Showing papers in "Catalysts in 2015"

Heterogeneous Catalyst Deactivation and Regeneration: A Review

Abstract: Deactivation of heterogeneous catalysts is a ubiquitous problem that causes loss of catalytic rate with time. This review on deactivation and regeneration of heterogeneous catalysts classifies deactivation by type (chemical, thermal, and mechanical) and by mechanism (poisoning, fouling, thermal degradation, vapor formation, vapor-solid and solid-solid reactions, and attrition/crushing). The key features and considerations for each of these deactivation types is reviewed in detail with reference to the latest literature reports in these areas. Two case studies on the deactivation mechanisms of catalysts used for cobalt Fischer-Tropsch and selective catalytic reduction are considered to provide additional depth in the topics of sintering, coking, poisoning, and fouling. Regeneration considerations and options are also briefly discussed for each deactivation mechanism.

Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

Abstract: The ethanol oxidation reaction (EOR) has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to CO2. This mini review is aimed at presenting an overview of the advances in the study of reaction mechanisms and electrocatalytic materials for EOR over the past two decades with a focus on Pt- and Pd-based catalysts. We start with discussion on the mechanistic understanding of EOR on Pt and Pd surfaces using selected publications as examples. Consensuses from the mechanistic studies are that sufficient active surface sites to facilitate the cleavage of the C–C bond and the adsorption of water or its residue are critical for obtaining a higher electro-oxidation activity. We then show how this understanding has been applied to achieve improved performance on various Pt- and Pd-based catalysts through optimizing electronic and bifunctional effects, as well as by tuning their surface composition and structure. Finally we point out the remaining key problems in the development of anode electrocatalysts for EOR.

Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions

Abstract: Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs) and nitrogen-doped graphene (NG), have attracted increasing attention for oxygen reduction reaction (ORR) in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e− transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

Deactivation of Pd Catalysts by Water during Low Temperature Methane Oxidation Relevant to Natural Gas Vehicle Converters

Abstract: Effects of H2O on the activity and deactivation of Pd catalysts used for the oxidation of unburned CH4 present in the exhaust gas of natural-gas vehicles (NGVs) are reviewed. CH4 oxidation in a catalytic converter is limited by low exhaust gas temperatures (500–550 °C) and low concentrations of CH4 (400–1500 ppmv) that must be reacted in the presence of large quantities of H2O (10–15%) and CO2 (15%), under transient exhaust gas flows, temperatures, and compositions. Although Pd catalysts have the highest known activity for CH4 oxidation, water-induced sintering and reaction inhibition by H2O deactivate these catalysts. Recent studies have shown the reversible inhibition by H2O adsorption causes a significant drop in catalyst activity at lower reaction temperatures (below 450 °C), but its effect decreases (water adsorption becomes more reversible) with increasing reaction temperature. Thus above 500 °C H2O inhibition is negligible, while Pd sintering and occlusion by support species become more important. H2O inhibition is postulated to occur by either formation of relatively stable Pd(OH)2 and/or partial blocking by OH groups of the O exchange between the support and Pd active sites thereby suppressing catalytic activity. Evidence from FTIR and isotopic labeling favors the latter route. Pd catalyst design, including incorporation of a second noble metal (Rh or Pt) and supports high O mobility (e.g., CeO2) are known to improve catalyst activity and stability. Kinetic studies of CH4 oxidation at conditions relevant to natural gas vehicles have quantified the thermodynamics and kinetics of competitive H2O adsorption and Pd(OH)2 formation, but none have addressed effects of H2O on O mobility.

