Effect of Si addition on the properties of nanocrystalline ZrO2-supported cobalt catalysts

Summary This study shows that Si addition during the glycothermal synthesis of nanocrystalline zirconia modified the properties of the zirconia, i.e. particle morphology and crystallite size, resulting in an improvement in the catalytic performance of Co/ZrO₂catalysts in CO hydrogenation.</o:p>     

Influence of alloying platinum for the hydrogenation of p-chloronitrobenzene over PtM/Al2O3 catalysts with MSn,Pb, Ge,Al, Zn

Hydrogenation of p-chloronitrobenzene (CNB) has been studied, in methanol suspension, at 303 K and atmospheric pressure, over a series of Pt/Al₂O₃ and PtM/Al₂O₃ catalysts (MSn, Pb, Ge, Al, Zn). The bimetallic catalysts were prepared by the so-called controlled surface reaction method by reacting organometallic compounds on the well-dispersed Pt/Al₂O₃ parent sample. The kinetics obeys a modified Langmuir-Hinshelwood model with competitive adsorption between CNB and hydrogen. The competition of adsorption no longer holds at high CNB concentration: on the Pt surface saturated by CNB, there are still Pt sites available for the chemisorption of the smaller hydrogen molecule. A rate law is then proposed which allows both adsorption and rate constants to be determined. Upon addition of the second metal M, the specific activity per Pt surface atom goes through a maximum value around a chemical composition M/Pt≌0.1–0.2. It is suggested that an electron-deficient species of the second metal promotes the reaction rate by activating the nitrogenoxygen bond; ionic tin species are better promoters for this purpose. At high CNB conversion (> 98%) the yield of the desired product, p-chloroaniline (CAN), increases from 82% on pure Pt/Al₂O₃ to 97.5% on PtSn/Al₂O₃ (Sn/Pt = 0.36). The improvement of selectivity to CAN is not due to a decrease in CAN dehalogenation rate, which is not affected by alloying. Actually, the promoting effect of the second metal decreases the relative strength of adsorption between CAN and CNB up to a factor of 10: CAN is then easily removed from the surface by CNB, thus preventing hydrodechlorination.     

Effect of rare earths on selective hydrogenation of p-chloronitrobenzene over PtMOx/CNTs catalysts

The effect of rare earths(Sm,Pr,Ce,Nd and La)on the hydrogenation properties of p-chloronitrobenzene(CNB)over Pt/CNTs catalyst was studied in ethanol at 303 K and normal pressure.The results exhibited that the hydrogenation of p-CNB could be carded out over PtMOx/CNTs catalysts.Both catalytic activities and yields of p-chloroaniline(CAN)were all improved.PtCeOx/ CNTs catalyst exhibited the best catalytic activity(TOF was 0.47 s~(-1))and the highest yield of p-CAN(97.5 mol%).PtCeOx/CNTs (1.0 wt%)catalyst ...     

Selective hydrogenation of o-chloronitrobenzene (o-CNB) over supported Pt and Pd catalysts obtained by laser vaporization deposition of bulk metals

Carbon nanotubes (CNTs), γ-alumina (γ-Al₂O₃) and silica (SiO₂) supported Pt and Pd catalysts were produced by laser vaporization deposition of respective bulk metals. The catalysts were characterized by inductive coupled plasma emission spectrometer (ICP), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The catalytic properties of the catalysts were investigated in the liquid phase hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN) under 333 K and 1.0 MPa hydrogen pressure. The results show that the catalytic properties are greatly affected by the supports. Pt/CNTs catalyst exhibits the best catalytic performance among the Pt-based catalysts, producing o-CAN with 99.6% selectivity at complete conversion. Pd/CNTs catalyst exhibits the best catalytic performance among the Pd-based catalysts, giving o-CAN with 95.2% selectivity at complete conversion. For Pt-based catalysts, geometric effect and the textures and properties of the supports play important roles on catalytic properties. On the other hand, geometric effect, electronic effect and the textures and properties of the supports simultaneously influence the catalytic properties of the Pd-based catalysts. In addition, hydrogenolysis of the C–Cl bond can be well inhibited over all catalysts prepared by laser vaporization deposition.     

