Nitride and carbide of molybdenum and tungsten as substitutes of iridium for the catalysts used for space communication

Satellites are equipped with microthrusters that control their orbit and attitude. The thrust is achieved by the catalytic decomposition of hydrazine by iridium supported on alumina. As nitrides and carbides of molybdenum and tungsten behave like noble metals in many catalytic reactions, they were tried in a 2 newton hydrazine microthruster. Their performance was similar to that of the iridium catalyst, with respect to ignition delay and thrust. Their mechanical resistance appears higher than that of iridium-based catalyst. This application is the first practical one for nitrides and carbides of early transition metals as substitutes of noble metals, a possibility first reported in 1973. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of nanocrystalline alumina by thermal decomposition of aluminum isopropoxide in 1-butanol and their applications as cobalt catalyst support

Nanocrystalline alumina powders were prepared by thermal decomposition of aluminum isopropoxide (AIP) in 1-butanol at 300 °C for 2 h and employed as cobalt catalyst supports. The crystallization of alumina was found to be influenced by the concentration of AIP in the solution. At low AIP content, wrinkled sheets-link structure of γ-Al₂O₃ was formed, while at high AIP concentrations, fine spherical particles of χ-Al₂O₃ were obtained. It was found that using these fine particles alumina as cobalt catalyst supports resulted in much higher amounts of cobalt active sites measured by H₂ chemisorption and higher CO hydrogenation activities.     

Ionic liquid‐catalyzed aminolysis of poly(ethylene terephthalate) waste

Aminolytic depolymerization of poly(ethylene terephthalate) (PET) bottle waste with ethanolamine and hydrazine hydrate under atmospheric conditions was investigated in the presence of room temperature ionic liquids. 1‐Hexyl‐3‐methylimidazolium trifluoromethanesulfonate (Hmim.TfO) and 1‐butyl‐3‐methylimidazolium hydrogen sulfate (Bmim.HSO₄). (Hmim.TfO) was found to be the most efficient catalyst to obtain high yields of the aminolysis products bis(2‐hydroxy ethylene) terephthalamide and terephthalic dihydrazide using ethanolamine and hydrazine hydrate, respectively. These products were characterized by IR spectroscopy, ¹H NMR, ¹³C NMR, mass spectroscopy, and differential scanning calorimetry. The influence of experimental parameters, such as the amount of catalyst, reaction time, molar ratio of ethanolamine, and hydrazine hydrate with respect to PET was investigated. This protocol proves to be efficient and environmentally benign in terms of high yields (>84%) and low reaction times (up to 30 min). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fe2O3/β-SiC: A new high efficient catalyst for the selective oxidation of H2S into elemental sulfur

Over the last decades, sulfur recovery from the H₂S-containing acid gases (issued from oil refineries or natural gas plants) has become more and more important due to the ever increasing standards of efficiency required by environmental protection pressures. The H₂S-tail gas was directly oxidized by oxygen to yield elemental sulfur. A significant improvement of the H₂S conversion and selectivity has been developed, however, the support which is the core of the process still needs to be improved. Recently, β-SiC has been reported to be an efficient and selective catalyst support for the H₂S-to-S reaction. One expected reason for this superior yield should be due to the high thermal conductivity of the support. The high thermal conductivity of the silicon carbide plays an important role in the maintenance of the high selectivity by avoiding the formation of hot spots on the catalyst surface which could favor secondary reactions. On the other hand, insulator supports such as alumina exhibit a poor selectivity due to catalyst surface temperature runaway.     

Kinetic study of hydrogen peroxide decomposition at high temperatures and concentrations in two capillary microreactors

On the background of the direct adipic acid synthesis from cyclohexene and H₂O₂, a kinetic model was derived for the H₂O₂ decomposition catalyzed by sodium tungstate at high H₂O₂ concentrations and high temperatures. A perfluoroalkoxy (PFA) and a stainless steel micro‐flow capillary match commonly used microreactor materials. In the PFA capillary, the decomposition of hydrogen peroxide increased with residence time, reaction temperature and catalyst loading. The reaction order with respect to hydrogen peroxide and sodium tungstate was zero and one, respectively. Simulated data fit well with experimental data in the PFA capillary. While showing a similar trend as that in the PFA capillary, the stainless steel capillary exhibited much higher reaction rates. The steel surface participated in the decomposition process as a heterogeneous catalyst. Key influencing factors of the H₂O₂ decomposition provided some clues on the reaction mechanism of the adipic acid synthesis and its process optimization. © 2016 American Institute of Chemical Engineers AIChE J, 63: 689–697, 2017     

