Characterization of LaRhO3 perovskites for dry (CO2) reforming of methane (DRM)

This work reports on the characterization of LaRhO₃ perovskite as a catalyst for dry reforming of methane. The catalyst was studied using CH₄-temperature programmed reduction (TPR), H₂-TPR, and temperature programmed surface reaction (TPSR), and the changes in the crystal structure of the catalyst due to these treatments were studied by X-ray diffraction (XRD). XRD pattern of the freshly calcined perovskites showed the formation of highly crystalline LaRhO₃ and La₂O₃ phases. H₂-TPR of the fresh calcined catalyst showed a shoulder at 342°C and a broad peak at 448°C, suggesting that the reduction of Rh in perovskite occurs in multiple steps. XRD pattern of the reduced catalyst suggests complete reduction of the LaRhO₃ phase and the formation of metallic Rh and minor amounts of La(OH)₃. The CH4-TPR data show qualitatively similar results as H₂-TPR, with a shoulder and a broad peak in the same temperature range. Following the H₂-TPR up to 950°C, the same batch of catalyst was oxidized by flowing 5 vol. % O₂/He up to 500°C and a second H₂-TPR (also up to 950°C) was conducted. This second H₂-TPR differed significantly from that of the fresh calcined catalyst. The single sharp peak at 163°C in the second H₂-TPR suggests a significant change in the catalyst, probably causedby the transformation of about 90 % of the perovskite into Rh/La₂O₃. This was confirmed by the XRD studies of the catalyst reduced after the oxidation at 500°C. TPSR of the dry reforming reaction on the fresh calcined catalyst showed CO and H₂ formation starting at 400°C, with complete consumption of the reactants at 650°C. The uneven consumption of reactants between 400°C and 650°C suggests that reactions other than DRM occur, including reverse water gas shift (RWGS) and the Boudouard reaction (BR), probably as a result of in-situ changes in the catalyst, consistent with the H₂-TPR results. TPSR, after a H₂-TPR up to 950°C, showed that the dry reforming reaction did not light off until 570°C, which is much higher temperature than the one observed using fresh calcined catalyst. This shows that the uniform sites produced during the 950°C H₂-TPR are catalytically less active than those of the fresh calcined catalyst, and that no significant side reactions such as RWGS or the Boudouard reaction occur. This suggests that reduction leads to the formation of a single type of sites which do not catalyze simultaneous side reactions.     

Direct oxidative C(sp3)─H/C(sp2)─H coupling reaction using recyclable Sr-doped LaCoO3 perovskite catalyst

A strontium-doped lanthanum cobaltite perovskite, La_0.6Sr_0.4CoO₃, was prepared and utilized as a recyclable heterogeneous catalyst for the direct oxidative C(sp³)─H/C(sp²)─H coupling reaction between cyclic ethers and alkenes or coumarins to achieve corresponding α-functionalized ethers. The α-functionalization of cyclic thioethers or amides with alkenes or coumarins was also achieved via this protocol. The La_0.6Sr_0.4CoO₃ catalyst exhibited better performance than a variety of homogeneous and heterogeneous catalysts. Utilizing a recyclable catalyst would offer a greener option for the direct oxidative C(sp³)─H/C(sp²)─H coupling reaction. To our best knowledge, the C(sp³)─H/C(sp²)─H coupling between olefins and ethers to generate α-functionalized ethers using a heterogeneous catalyst has not been previously reported, and the α-functionalization of cyclic thioethers or amides with alkenes or coumarins is new.     