Energies of electronic states of promoter ions in hydrodesulfurization catalysts

Poly-vinylpyrrolidone-anchored (PVP) supported platinum catalyst (PVP-Pt) and rare earth metals (Sm³⁺, Pr³⁺, Ce³⁺, Nd³⁺and La³⁺) promoted PVP-Pt catalysts were prepared and used in the hydrogenation of o- and m-chloronitrobenzene (CNB) in ethanol at 303 K and atmospheric pressure. It was found that rare earth metals improved the selectivity of chloronitrobenzene to chloroaniline (CAN), while the hydrogenation rate of CNB decreased. In the presence of NaOH, PVP-Pr-Pt and PVP-La-Pt catalysts exhibit the highest selectivity in the hydrogenation of CNB. At the same time different support materials of Pt catalyst (such as polyethylene glycol (PEG), ethyl cellulose (EC)) possessed great influence on catalytic activity and selectivity of p-CAN.This revised version was published online in December 2005 with corrections to the Cover Date.     

Transformation of n-hexane on Al2O3and SiO2supported Pt, Pt+Ga and Ir+Pt+Ga catalysts prepared by anchoring methods

Summary Transformation of n-hexane over Al₂O₃and SiO₂supported Pt, Pt+Ga and Ir+Pt+Ga catalysts was studied in a continuous-flow reactor operated under slug-pulse mode at 520°C. Bimetallic catalysts were prepared by introducing first Ga(OEt)₃and then diallylplatinum as precursor compounds. Iridium was then introduced viadecomposition of Ir₄(CO)₁₂adsorbed onto Pt+Ga catalysts. The addition of Ga to Pt/SiO₂catalyst decreased hydrogenation, aromatization and hydrogenolysis selectivity. Over Pt/Al₂O₃catalyst Ga increased hydrogenolysis selectivity and decreased isomerization and C₅-cyclization. The main effect of Ir was to increase hydrogenolysis selectivity and the stability of catalysts.</o:p>     

Low temperature complete combustion of dilute propane over Mn-doped ZrO2 (cubic) catalysts

Combustion of dilute propane (0.9 mol%) over Mn-doped ZrO₂ catalysts prepared using different precipitating agents (viz. TMAOH, TEAOH, TPAOH, TBAOH and NH₄OH), having different Mn/Zr ratios (0.05—0.67) and calcined at different temperatures (500—800°C), has been thoroughly investigated at different temperatures (300—500°C) and space velocities (25,000–100,000 cm³ g⁻¹ h⁻¹) for controlling propane emissions from LPG-fuelled vehicles. Mn-doped ZrO₂ catalyst shows high propane combustion activity, particularly when its ZrO₂ is in the cubic form, when its Mn/Zr ratio is close to 0.2 and when it is prepared using TMAOH as a precipitating agent and calcined at 500—600°C. Pulse reaction of propane in the absence of free-O₂ over Mn-doped ZrO₂ (cubic) and Mn-impregnated ZrO₂ (monoclinic) catalysts has also been investigated for studying the relative reactivity and mobility of the lattice oxygen of the two catalysts. Both reactivity and mobility of the lattice oxygen of Mn-doped ZrO₂ are found to be much higher than that of Mnimpregnated ZrO₂. Propane combustion over Mn-doped ZrO₂ catalyst involves a redox mechanism     

Liquid-Phase Hydrogenation of Chloronitrobenzene Over Pt-Sn-B Amorphous Catalyst Supported by Carbon Nanotubes