H2 production by selective decomposition of hydrous hydrazine over Raney Ni catalyst under ambient conditions

A noble metal‐free catalyst, Raney Ni, exhibited > 99% selectivity toward H₂ for hydrous hydrazine decomposition in basic solution at 30^°C. The particle size of the initial Ni‐Al alloy and the concentration of additional alkali influenced the H₂ selectivity on Raney Ni catalysts. This convenient route provides great potential for industrial application of hydrous hydrazine as a promising hydrogen storage material. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4297–4302, 2013     

Catalytic Performance of Activated Carbon Supported Tungsten Carbide for Hydrazine Decomposition

Activated carbon (AC) supported tungsten carbide was reported for the catalytic decomposition of hydrazine for the first time. It was found that the WC _x /AC-H catalyst prepared by a carbothermal hydrogen reduction process exhibited excellent catalytic performances both in the microreactor and in a 1 Newton hydrazine microthruster. The XRD, TEM and microcalorimetry results suggest that the formation of well crystallized W₂C phase, the restraining of the carbon deposition, as well as the prohibiting of the methanation should be responsible for the high activity and stability of the WC _x /AC-H catalyst in the hydrazine decomposition reaction.     

Catalytic activities of amino acid modified,starch‐grafted acrylamide for the decomposition of hydrogen peroxide

Acrylamide was grafted onto corn starch with ceric(IV) ions as an initiator. Starch‐graft‐polyacrylamide was modified with amino acids through a reaction with the sodium salts of glycine, β‐alanine, and phenylalanine. The catalytic activities of the iron(III) complexes of the amino acid modified grafted materials were investigated for the decomposition of hydrogen peroxide (H₂O₂). These new polymeric supports were found to be active in the catalytic decomposition of H₂O₂. The extent of decomposition varied with the composition of the support. The iron(III) complex of the glycine‐modified material was the most active of the amino acid supported catalysts. Factors that affected the rate of reaction, such as the concentration of H₂O₂, the amount of the catalyst, the pH, and the temperature, were investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 630–636, 2004     

Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina

Methanol steam reforming was studied over several catalysts made by deposition of copper and zinc precursors onto nanoparticle alumina. The results were compared to those of a commercially available copper, zinc oxide and alumina catalyst. Temperature programmed reduction, BET surface area measurements, and N₂O decomposition were used to characterize the catalyst surfaces. XRD was used to study the bulk structure of the catalysts, and XPS was used to determine the chemical states of the surface species. The nanoparticle-supported catalysts achieved similar conversions as the commercial reference catalyst but at slightly higher temperatures. However, the nanoparticle-supported catalysts also exhibited a significantly lower CO selectivity at a given temperature and space time than the reference catalyst. Furthermore, the turnover frequencies of the nanoparticle-supported catalysts were higher than that of the commercial catalyst, which means that the activity of the surface copper is higher. It was determined that high alumina concentrations ultimately decrease catalytic activity as well as promote undesirable CH₂O formation. The lower catalytic activity may be due to strong Cu-Al₂O₃ interactions, which result in Cu species which are not easily reduced. Furthermore, the acidity of the alumina support appears to promote CH₂O formation, which at low Cu concentrations is not reformed to CO₂ and H₂. The CO levels present in this study are above what can be explained by the reverse water-gas-shift (WGS) reaction. While coking is not a significant deactivation pathway, migration of ZnO to the surface of the catalyst (or of Cu to the bulk of the catalyst) does explain the permanent loss of catalytic activity. Cu₂O is present on the spent nanoparticle catalysts and it is likely that the Cu⁺/Cu⁰ ratio is of importance both for the catalytic activity and the CO selectivity.     

Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina

Methanol steam reforming was studied over several catalysts made by deposition of copper and zinc precursors onto nanoparticle alumina. The results were compared to those of a commercially available copper, zinc oxide and alumina catalyst. Temperature programmed reduction, BET surface area measurements, and N₂O decomposition were used to characterize the catalyst surfaces. XRD was used to study the bulk structure of the catalysts, and XPS was used to determine the chemical states of the surface species. The nanoparticle-supported catalysts achieved similar conversions as the commercial reference catalyst but at slightly higher temperatures. However, the nanoparticle-supported catalysts also exhibited a significantly lower CO selectivity at a given temperature and space time than the reference catalyst. Furthermore, the turnover frequencies of the nanoparticle-supported catalysts were higher than that of the commercial catalyst, which means that the activity of the surface copper is higher. It was determined that high alumina concentrations ultimately decrease catalytic activity as well as promote undesirable CH₂O formation. The lower catalytic activity may be due to strong Cu-Al₂O₃ interactions, which result in Cu species which are not easily reduced. Furthermore, the acidity of the alumina support appears to promote CH₂O formation, which at low Cu concentrations is not reformed to CO₂ and H₂. The CO levels present in this study are above what can be explained by the reverse water-gas-shift (WGS) reaction. While coking is not a significant deactivation pathway, migration of ZnO to the surface of the catalyst (or of Cu to the bulk of the catalyst) does explain the permanent loss of catalytic activity. Cu₂O is present on the spent nanoparticle catalysts and it is likely that the Cu⁺/Cu⁰ ratio is of importance both for the catalytic activity and the CO selectivity.     

Activation of Supported Pd Metal Catalysts for Selective Oxidation of Hydrogen to Hydrogen Peroxide

Catalytic activity of supported Pd metal catalysts (Pd metal deposited on carbon, alumina, gallia, ceria or thoria) showing almost no activity in the liquid-phase direct oxidation of H₂ to H₂O₂ (at 295 K) in acidic medium (0.02 M H₂SO₄) can be increased drastically by oxidizing them using different oxidizing agents, such as perchloric acid, H₂O₂, N₂O and air. In the case of the Pd/carbon (or alumina) catalyst, perchloric acid was found to be the most effective oxidizing agent. The order of the H₂-to-H₂O₂ conversion activity for the perchloric-acid-oxidized Pd/carbon (or alumina) and air-oxidized other metal oxide supported Pd catalysts is as follows: Pd/alumina < Pd/carbon < Pd/CeO₂ < Pd/ThO₂ < Pd/Ga₂O₃. The H₂ oxidation involves lattice oxygen from the oxidized catalysts. The catalyst activation results mostly from the oxidation of Pd metal from the catalyst producing bulk or sub-surface PdO. It also caused a drastic reduction in the H₂O₂ decomposition activity of the catalysts. There exists a close relationship between the H₂-to-H₂O₂ conversion activity and/or H₂O₂ selectivity in the oxidation process and the H₂O₂ decomposition activity of the catalysts; the higher the H₂O₂ decomposition activity, the lower the H₂-to-H₂O₂ conversion activity and/or H₂O₂ selectivity.     

Hydrogen peroxide formation in the interaction of oxygen with boron-containing Pd catalysts prereduced by hydrazine in aqueous acidic medium containing bromide anions

Interaction of molecular oxygen with Pd/BPO₄ or ZrO₂ (or Al₂O₃, CeO₂, TiO₂) - B₂O₃ catalysts, prereduced by hydrazine hydrate, in an aqueous acidic (H₂SO₄ or H₃PO₄) reaction medium containing bromide ions leads to the formation of H₂O₂. However, in the absence of boron in the catalyst and also in the absence of acid and/or bromide ions in the reaction medium, almost no H₂O₂ is formed.     

Catalytic decomposition of alcohols over size-selected Pt nanoparticles supported on ZrO2: A study of activity, selectivity, and stability

This article discusses the performance of ZrO₂-supported size-selected Pt nanoparticles for the decomposition of methanol, ethanol, 2-propanol, and 2-butanol. The potential of each alcohol for the production of H₂ and other relevant products in the presence of a catalyst is studied in a packed-bed mass flow reactor operating at atmospheric pressure. All the alcohols studied show some decomposition activity below 200 °C which increased with increasing temperature. In all cases, high selectivity towards H₂ formation is observed. With the exception of methanol, all alcohol conversion reactions lead to catalyst deactivation at high temperatures (T > 250 °C for 2-propanol and 2-butanol, T > 325 °C for ethanol) due to carbon poisoning. However, long-term catalyst deactivation can be avoided by optimizing reaction conditions such as operating temperature.     