Initiation behaviour in hydrogenation of pyrolysis gasoline over presulphided Ni-Mo-Zn/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

A presulphided treatment was applied to the oxidic Ni-Mo-Zn/Al₂O₃ catalyst (nickel catalyst) in order to avoid thermal run-away during initiation of the hydrogenation of pyrolysis gasoline. The physico-chemical properties of the prepared oxidic nickel catalyst, the reduced and passivated (RP) nickel catalyst and the sulphided (RPS) nickel catalyst were characterised using N₂ adsorption-desorption, X-ray diffraction, temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). The TPR results showed that the reducibility of the RP Ni-Mo-Zn/Al₂O₃ catalyst was improved over the oxidic nickel catalyst. The XPS spectra confirmed the binding energy of the RPS nickel catalyst to be higher than that of the oxidic nickel catalyst. The catalytic performance was evaluated on a fixed-bed reactor (reaction temperature between 30 °C and 70°C, at 2.8 MPa of total pressure and weight hourly space velocity of 2.0 h^?1, the volume of H₂/pyrogasoline = 200: 1). The rising temperature of the RPS nickel catalyst was almost 20°C lower than that of the oxidic nickel catalyst during the initial stage of the hydrogenation reaction. The results indicated that the RPS nickel catalyst exhibited better stability than the oxidic nickel catalyst during the start-up period, thereby providing a better selectivity in long-term operation.     

聚合物负载季鏻盐催化 CO2 与环氧化物的环加成反应

 制备了聚合物负载的季鏻盐催化剂, 并用于 CO₂ 与环氧氯丙烷环加成反应中. 采用红外光谱、热分析、原子吸收光谱和扫描电子显微镜等手段测定了催化剂的结构、热性能、磷元素含量和表面形貌等. 考察了 CO₂ 压力、温度、催化剂用量和反应时间等对环加成反应性能的影响. 结果表明, 在催化剂用量为 0.09 g, CO₂ 压力为 4.5 MPa, 于 150 ^oC 反应 6 h 时, 3-氯甲基环碳酸酯收率可达 97.7%, 选择性大于 99%. 且催化剂易分离回收, 重复使用 5 次后产物收率和选择性没有明显下降. 同时探讨了该催化剂上 CO₂ 环加成合成环碳酸酯的可能机理.     

Diphenylphosphorylated PEG (DPPPEG) as a new support for generation of nano-Pd(0) as catalyst for carbon–carbon bond formation via copper-free Sonogashira and homocoupling reactions of aryl halides in PEG

In this study, synthesis and application of diphenylphosphorylated PEG₂₀₀ (DPPPEG₂₀₀) are described. Herein, we report a very simple procedure for the preparation of DPPPEG₂₀₀ as a stable solid through the reaction of PEG₂₀₀ with ClPPh₂. This compound was used as a very suitable ligand for the in situ generation of nano-Pd(0) particles through its reaction with PdCl₂ as a pre-catalyst. Isolation of this catalyst is very simple through addition of diethyl ether to the reaction mixture and centrifugations. Full characterization of the nano-Pd(0)/DPPPEG200 was performed by XRD spectra, UV–Vis spectra, and also by TEM image. This nano-complex was used as an efficient catalyst for copper-free Sonogashira and homocoupling reactions of aryl halides. The sonogashira reaction of aryl halides was conducted at 80 °C in PEG. However, the homocoupling reaction was performed at 100 °C for aryl iodides and activated aryl bromides and at 130 °C for deactivated aryl bromides and aryl chlorides in PEG. The catalyst was recovered and recycled for four consecutive runs.     

氯化亚锡催化“一锅法”合成N1-取代的3,4-二氢嘧啶-2(1H)-酮

以芳香醛、乙酰乙酸乙酯(甲酯)、单取代脲为原料,氯化亚锡为催化剂,在无溶剂、80℃条件下,通过三组分"一锅法"合成了一系列N1-取代的3,4-二氢嘧啶-2(1H)-酮衍生物。考察了催化剂用量和反应温度对产品收率的影响。通过IR、~1H NMR、~(13)C NMR和元素分析对目标产物结构进行确证,提出了可能的催化作用机理。本文的合成方法具有催化剂活性高、廉价易得和反应时间短、条件温和、产率高、绿色环保等优点。     

Palladium(0)/PAr3‐Catalyzed Intermolecular Amination of C(sp3)H Bonds: Synthesis of β‐Amino Acids

An intermolecular C(sp³)? H amination using a Pd⁰/PAr₃ catalyst was developed. The reaction begins with oxidative addition of R₂N? OBz to a Pd⁰/PAr₃ catalyst and subsequent cleavage of a C(sp³)? H bond by the generated Pd? NR₂ intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed C? H arylation reactions. The electron‐deficient triarylphosphine ligand is crucial for this C(sp³)? H amination reaction to occur.     

