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To improve the stability of molybdenum carbide catalysts in dimethyl ether steam reforming (DSR), the inactivation mechanism and the performance of Pt modified catalyst has been investigated. The Mo2C oxidation induced by H2O is verified to be the main reason of catalytic deactivation. After modified with Pt, the H2 production rate and selectivity are greatly enhanced, reaches 1605 μmol min−1·gcat−1 at 350 °C, in comparison to that of the Mo2C/Al2O3 catalyst. Moreover, the 2%Pt–Mo2C/Al2O3 catalyst is more stable with only 20% activity loss after 50 h on stream compares to the 73% activity loss in 12 h with Mo2C/Al2O3 catalyst. By means of in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the enhancement brought by Pt is ascribed to the consumption acceleration of intermediate oxygen species on catalyst surface and the decline of onset temperature of DSR reaction. It is expected that these findings can lead us to more practical molybdenum carbide catalysts in DSR.

In this work, well-ordered platinum (Pt) nanocubes (NCs), with precise control on the size and the spatial arrangement, are synthesized from a microemulsion overgrowth in a block copolymer (BC) nanotemplate. The nanovials on this self-assembled BC template serve as microreactors for the reduction of the HCl/H

Designing Pt-based nanoparticle (NP) catalysts is of great interest for the lowering of Pt usage and the enhancement of catalytic activity on the proton-exchange membrane fuel cells (PEMFCs). However, it is still challenging to develop well-arrayed catalyst NPs on supports over multiple-length scales. Herein, we presented a facile strategy of producing well-ordered Pt-based NPs toward oxygen reduction reaction (ORR) catalysts assisted by the self-assembly of block copolymers. In contrast to the conventional Pt/C ORR catalysts with a random dispersion on carbon, the as-prepared Pt, PtCo, and PtCo@Pt NPs in our work were hexagonally arranged with a uniform quasi-spherical shape and ordered distribution. The systematic study related to their ORR activities revealed that the PtCo@Pt core-shell NP arrays were more active and more durable than PtCo, Pt, and the commercial Pt/C catalyst. In the rotating-disk electrode test, a half-wave potential (E1/2) of 0.86 V versus RHE and a 4-e ORR mechanism were found for PtCo@Pt. Single-cell performance showed that the current density and the peak power density of PtCo@Pt achieved 0.86 A/cm2@0.7 V and 1.05 W/cm2, respectively, with a Pt loading of ∼0.15 mg/cm2 on the cathode. Also, they held 81.4 and 82.9% retention, respectively, after the durability test in the single-cell test. Density functional theory calculation results revealed that PtCo@Pt NPs had a lower d-band center and a weaker oxygen binding energy compared to Pt and PtCo, which contributed to the enhancement of the ORR activity.

In this work, PtCo nanoparticles (NPs) on hierarchically ordered mesoporous carbon (PtCo/OMC) are synthesized for polymer electrolyte membrane fuel cells (PEMFCs) aiming to improve the activity and durability of the Pt-based catalyst towards oxygen reduction reaction (ORR). Specifically, the OMC is prepared through a solvent evaporation-induced self-assembly (EISA) method by using a triblock copolymer PEO-PPO-PEO as the structure agent, followed by annealing in the nitrogen atmosphere to decompose the structure agent and to carbonize the carbon precursor. PtCo nanoparticles (NPs) are fabricated with an average diameter of 3.3 nm by H2 reduction and galvanic replacement in an acid solution, and then are uniformly dispersed onto the OMC via impregnation. The typical mesoporous structure of the OMC enhances the uniformly distribution and thermal stability of the small-sized PtCo NPs. The activity and the durability of the as-prepared PtCo/OMC catalyst are investigated by cyclic voltammetry (CV) and single-cell test. In the electrochemical tests, PtCo/OMC exhibits a high ECSA value of 88.56 m2g−1, and a ECSA retention of 77.5% after 5000 CV cycles. The results show that the PtCo/OMC catalyst is more active and more stable than the commercial-carbon-supported PtCo catalyst (PtCo/XC-72). PtCo nanoparticles (NPs) on hierarchically ordered mesoporous carbon (PtCo/OMC) are synthesized aiming to improve the activity and stability of the Pt-based catalyst for the oxygen reduction reaction (ORR). Due to the natural mesoporous and graphite-carbon nanostructure of the OMC, the as-prepared PtCo/OMC catalyst is more active and more stable than the PtCo NPs on the commercial Vulcan@ XC-72 support (PtCo/XC-72), showing great potential in proton exchange membrane fuel cells (PEMFCs).