Magnetically Separable and Sustainable Nanostructured Catalysts for Heterogeneous Reduction of Nitroaromatics

Abstract: This review is focused on the strategies and designs of magnetic nanostructured catalysts showing the enhanced and sustainable catalytic performances for the heterogeneous reduction of nitoaromatics. Magnetic catalysts have the benefits of easy recovery and reuse after the completion of the reactions and green chemical processes. Magnetic separation, among the various procedures for removing catalysts, not only obviates the requirement of catalyst filtration or centrifugation after the completion of reactions, but also provides a practical technique for recycling the magnetized nanostructured catalysts. Consequently, discussions will address the methodologies and exemplars for the reusable magnetic composite catalysts. Because the synthesis of ideal magnetic nanostructured catalysts is of primary importance in the development of high-quality sustainable processes, the designs, preparation methods and recyclability of various recoverable magnetic nanostructured catalysts are emphasized. The representative methods and strategies for the synthesis of durable and reusable magnetic nanostructured catalysts are highlighted. The advantages, disadvantages, recyclability and the efficiency of the introduced heterogeneous systems have been explored in the reduction of nitrobenzene derivatives.

Catalytic Conversion of Glucose into 5-Hydroxymethylfurfural by Hf(OTf)4 Lewis Acid in Water

Abstract: A series of Lewis acidic metal salts were used for glucose dehydration to 5-hydroymethylfurfural (HMF) in water. Effect of valence state, ionic radii of Lewis acidic cation, and the type of anions on the catalytic performance have been studied systematically. The experimental results showed that the valence state played an important role in determining catalytic activity and selectivity. It was found that a higher glucose conversion rate and HMF selectivity could be obtained over high valent Lewis acid salts, where the ionic radii of these Lewis acidic metal salts are usually relatively small. Analysis on the effect of the anions of Lewis acid salts on the catalytic activity and the selectivity suggested that a higher glucose conversion and HMF selectivity could be readily obtained with Cl−. Furthermore, the recyclability of high valence state Lewis acid salt was also studied, however, inferior catalytic performance was observed. The deactivation mechanism was speculated to be the fact that high valence state Lewis acid salt was comparatively easier to undergo hydrolysis to yield complicated metal aqua ions with less catalytic activity. The Lewis acidic activity could be recovered by introducing a stoichiometric amount of hydrochloric acid (HCl) to the catalytic before the reaction.

Surface Reaction Kinetics of Steam- and CO2-Reforming as Well as Oxidation of Methane over Nickel-Based Catalysts

Abstract: An experimental and kinetic modeling study on the Ni-catalyzed conversion of methane under oxidative and reforming conditions is presented. The numerical model is based on a surface reaction mechanism consisting of 52 elementary-step like reactions with 14 surface and six gas-phase species. Reactions for the conversion of methane with oxygen, steam, and CO2 as well as methanation, water-gas shift reaction and carbon formation via Boudouard reaction are included. The mechanism is implemented in a one-dimensional flow field description of a fixed bed reactor. The model is evaluated by comparison of numerical simulations with data derived from isothermal experiments in a flow reactor over a powdered nickel-based catalyst using varying inlet gas compositions and operating temperatures. Furthermore, the influence of hydrogen and water as co-feed on methane dry reforming with CO2 is also investigated.

Abatement of VOCs with Alternate Adsorption and Plasma-Assisted Regeneration: A Review

Abstract: Energy consumption is an important concern for the removal of volatile organic compounds (VOCs) from waste air with non-thermal plasma (NTP). Although the combination of NTP with heterogeneous catalysis has shown to reduce the formation of unwanted by-products and improve the energy efficiency of the process, further optimization of these hybrid systems is still necessary to evolve to a competitive air purification technology. A newly developed innovative technique, i.e., the cyclic operation of VOC adsorption and NTP-assisted regeneration has attracted growing interest of researchers due to the optimized energy consumption and cost-effectiveness. This paper reviews this new technique for the abatement of VOCs as well as for regeneration of adsorbents. In the first part, a comparison of the energy consumption between sequential and continuous treatment is given. Next, studies dealing with adsorption followed by NTP oxidation are reviewed. Particular attention is paid to the adsorption mechanisms and the regeneration of catalysts with in-plasma and post-plasma processes. Finally, the influence of critical process parameters on the adsorption and regeneration steps is summarized.