The Pt-Sn-B/carbon nanotubes (CNTs) catalyst was prepared by impregnation-chemical reduction method. Its catalytic performance was evaluated by liquid-phase hydrogenation of chloronitrobenzene (CNB). The results showed that the catalyst had higher catalytic performance than common hydrogenation catalysts. The conversion of CNB could reach 99.9%, and the dechlorination of chloroaniline (CAN) was less than 1.9% when catalyzed by Pt-Sn-B/CNTs and more than 8.0% when catalyzed by common hydrogenation catalysts. X-ray diffraction and selected area electron diffraction analysis showed that Pt-Sn-B/CNTs had an amorphous alloy structure that can improve catalytic performance. Transmission electron micrograph image showed that the catalyst particles were highly distributed on the surface of CNTs. The hydrodechlorination of CNB was mainly affected by the unique structure of CNTs and the nature of the amorphous metals on the surface of CNTs. The relationship between the interaction of CNTs and amorphous metals and the catalytic performance of the catalyst is also discussed. Translated from the Chinese Journal of Catalysis, 2005, 26(3) (in Chinese)     

Selective hydrogenation of α,β-unsaturated aldehydes over Pt supported on cerium–zirconium mixed oxide of different composition

Cerium–zirconium mixed oxides with different Ce/Zr ratio were prepared and used as supports for Pt-containing catalysts. The study of the catalysts in the cinnamaldehyde hydrogenation reaction has shown that cinnamaldehyde conversion and cinnamyl alcohol selectivity strongly depend on the CeO₂ content in the support. The highest cinnamyl alcohol yield of 81% was obtained in 105 min at room temperature and atmospheric pressure over the 1%Pt/CeO₂–ZrO₂ catalyst with Ce : Zr atomic ratio equal to 4 : 1.     

Preparation,Characterization, and Catalytic Behavior of Nanostructured Mesoporous CuO/ZrO2 Catalysts for Low-Temperature CO Oxidation

High-surface area mesoporous 20 mol% CuO/ZrO₂ catalyst was prepared by a surfactant-assisted method of nanocrystalline particle assembly, and characterized by x-ray powder diffraction (XRD), N₂ adsorption, transmission electron microscopy (TEM), H₂-TPR, TG-DTA, and x-ray photoelectron spectra (XPS) techniques. The catalytic properties of the CuO/ZrO₂ nanocatalysts calcined at different temperature were evaluated by low-temperature carbon monoxide oxidation using a CATLAB system. The results showed that these mesoporous nanostructured CuO/ZrO₂ catalysts were very active for low-temperature CO oxidation and the CuO/ZrO₂ catalyst calcined at 400°C exhibited the highest catalytic activity.     

The transformations of toluene on alumina and bifunctional catalysts

The activity of Pt, Rh, and Ni catalysts deposited on Al₂O₃ and tungsten-containing catalysts 20% H₄SiW₁₂O₄₀/ZrO₂ and 15% WO_x/ZrO₂ in the hydrogenation of toluene and toluene ring opening and isomerization in the presence of hydrogen was studied. Under experimental conditions (160–360°C, 2.2 MPa), the main reactions on Rh/Al₂O₃ were the hydrogenation of toluene into methylcyclohexane, hydrogenolysis into isoheptanes, and hydrocracking into alkanes C₁–C₆. On Pt, Rh, and Ni catalysts on carriers with strong acid properties, the isomerization of the six-membered into five-membered ring followed by hydrogenolysis (hydrocracking) of alkylcyclopentanes occurred. The yield of heptane isomers, however, did not exceed 13%. The activity of Pt and Rh catalysts on a high-acidity carrier (WO_x/ZrO₂) in hydrocracking was much higher than that of catalysts based on deposited heteropoly acid. The yields of hydrogenolysis (hydrocracking) products on Ni/WO_x/ZrO₂ were much lower than on Pt(Rh)/WO_x/ZrO₂. The highest yield of ring opening products (isoheptanes and n-heptane) was obtained with layered loading of two catalysts; it reached 58 wt % at 300°C and a 2.2 MPa pressure, which was 4.5 and 2 times higher than the yield obtained on Ni-Pt/WO_x/ZrO₂ and 2% Rh/Al₂O₃ catalysts. Hydrodemethylation was not the main direction of toluene transformations on any of the catalysts studied.     