Self-assembly of di-blcok copolymers (di-BCs) with precise control on morphologies and structures of nanomaterials makes it a promising technology for catalyst preparation. However, applications of the BC-synthesized Pt nanoparticles (NPs) on fuel cell have less been discussed. The major challenge may be the difficulty in achieving high-density nanopatterns which require a low degree of polymerization but a high effective segment-segment interaction parameter of the BC templates. As a resolution, sequentially double- or triple-layered BC route provides a new density-increased idea of harnessing these materials. In present work, monolayer of ordered and high-dispersed Pt-NP arrays with a density 27-folded has been achieved by the multiple di-BC routes consisted of identical self-assembly and plasma-cleaning processes. The multiplication has been proved to be equivalent to the duplication and oriented translation of the initial Pt-NP arrays, which provides not only a well-defined approach to control the spacing precisely, but also a bottom-up process to synthesize hexagonal-arranged arrays with predicable densities. Electrochemistry shows that the density multiplication has no negative effects on the Pt utilization of the monolayer arrays, and a remarkable ECSA value of ∼114.5 m2 g−1 is found. Further characterization of the monolayer arrays as cathodic catalysts for PEMFC reveals that, neither the ohmic losses nor the mass-transport losses are enhanced after the density multiplication, and the power density of the PEMFC assembled here is significantly higher than that using commercial Pt/C catalysts. All the results demonstrate that the multiple di-BC approach has great potential in preparation of BC-synthesized Pt-NP arrays for fuel cell applications.

A series of Ni-modified Mo2C catalysts with La2O3-stabilized ZrO2 supports were synthesized via template method coupled with incipient wetness impregnation and temperature-programmed carbonization. The catalyst was tested in dry reforming of methane (DRM) reaction at the temperature range from 973 to 1173 K in a fixed-bed quartz reactor under atmospheric pressure. XRD, Raman, BET, H2-TPD, SEM, EDS and TEM were conducted to characterize the phase constitution, the pore structure, the morphology and the crystal structure of the catalysts. Ni–Mo2C nanoparticles of ~ 3 nm diameter were obtained for these catalysts, and the La2O3–ZrO2 supports exhibited a cubic lattice structure with a sheet shape, which is believed to contain an abundant of oxygen vacancies. And the synergistic interaction between the oxygen vacancy in La–Zr–O solid solution and the Ni–Mo2C particles could decrease the apparent activation energy of CO2. Both of them are beneficial for accelerating DRM reaction. CH4 conversion of the best specimen catalyst reaches 94% at 1173 K, and the catalyst maintains its stability after 100-h reaction. The superior catalytic activity of NMLZ-7.5 is attributed to the improved BET surface area (33.2 m2/g), smaller crystallites, grain boundaries and oxidation–carbonization cycle of Ni–Mo2C.

To fabricate effective and stable OER electrode in water electrolysis, self-doped TiO2 nanotube arrays which has a higher electrical conductivity than pristine TiO2 nanotube arrays was used as the support for loading IrO2. The self-doped TNTA was fabricated by a simple electrochemical reduction of TNTA in neutral electrolyte solution, and then IrO2 nano particles were deposited by pulse electro-deposition method. The cyclic voltammetric behavior, electrical conductivity and micro structure of self-doped TNTA prepared at different reduction potential were characterized to obtain an optimal performance, and self-doped TNTA prepared under −1.9 V (vs. Ag/AgCl) shows the best electrochemical performance. After depositing IrO2, the OER activity and stability of new electrodes were also determined. Due to the enhanced electrical conductivity of support, the mass activity of IrO2/self-doped TNTA are 50 times higher than IrO2/TNTA. The OER stability of new electrode was evaluated under constant current of 5 mA/cm2, IrO2/TNTA and IrO2/Ti were also tested for comparison. A higher stability of IrO2/self-doped TNTA electrode is observed than the other two electrodes, and XPS studies indicate a lower oxidation state of Ir in IrO2/self-doped TNTA, this shows a possible interactions between IrO2 and the new support.