Deactivation and Regeneration of Commercial Type Fischer-Tropsch Co-Catalysts—A Mini-Review

Abstract: Deactivation of commercially relevant cobalt catalysts for Low Temperature Fischer-Tropsch (LTFT) synthesis is discussed with a focus on the two main long-term deactivation mechanisms proposed: Carbon deposits covering the catalytic surface and re-oxidation of the cobalt metal. There is a great variety in commercial, demonstration or pilot LTFT operations in terms of reactor systems employed, catalyst formulations and process conditions. Lack of sufficient data makes it difficult to correlate the deactivation mechanism with the actual process and catalyst design. It is well known that long term catalyst deactivation is sensitive to the conditions the actual catalyst experiences in the reactor. Therefore, great care should be taken during start-up, shutdown and upsets to monitor and control process variables such as reactant concentrations, pressure and temperature which greatly affect deactivation mechanism and rate. Nevertheless, evidence so far shows that carbon deposition is the main long-term deactivation mechanism for most LTFT operations. It is intriguing that some reports indicate a low deactivation rate for multi-channel micro-reactors. In situ rejuvenation and regeneration of Co catalysts are economically necessary for extending their life to several years. The review covers information from open sources, but with a particular focus on patent literature.

Phosphorus and Nitrogen Dual Doped and Simultaneously Reduced Graphene Oxide with High Surface Area as Efficient Metal-Free Electrocatalyst for Oxygen Reduction

Abstract: A P, N dual doped reduced graphene oxide (PN-rGO) catalyst with high surface area (376.20 m2·g−1), relatively high P-doping level (1.02 at. %) and a trace amount of N (0.35 at. %) was successfully prepared using a one-step method by directly pyrolyzing a homogenous mixture of graphite oxide (GO) and diammonium hydrogen phosphate ((NH4)2HPO4) in an argon atmosphere, during which the thermal expansion, deoxidization of GO and P, N co-doping were realized simultaneously. The catalyst exhibited enhanced catalytic performances for oxygen reduction reaction (ORR) via a dominated four-electron reduction pathway, as well as superior long-term stability, better tolerance to methanol crossover than that of commercial Pt/C catalyst in an alkaline solution.

Recent Advances in Carbon Supported Metal Nanoparticles Preparation for Oxygen Reduction Reaction in Low Temperature Fuel Cells

Abstract: The oxygen reduction reaction (ORR) is the oldest studied and most challenging of the electrochemical reactions. Due to its sluggish kinetics, ORR became the major contemporary technological hurdle for electrochemists, as it hampers the commercialization of fuel cell (FC) technologies. Downsizing the metal particles to nanoscale introduces unexpected fundamental modifications compared to the corresponding bulk state. To address these fundamental issues, various synthetic routes have been developed in order to provide more versatile carbon-supported low platinum catalysts. Consequently, the approach of using nanocatalysts may overcome the drawbacks encountered in massive materials for energy conversion. This review paper aims at summarizing the recent important advances in carbon-supported metal nanoparticles preparation from colloidal methods (microemulsion, polyol, impregnation, Bromide Anion Exchange…) as cathode material in low temperature FCs. Special attention is devoted to the correlation of the structure of the nanoparticles and their catalytic properties. The influence of the synthesis method on the electrochemical properties of the resulting catalysts is also discussed. Emphasis on analyzing data from theoretical models to address the intrinsic and specific electrocatalytic properties, depending on the synthetic method, is incorporated throughout. The synthesis process-nanomaterials structure-catalytic activity relationships highlighted herein, provide ample new rational, convenient and straightforward strategies and guidelines toward more effective nanomaterials design for energy conversion.

VOx Surface Coverage Optimization of V2O5/WO3-TiO2 SCR Catalysts by Variation of the V Loading and by Aging

Abstract: V2O5/WO3-TiO2 selective catalytic reduction (SCR) catalysts with a V2O5 loading of 1.7, 2.0, 2.3, 2.6, 2.9, 3.2 and 3.5 wt. % were investigated in the fresh state and after hydrothermal aging at 600 °C for 16 h. The catalysts were characterized by means of nitrogen physisorption, X-ray diffraction and X-ray absorption spectroscopy. In the fresh state, the SCR activity increased with increasing V loading. Upon aging, the catalysts with up to 2.3 wt. % V2O5 exhibited higher NOx reduction activity than in the fresh state, while the catalysts with more than 2.6 wt. % V2O5 showed increasing deactivation tendencies. The observed activation and deactivation were correlated with the change of the VOx and WOx surface coverages. Only catalysts with a VOx coverage below 50% in the aged state did not show deactivation tendencies. With respect to tungsten, above one monolayer of WOx, WO3 particles were formed leading to loss of surface acidity, sintering, catalyst deactivation and early NH3 slip. An optimal compromise between activity and hydrothermal aging resistance could be obtained only with V2O5 between 2.0 and 2.6 wt. %.

