Evaluation of the Performance of Carbon Supported Pt–Ru–Ni–P as Anode Catalyst for Methanol Electrooxidation

This research is aimed to improve the activity and stability of ternary alloy Pt–Ru–Ni/C catalyst. A novel anodic catalyst for direct methanol fuel cell (DMFC), carbon supported Pt–Ru–Ni–P nanoparticles, has been prepared by chemical reduction method by using NaH₂PO₂ as a reducing agent. One glassy carbon disc working electrode is used to test the catalytic performances of the homemade catalysts by cyclic voltammetric (CV), chronoamperometric (CA) and amperometric i–t measurements in a solution of 0.5 mol L^–1 H₂SO₄ and 0.5 mol L^–1 CH₃OH. The compositions, particle sizes and morphology of home‐made catalysts are evaluated by means of energy dispersive analysis of X‐ray (EDAX), X‐ray diffraction (XRD) and transmission electron micrographs (TEM), respectively. TEM images show that Pt–Ru–Ni–P nanoparticles have an even size distribution with an average diameter of less than 2 nm. The results of CV, CA and i–t curves indicate that the Pt–Ru–Ni–P/C catalyst shows significantly higher activity and stability for methanol electrooxidation due to the presence of non‐metal phosphorus in comparison to Pt–Ru–Ni/C one. All experimental results indicate that the addition of non‐metallic phosphorus into the Pt–Ru–Ni/C catalyst has definite value of research and practical application for enhancing the performance of DMFC.     

Hydrogen production by partial oxidation of methanol over bimetallic Au–Ru/Fe2O3 catalysts

Hydrogen production by partial oxidation of methanol (POM) was investigated over Au–Ru/Fe₂O₃ catalyst, prepared by deposition–precipitation. The activity of Au–Ru/Fe₂O₃ catalyst was compared with bulk Fe₂O₃, Au/Fe₂O₃ and Ru/Fe₂O₃ catalysts. The reaction parameters, such as O₂/CH₃OH molar ratio, calcination temperature and reaction temperature were optimized. The catalysts were characterized by ICP, XRD, TEM and TPR analyses. The catalytic activity towards hydrogen formation is found to be higher over the bimetallic Au–Ru/Fe₂O₃ catalyst compared to the monometallic Au/Fe₂O₃ and Ru/Fe₂O₃ catalysts. Bulk Fe₂O₃ showed negligible activity towards hydrogen formation. The enhanced activity and stability of the bimetallic Au–Ru/Fe₂O₃ catalyst has been explained in terms of strong metal–metal and metal–support interactions. The catalytic activity was found to depend on the partial pressure of oxygen, which also plays an important role in determining the product distribution. The catalytic behavior at various calcination temperatures suggests that chemical state of the support and particle size of Au and Ru plays an important role. The optimum calcination temperature for hydrogen selectivity is 673 K. The catalytic performance at various reaction temperatures, between 433 and 553 K shows that complete consumption of oxygen is observed at 493 K. Methanol conversion increases with rise in temperature and attains 100% at 523 K; hydrogen selectivity also increases with rise in temperature and reaches 92% at 553 K. The overall reactions involved are suggested as consecutive methanol combustion, partial oxidation, steam reforming and decomposition. CO produced by methanol decomposition is subsequently transformed into CO₂ by the water gas shift and CO oxidation reactions.     

Carbon-supported Ru catalyst with lithium promoter for ammonia synthesis

The electronegativity of Li is much higher than that of Na or K, but the ammonia synthesis activities of Li-promoted Ru/AC catalysts were comparable to the values of Ru catalyst promoted with K, which were much higher than those over Ru catalyst with Na promoter. The presence of Li increased the catalytic activity by changing the chemisorption properties such as hydrogen adsorption and nitrogen adsorption for carbon-supported Ru catalysts, rather than affecting the sizes of Ru particles or the electron density of Ru metal.     

