Strategic regulation of nitrogen-containing intermediates for enhanced nitrate reduction over Co_(3)O_(4)/SiC catalyst having multiple active centers

Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst.Here,a family of n%-Co_(3)O_(4)/SiC(n=5,8,12,20)catalysts with a delicate percentage of Co^(2+)and Co^(3+)were prepared for NO_(3)RR.We found that Co^(3+)primarily acts as the active site for NO_(3)^(−)reduction to NO_(2)^(−),while Co^(2+)is responsible for the conversion of NO_(2)^(−)to NH_(3).Moreover,the conversion of these intermediates over the active sites is autonomous and separately controllable.Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia.Combining the experimental studies and density functional theory(DFT)calculations,it is discovered the pathway(^(*)NHO→^(*)NHOH→^(*)NH_(2)OH→^(*)NH_(2)→^(*)NH_(3))is more favorable due to the lowerΔG value(0.25 eV)for the rate-limiting step(^(*)NO→^(*)NHO).The NH_(3)yield rate of 8%-Co_(3)O_(4)/SiC reached 1.08 mmol/(cm^(2)h)with a Faradaic efficiency of 96.4%at−0.89 V versus the reversible hydrogen electrode(RHE),surpassing those of most reported non-noble NO_(3)RR catalysts.This strategy not only provides an efficient catalyst for NO_(3)RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites,thereby presenting a new approach to enhance the efficiency of intricate reactions.

SiC管中微波辅助芳烃钌（Ⅱ）化合物[（η^6-C6H6）Ru（H2iiP）Cl]Cl的合成

使用SiC管为反应容器,在微波辐射条件下以[(η6-C6H6)RuCl2]2为原料与2-(吲哚基)咪唑[4,5-f]-[1,10]菲啰啉(H2iiP)反应,制得芳烃钌(Ⅱ)化合物[(η6-C6H6)Ru(H2iiP)Cl]Cl(1),并对其进行了表征.采用正交实验法确定反应的最佳合成条件为:投料比n([(η6-C6H6)RuCl2]2)∶n(H2iiP)=1∶2.2,反应温度90℃,微波辐射时间30 min.该反应的平均产率达到96.0%,反应产率的相对标准偏差(RSD)为1.28%,说明微波辐射条件下,在SiC管中能够高产率地制备芳烃钌化合物,并且反应具有良好的重现性.进一步采用MTT方法研究发现,芳烃钌(Ⅱ)化合物1能够选择性抑制MCF-7乳腺癌的生长.

Selective CO Methanation over Ru Catalysts Supported on Nanostructured TiO2 with Different Crystalline Phases and Morphology

Nanostructured titanium dioxides were synthesized via various post-treatments of titanate nanofibers obtained from titanium precursors by hydrothermal reactions. The microstructures of TiO2 and supported Ru/TiO2 catalysts were characterized with X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray analysis, and nitrogen adsorption isotherms. The phase structure, particle size, morphology, and specific surface area were determined. The supported Ru catalysts were applied for the selective methanation of CO in a hydrogen-rich stream. The results indicated that the Ru catalyst supported on rutile and TiO2-B exhibited higher catalytic performance than the counterpart supported on anatase, which suggested the distinct interaction between Ru nanoparticles and TiO2 resulting from different crystalline phases and morphology.

Effect of the graphitic degree of carbon supports on the catalytic performance of ammonia synthesis over Ba-Ru-K/HSGC catalyst

A series of high surface area graphitic carbon materials （HSGCs） were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x （x is the ball-milling time in hour） catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.

Inhibiting effect of tungstic compounds on glucose hydrogenation over Ru/C catalyst

The effect of acid component including various conventional acids and tungstic compounds on glucose hydrogenation over a series of binary catalyst system containing Ru/C catalyst was investigated. The results showed that HC1, H2SO4, H3BO3, H3PO4, and HNO3 had negligible effect, while all the tungstic compounds imposed inhibiting effects on the hydrogenation of glucose over Ru/C catalyst, and the suppressing effect followed the order of H2WO4〉HPW〉WO3〉AMT〉HSiW. This order is the same as the order of ethylene glycol （EG） yields in the one-pot conversion of glucose to EG, suggesting the important role of competition between glucose hydrogenation and retro-aldol condensation in controlling the selectivity of EG.