Recent Development of Pd-Based Electrocatalysts for Proton Exchange Membrane Fuel Cells

Abstract: This review selectively summarizes the latest developments in the Pd-based cataysts for low temperature proton exchange membrane fuel cells, especially in the application of formic acid oxidation, alcohol oxidation and oxygen reduction reaction The advantages and shortcomings of the Pd-based catalysts for electrocatalysis are analyzed The influence of the structure and morphology of the Pd materials on the performance of the Pd-based catalysts were described Finally, the perspectives of future trends on Pd-based catalysts for different applications were considered

Recent Progress on Fe/N/C Electrocatalysts for the Oxygen Reduction Reaction in Fuel Cells

Abstract: In order to reduce the overall system cost, the development of inexpensive, high-performance and durable oxygen reduction reaction (ORR)N, Fe-codoped carbon-based (Fe/N/C) electrocatalysts to replace currently used Pt-based catalysts has become one of the major topics in research on fuel cells. This review paper lays the emphasis on introducing the progress made over the recent five years with a detailed discussion of recent work in the area of Fe/N/C electrocatalysts for ORR and the possible Fe-based active sites. Fe-based materials prepared by simple pyrolysis of transition metal salt, carbon support, and nitrogen-rich small molecule or polymeric compound are mainly reviewed due to their low cost, high performance, long stability and because they are the most promising for replacing currently used Pt-based catalysts in the progress of fuel cell commercialization. Additionally, Fe-base catalysts with small amount of Fe or new structure of Fe/Fe3C encased in carbon layers are presented to analyze the effect of loading and existence form of Fe on the ORR catalytic activity in Fe-base catalyst. The proposed catalytically Fe-centered active sites and reaction mechanisms from various authors are also discussed in detail, which may be useful for the rational design of high-performance, inexpensive, and practical Fe-base ORR catalysts in future development of fuel cells.

Catalytic Oxidation of Propene over Pd Catalysts Supported on CeO2, TiO2, Al2O3 and M/Al2O3 Oxides (M = Ce, Ti, Fe, Mn)

Abstract: In the following work, the catalytic behavior of Pd catalysts prepared using different oxides as support (Al2O3, CeO2 and TiO2) in the catalytic combustion of propene, in low concentration in excess of oxygen, to mimic the conditions of catalytic decomposition of a volatile organic compound of hydrocarbon-type is reported. In addition, the influence of different promoters (Ce, Ti, Fe and Mn) when added to a Pd/Al2O3 catalyst was analyzed. Catalysts were prepared by the impregnation method and were characterized by ICP-OES, N2 adsorption, temperature-programmed reduction, temperature-programmed oxidation, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Catalyst prepared using CeO2 as the support was less easily reducible, due to the stabilization effect of CeO2 over the palladium oxides. Small PdO particles and, therefore, high Pd dispersion were observed for all of the catalysts, as confirmed by XRD and TEM. The addition of Ce to the Pd/Al2O3 catalysts increased the metal-support interaction and the formation of highly-dispersed Pd species. The addition of Ce and Fe improved the catalytic behavior of the Pd/Al2O3 catalyst; however, the addition of Mn and Ti decreased the catalytic activity in the propene oxidation. Pd/TiO2 showed the highest catalytic activity, probably due to the high capacity of this catalyst to reoxidize Pd into PdO, as has been found in the temperature-programmed oxidation (TPO) experiments.