抑制碳负载钌基氨合成催化剂甲烷化的研究

The effects of promoters K, Ba, Sm on the resistance to carbon-methanation and catalytic activity of ruthenium supported on active carbon (Ru/AC) for ammonia synthesis have been studied by means of TG-DTG (thermalgravity-differential thermalgravity), temperature-programmed desorption, and activity test. Promoters Ba,K, and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly. Much higher activity can be reached for Ru/AC catalyst with bi- or tri-promoters. Indeed, the triply promoted catalyst showed the highest activity, coupled to a surprisingly high resistance to methanation. The ability of resistance of promoter to methanation of Ru/AC catalyst is dependent on the adsorption intensity of hydrogen. The strong adsorption of hydrogen would enhance methanation and impact the adsorption of nitrogen, which results in the decrease of catalytic activity.     

Influence of catalyst pretreatment on catalytic properties and performances of Ru–Re/SiO2 in glycerol hydrogenolysis to propanediols

Bimetallic Ru–Re/SiO₂ and monometallic Ru/SiO₂ catalysts were prepared by impregnation method and their catalytic performances were evaluated in the hydrogenolysis of glycerol to propanediols (1,2-propanediol and 1,3-propanediol) with a batch type reactor (autoclave) under the reaction conditions of 160 °C, 8.0 MPa and 8 h. Ru–Re/SiO₂ showed much higher activity in the hydrogenolysis of glycerol than Ru/SiO₂, and the pretreatment conditions of the catalyst precursors had great influence on the catalytic performance of both Ru–Re/SiO₂ and Ru/SiO₂ catalysts. The physicochemical properties of Ru–Re/SiO₂ and Ru/SiO₂, such as specific surface areas, crystal phases, morphologies/microstructures, surface element states, reduction behaviors and dispersion of Ru metal, were characterized by N₂ adsorption/desorption, XRD, Raman, TEM–EDX, XPS, H₂-TPR and CO chemisorption. The results of XRD, TEM–EDX and CO chemisorption characterizations showed that Re component had an effect on promoting the dispersion of Ru species on the surface of SiO₂, and the measurements of H₂-TPR revealed that the co-existence of Re and Ru components on SiO₂ changed the respective reduction behavior of Re or Ru alone. High pre-reduction temperatures would decrease the activities of Ru–Re/SiO₂ and Ru/SiO₂ catalysts, compared with the corresponding calcined catalysts (without pre-reduction), which actually went through an in-situ reduction during the reaction. XPS analysis indicated that Ru species was in Ru⁰ metal state, while Re species was mostly in Re oxide state in the spent Ru–Re/SiO₂ sample. Re component was probably in rhenium oxide state rather than Re⁰ metal state to take part in the reaction via interaction with Ru⁰ metal.     

Catalytic ammonia decomposition over CMK-3 supported Ru catalysts: Effects of surface treatments of supports

CMK-3 carbon was used as a catalyst support for Ru catalyst for ammonia decomposition. The supports were treated with acid, and the effects of treatment on the properties of CMK-3 supports were studied by N₂ adsorption, XRD, XPS and mass titration. The chemical treatment of carbon support cause significant changes in carbon surface chemistry and in turn had significant effects on both catalyst dispersion and catalytic activity. It is found that the as-synthesized CMK-3 carbon is not a good catalyst support for this reaction. However, surface functional groups produced by acid treatments led to larger Ru catalyst particles, while alkali treatments made the Ru catalyst dispersion even worse due to the residue alkali or earth alkali metals. Interestingly, relatively larger Ru catalyst particles but still well dispersed in the channel of the mesoporous structures of the carbon improves NH₃ conversion into H₂. This is determined by the chemical reaction rate-limiting step of ammonia decomposition. The catalytic activity follows the order: Ru-K/CMK-3 > Ru-Na/CMK-3 > Ru-Ca/CMK-3 > Ru-Cl/CMK-3 > Ru-SO₄/CMK-3 > Ru-PO₄/CMK-3 > Ru/CMK-3 > Ru-Li/CMK-3. CMK-3 is not a good carbon catalyst support due to its amorphous structure resulting in the poor electron conductivity.     