Solvent-free crystallization of ZSM-5 zeolite on SiC foam as a monolith catalyst for biofuel upgrading

Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy.Here,we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a honeycomb structure(ZSM-5/SiC).Characterizations of the ZSM-5/SiC by scanning electron microscopy,N2 sorption,and X-ray diffraction indicate that the zeolite sheath has been ideally coated on the surface of the SiC foam with high purity and crystallinity.Fixing Pd nanoparticles within the ZSM-5 zeolite crystals delivers a bifunctional Pd@ZSM-5/SiC catalyst,which exhibits high activity and selectivity toward diesel range paraffins in the hydrodeoxygenation of methyl oleate,a model molecule for biofuel.In comparison to the powder Pd@ZSM-5,the Pd@ZSM-5/SiC monolith catalyst shows more efficiency,which is attributed to the fast mass transfer and high heat conductivity on the honeycomb SiC structure.The durability test indicates that the Pd@ZSM-5/SiC catalyst is stable under the reaction and high-temperature regeneration conditions.

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl_3/SiO_2-templated approach

Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance.Hence,searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology.Here,we report a Ba‐K/Ru‐MC catalyst with Ru particle size of 1.5–2.5 nm semi‐embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba‐Ru‐K/MC catalyst,although both have similar metal particle sizes for ammonia synthesis.Further,the Ba‐K/Ru‐MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts.Characterization techniques such as high‐resolution transmission electron microscopy,N2 physisorption,CO chemisorption,and temperature‐programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba‐K/Ru‐MC,which may facilitate electron transport better than supported nanoparticles.

Effects of Reaction Conditions on Performance of Ru Catalyst and Iron Catalyst for Ammonia Synthesis

Activated carbon-supported Ru-based catalyst and A301 iron catalyst were prepared,and the influences of reaction temperature,space velocity,pressure,and H2/N2 ratio on performance of iron catalyst coupled with Ru catalyst in series for ammonia synthesis were investigated.The activity tests were also performed on the single Ru and Fe catalysts as comparison.Results showed that the activity of the Ru catalyst for ammonia synthesis was higher than that of the iron catalyst by 33.5%-37.6% under the reaction conditions：375-400 °C,10 MPa,10000 h-1,H2︰N2 3,and the Ru catalyst also had better thermal stability when treated at 475 °C for 20 h.The outlet ammonia concentration using Fe-Ru catalyst was increased by 45.6%-63.5% than that of the single-iron catalyst at low tem-perature （375-400 °C）,and the outlet ammonia concentration increased with increasing Ru catalyst loading.

Highly selective CO methanation over amorphous Ni-Ru-B/ZrO_2 catalyst

Amorphous Ni-Ru-B/ZrO2 catalyst was prepared by the means of chemical reduction, and selective CO methanation as a strategy for CO removal in fuel processing applications was investigated over the amorphous Ni-Ru-B/ZrO2 catalyst. The result showed that, at the temperature of 210-230 ℃, the catalyst was shown to be capable of reducing CO in a hydrogen-rich reformate to less than 10 ppm, while keeping the CO2 conversion below 1.55% and the hydrogen consumption below 6.50%. ？2009 Xin Fa Dong. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Study on the Nanosized Amorphous Ru-Fe-B/ZrO_2 Alloy Catalyst for Benzene Selective Hydrogenation to Cyclohexene

A novel nanosized amorphous Ru-Fe-B/ZrO2 alloy catalyst for benzene selective hydrogenation to cyclohexene was investigated. The superior properties of this catalyst were attributed to the combination of the nanosize and the amorphous character as well as to its textural character. In addition, the concentration of zinc ions, the content of ZrO2 in the slurry, and the pretreatment of the catalyst were found to be effective in improving the activity and the selectivity of the catalyst.