Advances in Ceramic Supports for Polymer Electrolyte Fuel Cells

Abstract: Durability of catalyst supports is a technical barrier for both stationary and transportation applications of polymer-electrolyte-membrane fuel cells. New classes of non-carbon-based materials were developed in order to overcome the current limitations of the state-of-the-art carbon supports. Some of these materials are designed and tested to exceed the US DOE lifetime goals of 5000 or 40,000 hrs for transportation and stationary applications, respectively. In addition to their increased durability, the interactions between some new support materials and metal catalysts such as Pt result in increased catalyst activity. In this review, we will cover the latest studies conducted with ceramic supports based on carbides, oxides, nitrides, borides, and some composite materials.

Catalytic Hydrogenation of CO2 to Methanol: Study of Synergistic Effect on Adsorption Properties of CO2 and H2 in CuO/ZnO/ZrO2 System

Abstract: A series of CuO/ZnO/ZrO2 (CZZ) catalysts with different CuO/ZnO weight ratios have been synthesized by citrate method and tested in the catalytic hydrogenation of CO2 to methanol. Experimental results showed that the catalyst with the lowest CuO/ZnO weight ratio of 2/7 exhibited the best catalytic performance with a CO2 conversion of 32.9%, 45.8% methanol selectivity, and a process delivery of 193.9 gMeOH·kgcat−1·h−1. A synergetic effect is found by systematic temperature-programmed-desorption (TPD) studies. Comparing with single and di-component systems, the interaction via different components in a CZZ system provides additional active sites to adsorb more H2 and CO2 in the low temperature range, resulting in higher weight time yield (WTY) of methanol.

Activated Carbon, Carbon Nanofiber and Carbon Nanotube Supported Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

Abstract: Molybdenum carbide was supported on three types of carbon support—activated carbon; multi-walled carbon nanotubes; and carbon nanofibers—using ammonium molybdate and molybdic acid as Mo precursors. The use of activated carbon as support afforded an X-ray amorphous Mo phase, whereas crystalline molybdenum carbide phases were obtained on carbon nanofibers and, in some cases, on carbon nanotubes. When the resulting catalysts were tested in the hydrodeoxygenation (HDO) of guaiacol in dodecane, catechol and phenol were obtained as the main products, although in some instances significant amounts of cyclohexane were produced. The observation of catechol in all reaction mixtures suggests that guaiacol was converted into phenol via sequential demethylation and HDO, although the simultaneous occurrence of a direct demethoxylation pathway cannot be discounted. Catalysts based on carbon nanofibers generally afforded the highest yields of phenol; notably, the only crystalline phase detected in these samples was Mo2C or Mo2C-ζ, suggesting that crystalline Mo2C is particularly selective to phenol. At 350 °C, carbon nanofiber supported Mo2C afforded near quantitative guaiacol conversion, the selectivity to phenol approaching 50%. When guaiacol HDO was performed in the presence of acetic acid and furfural, guaiacol conversion decreased, although the selectivity to both catechol and phenol was increased.

Microwave Synthesis of High Activity FeSe2/C Catalyst toward Oxygen Reduction Reaction

Abstract: The carbon supported iron selenide catalysts (FeSe2/C) were prepared with various selenium to iron ratios (Se/Fe), namely, Se/Fe = 2.0, 2.5, 3.0, 3.5 and 4.0, through facile microwave route by using ferrous oxalate (FeC2O4·2H2O) and selenium dioxide (SeO2) as precursors. Accordingly, effects of Se/Fe ratio on the crystal structure, crystallite size, microstructure, surface composition and electrocatalytic activity for oxygen reduction reaction (ORR) of FeSe2/C in an alkaline medium were systematically investigated. The results revealed that all the FeSe2/C catalysts obtained with the Se/Fe ratios of 2.0–4.0 exhibited almost pure orthogonal FeSe2 structure with the estimated mean crystallite sizes of 32.9–36.2 nm. The electrocatalytic activities in potassium hydroxide solutions were higher than those in perchloric acid solutions, and two peak potentials or two plateaus responded to ORR were observed from cyclic voltammograms and polarization curves, respectively. The ORR potentials of 0.781–0.814 V with the electron transfer numbers of 3.3–3.9 at 0.3 V could be achieved as the Se/Fe ratios varied from 2.0 to 4.0. The Fe and Se were presented at the surface of FeSe2/C upon further reduction on FeSe2. The Se/Fe ratios slightly influenced the degree of graphitization in carbon support and the amount of active sites for ORR.