A study about the effect of the temperature of hydrogen treatment on the properties of Ru/Al2O3 and Ru/C and their catalytic behavior during 1-heptyne semi-hydrogenation

The 1-heptyne selective hydrogenation carried out at 150 kPa, and at 283 and 303 K using Ru/Al₂O₃ and Ru/C as catalysts, was studied. Catalysts were prepared by the incipient wetness impregnation technique using RuCl₃ as precursor. Ru/Al₂O₃ was treated in hydrogen at 373 or 573 K and Ru/C only at the last temperature. Catalysts were characterized by hydrogen chemisorption, TPR and XPS. Ru dispersion after treatment in hydrogen at the highest temperature is similar for both catalysts. Ru is present as Ru⁰ in Ru/C, while Ru⁰ and Ru electron-deficient species are present on the catalysts surface after hydrogen treatment at the two temperatures using Al₂O₃ as support. The best catalytic behavior was observed for the highest temperature of hydrogen treatment and for 303 K reaction temperature. As a consequence of a shape selectivity effect of the C support, the best conversion is obtained with the alumina supported catalyst.     

Effect of the Preparation Conditions of Ru/CeO2 Catalysts for the Liquid Phase Oxidation of Benzyl Alcohol

Ceria colloidal particles with a mean crystallite size of 2 nm were synthesized by a solvothermal reaction. The Ru/CeO₂ catalyst prepared from the CeO₂ colloids exhibited higher activity than the catalyst prepared from Ce(NO₃)₃. Temperature-programmed reduction analysis indicated that the reduction of surface Ce⁴⁺ was accelerated by highly dispersed Ru species on the CeO₂ particles and occurred at low temperatures. The single component CeO₂ sample prepared by the coagulation of the CeO₂ colloid was more easily reduced and re-oxidized than the CeO₂ sample prepared by the precipitation method from Ce(NO₃)₃. The higher activity of Ru/CeO₂ prepared from the CeO₂ colloids came from the inherent nature of the CeO₂ support itself.     

Ru/12SrO–7Al2O3 (S12A7) catalyst prepared by physical mixing with Ru (PPh3)3Cl2 for steam reforming of toluene

Steam reforming of toluene as a model of aromatics was performed over various Ru/12SrO–7Al₂O₃ (S12A7) catalysts, and the effects of Ru precursor, calcination and pre-treatment conditions on the catalytic activity and durability of Ru/S12A7catalysts were investigated. The catalytic activity of prepared Ru/S12A7 catalysts exhibited higher than that of a commercial Ru/Al₂O₃ (RA), despite low Ru loading. The catalysts prepared by the physical mixing of Ru (PPh₃)₃Cl₂ and S12A7 (PPH) had higher catalytic activities than the catalysts prepared by the impregnation with RuCl₃ nH₂O (CL). It is interesting that the N₂ pre-treated PPH and CL catalysts especially had higher catalytic activities than the H₂ pre-treated PPH and CL catalysts. In their catalysts, there was a linear relationship between the catalytic activity and the Ru dispersion estimated by CO chemisorption. The catalytic activity of the N₂ pre-treated PPH catalyst has little decreased with time on stream, whereas the catalytic activities of the N₂ pre-treated CL catalyst and H₂ pre-treated PPH catalyst gradually decreased with time on stream.     

Carbon nanofibers supported Ru catalyst for sorbitol hydrogenolysis to glycols: Effect of calcination

Carbon nanofiber (CNFs) supported Ru catalysts for sorbitol hydrogenolysis to ethylene glycol and propylene glycol were prepared by incipient wetness impregnation, calcination and reduction. The effect of calcination on catalyst properties was investigated using thermal gravimetry analysis, temperature-programmed reduction, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and N₂ physisorption. The results indicated that calcination introduced a great amount of surface oxygen-containing groups (SOCGs) onto CNF surface and induced the phase transformation of Ru species, but slightly changed the texture of Ru/CNFs. The catalytic performance in sorbitol hydrogenolysis showed that Ru/CNFs catalyst calcined at 240 °C presented the highest glycol selectivities and reasonable glycol yields. It was believed that the inhibition and confinement effect of SOCGs around Ru particles as well as the high dispersion of Ru particles was the key factor for the catalytic activity.     