This work offers a typical understanding of the factors that govern the nanostructures of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine) (P4VP-b-PS-b-P4VP) block copolymers (BCs) in dioxane/water, in which water is a selective solvent for the P4VP block. It is achieved through an investigation of the amphiphilic triblock copolymer micelles by variation of three different factors, including water content (above CWC but under the immobile concentration), temperature (ranging from 20 °C to 80 °C), and copolymer composition (low and high PS block length). Transition of bead-like micelles to vesicles is observed with the increase of water content due to the increase of interfacial energy between the copolymer and the solvent. Effect of temperature superposed on that of water content results in various morphologies, such as beads, fibers, rods, capsules, toroids, lamellae, and vesicles. The interfacial tension between the BC and the solvent increases with the increase of water content but decreases with the increase of temperature, indicating that the micellar morphologies are resulted from the competitive interplay between the temperature and the water content and always change in a direction that decreases the interfacial energy. Based on the micellar structures obtained in this work and the effects of temperature superposed on water concentration, a diagram of phase evolution of different micellar morphologies is illustrated here, covering the temperature range from 20 °C to 80 °C and the water content changing from 20 vol% to 35 vol%. For the investigation of BC composition, morphological transition of vesicle-to-fiber, for high PS length, is observed as compared with bead-to-capsule for low PS length, as the temperature changes from 20 °C to 80 °C. Our research complements the protocols to control over the morphologies and the phase diagram describing P4VP-b-PS-b-P4VP micellar nanostructures in aqueous solution.

This work offers an effective size-controlled synthesis of platinum nanoparticle (Pt NP) arrays for electrocatalyst through self-assembled nanopatterns of block copolymers on titanium (Ti) wafers. Size, spacing and uniformity of Pt NP with loading of Pt to a minimum were investigated to be controlled and adjusted in order to improve the electrochemically active surface area (ECSA) and ECSA stability, and Pt concentration in copolymer/chloroplatinic acid (H2PtCl6) solution was verified to be one of the most important factors to control the arrays’ structure. In our case, the Pt NPs with predictable size of 5–16.5 nm could be obtained when the Pt concentration is larger than 0.05 mg ml−1, which the dominant diameter is proved to be proportional to one-third power of the Pt concentration according to the linear relation of templates’ Pt/N mass ratio versus Pt concentration, and the Pt NPs remain highly ordered arrays with predictable spacing when the Pt concentration is larger than 0.125 mg ml−1. Decrease in Pt concentration from 2 to 0.125 mg ml−1 is an effective method to improve the ECSA and durability simultaneously. The Pt NP arrays exhibit not only a remarkable initial ECSA value of 106.2 m2 g−1, but also a pseudo-zero particle aggregation possibility during 3000-cycle voltammetry, which is attributed to the high Pt NP dispersion and the ordered arrays that improve the Pt utilization and lower the possibility of aggregation.

Sorption enhanced steam reforming of acetic acid over sorbent assisted catalyst of Ni-CaO-La2O3 were investigated for high-purity H2 production. Ni-CaO-La2O3 with 8, 16 and 20 wt% Ni were developed by sol-gel combustion synthesis and were characterized by TG, TPR, BET, SEM, XRD and XPS. The catalytic activities and stability of the catalysts were tested in a fixed reactor. H2 yield and H2 concentration through Ni-CaO-La2O3 with 20 wt% Ni reaches 86.02% and 92.24% during pre-breakthrough period, respectively, which is attributed to sufficient Ni active sites on the surface and good Ni dispersion. Catalytic activities of Ni-CaO-La2O3 with 20 wt% Ni maintain stable during sorption-enhanced steam reforming reaction, but CO2 sorption capacity slightly decreases due to blockage of pores and size increase of CaO particles within nine sorption/desorption cycles.