Jet-Fuel Range Hydrocarbons from Biomass-Derived Sorbitol over Ni-HZSM-5/SBA-15 Catalyst

Abstract: Aromatics and cyclic-hydrocarbons are the significant components of jet fuel with high energy-density. However, conventional technologies for bio-fuel production cannot produce these products without further aromatization and isomerization. In this work, renewable liquid fuel with high content of aromatics and cyclic-hydrocarbons was obtained through aqueous catalytic conversion of biomass sorbitol over Ni-HZSM-5/SBA-15 catalyst. Texture characteristics of the catalyst were determined by physisorption of N2, which indicated its bimodal pore structures were microporous (HZSM-5, pore width: 0.56 nm) and mesoporous (SBA-15, pore width: 8 nm). The surface acidity included weak and strong acid sites, predominantly Lewis type, and was further confirmed by the NH3-TPD and Py-IR analysis. The catalytic performances were tested in a fixed-bed reactor under the conditions of 593 K, WHSV of 0.75 h−1, GHSV of 2500 h−1 and 4.0 MPa of hydrogen pressure, whereby oil yield of 40.4 wt. % with aromatics and cyclic-hydrocarbons content of 80.0% was obtained.

Zr-SBA-15 Lewis Acid Catalyst: Activity in Meerwein Ponndorf Verley Reduction

Abstract: Zr-SBA-15 Lewis acid catalyst has demonstrated an outstanding catalytic activity in the reduction of several carbonyl compounds by means of Meerwein Ponndorf Verley (MPV) reaction, using several secondary alcohols, and showing a very high selectivity towards the desired products. Special focus was addressed in the catalytic activity of Zr-SBA-15 material in the production of furfuryl alcohol from furfural, which is an important reaction for the lignocellulosic biomass valorization. In this transformation, both the reaction temperature and the i-PrOH:Furfural molar ratio exert a positive influence on the rate of the MPV transformation, with the influence of the former being much higher. i-propyl-furfuryl ether, a by-product resulting from the etherification of the target product with the sacrificing alcohol, is also found together with the main product. The production of this side-product is highly influenced by the reaction temperature, so that low temperatures and high sacrificing alcohol to substrate molar ratios have to be applied to keep its production at low levels.

Supported Photocatalyst for Removal of Emerging Contaminants from Wastewater in a Continuous Packed-Bed Photoreactor Configuration

Abstract: Water pollution from emerging contaminants (ECs) or emerging pollutants is an important environmental problem Heterogeneous photocatalytic treatment, as advanced oxidation treatment of wastewater effluents, has been proposed to solve this problem In this paper, a heterogeneous photocatalytic process was studied for emergent contaminants removal using paracetamol as a model contaminant molecule TiO2 photocatalytic activity was evaluated using two photocatalytic reactor configurations: Photocatalyst solid suspension in wastewater in a stirred photoreactor and TiO2 supported on glass spheres (TGS) configuring a packed bed photoreactor The surface morphology and texture of the TGS were monitored by scanning electron microscope (SEM) The influence of photocatalyst amount and wastewater pH were evaluated in the stirred photoreactor and the influence of wastewater flowrate was tested in the packed bed photoreactor, in order to obtain the optimal operation conditions Moreover, results obtained were compared with those obtained from photolysis and adsorption studies, using the optimal operation conditions Good photocatalytic activities have been observed and leads to the conclusion that the heterogeneous photocatalytic system in a packed bed is an effective method for removal of emerging pollutants

Effect of Particle Size and Operating Conditions on Pt3Co PEMFC Cathode Catalyst Durability

Abstract: The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC) cathodes with Pt3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm) with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA) and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes with the smallest Pt3Co particle size was the highest and that of the largest Pt3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s), the relative improvement in performance of the cathode based on 8.1 nm Pt3Co over the 4.9 nm Pt3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA) of the decayed membrane-electrode assembly (MEA) showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.

