Activity and selectivity of iron–molybdenum catalysts in synthesis of formaldehyde in an industrial installation

The results of operation of F-1 and F-2 iron–molybdenum formaldehyde synthesis catalysts in an industrial installation consisting of two series-connected tubular reactor are analyzed. The physicochemical properties of the catalysts were studied, and the relationship between the characteristics of acid–base sites, on the one hand, and the activity and selectivity, on the other hand, was determined. The formation of hydrogen on the industrial catalysts is improbable.     

Effect of crystallinity in HZSM-5-amorphous alumosilica systems on their catalytic properties in the synthesis of dimethoxymethane

Granulated catalysts with 3–5% H-ZSM-5 phase were obtained from a highly dispersed alumosilica and were used for the synthesis of dimethoxymethane (DMM) from methanol and formaldehyde. The activity of these catalysts is greater than the activity of pure zeolite. A linear correlation was found between the yield of DMM and the content of Brönsted acid sites in the catalysts.     

Precise 2D-Patterned Incompatible Catalysts for Reactions in One-Pot

Precise and direct two-dimensional (2D) printing of the incompatible polymer acid–base catalysts and their utility in one-pot two-step reactions were shown. Multistep catalytic reactions using incompatible catalysts in a one-pot reaction cascade requires special methods and materials to isolate the catalysts from each other. In general, this is a tedious process requiring special polymer architectures as the carrier for the catalysts to preserve the activity of otherwise incompatible catalysts. We propose the immobilization of incompatible polymer catalysts, such as polymer acid and base catalysts, on a substrate in variable sizes and amounts by precise 2D printing. The terpolymers with basic (4-vinylpyridine) and acidic (styrene sulfonic acid) functionalities and methacryloyl benzophenone as a UV cross-linking unit were used for 2D printing on poly(ethylene terephthalate) (PET). The printed meshes were immersed together in a reaction solution containing (dimethoxymethyl)benzene and ethyl cyanoformate, resulting in a two-step acid–base catalyzed cascade reaction; that is, deacetalization followed by carbon-building reaction. The time-dependent consumption of (dimethoxymethyl)benzene to the intermediate benzaldehyde and the product was monitored, and a kinetic model was developed to investigate the underlying reaction dynamics. The complexity of multistep Wolf–Lamb-type reactions was generally significantly decreased by using our approach because of the easy polymerization and immobilization procedure.     

Bimetallic oxide nanoparticles confined in ZIF‐67‐derived carbon for highly selective oxidation of saturated C–H bond in alkyl arenes

Zeolite imidazolate frameworks (ZIFs) have recently emerged as an ideal type of carbon precursors with abundant tailorability. In this work, a series of ZIF‐derived porous carbon catalysts have been prepared with encapsulation of bimetallic oxide nanoparticles via simple thermal treatment. The composition and structure of these catalysts were confirmed in detail by different characterization methods. The bimetallic oxide (Mn/Co, Fe/Co, and Cu/Co) nanoparticles were encapsulated in the nitrogen‐doped graphitized carbon matrix. Moreover, the hierarchically porous structure and carbon defects were successfully constructed in the carbon catalysts. Additionally, in the selective oxidation of saturated C–H bonds in alkyl arenes, the carbon catalysts demonstrate outstanding performance for the oxidation of C–H bonds to corresponding carboxyl groups. This was due to their unique structure can greatly promote mass transfer and molecular oxygen activation, resulting in high conversion and high selectivity. Remarkably, this work here could also provide a novel strategy to the controllable synthesis of metal–organic frameworks (MOFs)‐derived carbon catalysts for enhanced performance in heterogeneous catalysis.     

Selectivity in the Catalytic Hydrogenation of 2-Hydroxycyclohexanone

The catalytic hydrogenation of 2–hydroxycyclohexanone has been investigated on ruthenium, nickel, rhodium, platinum and palladium. The reaction was completed usually within several hours under an atmospheric pressure of hydrogen at room temperature. It was found that ruthenium and nickel catalysts produce more cis–cyclohexane–1, 2–diol than trans-diol; while platinum and palladium catalysts give rise to more trans–diol than cis– form. Two adsorbed models, weak and strong, for the substrate were presented to account for the observed hydrogenation selectivity.     

Supported ruthenium hydride catalysts for direct conversion of alcohols to carboxylic acids using styrene oxide as oxidant

In the present work, the ability of two ruthenium hydride catalysts supported on multiwall carbon nanotubes, [Ru–H@EDT–MWCNT], and gold nanoparticles cored triazine dendrimer, [Ru–H@AuNPs–TD], in the direct conversion of alcohols to carboxylic acids via transfer hydrogenation using styrene oxide as oxidant is reported. Different alcohols were successfully converted to their corresponding carboxylic acids. The results showed that these two heterogeneous catalysts are more efficient than the homogeneous counterpart. In addition, the catalysts were reused several times.     