In situ FT-IR study on CO2 hydrogenation over SiO2-supported PtM (M = Cr, Mo, W) complex catalysts

The in situ FT-IR spectra were used to study the CO₂ hydrogenation reaction over the SiO₂-supported heterobinuclear metal complex catalysts, PtM (M=Cr, Mo, W). The bands, which correspond to the formate species absorbed on the catalysts, were observed. During the hydrogenation reactions, the adsorbed linear and bridging CO was not observed. The experimental results suggest that for the CO₂ and CO hydrogenation reaction over the same catalysts, their catalytic active intermediate species and the reaction mechanisms should be different.     

Ordered mesoporous silicates of MCM-41 type as support of pt catalysts for the enantioselective hydrogenation of 1-phenyl-1,2-propanedione

Summary Platinum catalysts (1 wt.%) supported on MCM-41 type and SiO₂have been prepared, characterized and evaluated in the enantioselective hydrogenation of 1-phenyl-1,2-propanedione at 298 K and 20 bar of hydrogen pressure, using cinchonidine (CD) as chiral modifier. Chemisorption and TEM results revealed that both catalysts posses similar metal dispersion, however, significant differences in the catalytic behavior were observed. With dichloromethane as solvent, high hydrogenation rates and ee values around 47% were obtained for the Pt/MCM-41 catalyst. This fact is attributed to a confinement effect. The initial reaction rate is strongly dependent on the CD concentration, and the reaction rate (or ee) vsCD concentration plot exhibits bell-type curves. The main products were (R) -1-hydroxy-1-phenylpropanone and (S) -1-hydroxy-1-phenylpropanone.</o:p>     

High catalytic activity of V2O5-ZrO2 modified with H2SO4 for propene partial oxidation

For V₂O₅–ZrO₂ catalysts, up to 10 mol% the crystalline structure of V₂O₅ was not observed, indicating a good dispersity the surface of ZrO₂. V₂O₅–ZrO₂ catalyst modified with H₂SO₄ exhibited much on higher catalytic activity for propene partial oxidation than unmodified catalysts due to the increased acidity and acid strength of modified catalyst.     

Au/ZrO2催化CO氧化反应中ZrO2纳米粒子的尺寸效应

从同一ZrO(OH)₂出发制备了三种不同尺寸的ZrO₂纳米颗粒(ZrO₂-CP: 40～200 nm, ZrO₂-AN: 18～25 nm, ZrO₂-AD: 10～15 nm), 采用沉积-沉淀方法制备了相应的Au/ZrO₂催化剂. 用XRD, XRF, TEM和低温N₂吸附对ZrO₂和Au/ZrO₂进行了表征. XRD和TEM分析表明Au/ZrO₂样品中Au粒子的平均尺寸为4～5 nm, 而ZrO₂的晶相和颗粒大小没有因为“负载”Au粒子而发生变化. CO催化氧化反应的结果表明, Au/ZrO₂催化活性随着ZrO₂纳米粒子尺寸的减小活性明显增加. TEM/HRTEM结果表明, Au/ZrO₂催化剂中Au粒子与ZrO₂颗粒接触界面随ZrO₂颗粒尺寸的减小而明显增加, 这很可能是含有更小尺寸ZrO₂纳米粒子的Au/ZrO₂催化剂具有更高催化活性的重要原因.     

Metal–organic framework derived Pd/ZrO2@CN as a stable catalyst for the catalytic hydrogenation of 2,3,5‐trimethylbenzoquinone