Co-Al Mixed Oxides Prepared via LDH Route Using Microwaves or Ultrasound: Application for Catalytic Toluene Total Oxidation

Abstract: Co6Al2HT hydrotalcite-like compounds were synthesized by three different methods: co-precipitation, microwaves-assisted and ultrasound-assisted methods. The mixed oxides obtained after calcination were studied by several techniques: XRD, TEM, H2-TPR and XPS. They were also tested as catalysts in the reaction of total oxidation of toluene. The physico-chemical studies revealed a modification of the structural characteristics (surface area, morphology) as well as of the reducibility of the formed mixed oxides. The solid prepared by microwaves-assisted synthesis was the most active. Furthermore, a relationship between the ratio of Co2+ on the surface, the reducibility of the Co-Al mixed oxide and the T50 in toluene oxidation was demonstrated. This suggests a Mars Van Krevelen mechanism for toluene total oxidation on these catalysts.

Direct Conversion of Carbohydrates into Ethyl Levulinate with Potassium Phosphotungstate as an Efficient Catalyst

Abstract: A series of metal-modified phosphotungstates were prepared and performed for direct synthesis of ethyl levulinate from fructose in ethanol. Considering the cost of catalysts, catalytic activity of catalysts, and easy separation of catalysts together, K-HPW-1 was chosen as the most suitable catalyst for synthesis of ethyl levulinate from fructose. A high ethyl levulinate yield of 64.6 mol% was obtained at 150 °C within 2 h in ethanol. The introduction of low polar toluene as a co-solvent improved the yield of ethyl levulinate to 68.7 mol%. The recovered catalyst remained high activity with the yield of ethyl levulinate converted from fructose above 50 mol% after being used five times. Moreover, the generality of the catalyst was further demonstrated by glucose, sucrose, inulin, and cellulose with ethyl levulinate yielding 14.5, 35.4, 52.3, and 14.8 mol%, respectively.

Removal of Toluene over NaX Zeolite Exchanged with Cu2

Abstract: Toluene is a major air pollutant emitted from painting and metal coating processes and might have some health effects. Adsorption and catalytic complete oxidation are promising ways to retain or convert toluene into harmless products. The present work aims to develop a bifunctional material which can be used as an adsorbent and catalyst for low-temperature toluene removal. Copper zeolites were obtained by exchanging the sodium in the parent NaX zeolite with copper from aqueous solutions of Cu(NO3)2∙2.5H2O. Several characterization techniques, H2-TPR, XPS, XRD and N2 physisorption, were used in order to evaluate the redox, surface, structural and textural properties of the materials, respectively. The various materials were tested in adsorption and catalytic processes. The sample with low copper content (1 wt. %) exhibited promising features in terms of toluene adsorption capacity and total oxidation. The results can be correlated to the presence of micropores and well-dispersed CuO species.

Pt/MOx/SiO2, Pt/MOx/TiO2, and Pt/MOx/Al2O3 Catalysts for CO Oxidation

Abstract: Conventional supported Pt catalysts have often been prepared by loading Pt onto commercial supports, such as SiO2, TiO2, Al2O3, and carbon. These catalysts usually have simple metal-support (i.e., Pt-SiO2) interfaces. To tune the catalytic performance of supported Pt catalysts, it is desirable to modify the metal-support interfaces by incorporating an oxide additive into the catalyst formula. Here we prepared three series of metal oxide-modified Pt catalysts (i.e., Pt/MOx/SiO2, Pt/MOx/TiO2, and Pt/MOx/Al2O3, where M = Al, Fe, Co, Cu, Zn, Ba, La) for CO oxidation. Among them, Pt/CoOx/SiO2, Pt/CoOx/TiO2, and Pt/CoOx/Al2O3 showed the highest catalytic activities. Relevant samples were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), CO temperature-programmed desorption (CO-TPD), O2 temperature-programmed desorption (O2-TPD), and CO2 temperature-programmed desorption (CO2-TPD).