Anodic catalysts for polymer electrolyte fuel cells: the catalytic activity of Pt/C,Ru/C and Pt-Ru/C in oxidation of CO by O2

The catalytic activity for oxidation of CO by O₂ was investigated on commercial Pt/C, Pt-Ru/C (Pt/Ru atomic ratio = 20, 3, 1, 1/3) and Ru/C. All samples contained 20 wt.% metal. Assuming equal surface and bulk composition, the number of surface Pt and Ru atoms was calculated from the average size of the supported metal particle as determined by TEM. On Pt-Ru/C alloys, the turnover frequency per Ru atom, N_Ru/molecules s⁻¹ Ru-atom⁻¹, was independent of chemical composition. This finding suggests that the active site in these alloys is Ru. In the temperature range 300–400 K, the turnover frequency per active metal atom was 50–300 times higher on Pt-Ru/C than on Pt/C. The turnover frequency was 400 times higher on Ru/C than on Pt/C at 313 K and 90 times higher at 353 K. Addition of water vapor to the reactant mixture left the catalytic activity of Ru/C unchanged but slightly increased the activity of Pt/C. On both catalysts the activation energy and reaction orders were nearly the same as in dry atmosphere. Conversely, the addition of water markedly decreased the activation energy for Pt-Ru(1 : 1)/C alloy (from 19 to 11 kcal mol⁻¹). These findings suggest that fuel cells equipped with Pt-Ru/C anodes perform better than cells with Pt/C anodes. They do so because Ru effectively oxidizes the carbon monoxide present as an impurity in the H₂-reformed fuel.     

超临界流体技术制备Ru/C催化剂的研究

以活性炭为载体、氯化钌为活性前驱体,采用超临界CO2流体沉积技术制备了Ru/C催化剂,用葡萄糖加氢生产山梨醇反应考察催化剂的催化活性.用正交实验考察了温度、CO2的量和还原剂KBH4的量等因素对制备Ru/C催化剂催化活性的影响规律;用红外光谱(IR)和扫描电镜(SEM)对Ru/C催化剂样品进行了结构表征.结果表明:制备...     

Ammonia synthesis over ruthenium catalyst supported on perovskite type BaTiO3

Ammonia synthesis reaction was performed over a novel ruthenium catalyst supported on perovskite-type BaTiO₃. It was quite worth noting that Ru/BaTiO₃ catalyst exhibited outstanding activity for ammonia synthesis. The results of XRD, CO₂-TPD, H₂-TPR and TEM indicated that the strong metal–support interaction (SMSI) between a partially reduced support and Ru combined with strong basicity of support was responsible for such high catalytic activity. The electrons could be easily transferred from the support to the surface of Ru particles by the SMSI effect facilitated the cleavage of NN and greatly enhanced the activity for ammonia synthesis.     

Promoting effect of rhenium on catalytic performance of Ru catalysts in hydrogenolysis of glycerol to propanediol

Ru/Al₂O₃, Ru/C and Ru/ZrO₂ catalysts were applied to the hydrogenolysis of glycerol to propanediol, and the effect of Re as an additive on the catalytic performance of Ru catalysts was examined. The catalyst systems were characterized by N₂ adsorption/desorption, XRD, TEM-EDX and XPS. The hydrogenolysis of glycerol was carried out under the conditions of 120–180 °C, 4–10 MPa hydrogen pressure and 4–8 h, and the conversion of glycerol varied from 18.7% to 29.7% over Ru/Al₂O₃, Ru/C and Ru/ZrO₂ catalysts. The reaction results indicate that Re possesses high promoting effect on the catalytic performance of Ru catalysts in glycerol hydrogenolysis.     

Potential dependence of segregation and surface alloy formation of a Ru modified carbon supported Pt catalyst

Ruthenium modified carbon supported platinum catalysts have been shown to have a similar activity towards carbon monoxide oxidation as conventionally prepared bimetallic PtRu alloy catalysts. In this study the effect of the applied electrode potential and potential cycles on the location and oxidation state of the Ru species in such Ru modified Pt/C catalysts was investigated using in situ EXAFS collected at both the Ru K and Pt L₃ absorption edges. The as prepared catalyst was found to consist of a Pt core with a Ru oxy/hydroxide shell. The potential dependent data indicated alloying to form a PtRu phase at 0.05 V versus RHE and subsequent dealloying to return to the Ru oxy/hydroxide decorated Pt surface at potentials greater than 0.7 V. The Ru-O distances obtained indicate that both Ru³⁺ and Ru⁴⁺ species are present on the surface of the Pt particles at oxidising potentials; the former is characteristic of the as prepared Ru modified Pt/C catalyst and following extensive periods at potentials above 0.7 V and the latter of the Ru oxide species on the PtRu alloy.     