Porous silica coated Ni/CeO 2 ZrO 2 catalysts were synthesized for steam reforming of acetic acid. The silica coated Ni/CeO 2 ZrO 2 catalyst showed a significantly enhanced activity (95% acetic acid conversion) than the Ni/CeO 2 ZrO 2 catalysts (62% acetic acid conversion) at a low temperature (550 °C). Interaction between Ni/CeO 2 ZrO 2 and silica layer was proved to be a crucial role on enhancing of catalytic activities. Further characterization (XPS, H 2 -TPR) indicates this interaction facilitates the steam reforming reaction and raises the selectivity of CO by modifying the surface Ni electronic structure. In addition, the coated catalyst also exhibited a good stability and no obvious deactivation was detected at 550 °C and 600 °C within 30 h.

This contribution focuses on the impact of shear flow on size and nanostructure of PS-based amphiphilic block copolymer (BC) micelles by varying the stirring rate and copolymer composition. The results show that the vesicles formed from diblock copolymer (di-BC) of PS-b-PAA remain with vesicular morphology, although the average size decreases, with the increase of stirring rate. However, the multi-compartment micelles (MCMs) formed from tri-block copolymer (tri-BC) of PS-b-P2VP-b-PEO are quite intricate, in which the copolymer first self-assembles into spheres, then to clusters, to large compound micelles (LCMs), and finally back to spheres, as stirring rate increases from 100 r/min to 2200 r/min. Formation mechanism studies manifest that vesicles form simultaneously as water is added to the di-BC solution, termed as directassembly, and remain with vesicular structure in the flowing process. While for the PS-b-P2VP-b-PEO copolymer, spherical micelles at initial stage can further assemble into clusters and LCMs, termed as second-assembly, due to the speeding-up-aggregation of the favorable stirring. As a result, an invert V-relationship between tri-BC micelle dimension and stirring rate is observed in contrast to the non-linear decreasing curve of di-BC vesicles. It is by investigating these various amphiphilic BCs that the understanding of shear dependence of size and morphology of micelles is improved from self-assembly to second-assembly process.

A multistep synthesis method is introduced to fabricate high performance IrOx/W-TiO2 catalyst for noble metal reduction in PEM water electrolyzers. The performances of the IrOx/W-TiO2 catalyst for oxygen evolution reaction (OER) are measured in half-cells and single-cells and compared with unsupported IrOx and commercial IrO2. In half-cell tests, IrOx/W-TiO2 displays an improved Ir mass activity compared with the unsupported IrOx, demonstrating a positive effect of the support material. In single-cell tests, the performance of IrOx/W-TiO2 also exceeds both the unsupported and commercial IrO2. The cell voltage reaches 1.602V at 1 A cm−2 (Nafion 212) with total noble metal loading less than 0.2 mg cm−2, suggesting that significant Ir reductions are possible by using IrOx/W-TiO2 without sacrificing the cell performance. It also shows improved durability than other unsupported catalysts at reduced Ir loading. In-situ electrochemical test reveals that the performance is associated with the enhanced conductivity of the catalyst layer.

IrO2 was electro-deposited on hydrogenated TiO2 nanotube arrays (TNTA) to form IrO2/H-TNTA for oxygen evolution reaction (OER). Hydrogenation by calcining in H2 atmosphere was conducted to improve the electric conductivity, which was owing to partially reduce of Ti4+ in TNTA. It was found that hydrogenated TiO2 can facilitate the electro-deposition of IrO2, and elevate the OER activity compared to that of non-calcined and air-calcined TNTA, which would be due to the improved conductivity of H-TNTA. IrO2/H-TNTA shows a five-fold higher activity than IrO2/air-TNTA with the same loading amount. The coverage of IrO2 on the surface of hydrogenated TNTA is crucial to the stability of catalyst and with the increased loading amount of IrO2, IrO2/H-TNTA shows much higher stability.