Scission of C–O and C–C linkages in lignin over RuRe alloy catalyst

The performance of lignin depolymerization is basically determined by the interunit C–O and C–C bonds.Numerous C–O bond cleavage strategies have been developed, while the cleavage of C–C bond between the primary aromatic units remains a challenging task due to the high dissociation energy of C–C bond.Herein, a multifunctional Ru Re alloy catalyst was designed, which exhibited exceptional catalytic activity for the cleavage of both C–O and C–C linkages in a broad range of lignin model compounds(β-1, a-5, 5–5,β-O-4, 4-O-5) and two stubborn lignins(kraft lignin and alkaline lignin), affording 97.5% overall yield of monocyclic compounds from model compounds and up to 129% of the maximum theoretical yield of monocyclic products based on C–O bonds cleavage from realistic lignin. Scanning transmission electron microscopy(STEM) characterization showed that Ru Re(1:1) alloy particles with hexagonal close-packed structure were homogeneously dispersed on the support. Quasi-in situ X-ray photoelectron spectroscopy(XPS), and X-ray absorption spectroscopy(XAS) indicate that Ru species were predominantly metallic state, whereas Re species were partially oxidized;meanwhile, there was a strong interaction between Ru and Re, where the electron transfer from Re to Ru was occurred, resulting in great improvement on the capability of C–O and C–C bonds cleavage in lignin conversion.

Ru surface density effect on ammonia synthesis activity and hydrogen poisoning of ceria-supported Ru catalysts

Evaluating the effect of metal surface density on catalytic performance is critical for designing high-activity metal-based catalysts.In this study,a series of ceria(CeCO_(2))-supported Ru catalysts(Ru/CeCO_(2))were prepared to analyze the effect of Ru surface density on the catalytic performance of Ru/CeCO_(2) for ammonia synthesis.For the Ru/CeCO_(2) catalysts with Ru surface densities lower than 0.68 Ru nm^(-2),the Ru layers were in close contact with CeCO_(2),and electrons were transferred directly from the CeCO_(2) defect sites to the Ru species.In such cases,the adsorption of hydrogen species on the Ru sites in the vicinity of 0 atoms was high,leading to a high ammonia synthesis activity and strong hydrogen poisoning.In contrast,the preferential aggregation of Ru species into large particles on top of the Ru overlayer resulted in the coexistence of Ru clusters and particles,for catalysts with a Ru surface density higher than 1.4 Ru nm^(-2),for which Ru particles were isolated from the direct electronic influence of CeCO_(2).Consequently,the Ru-Ceth interactions were weak,and hydrogen poisoning can be significantly alleviated.Overall,electron transfer and hydrogen adsorption synergistically affected the synthesis of ammonia over Ru/CeCO_(2) catalysts,and catalyst samples with a Ru surface density lower than 0.31 Ru nm^(-2) or exactly 2.1 Ru nm^(-2) exhibited high catalytic activity for ammonia synthesis.

Ru/FeO_x catalyst performance design: Highly dispersed Ru species for selective carbon dioxide hydrogenation

A series of Ru/FeOx catalysts were synthesized for the selective hydrogenation of CO2to CO.Detailed characterizations of the catalysts through X‐ray diffraction,X‐ray photoelectron spectroscopy,transmission electron microscopy,and temperature‐programmed techniques were performed to directly monitor the surface chemical properties and the catalytic performance to elucidate the reaction mechanism.Highly dispersed Ru species were observed on the surface of FeOx regardless of the initial Ru loading.Varying the Ru loading resulted in changes to the Ru coverage over the FeOx surface,which had a significant impact on the interaction between Ru and adsorbed H,and concomitantly,the H2activation capacity via the ability for H2dissociation.FeOx having0.01%of Ru loading exhibited100%selectivity toward CO resulting from the very strong interaction between Ru and adsorbed H,which limits the desorption of the activated H species and hinders over‐reduction of CO to CH4.Further increasing the Ru loading of the catalysts to above0.01%resulted in the adsorbed H to be easily dissociated,as a result of a weaker interaction with Ru,which allowed excessive CO reduction to produce CH4.Understanding how to selectively design the catalyst by tuning the initial loading of the active phase has broader implications on the design of supported metal catalysts toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Selective CO methanation over amorphous Ni-Ru-B/ZrO_2 catalyst for hydrogen-rich gas purification

Amorphous Ni-Ru-B/ZrO2 catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni61Ru9B30/ZrO2 catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230℃-250℃, and the CO2 conversion was kept under the level of 0.9%.