Aqueous-phase hydrodechlorination of model chlorinated organic compounds over Ru/C catalyst

Effluents from the pharmaceutical and dye industries contain chlorinated organic pollutants. The effective treatment of such effluents constitutes a challenging task. In this work, 4-chlororesorcinol (PCRE) and 4-chloro-2-aminophenol (PCAP) were selected as model chloro-organic compounds. Catalytic hydrodechlorination (HDC) of PCRE and PCAP in the aqueous phase was investigated in a slurry reactor using commercial carbon supported ruthenium catalyst. HDC reactions of PCRE and PCAP were studied over the ranges in temperature, 313–353?K, H₂ partial pressure, 0.69–2.76?MPa, and catalyst loading, 0.2–1.2?kg/m³. The performance of Ru/C catalyst for hydrodechlorination and ring saturation was promising. The kinetic data were modeled using Langmuir–Hinshelwood–Hougen–Watson kinetics. The HDC reaction of PCRE and PCAP using Ru/C catalyst proceeds via a dual-site mechanism, wherein atomic H₂ reacts with the adsorbed organic substrate. The activation energy for the hydrodechlorination reactions of PCRE and PCAP was 41.6 and 49.4?kJ/mol, respectively.     

Synthesis and Catalytic Performance of Highly Ordered Ru-Containing Mesoporous Carbons for Hydrogenation of Cinnamaldehyde

Highly ordered Ru-containing mesoporous carbons (Ru-OMC) were for the first time synthesized by a one-pot method. Comparing with our previously reported Ir-OMC, the Ru precursor must be added after the formaldehyde was consumed by polycondensation with resorcinol to obtain a small particle size. The resultant Ru-OMC samples with different Ru contents were characterized with X-ray diffraction (XRD), N₂ adsorption-desorption, and Transmission electron microscopy (TEM). The results evidenced the formation of highly ordered mesostructure, in which Ru particles were imbedded. The new carbon materials were further evaluated in the selective hydrogenation of cinnamaldehyde (CMA). By comparison with the traditional Ru/AC catalyst, our Ru-OMC samples exhibited much higher activity (2–14-fold) and up to 60% of selectivity to cinnamyl alcohol (CMO).     

Gold catalysts supported on titanium oxide for catalytic wet air oxidation of succinic acid

Catalytic wet air oxidation of a representative organic compound (aqueous solution of 5 g l⁻¹ succinic acid at 190 °C and 50 bar total air pressure) was investigated over gold on titania prepared from the deposition–precipitation method (with urea or NaOH) and compared to experiments performed over a Ru/TiO₂ catalyst. These preliminary results demonstrate that gold catalysts are efficient for the degradation of this organic acid. The catalytic activity is strongly dependent on the gold particle size characterized by transmission electron microscopy (TEM) with smaller particles producing higher turnover frequencies. Modification of metal dispersion occurs during reaction, leading to minor activity.     

钌基氨合成催化剂氢氮吸附性能的研究

The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispers     

Highly efficient Ru/Sm2O3-CeO2 catalyst for ammonia synthesis

A series of Ru/Sm₂O₃–CeO₂ catalysts were prepared by using a co-precipitation (CP) method and characterized by XRD, BET, SEM, H₂-TPD-MS, H₂-TPR and CO chemisorption. The activity test shows that ammonia concentration of the catalyst with 7% Sm is 13.4% at 10 MPa, 10,000 h^− 1, 425 °C, which is 21% higher than that of Ru/CeO₂. Such high catalytic activity was due to three effects: the morphology changes of catalyst, electrodonating property of partially reduced CeO_2 − x to Ru metal and the property of easily hydrogen desorption derived from the presence of Sm³⁺ in ceria.