Oxygen Reduction Reaction Activity and Durability of Pt Catalysts Supported on Titanium Carbide

Abstract: We have prepared Pt nanoparticles supported on titanium carbide (TiC) (Pt/TiC) as an alternative cathode catalyst with high durability at high potentials for polymer electrolyte fuel cells. The Pt/TiC catalysts with and without heat treatment were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Hemispherical Pt nanocrystals were found to be dispersed uniformly on the TiC support after heat treatment at 600 °C in 1% H2/N2 (Pt/TiC-600 °C). The electrochemical properties (cyclic voltammetry, electrochemically active area (ECA), and oxygen reduction reaction (ORR) activity) of Pt/TiC-600 °C and a commercial Pt/carbon black (c-Pt/CB) were evaluated by the rotating disk electrode (RDE) technique in 0.1 M HClO4 solution at 25 °C. It was found that the kinetically controlled mass activity for the ORR on Pt/TiC-600 °C at 0.85 V (507 A g−1) was comparable to that of c-Pt/CB (527 A g−1). Moreover, the durability of Pt/TiC-600 °C examined by a standard potential step protocol (E = 0.9 V↔1.3 V vs. RHE, holding 30 s at each E) was much higher than that for c-Pt/CB.

Effect of ZIF-8 Crystal Size on the O2 Electro-Reduction Performance of Pyrolyzed Fe-N-C Catalysts

Abstract: The effect of ZIF-8 crystal size on the morphology and performance of Fe–N–C catalysts synthesized via the pyrolysis of a ferrous salt, phenanthroline and the metal-organic framework ZIF-8 is investigated in detail. Various ZIF-8 samples with average crystal size ranging from 100 to 1600 nm were prepared. The process parameters allowing a templating effect after argon pyrolysis were investigated. It is shown that the milling speed, used to prepare catalyst precursors, and the heating mode, used for pyrolysis, are critical factors for templating nano-ZIFs into nano-sized Fe–N–C particles with open porosity. Templating could be achieved when combining a reduced milling speed with a ramped heating mode. For templated Fe–N–C materials, the performance and activity improved with decreased ZIF-8 crystal size. With the Fe–N–C catalyst templated from the smallest ZIF-8 crystals, the current densities in H2/O2 polymer electrolyte fuel cell at 0.5 V reached ca. 900 mA cm−2, compared to only ca. 450 mA cm−2 with our previous approach. This templating process opens the path to a morphological control of Fe–N–C catalysts derived from metal-organic frameworks which, when combined with the versatility of the coordination chemistry of such materials, offers a platform for the rational design of optimized Metal–N–C catalysts.

B-Site Metal (Pd, Pt, Ag, Cu, Zn, Ni) Promoted La1−xSrxCo1−yFeyO3–δ Perovskite Oxides as Cathodes for IT-SOFCs

Abstract: Perovskite oxides La1−xSrxCo1−yFeyO3–δ (LSCF) have been extensively investigated and developed as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) due to mixed ionic–electronic conductivity and high electrooxygen reduction activity for oxygen reduction. Recent literature investigations show that cathode performances can be improved by metal surface modification or B-site substitution on LSCF. Although the specific reaction mechanism needs to be further investigated, the promoting effect of metal species in enhancing oxygen surface exchange and oxygen bulk diffusion is well recognized. To our knowledge, no previous reviews dealing with the effect of metal promotion on the cathodic performances of LSCF materials have been reported. In the present review, recent progresses on metal (Pd, Pt, Ag, Cu, Zn, Ni) promotion of LSCF are discussed focusing on two main aspects, the different synthesis approaches used (infiltration, deposition, solid state reaction, one pot citrate method) and the effects of metal promotion on structural properties, oxygen vacancies content and cathodic performances. The novelty of the work lies in the fact that the metal promotion at the B-site is discussed in detail, pointing at the effects produced by two different approaches, the LSCF surface modification by the metal or the metal ion substitution at the B-site of the perovskite. Moreover, for the first time in a review article, the importance of the combined effects of oxygen dissociation rate and interfacial oxygen transfer rate between the metal phase and the cathode phase is addressed for metal-promoted LSCF and compared with the un-promoted oxides. Perspectives on new research directions are shortly given in the conclusion.