Metal–organic frameworks (MOFs) have recently been identified as versatile sacrificing templates to construct functional nanomaterials for heterogeneous catalysis. Herein, we report a thermal transformation strategy to directly fabricate metal Pd nanoclusters inlaid within a ZrO₂@nitrogen‐doped porous carbon (Pd/ZrO₂@CN) composite using Pd@NH₂‐UiO‐66(Zr) as a precursor that was pre‐synthesized by a one‐pot hydrothermal method. The developed Pd/ZrO₂@CN as a robust catalyst delivered remarkable stability and activity to the catalytic hydrogenation of 2,3,5‐trimethylbenzoquinone (TMBQ) to 2,3,5‐trimethylhydroquinone (TMHQ), a key reaction involved in vitamin E production. The hydrogenation was carried out at 110 °C with 1.0 MPa H₂, and it resulted in 98% TMHQ yield as the sole product over five consecutive cycles, outperforming the analogue Pd/ZrO₂@C without nitrogen doping templated from Pd@UiO‐66(Zr). The excellent catalytic properties of Pd/ZrO₂@CN likely originated from the highly stable ultrafine Pd nanoclusters inlaid within ZrO₂@CN matrix on account of the strong interaction between N and Pd, as well as on the Lewis acidity of ZrO₂, which was beneficial to the hydrogenation.     

Development of high performance Cu/ZnO-based catalysts for methanol synthesis and the water-gas shift reaction

Our groups studies on Cu/ZnO-based catalysts for methanol synthesis via hydrogenation of CO₂ and for the water-gas shift reaction are reviewed. Effects of ZnO contained in supported Cu-based catalysts on their activities for several reactions were investigated. The addition of ZnO to Cu-based catalyst supported on Al₂O₃, ZrO₂ or SiO₂ improved its specific activity for methanol synthesis and the reverse water-gas shift reaction, but did not improve its specific activity for methanol steam reforming and the water-gas shift reaction. Methanol synthesis from CO₂ and H₂ over Cu/ZnO-based catalysts was extensively studied under a joint research project between National Institute for Resources and Environment (NIRE; one of the former research institutes reorganized to AIST) and Research Institute of Innovative Technology for the Earth (RITE). It was suggested that methanol should be produced via the hydrogenation of CO₂, but not via the hydrogenation of CO, and that H₂O produced along with methanol should greatly suppress methanol synthesis. The Cu/ZnO-based multicomponent catalysts such as Cu/ZnO/ZrO₂/Al₂O₃ and Cu/ZnO/ZrO₂/Al₂O₃/Ga₂O₃ were highly active for methanol synthesis from CO₂ and H₂. The addition of a small amount of colloidal silica to the multicomponent catalysts greatly improved their long-term stability during methanol synthesis from CO₂ and H₂. The purity of the crude methanol produced in a bench plant was 99.9 wt% and higher than that of the crude methanol from a commercial methanol synthesis from syngas. The water-gas shift reaction over Cu/ZnO-based catalysts was also studied. The activity of Cu/ZnO/ZrO₂/Al₂O₃ catalyst for the water-gas shift reaction at 523 K was less affected by the pre-treatments such as calcination and treatment in H₂ at high temperatures than that of the Cu/ZnO/Al₂O₃ catalyst. Accordingly, the Cu/ZnO/ZrO₂/Al₂O₃ catalyst was considered to be more suitable for practical use for the water-gas shift reaction. The Cu/ZnO/ZrO₂/Al₂O₃ catalyst was also highly active for the water-gas shift reaction at 673 K. Furthermore, a two-stage reaction system composed of the first reaction zone for the water-gas shift reaction at 673 K and the second reaction zone for the reaction at 523 K was found to be more efficient than a one-stage reaction system. The addition of a small amount of colloidal silica to a Cu/ZnO-based catalyst greatly improved its long-term stability in the water-gas shift reaction in a similar manner as in methanol synthesis from CO₂ and H₂.     