Hydrodechlorination of chlorobenzene in the presence of Ni/Al2O3 prepared by laser electrodispersion and from a colloidal dispersion

The low-percentage Ni/Al₂O₃ catalysts with active metal contents of 0.0002–0.1 wt % were prepared using the laser electrodispersion (LED) method and by means of supporting from a colloidal dispersion (CD). Their composition and physicochemical properties were determined by atomic absorption spectrometry, transmission electron microscopy (TEM), and XPS. With the use of TEM, it was found that average size of nickel particles in the LED catalysts was smaller than that in the CD catalysts. According to XPS data, the supporting of a metal onto a substrate by the LED method makes it possible to obtain samples containing Ni metal with a low active metal content (0.03 wt %). They exhibited a high initial activity in the hydrodechlorination reaction of chlorobenzene in a vapor phase, which was performed in a flow system at temperatures of 100–350°C. The CD catalysts were active in this reaction only at temperatures of 300–350°C. Reductive treatment led to the deactivation of LED catalysts and increased the activity and stability of samples prepared by supporting from a CD. The possible reasons for the observed changes are considered.     

Mesoporous Nickel–Alumina Catalysts for Hydrogen Production by Steam Reforming of Liquefied Natural Gas (LNG)

Recent progress on the mesoporous nickel–alumina catalysts for hydrogen production by steam reforming of liquefied natural gas (LNG) was reported in this review. A number of mesoporous nickel–alumina composite catalysts were prepared by a single-step surfactant-templating method using cationic, anionic, and non-ionic surfactant as structure-directing agents for use in hydrogen production by steam reforming of LNG. For comparison, nickel catalysts supported on mesoporous aluminas were also prepared by an impregnation method. The effect of preparation method and surfactant identity on physicochemical properties and catalytic activities of mesoporous nickel–alumina catalysts in the steam reforming of LNG was investigated. Regardless of preparation method and surfactant identity, nickel oxide species were finely dispersed on the surface of mesoporous nickel–alumina catalysts through the formation of surface nickel aluminate phase. However, nickel dispersion and nickel surface area of mesoporous nickel–alumina catalysts were strongly affected by the preparation method and surfactant identity. It was found that nickel surface area of mesoporous nickel–alumina catalyst served as one of the important factors determining the catalytic performance in hydrogen production by steam reforming of LNG. Among the catalysts tested, a mesoporous nickel–alumina composite catalyst prepared by a single-step non-ionic surfactant-templating method exhibited the best catalytic performance due to its highest nickel surface area.     

Pt- and Ir-based disperse catalysts synthesized in a magnetron for water electrolyzers with a solid polymer electrolyte

Disperse catalytic compositions for water electrolysis in electrolyzers with a solid polymer electrolyte were obtained by magnetron sputtering of C–Pt and Mo–Ir sectional targets. The catalysts were studied by X-ray diffraction analysis, electron microscopy, and voltammetry. The synthesized Pt–С and Ir–Mo catalysts with lowered contents of the precious component were subjected to prolonged trials in an electrolysis cell with a solid polymer electrolyte and showed high activity and stability.     

Macromolecular metal complexes as catalysts with improved stability

Polymer-bound tertiary amine–copper complexes and polymer-bound phosphite–rhodium complexes were studied as catalysts for oxidative coupling of phenols and hydroformylation of alkenes, respectively. The activity and stability of these catalysts could be tuned or optimized by adapting the structure of the ligands and by changing the distance between adjacent ligands along the polymer chains. The latter effect has been described in terms of strain in the intermediate chain segments in the copper complexes or enhancement of the effective local ligand concentration around the rhodium complexes. So-called immobilized homogeneous catalysts were obtained by end-grafting of both types of macromolecular catalysts on to inert and insoluble silica particles. These immobilized polymeric catalysts could easily be separated and recovered. Under proper conditions a grafted polymerbound imidazole–copper complex and a new type of polymer-bound triphenyl–phosphite–rhodium complex showed excellent stability in continuous processes.     