Low Temperature Synthesis of High Alumina Cements by Novel Co‐Melt Precursors and Their Implementation as Castables with Some Micro Fine Additives

In the present investigations nano size high alumina cements (HAC) were prepared by very effective co‐melt precursor sintering technique from their metal nitrate precursors. The prime cementing phases observed were CA, CA₂, and C₁₂A₇. The addition of nano structured cements in refractory castables has improved the thermo‐chemical‐mechanical properties to a significant extent. Each batch of low cement castables (LCC) was prepared from calcined Chinese bauxite, HAC, and superfine additives. The effect of HAC in bauxite castable with the additives similar to Silicon Carbide, reactive alumina, and micro‐fine silica on the sinterability and properties of these castables was investigated. Physical properties such as apparent porosity and bulk density, mechanical properties such as hot modulus of rupture (HMOR), cold and hot modulus of rupture (CMOR), and cold crushing strength (CCS) of hydrated and sintered castables were studied. The sintered castables were also characterized for their solid phase compositions and microstructure using X‐ray diffraction (XRD) and FE‐SEM, respectively. In the castables new phases such as mullite, α‐alumina were formed at the expense of bauxite and silica. Solid solution of mullite formed at high temperature acts as a bonding phase and is accounted for high HMOR, CMOR, and CCS values. These excellent properties of such castables may enable their uses in various applications such as refractory lining for fabrication of steel, aluminium, copper, glass, cement, chemicals, and ceramics.     

CO hydrogenation over supported cobalt catalysts: FTIR and gravimetric studies

The hydrogenation of CO over supported cobalt catalysts has been studied using in situ FTIR spectroscopy and gravimetry at P = 6 bar, T = 473–723 K and H₂/CO = 2–3. On both silica- and alumina-supported catalysts IR absorption bands corresponding to linearly adsorbed CO on metallic cobalt were observed. On alumina an additional pair of bands at lower frequencies was attributed to bridge-bonded CO. Absorption bands corresponding to adsorbed hydrocarbons (3050–2700 cm^?1) and to oxygen containing species (1800–1200 cm^?1) were found to correspond to adsorbed products or unreactive species. The gravimetric studies showed a significant difference between the supports. On the silica-supported catalyst the weight uptake decreased with increasing temperature (473–573 K). The weight increase during reaction was attributed to adsorbed hydrocarbon reaction products. On the alumina-supported catalyst the weight uptake increased with increasing temperature, and there was also a significant weight increase with the support alone. Most of the weight uptake can be attributed to the formation of stable formate and carbonate species on the alumina support. At 723 K the deposits formed were stable in H₂, and the shape of the curves indicated different mechanisms for deposition of material. In particular the Co/Al₂O₃ sample showed a very high and linear rate of weight gain, which was an order of magnitude higher than for the other samples.     

A site-isolated mononuclear iridium complex catalyst supported on MgO: Characterization by spectroscopy and aberration-corrected scanning transmission electron microscopy

Supported mononuclear iridium complexes with ethene ligands were prepared by the reaction of Ir(C₂H₄)₂(acac) (acac is CH₃COCHCOCH₃) with highly dehydroxylated MgO. Characterization of the supported species by extended X-ray absorption fine structure (EXAFS) and infrared (IR) spectroscopies showed that the resultant supported organometallic species were Ir(C₂H₄)₂, formed by the dissociation of the acac ligand from Ir(C₂H₄)₂(acac) and bonding of the Ir(C₂H₄)₂ species to the MgO surface. Direct evidence of the site-isolation of these mononuclear complexes was obtained by aberration-corrected scanning transmission electron microscopy (STEM); the images demonstrate the presence of the iridium complexes in the absence of any clusters. When the iridium complexes were probed with CO, the resulting IR spectra demonstrated the formation of Ir(CO)₂ complexes on the MgO surface. The breadth of the ν_CO bands demonstrates a substantial variation in the metal–support bonding, consistent with the heterogeneity of the MgO surface; the STEM images are not sufficient to characterize this heterogeneity. The supported iridium complexes catalyzed ethene hydrogenation at room temperature and atmospheric pressure in a flow reactor, and EXAFS spectra indicated that the mononuclear iridium species remained intact. STEM images of the used catalyst confirmed that almost all of the iridium complexes remained intact, but this method was sensitive enough to detect a small degree of aggregation of the iridium on the support.     