A Novel Ultrafine Ru-B Amorphous Alloy Catalyst for Glucose Hydrogenation to Sorbitol

An ultrafine Ru-B amorphous alloy catalyst was prepared by chemical reduction with KBH4 in aqueous solution, which exhibited perfect selectivity to sorbitol (~100%) and very high activity during the liquid phase glucose hydrogenation, much higher than the corresponding crystallized Ru-B, the pure Ru powder, and Raney Ni catalysts. The correlation of the catalytic activity to both the structural and surface electronic characteristics was discussed briefly.

Tuned selectivity and enhanced activity of CO_(2) methanation over Ru catalysts by modified metal-carbonate interfaces

Carbonate-modified metal-support interfaces allow Ru/MnCO_(3) catalyst to exhibit over 99% selectivity,great specific activity and long-term anti-CO poisoning stability in atmospheric CO_(2) methanation.As a contrast,Ru/MnO catalyst with metal-oxide interfaces prefers reverse water-gas shift rather than methanation route,along with a remarkably lower activity and a less than 15% CH_(4) selectivity.The carbonatemodified interfaces are found to stabilize the Ru species and activate CO_(2) and H_(2) molecules.Ru-CO^(4) species are identified as the reaction intermediates steadily formed from CO_(2) dissociation,which show moderate adsorption strength and high reactivity in further hydrogenation to CH_(4),Furthermore,carbonates of Ru/MnCO_(3) are found to be consumed by hydrogenation to form CH_(4) and replenished by exchange with CO_(2),which are in a dynamic equilibrium during the reaction.Modification with surface carbonates is proved as an efficient strategy to endow metal-support interfaces of Ru-based catalysts with unique catalytic functions for selective CO_(2) hydrogenation.

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.

CO selective methanation in hydrogen-rich gas mixtures over carbon nanotube supported Ru-based catalysts

Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-bed quartz tubular reactor at ambient pressure. It was found that the metal promoter, reduction temperature and metal loading affected the catalytic properties significantly. The most excellent performance was presented by 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃. Since it decreased CO concentration to below 10 ppm from 12000 ppm by CO selective methanation at the temperature range of 180-240 ℃, and kept CO selectivity higher than 85% at the temperature below 200 ℃. Characterization using XRD, TEM, H2-TPR and XPS suggests that Zr modification of Ru/CNTs results in the weakening of the interaction between Ru and CNTs, a higher Ru dispersion and the oxidization of surface Ru. Amorphous and high dispersed Ru particles with small size were obtained for 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃, leading to excellent catalytic performance in CO selective methanation.

Carbon nanotubes-Nafion composites as Pt-Ru catalyst support for methanol electro-oxidation in acid media

Carbon nanotubes-Nafion （CNTs-Nation） composites were prepared by impregnated CNTs with Nation in ethanol solution and characterized by FT-IR. Pt-Ru catalysts supported on CNTs-Nafion composites were synthesized by microwave-assisted polyol process. The physical and electrochemical properties of the catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, CO stripping voltammetry, cyclic voltammetry （CV） and chronoamperometry （CA）. The results showed that the Nation incorporation in CNTs-Nation composites did not significantly alter the oxygen-containing groups on the CNTs surface. The Pt-Ru catalyst supported on CNTs-Nafion composites with 2 wt% Naton showed good dispersion and the best CO oxidation and methanol electro-oxidation activities.

Solvent effects on Pt-Ru/C catalyst for methanol electro-oxidation

Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying degree of the object substance, which lead to a great positive impact on its properties. In this work, three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction （XRD） and Transmission electron microscopy （TEM）. The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry （CV） and Chronoamperometry （CA）. Pt-Ru/C catalyst prepared in H2O or binary solvents of H2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems, Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity, lower onset and peak potentials, compared with the above catalysts. Moreover, the catalyst prepared in ternary solvents of isopropanol, water and tetrahydrofuran had the smallest particle size, and the high alloying degree and the dispersion kept unchanged. Therefore, this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.