Low Temperature WGS Catalysts for Hydrogen Station and Fuel Processor Applications

Generally, water gas shift (WGS) reaction is a very important step in the industrial production of hydrogen, ammonia and other bulk chemicals utilizing synthesis gases. In this paper, we are reporting WGS reaction carried out in our research group for the application of hydrogen station and fuel processor. We prepared various Mo₂C, Pt–Ni-based and Cu-based catalysts for low temperature WGS reaction. The characteristics of the prepared catalyst were analyzed by N₂ physisorption, CO chemisorptions, XRD, SEM and TEM technologies, and compared with that of commercial Cu-Zn/Al₂O₃ catalyst. It was found that prepared catalysts displayed reasonably good activity and thermal cycling stability than commercial LTS (Cu–Zn/Al₂O₃) catalyst. It was found that the deactivation of commercial LTS catalyst during the thermal cycling run at 250 °C was caused by the sintering of active metal even though it shows high activity at less than 250 °C. The deactivation of Mo₂C catalyst during the thermal cycling run was caused by the transition of Mo^δ+, Mo^IV and Mo₂C on the surface of Mo₂C catalyst to Mo^VI(MoO₃) with the reaction of H₂O in reactants. However, they showed higher stability than the commercial LTS catalyst during thermal cycling test. The Pt–Ni/CeO₂ catalyst after the thermal cycling shows slightly deactivation due to the sintering of Ni metal. Among Cu-based catalysts, it was found that Cu–Mo/Ce_0.5Zr_0.5O₂ catalyst has higher WGS activity and stability over commercial LTS catalyst. The results suggested that Pt–Ni/CeO₂ and Cu–Mo/Ce_0.5Zr_0.5O₂ catalysts are desirable candidates for application in hydrogen station and fuel processor system even though all other catalysts deactivated slowly during the thermal cycling run.     

Palladium(0)/PAr3‐Catalyzed Intermolecular Amination of C(sp3)?H Bonds: Synthesis of β‐Amino Acids

An intermolecular C(sp³) H amination using a Pd⁰/PAr₃ catalyst was developed. The reaction begins with oxidative addition of R₂N OBz to a Pd⁰/PAr₃ catalyst and subsequent cleavage of a C(sp³) H bond by the generated Pd NR₂ intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed C H arylation reactions. The electron‐deficient triarylphosphine ligand is crucial for this C(sp³) H amination reaction to occur.     

Stereospecific polymerization of isobutyl vinyl ether catalyzed by calcined iron sulfate

The polymerization of isobutyl vinyl ether was studied in a heterogeneous system using iron (II) sulfate calcined in air at various temperatures as a catalyst. The maximum activity was shown by the catalyst calcined at 700°C, which effected the polymerization at room temperature in a few seconds, while the sulfate treated at 750°C was totally inactive. Poly(vinyl ethyl ether) was also obtained by the FeSO₄ (700°C) catalyst at room temperature. This catalyst formed the crystalline polymer (melting temperature 135–138°C) when the reaction was performed in toluene as solvent at room temperature. Poisoning experiments with Hammett indicators were carried out with the FeSO₄ (700°C) catalyst. The treatment with n-butylamine rendered it inactive in the reaction of isobutyl vinyl ether, while its catalytic activity was little affected by dicinnamalacetone. On the basis of the observed results, the nature of active sites of catalyst is discussed.     