Hydrocracking vegetable oil on borate-containing catalysts: Effect of nature of support

The structure, texture, and acid properties of platinum catalysts on oxide (Al₂O₃, ZrO₂, ZrO₂–Al₂O₃) and borate-containing supports (B₂O₃–Al₂O₃, B₂O₃–ZrO₂) are studied. The catalysts are tested in the process of hydrocracking sunflower-seed oil at 380°C, 4.0 MPa, and a weight stock feed rate of 1.0 h^–1. It has been found that aluminum oxide (A) contains the γ-Al₂O₃ phase, zirconium dioxide (Z) includes 85 and 15 rel. % of the monoclinic (M) and tetragonal (T) phases, respectively, while zirconium dioxide with the addition of 2.5 wt % Al₂O₃ (ZA) comprises 14 and 86 rel. % of the M–ZrO₂ and T–ZrO₂ phases, respectively. The B₂O₃–Al₂O₃ (BA) and B₂O₃–ZrO₂ (BZ) systems modified with boron oxide (20 wt %) are X-ray amorphous. A Pt/BA catalyst differs from a Pt/A catalyst, while a Pt/BZ catalyst has a larger specific surface area and acidity than Pt/Z and Pt/ZA catalysts and contains Bronsted acidic centers (BACs) along with Lewis acidic centers (LACs). Only LACs are present on the surface of Pt/A, Pt/Z, and Pt/ZA catalysts. The LAC/BAC ratio in Pt/BA and Pt/BZ catalysts is 0.3 and 1.0, respectively. All the catalysts provide complete oil conversion to give C₅₊ hydrocarbons with a yield of 81.7–87.3 wt %. Pt/A catalyzes mainly decarboxylation and hydrogenation–dehydration reactions, while Pt/Z and Pt/ZA provide decarboxylation. The yield of diesel fraction reaches 71.8–73.9 wt % with an n-alkane content of 94.0–95.9 wt %. One-stage oil hydrocracking with the prevalence of hydrodecarbonylation and hydrogenation–dehydration reactions occurs on Pt/BA and Pt/BZ catalysts for 20 h to give the yield of the diesel fraction of at least 81.4 and 74.4 wt % and the total content of iso-alkanes and cycloalkanes of at least 28.3 and 60.7 wt %, respectively.     

合成方法对Rh/CeO2-ZrO2-La2O3催化剂的结构、表面性能及DeNOx活性的影响

用沉积沉淀法合成两种不同系列的CeO2-ZrO2-La2O3混合氧化物(ZrO2和La2O3沉积CeO2粒子(标记为A-x)以及CeO2和La2O3沉积ZrO2粒子(标记为B-x)),并用作Rh催化剂的载体。XRD、拉曼、TPR、XPS和O2脉冲等表征结果显示出不同的沉积顺序将导致不同的结构和氧化还原性能,且B-x具有更高的氧迁移性、储氧能力和表面Ce浓度。当其负载Rh后,Rh/B-x催化剂具有更高的NO和CO转化率及N2选择性,且Ce的最佳含量为50at%。这可能归因于Rh负载于富铈表面形成更多有利于NO分解的表面Ce3+活性位。     

Hydrogenation of chloronitrobenzenes over Pd and Pt catalysts supported on cationic resins

Liquid phase hydrogenation of chloronitrobenzene isomers (x-CNB x = 2, 3, 4) to the corresponding chloroanilines (x-CAN) at mild reaction conditions (0.6 MPa, 25°C, diethyl ether-methanol as solvents) over palladium and platinum catalysts containing 1 mass % of metal on trimethylammonium functionalized poly{styrene-co-divinylbenzene} (Dowex-D) was studied. The average selectivities to x-CAN over Pd/D-Cl and Pd/D-OH catalysts were 72 % and 42 %, respectively, at the x-CNB conversion of about 80 %. The average selectivities of 81 % and 84 % were achieved using Pt/D-Cl and Pt/D-OH, respectively, at the x-CNB conversion of approximately 90 %, whereas the average starting reaction rates were 1.2 × 10^?3 mol g^?1 s^?1 and 2.6 × 10^?3 mol g^?1 s^?1 (hydrogen consumption rate per mass of platinum), respectively. Under similar reaction conditions, using palladium catalysts supported on a resin with anionic groups anchored to polymeric chains at the average reaction rate equal to 3.8 × 10^?3 mol g^?1 s^?1 (hydrogen consumption rate per mass of palladium), the selectivities from 85 % (2-CAN and 3-CAN) to 95 % (4-CAN) were achieved (Kratky et al., 2002).