Reversible transition of self-assembly and disassembly for PS 720 -P2VP 200 -PEO 375 multicompartment micelles in aqueous solution induced solely by changing temperature has been investigated. The shuttle-like micelles, formed from a second self-assembly of nano-sized spheres at 20 °C, will disassemble to small spherical micelles as the temperature increases to 40 °C. Cooling the system back to 20 °C regenerates the large-sized micelles, while the regeneration at low temperature is much slower than the disassembly at high temperature. A critical temperature is found at the intermediate regime of 30 °C, at which the micelle reaches the maximum dimension. However, the critical temperature is observed to be varied with the variation of the molecular weights of triblock copolymers and shifts to lower region with the decrease of the fraction of hydrophilic blocks. This reversible transition is considered as a result from the combination of the second-assembly of spherical micelles and the interaction parameter between the solvent and the hydrophobic block, and has great potential in application in drug delivery and release triggered by temperature.

This work contributes to a new protocol of patterning gold nanoparticles (NPs) via secondary phase-separation of micelle template of PS- b -P2VP- b -PEO block copolymer. The immiscibility between hydrophobic PS and hydrophilic P2VP and PEO leads to a bulk phase-separation in large compound micelles (LCMs) when heated at the temperature of 130 °C. The bulk-separated template then constitutes an ideal precursor for Au NPs loading by an immersion in an aqueous solution bath of chloroauric acid such that the primed P2VP domains would coordinate to the charged [AuCl 4 ] − through electrostatic interactions. With the following treatment of air plasma, pseudo-hexagonal nanopatterns are created with Au NPs on P2VP matrix.

For a typical Proton exchange membrane (PEM) water electrolysis system, reducing the amount of Ir loading at the anode in membrane electrode assembly (MEA), while maintaining the performance, is still a big challenge. Here, to improve the performance of catalyst layer for oxygen evolution reaction (OER) in an acidic medium, vertical aligned IrOx nanoarrays (IrOx NAs) were synthesized by electrodeposition with TiO2 nanotube arrays (TNTA) as template. By tuning the scan rate in the electrodeposition process, IrOx open-end nanotube arrays with tunable length ranged from 500 nm to 1400 nm and hollow nanorod arrays were obtained due to a diffusion-controlled deposition process. By constructing 3-D electrode of 1-D catalyst with enhanced ion transfer, IrOx NAs performed almost the same current density of OER with 1/20 Ir loading amount compared with commercial IrO2 nanoparticles, which could significantly reduce the cost of catalyst in PEM water electrolyser. Moreover, no apparent current decrease was observed even after 10 h’ anodic polarization under 1.55 V, which exhibit excellent OER durability.

Ordered electrode is believed to be the next generation of MEA. One-dimensional-arrays material possesses high surface area, oriented electron transfer pathway and facile mass transfer pathway, which shows great potential as electrocatalyst. For OER electrode, IrO2 is still the irreplacable choice at present status. To construct IrOx based nanotube/nanowire arrays could increase the performance of OER electrode with reduced loading amount of Iridium. Titanium oxide nanotube arrays (TNTA) is a promising candidate for the preparation of 1-D arrays electrode as its prominent stability, ordered structure and sufficient conductivity with simple modification. In order to achieve the open-end nanotube structure for the fully utilization of noble metal catalyst, controlled electrochemical deposition is applied. In our previous work, IrOx nanotube arrays performs similar current density with 1/20 loading amount of commercial IrO2 nanoparticle at the same potential. To achieve the length control of IrOx nanotube arrays, the electrodeposition of IrOx on TNTA with cyclic voltametry method was studied. By altering the scan rate, continuous IrOx nanotube arrays with different length ranged from 500 nm to 1400 nm was achieved. This phenomenon may probably due to that the deposition in the tube is diffusion controlled, while the deposition at the mouth of TNTA keeps constant due to sufficient supplement of precursor form the bulk electrolyte. In a single cycle, as the depositing goes on, the concentration gradient along the tube forms and results in uneven deposition. Different scan rate results in different duration of depositing in a single cycle. And longer duration means more uneven deposition, and leads to shorter nanotube. At present, to obtain IrOx nanotube arrays with uniform tube wall, control deposition with pulsed potential deposition method is studied. By altering the relaxation and deposition time, IrOx with uniform thickness and tunable length can be achieved. And the thickness of IrOx tube wall can be controlled, too. By achieving uniform and thinner tube wall, the utilization rate of Iridium can be further increased.