Synthesis of ϵ‐Caprolactam from Cyclohexanone Oxime Using Zeolites Hβ, HZSM‐5, and Alumina Pillared Montmorillonite

The Beckmann rearrangement of cyclohexanone oxime (CHO) to ?‐caprolactam (?‐C) was studied in a plug flow reactor at 300–400°C under atmospheric pressure by using Hβ, ZSM‐5, and alumina pillared montmorillonite. With Hβ(X) Y zeolites, raising the SiO₂/Al₂O₃ molar ratio (X) results in the enhancement of catalyst acid strength with concomitant decrease of the total acid amount. In creasing the calcination temperature (Y) causes remarkable diminution of catalyst surface area, acid strength, and acid amount. A similar trend was found for AlPMY catalysts. In there action of CHO, the initial catalytic activity correlates well with the total acid amount of various catalysts except for Hβ(10) Y (Y > 600°C). The reaction proceeds on both Brönsted and Lewis acid sites and the catalyst deactivation most likely occurs at the strong Brönsted acid sites. The effect of solvents in the feed on the catalytic results was also investigated; it was found that polar solvents such as ethanol or n‐butanol give high ?‐C yield and longer catalyst life time. In the reaction of CHO/C₂H₅OH over Hβ(10)800 at 400°C and W/F 74.6 gh/mol, the CHO conversion and ?‐C yield remain 100% and 92%, respectively, for at least 20 h time‐on‐stream. The reaction paths and the mechanism for ?‐C formation are proposed.     

A new palladium complex supported on magnetic nanoparticles and applied as an catalyst in amination of aryl halides,Heck and Suzuki reactions

A simple, efficient and less expensive protocol for the phosphine-free C–C coupling reactions and synthesis of anilines in the presence of 2-aminobenzamide complex of palladium supported on Fe₃O₄ magnetic nanoparticles (Pd(0)-ABA-Fe₃O₄) has been reported. The Suzuki reaction was carried out in water or PEG using phenylboronic acid (PhB(OH)₂) or sodium tetraphenyl borate (NaBPh₄). Pd(0)-ABA-Fe₃O₄ has been found promising for Heck reaction of butyl acrylate, styrene or acrylonitrile with aryl halides (including Cl, Br and I). Also, Pd(0)-ABA-Fe₃O₄ has been found as efficient catalyst for the amination of aryl halides using aqueous ammonia. The products have been obtained in short reaction times and high yields. The catalyst was easily separated using an external magnet from the reaction mixture and reused for several runs without significant loss of its catalytic efficiency or palladium leaching. The leaching of catalyst has been examined by hot filtration and ICP-OES technique. The nanomagnetical catalyst was characterized by FTIR, TGA, XRD, VSM, TEM, SEM, EDS, DLS and ICP-OES techniques.     

高效组合型 Pd/C 催化剂用于 Suzuki 偶联反应

 采用有机金属 Pd2(dba)3 (dba 为二亚苄基丙酮) 还原分解法制得均匀分布的 Pd 纳米颗粒 (粒径为 3~6 nm) 混合液, 并用活性炭直接吸附得到了组合型 Pd/C 纳米催化剂. 采用透射电子显微镜、X 射线光电子能谱和 X 射线衍射等手段测定了催化剂表面 Pd 颗粒大小分布、晶型和化学态等. 将该催化剂用于 Suzuki 碳-碳偶联反应, 其催化活性比浸渍法制备的 Pd/C 催化剂高 2 倍以上. 以溴代芳烃为底物时, 在 80 oC 下 0.5 h 后偶联产物收率可达 98% 以上. 以邻氯硝基苯为底物时, 在 110 oC 下 1 h 后偶联产物收率可达 64%; 延长反应时间, 产物收率可达 90% 以上.     

Ethylene production by the oxidative condensation of methane in the presence of MnMW/SiO<Subscript>2</Subscript> catalysts (M = Na,K, and Rb)

The samples of MnMW/SiO₂ (M = Na, K, and Rb) were synthesized using various synthesis methods under varied heat treatment conditions and their physicochemical properties and activity in the reaction of the oxidative condensation of methane (OCM) were studied for the development of an effective catalyst for the resource-saving process of natural gas conversion into ethylene. It was found that the preparation method exerts an effect on the textural characteristics of the samples and the reducing properties of the cations of manganese and tungsten. It was determined that the composition of a W-containing phase depends on the alkali metal, and a ratio between the polymorphous modifications of SiO₂ is controlled by the method of synthesis and the conditions of catalyst heat treatment. It was established that the yield of C₂ hydrocarbons in the OCM reaction increased with the use of incipient wetness impregnation instead of the method of mixing with a suspension for catalyst preparation and with an increase in the catalyst heat treatment temperature from 700 to 1000°C. The optimum composition of the catalyst and the condition of its synthesis were found: 2Mn_0.8Na₃W/SiO₂ obtained by the impregnation method and calcined at 1000°C ensured the yield of target products of ~20% with a CH₄ conversion of ~35% at a reaction temperature of 850°C.     