A new sol‐gel route alumina for selective oxidation of H2S to sulphur

In this study, a new synthesis method was developed for the production of modified sol‐gel alumina (SG‐M) for the selective oxidation of H₂S to elemental sulphur. The catalytic activity of this modified alumina without any active metal incorporation was then compared with the activity of commercial alumina (alumina‐com) for H₂S selective oxidation. The N₂ adsorption‐desorption isotherm showed that the SG‐M alumina synthesized in this work has a mesoporous structure with well‐defined hysteresis loops. Both alumina materials showed a γ‐Al₂O₃ crystalline phase with an amorphous structure in their crystal structure. The surface acidity of the alumina materials was determined using pyridine‐adsorbed FTIR analyses, and both alumina showed Lewis acid sites on their surfaces. The catalytic activity tests were performed at 250°C using a feed ratio of O₂/H₂S:0.5. The complete conversion of H₂S over SG‐M was achieved during 400 minutes of reaction time. However, the commercial alumina lost its activity at earlier reaction times. Lewis acid sites and surface hydroxyl groups caused the alumina to be active in H₂S selective catalytic oxidation, and the formation of Al‐S bonds, observed when the H₂S conversion fell, caused a decrease in the catalytic activity of the alumina materials. A high sulphur yield (≥95%) was obtained over SG‐M, even though there was no active metal incorporation and even in the presence of excess oxygen. Considering the catalytic activities, the new sol‐gel alumina synthesized in this work is superior to commercial alumina. It was concluded that, as a catalyst without any active metal, SG‐M is a promising catalyst in H₂S selective oxidation to sulphur.     

Mechanical properties of sol–gel prepared nanocomposite coatings in the presence of titania and alumina-derived nanoparticles

Hybrid nanocomposite coatings were prepared by sol–gel method using silica, titania and alumina nanoparticles derived from their alkoxides precursors; in the presence of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and bisphenol A (BPA) on 1050 aluminium alloy substrate. The effect of type and ratio of nanoparticles on mechanical behaviour of the coatings were investigated by dynamic mechanical thermal analysis (DMA) and nanoindentation experiments. DMA results demonstrated that the values of the glass transition temperature (T_g) and the temperature at maximum tan (δ), (T_t) as well as the storage modulus of the hybrid samples depend mainly on the silane content and titania to alumina molar ratio of nanoparticles in the coating composition. In addition, nanoindentaion experiments were performed to study the mechanical properties such as hardness, elastic modulus and E/H ratio for the nanocomposite hybrid coatings. Nanoindentation results indicate that the homogenous reinforced structure was formed in the surface of nanocomposite coating with incorporation of titania and alumina-derived nanoparticles. The incorporation of TiO₂ in comparison with AlOOH nanoparticles in the GPTMS-based coatings showed an improving effect on E/H ratio.     

Process Optimisation of In Situ H2 Generation From Ammonia Using Ni on Alumina Coated Cordierite Monoliths

A catalyst of Ni supported on alumina coated monolith has been prepared, characterized and tested in NH₃ decomposition. The characterization of the catalyst by XPS and TPR showed that there is no formation of aluminates after catalyst use. It is studied the effect of the space velocity, by varying the feed flow rate and the catalyst??s length. Some evidences are shown about the reaction inhibition by produced H₂ and about the reasons for the better performance of the monolith than packed bed catalyst.     

Highly Enantioselective Hydrogenation of Quinoline and Pyridine Derivatives with Iridium‐(P‐Phos) Catalyst

The use of a chiral iridium catalyst generated in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl]₂, the P‐Phos ligand [4,4′‐bis(diphenylphosphino)‐2,2′,6,6′‐tetramethoxy‐3,3′‐bipyridine] and iodine (I₂) for the asymmetric hydrogenation of 2,6‐substituted quinolines and trisubstituted pyridines [2‐substituted 7,8‐dihydroquinolin‐5(6H)‐one derivatives] is reported. The catalyst worked efficiently to hydrogenate a series of quinoline derivatives to provide chiral 1,2,3,4‐tetrahydroquinolines in high yields and up to 96% ee. The hydrogenation was carried out at high S/C (substrate to catalyst) ratios of 2000–50000, reaching up to 4000 h⁻¹ TOF (turnover frequency) and up to 43000 TON (turnover number). The catalytic activity is found to be additive‐controlled. At low catalyst loadings, decreasing the amount of additive I₂ was necessary to maintain the good conversion. The same catalyst system could also enantioselectively hydrogenate trisubstituted pyridines, affording the chiral hexahydroquinolinone derivatives in nearly quantitative yields and up to 99% ee. Interestingly, increasing the amount of I₂ favored high reactivity and enantioselectivity in this case. The high efficacy and enantioselectivity enable the present catalyst system of high practical potential.