Complex formation between catalysts,alcohols, and isocyanates in the preparation of urethanes

The mechanism of the catalyzed reaction between alcohols and isocyanates was investigated by means of NMR, infrared, and ultraviolet spectroscopy. The shift of the ? OH proton resonance in the NMR spectra indicated the existence of a 1 : 1 complex in the system dibutyltin dilaurate (DBTDL)–1-methoxy-2-propanol. Complex formation was also observed when lead naphthenate or triethylamine (TEA) were substituted for the DBTDL. Mixtures of the DBTDL–TEA catalysts caused a shift of the ? OH proton resonance greater than that observed for either catalyst alone. This correlates with the synergistic effect noted when preparing urethanes with a mixture of these catalysts. No direct evidence of alcohol–catalyst complex formation could be obtained by infrared spectroscopy. Efforts were also made to detect complex formation in mixtures of phenyl isocyanate and catalysts. These complexes could not be detected by NMR, infrared, or ultraviolet spectroscopy.     

The Oxidation of Carbon Monoxide as an Integrated Part of the Coupled Alkane Oxidation Process: Gas-Phase Oxidation over Supported Metal-Complex Catalysts

Heterogeneous rhodium–copper chloride catalysts for gas-phase oxidation processes were prepared via the cold impregnation of γ-Al₂O₃ with aqueous RhCl₃ and CuCl₂ solutions. Heptafluorobutyric or pentafluorobenzoic acids were additionally deposited onto these catalysts to simulate the action of homogeneous rhodium–copper chloride catalytic systems in the coupled alkane–carbon monoxide oxidation reaction. The catalysts were studied in the reactions of carbon monoxide oxidation and coupled propane–CO oxidation with dioxygen by diffuse reflectance IR Fourier transform spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR). The obtained data indicate the probable transfer of electrons between rhodium and copper compounds.     

Charge-tagged polar phosphine ligands in Pd-catalysed reactions in aqueous and ionic media

A new range of polar imidazolium and phosphate-containing ligands was synthesised from readily available starting materials in high yielding multi-step transformations. These ligands were used to generate Pd catalysts for Suzuki and Heck C–C coupling reactions in organic and organic/aqueous media. The catalysts performed well in aqueous media in the Suzuki reaction and less well in the Heck reaction, related to substrate solubility in the aqueous media. When moving to ionic liquids, the Heck reaction dramatically improved, especially in media compatible with the polar catalysts and the non-polar reagents. In all cases, the catalysts were stable to the formation of Pd black, a form of degradation that frequently befalls Pd catalysts. The catalysts could be successfully recycled without loss of activity.     

Study of the early deactivation in pyrolysis of polymers in the presence of catalysts

In this work, the early degradation step of the pyrolysis of some polymers in the presence of certain catalysts has been studied using thermogravimetric analysis (TGA). Three commercial polymers (PE, PP and EVA) and three catalysts were studied (ZSM-5, MCM-41a, and MCM-41b), and the MCM-41a catalyst has been selected for the analysis of the earlier steps of the pyrolysis process carried out in the presence of catalysts. Several cycles of heating–cooling were performed using a thermobalance, in order to analyze the influence of the first stages of decomposition on the activity of the more accessible active sites involved. In this way, the behaviour of the polymer–catalyst mixtures (20% (w/w) of catalyst) was studied and compared with that observed in the corresponding thermal degradation as well as in the pyrolysis in the presence of catalysts, in a single heating cycle.The results obtained clearly show the existence of an early degradation step. For a polymer–catalyst system with low steric hindrances such as PE-MCM-41, this early degradation step causes a noticeable decrease of the catalyst activity for the main decomposition step (i.e., cracking of the chain). The decrease of the catalytic activity is lower for a polymer–catalyst system with higher steric restrictions, as occurs in the EVA-MCM-41 degradation process. However, in this case, the catalyst activity in the first decomposition step (i.e., the loss of the acetoxi groups) is noticeable decreased after one pyrolysis run, thus reflecting that the active sites involved are mainly the most accessible ones.     

An Effect of a Support Nature and Active Phase Morphology on Catalytic Properties of Ni-Containing Catalysts in Hydrogenation of Biphenyl

Ni/Sup catalysts were prepared, where SBA-15, γ-Al₂O₃, SiO₂ were used as supports (Sup). The synthesized catalysts were investigated by the methods of low-temperature nitrogen adsorption, temperatureprogrammed reduction (TPR), and high-resolution transmission electron microscopy. The catalytic properties of the prepared catalysts were tested in liquid phase hydrogenation of biphenyl under conditions of a flow installation at temperatures of 60–100°C, pressure of 4 MPa, volumetric feed rate of 4–10 h^–1 and H₂: feed ratio of 1500 nM.. A 1 wt % solution of biphenyl in heptane,, as a model mixture, was used. It has been established that the activity of nickel hydrogenation catalysts depends on the nickel content and the type of support. The activity of supported nickel catalysts decreases in the series Ni-12/SBA-15 > Ni-12/SiO₂ >> Ni-12/Al₂O₃. The kinetic characteristics of the biphenyl hydrogenation reaction were determined: the rate constants and activation energy for the hydrogenation of the first and second aromatic rings of the substrate molecule.     