Hydrosilylation reactions catalysed by decacarbonyldimanganese(O)

Decacarbonyldimanganese(O) complex, Mn₂(CO)₁₀, has been evaluated as a catalyst for hydrosilylation reactions of 1-hexene with tertiary silanes, Et₃SiH and (EtO)₃SiH. The reaction of Et₃SiH appears to be first order with respect to the catalyst, to the hexene and to the silane, although catalyst deactivation occurs when relatively high silane concentrations are used. The reaction rate is slightly affected by varying the type of the silane used. The rate of disappearance of the tertiary silane is consistent with that of the 1-hexene, which means that the catalyst is selective to hydrosilylation reactions. This was confirmed by following the rates of disappearance of Si-H and CC IR bands at 2210, 2100 and 1650 cm⁻¹ for (EtO)₃SiH, Et₃SiH and 1-hexene respectively. A comparison of the behaviour of Mn₂(CO)₁₀ with that of Co₂(CO)₈ is reported here, together with a suggested mechanism for the manganese catalyst.     

Catalytic deoxygenation of waste soybean oil over hybrid catalyst for production of bio-jet fuel: in situ supply of hydrogen by aqueous-phase reforming (APR) of glycerol

A one-pot reaction was performed to produce oxygen-free saturated hydrocarbons via the catalytic deoxygenation and hydrogenation of waste soybean oil over a hybrid catalyst (Pd/C and NiO/γ-Al₂O₃). We utilized in situ hydrogen generated from a reforming reaction of glycerol, a byproduct of triglyceride hydrolysis, for the one-pot reaction to produce hydrocarbons. When NiO/γ-Al₂O₃ (2 g) was used along with Pd/C (1 g), most of the unsaturated free fatty acids (FFAs) were hydrogenated into saturated FFAs, and the percentage of desirable hydrocarbons in the liquid product increased, in contrast to the case when only Pd/C (1 g) was used. This result means that using a hybrid catalyst is better for promoting the catalytic deoxygenation reaction than increasing the degree of loading of Pd/C, and suggests that it should be possible to decrease the amount of precious metal catalysts to be used for deoxygenation reaction.     

Novel synthesis of a highly active carbon-supported Ru85Se15 chalcogenide catalyst for the oxygen reduction reaction

A carbon-supported Ru₈₅Se₁₅ chalcogenide catalyst was synthesized via a microwave-assisted polyol process using RuCl₃ and Na₂SeO₃ as the Ru and Se precursors. The Ru₈₅Se₁₅ chalcogenide catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The XRD pattern for Ru₈₅Se₁₅/C clearly exhibited the characteristic reflections of metallic ruthenium. The TEM image indicated that the Ru₈₅Se₁₅ chalcogenide catalyst was well dispersed on the surface of the carbon support with a narrow particle size distribution. Rotating disk electrode (RDE) and single-cell measurements were carried out to evaluate the electrocatalytic activity of the Ru₈₅Se₁₅ chalcogenide catalyst. The oxygen reduction reaction (ORR) activity of the Ru₈₅Se₁₅/C catalyst was compared with the commercial Pt/C catalyst with the absence/presence of methanol. In the absence of methanol, the Ru₈₅Se₁₅/C catalyst showed a comparable ORR activity with the Pt/C catalyst. However, in the presence of methanol, the Ru₈₅Se₁₅/C catalyst showed a better ORR activity than the Pt/C catalyst. The performance of the membrane electrode assembly (MEA) prepared with Ru₈₅Se₁₅/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) showed the maximum power density of 400 mW cm⁻² at the current density of 1300 mA cm⁻².     

