structural change of the neighboring Mn-rich domains during the next second plateau at 4.1 V, which can ease delithiation in the Mn-rich domains through more flexible reaction of the local structure in the Mn octahedra.     

All-solid-state lithium battery with a three-dimensionally ordered Li1.5Al0.5Ti1.5(PO4)3 electrode

To fabricate all-solid-state Li batteries using three-dimensionally ordered macroporous Li_1.5Al_0.5Ti_1.5(PO₄)₃ (3DOM LATP) electrodes, the compatibilities of two anode materials (Li₄Mn₅O₁₂ and Li₄Ti₅O₁₂) with a LATP solid electrolyte were tested. Pure Li₄Ti₅O₁₂ with high crystallinity was not obtained because of the formation of a TiO₂ impurity phase. Li₄Mn₅O₁₂ with high crystallinity was produced without an impurity phase, suggesting that Li₄Mn₅O₁₂ is a better anode material for the LATP system. A Li₄Mn₅O₁₂/3DOM LATP composite anode was fabricated by the colloidal crystal templating method and a sol-gel process. Reversible Li insertion into the fabricated Li₄Mn₅O₁₂/3DOM LATP anode was observed, and its discharge capacity was measured to be 27 mA h g⁻¹. An all-solid-state battery composed of LiMn₂O₄/3DOM LATP cathode, Li₄Mn₅O₁₂/3DOM LATP anode, and a polymer electrolyte was fabricated and shown to operate successfully. It had a potential plateau that corresponds to the potential difference expected from the intrinsic redox potentials of LiMn₂O₄ and Li₄Mn₅O₁₂. The discharge capacity of the all-solid-state battery was 480 μA h cm⁻².     

Induced effect of Mn3O4 on formation of MnO2 crystals favourable to catalysis of oxygen reduction

Catalysts prepared from a mixture of Mn₃O₄ powders and carbon blacks carrying pyrolytic MnO₂ were investigated for catalysis of oxygen reduction. It was found that the introduction of Mn₃O₄ to the pyrolysis process of manganous nitrate carried out on carbon blacks improved the performance of air electrodes as the amount of Mn₃O₄ was controlled within 15 wt% relative to the weight of carbon carrier. The mechanism of this improved behaviour was also investigated using X-ray diffraction (XRD). The results showed that Mn₃O₄ induced the formation of favourable MnO₂ crystalline grains during the pyrolysis of manganous nitrate. The induced effect and the blocking effect of Mn₃O₄ on the catalysis of air electrodes catalysed by pyrolytic MnO₂ were demonstrated both on carbon black and porous carbon carriers.     

Solid-State Construction of CuOx/Cu1.5Mn1.5O4 Nanocomposite with Abundant Surface CuOx Species and Oxygen Vacancies to Promote CO Oxidation Activity

Carbon monoxide (CO) oxidation performance heavily depends on the surface-active species and the oxygen vacancies of nanocomposites. Herein, the CuO_x/Cu_1.5Mn_1.5O₄ were fabricated via solid-state strategy. It is manifested that the construction of CuO_x/Cu_1.5Mn_1.5O₄ nanocomposite can produce abundant surface CuO_x species and a number of oxygen vacancies, resulting in substantially enhanced CO oxidation activity. The CO is completely converted to carbon dioxide (CO₂) at 75 °C when CuO_x/Cu_1.5Mn_1.5O₄ nanocomposites were involved, which is higher than individual CuO_x, MnO_x, and Cu_1.5Mn_1.5O₄. Density function theory (DFT) calculations suggest that CO and O₂ are adsorbed on CuO_x/Cu_1.5Mn_1.5O₄ surface with relatively optimal adsorption energy, which is more beneficial for CO oxidation activity. This work presents an effective way to prepare heterogeneous metal oxides with promising application in catalysis.     

Probing the bimetallic RhCo3 cluster preserved on SiO2 after thermal treatment under O2 by hydroformylation

RhCo₃(CO)₁₂/SiO₂, after decarbonylation under atmospheric O₂ at 623 K, exhibits excellent catalytic performances in atmospheric ethylene hydroformylation at 423 K, which is consistent with the corresponding catalysis by the bimetallic cluster catalyst RhCo₃/SiO₂.     

Rhodium supported in basic zeolite Y: A selective and stable catalyst for CO hydrogenation

Catalysts prepared by a condensation reaction of Rh(CO)₂(acac) within the supercages of zeolite Y made basic by treatment with NaN₃ are active for CO hydrogenation and selective for low-molecular-weight olefins and methanol. High partial pressures of CO (or CO + H₂) stabilize the catalyst. The predominant species in the catalyst are suggested to be rhodium carbonyl clusters trapped in the zeolite cages.     

Surface-grafted triruthenium ketenylidene clusters and their catalytic activity in co exchange and hydroformylation of ethylene

A triruthenium ketenylidene cluster [PPN]₂[Ru₃(CO)₉(CCO)] was deposited on MgO, SiO₂, and SiO₂-Al₂O₃, and the nature of surface species on the oxides were studied by an IR spectroscopic study along with catalytic performances in¹³CO exchange reaction and hydroformylation of ethylene. The IR study suggested the stoichiometric protonation of [Ru₃(CO)₉(CCO)]^2-with surface hydroxyl groups on SiO₂ and SiO₂-Al₂O₃ to give [HRu₃(CO)₉(CCO)]^– and H₂Ru₃(CO)₉(CCO), respectively. H₂Ru₃(CO)₉(CCO)/SiO_2– Al₂O₃ was active for¹³CO exchange reaction, while [Ru₃(CO)₉(CCO)]^2–/MgO showed high activity and selectivity toward propanol in hydroformylation of ethylene.     

New evidence on the factors affecting bridging and semibridging character of carbonyl ligands. The structures of Mn2(CO)7(μ-SCH2CH2S) and its phosphine derivatives Mn2(CO)7-X(PMe2Ph)X(μ-SCH2CH2S), × = 1,2

The new ethanedithiolate—dimanganese carbonyl complex, Mn₂(μ-SCH₂CH₂S)(CO)₇, 1 , was prepared in 28% yield from the reaction of 1,2,5,6-tetrathiacyclooctane with Mn₂(CO)₉(NCMe). Complex 1 was characterized crystal-lographically. It contains two Mn(CO)₃ groups joined by a Mn–Mn bond of 2.6470(6) Å in length, a dihapto-bridging ethanedithiolate ligand, and one strong semibridging CO ligand. The reaction of 1 with PMe₂Ph yielded two derivatives: Mn₂(μ-SCH₂CH₂S)(CO)₆(PMe₂Ph), 2 , and gem-Mn₂(μ-SCH₂CH₂S)(CO)₅(PMe₂Ph)₂, 3a , in 48% and 6% yields, respectively. When heated at 40 °C, compound 3a was transformed into three isomers, iso-gem-Mn₂(μ-SCH₂CH₂S)(CO)₅(PMe₂Ph)₂, 3b , 1,2-Mn₂(μ-SCH₂CH₂S)(CO)₅(PMe₂Ph)₂, 3c , and cis-Mn₂(μ-SCH₂CH₂S)-(CO)₅(PMe₂Ph)₂, 3d . Compounds 3b and 3c were characterized by single-crystal X-ray diffraction analyses. The introduction of phosphine ligand into the complexes strongly affects the semibridging character of the carbonyl ligand.