Baeyer–Villiger oxidation of cyclohexanone by molecular oxygen with Fe–Sn–O mixed oxides as catalysts

Fe–Sn–O mixed oxides were synthesized and used as catalysts for Baeyer–Villiger oxidation of cyclohexanone, which showed both high catalytic activity and selectivity. X‐ray powder diffraction and scanning electron microscopy suggested that the Fe–Sn–O catalysts had a tetragonal structure with a grain size of 29.3 nm. An ε‐caprolactone yield as high as 98.8% was obtained in a small‐scale experiment (5 mmol of cyclohexanone). In a scale‐up test (20 mmol of cyclohexanone), the cyclohexanone conversion and ε‐caprolactone yield were 96.7 and 96.5%, respectively. In addition, the catalysts can be reused five times without any major decline in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of addition of iron on morphology and catalytic activity of PdCu nanoalloy thin film as catalyst in Sonogashira coupling reaction

Palladium‐supported catalysts are complex assemblies with a challenging preparation. Minor changes in their preparation conditions can affect the activity, selectivity and lifetime of these catalysts. PdCuFe nanoparticle (NP) thin films were supported on reduced graphene oxide (RGO) by the reduction of the organometallic complex [PdCl_2‌(cod)] (cod = cis ,cis ‐1,5‐cyclooctadiene), and [Cu(acac)₂] and [Fe(acac)₃] (acac = acetylacetonate) complexes at a toluene–water interface. We have investigated the application of the liquid–liquid interface method for preparing ultrathin films of catalysts and have evaluated the catalytic activity of the prepared NPs for the Sonogashira coupling reaction in micelle media. Also, we have investigated the effect of the addition of iron on the morphology, size and catalytic activity of PdCu/RGO NPs. Our study shows that both of the prepared catalysts (PdCu/RGO and PdCuFe/RGO) are efficient and recoverable catalysts for the Sonogashira carbon–carbon coupling reaction. This method has advantages compared to other routes, such as short reaction times, high to excellent yields, facile and low‐cost method for the preparation of the catalysts, and easy separation and reusability of the catalysts.     

Impact of ageing on the distribution of platinum group elements and catalyst poisoning elements in automobile catalysts

The distribution of platinum group elements (PGEs) and catalyst poisoning elements (Pb, Zn, P and S) on the surface of gasoline and diesel automobile catalysts was investigated within this study. Laser ablation–inductively coupled plasma mass spectrometry (LA–ICPMS) provides both the sensitivity and the spatial resolution required for the surface analysis of sectioned automobile catalysts, and scanning along channels reveals the distribution of longitudinal changes in PGE and catalyst poisoning elements. Changes in catalyst surface features were studied for fresh catalysts and after ageing of the catalyst up to 80 000 km for both types of catalysts studied. The PGEs in the gasoline catalyst were found to decrease at the front of the catalyst after ageing, whereas the diesel catalyst presented a more constant loss along the catalyst. The fraction of poisoning elements (Pb, P and Zn for the gasoline catalyst and P and Zn for the diesel catalyst) retained by the catalyst is distributed non‐uniformly over the length of the catalyst. This could indicate different ageing mechanisms for gasoline and diesel catalysts. Copyright © 2003 John Wiley & Sons, Ltd.     

负载金催化剂上CO氧化反应活性与金属氧化物载体中金属-氧结合能之间的关系

讨论了金属氧化物载体(MOx)对其负载纳米金催化剂(Au/MOx)上CO氧化反应的影响。采用典型的共沉淀法和沉积-沉淀法在完全相同的焙烧条件下制备了一系列MOx负载金催化剂,以CO氧化转化50%时的反应温度(T1/2)定量评价了MOx载体和Au/MOx催化剂的催化活性。进一步将MOx载体与相应Au/MOx催化剂的T1/2值之差对MOx载体的金属-氧结合能做曲线进行关联,发现二者呈明显的火山型关系。这一结果表明,采用具有适当金属-氧结合能(300–500 atom O)的MOx可大大提高沉积于其上的Au纳米颗粒的催化活性。     

Synthesis and Activity of Nanodispersed SnO2–CeO2 Catalyst in the Oxidation Reactions of Carbon Monoxide and Methane

Kinetics and Catalysis - Nanodispersed SnO2–CeO2 catalysts for the oxidation of CO and СН4 were synthesized by coprecipitation in a water–isopropanol solution followed by...