Statistical optimization of biodiesel production from para rubber seed oil by SO3H-MCM-41 catalyst

The experimental parameters for biodiesel production from para rubber seed oil and methanol using a SO₃H-MCM-41 catalyst were optimized statistically. The SO₃H-MCM-41 catalyst was synthesized by co-condensation in the presence of tetraethyl orthosilicate, 3-mercaptopropyl (methyl) dimethoxysilane (MPMDS) and cetyl-trimethylammonium bromide. In the last step, the solid catalyst (SH-MCM41) was oxidized by H₂O₂ to SO₃H-MCM-41. The acid capacity of the obtained SO₃H-MCM-41 catalyst was quantified by back titration with 0.1 M sodium hydroxide. The physical and chemical properties of the SO₃H-MCM-41 were characterized by nitrogen adsorption/desorption, X-ray diffractometry, Fourier transform infrared spectroscopy and thermogravimetric analysis. The effect of varying the catalyst loading (wt.%), reaction time (h) and temperature (°C) and molar composition of MPMDS on the biodiesel yield were investigated using a 2^k factorial design. The optimal conditions to maximize the biodiesel yield, obtained from the response surface analysis using a Box–Behnken design, was a 14.5 wt.% catalyst loading, and a reaction time and temperature of 48 h and 129.6 °C. Under these conditions a fatty acid methyl ester (biodiesel) yield of 84% was predicted, and an 83.10 ± 0.39% yield experimentally obtained.     

High catalytic activity of a new Ag phosphorus ylide complex supported on montmorillonite: synthesis,characterization, and application for room temperature nitro reduction

In this work, the phosphorus ylide, [PPh₃CHC(O)CH₂Cl], was reacted with AgNO₃ to give the [Ag{C(H)PPh₃C(O)CH₂Cl}₂]⁺NO₃ ^? as the product. Then, it was supported on the modified montmorillonite nanoclay to prepare a new catalyst for the reduction reaction. The structure and morphology of the nanoclay catalyst were characterized by FT-IR, X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray analysis and transmission electron microscopy techniques; also, the content of silver was obtained by inductively coupled plasma analyzer. This composition was exploited to study its catalytic activity in the reduction in aromatic nitro compounds; it displayed the high catalytic activity. Factors such as catalyst amount, solvent, temperature and reaction time were all systematically investigated to elucidate their effects on the yield of catalytic reduction in nitroarenes. This catalytic system exhibited high activity toward aromatic nitro compounds under mild conditions. The catalyst was reused five times without any significant loss in its catalytic activity.     

Liquid Phase Selective Oxidation of Alcohols over VPO Catalysts Supported on Mesoporous Hexagonal Molecular Sieves (HMS)

The vanadium phosphorous oxide (VPO) catalysts, supported on mesoporous hexagonal molecular sieves (HMS) with different vanadium loadings, were prepared by precipitation method on organic phase. Techniques such as XRD, BET and SEM, were used for characterization of the catalyst. The bulk VPO catalyst contains vanadyl pyrophosphate phase ((VO)₂P₂O₇), and a small amount of VOPO₄. The high surface area, large pore volume and pore size of HMS in VPO/HMS samples, provide an excellent dispersion of same phase of VPO compound on the support surface. Oxidation of various alcohols was studied in the liquid phase over VPO/HMS catalyst, using tert‐butylhydroperoxide (TBHP) as an oxidant. The activity of VPO/HMS samples were considerably increased with respect to bulk VPO catalyst. At 90 °C, the obtained activities were 0.567 and 6.545 g_pro.g^?1_VPOh^?1 over the bulk VPO and 20 wt% VPO/HMS catalysts, respectively. The effects of substrates, reaction time, reaction temperature, solvents, catalyst recycling and leaching of VPO in liquid phase reaction were also investigated. The following order has been observed for the percentage of conversions of alcohols: Benzylic alcohol > Secondary alcohol ～ Primary alcohol. The kinetic of benzyl alcohol oxidation using excess TBHP over VPO/HMS catalyst was investigated at temperatures of 27, 60 and 90 °C, and followed a pseudo‐first order with respect to benzyl alcohol.