A series of Ni-based catalysts supported on Ce–Zr–O were synthesized via impregnation and applied in the reverse water gas shift reaction (RWGS). BET, XRD, TPR, SEM, TEM and XPS were employed as the characterization of catalysts. Catalytic activities of Ni/Ce–Zr–O with different Ni contents were evaluated in RWGS under atmospheric pressure and at the temperature range of 550–750 °C in a fixed-bed quartz reactor. CO2 conversion reaches 49.66% and maintains stable after 80 h of reaction over 3 wt% Ni/Ce–Zr–O. CO selectivity can reach 99.65% for the catalyst with 10 wt% Ni at 750 °C. The Ni/Ce–Zr–O catalyst provides high activity, stability and selectivity in the conversion of CO2 to CO at high temperature. Ce–Zr–O solid solution is formed by co-precipitation and Ni is able to be incorporated into the Ce–Zr–O lattice via impregnation. The Ni species on catalyst surface can be considered as the active site for RWGS.

The effect of various strain rates on the tensile behavior of a single crystal nickel-base superalloy was studied. Single crystals with (001) crystal orientation were tested at 800 and 1000 degrees C under three kinds of strain rate of 10(-3), 10(-4) and 6x10(-5) s(-1). The yield strength increased with the increase of strain rate, while the configuration of the stress-strain curves was independent of strain rate. Additionally, fracture surface was related to strain rate at two temperatures. At 800 degrees C the amount of cleavage surface was different at three strain rates, which resulted from the difference of activated slip systems. The elongation increased with the decrease of strain rate, which was influenced by the heterogeneous ductile deformation. At 1000 degrees C the difference of fracture Surface was attributed to the microvoid at higher strain Fate, while the gamma/gamma' interfaces also played an important role at lower strain rate; elongation rate was independent of strain rate. (c) 2008 Elsevier B.V. All rights reserved.

A Ni-base single crystal superalloy was transient liquid phase (TLP) bonded using a Ni-Cr-B amorphous foil at 1230 degrees C for 8 h. Stress rupture tests of the TLP joint and a matrix sample were carried out at 982 degrees C/248 MPa and 1010 degrees C/248 MPa. The microstructures and fracture surfaces were studied using scanning electron microscopy (SEM). Transmission electron microscopy (TEM) investigations were performed after creep rupture testing to examine the deformation substructures. The results show that the stress rupture ductility of TLP joints is significantly decreased compared to the matrix sample. This reduction of the ductility of TLP joints can be attributed to solid solution strengthening by boron atoms, subgrain boundaries formed in the bonding zone and the concentration of creep cavities formed during the last stage of the stress rupture test. (c) 2006 Elsevier Inc. All rights reserved.

Effect of minor carbon addition on the creep properties of an experimental Ni-based single crystal superalloy has been investigated. Three alloys with different level of carbon addition were subjected to creep tests of 871 °C/552 MPa and 1038 °C/172 MPa. With the increase of carbon addition, the creep properties of alloys presented different trends. Detailed microstructural analysis have revealed that precipitation of M6C carbide and reduction of casting pores are beneficial to the creep properties, and the improvement at high temperature and low stress is stronger than that at low temperature and high stress. The larger γ′ particle, eutectic and MC carbide are the weakening factors for creep properties; however, the weakening effect at high temperature and low stress is weaker than that at low temperature and high stress.

The microstructure of experimental nickel-base single crystal superalloys with different levels of carbon has been studied. With increasing carbon addition, the incipient melting point decreases obviously and the carbide morphology is changed from blocky to script-like shape. Minor carbon addition also affects the shrinkage porosity and eutectic in as-cast state. The segregation behavior of elements W and Ta is also influenced by the minor carbon addition.

Microstructural evolution of a nickel-base single crystal superalloy during thermal exposure at 900 and 1000 degreesC was investigated. In addition to growing and linking of gamma' particles, carbides M6C and M23C6 precipitated in this testing alloy. During exposure at 900 degreesC, M6C carbide precipitated in cubic shape, while at 1000 degreesC, M6C carbide was separated out in needle-like or cubic shape. M23C6 carbide was all precipitated in the gamma matrix channel. The TCP phase was not found in this alloy during thermal exposure both at 900 and 1000 degreesC before 1500 h. (C) 2003 Elsevier Science B.V. All rights reserved.