Solid-state NaBH4 composites for hydrogen generation: Catalytic activity of nickel and cobalt catalysts

Hydrogen generation from tablets of sodium borohydride with chlorides of nickel and cobalt was studied. The nickel catalysts were shown to be less active in the borohydride hydrolysis than the cobalt catalysts. One of the reasons for the lower activity of the nickel catalyst was the presence of hydrogen on its surface, which hampered the adsorption of reactants. The addition of cobalt to the nickel catalyst increases the hydrogen generation rate. This is due to the introduction of active metal with low adsorption capacity for hydrogen and the higher dispersion of the active component.     

Effect of anode iridium oxide content on the electrochemical performance and resistance to cell reversal potential of polymer electrolyte membrane fuel cells

An ideal polymer electrolyte membrane fuel cell (PEMFC) is one that continuously generates electricity as long as hydrogen and oxygen (or air) are supplied to its anode and cathode, respectively. However, internal and/or external conditions could bring about the degradation of its electrodes, which are composed of nanoparticle catalysts. Particularly, when the hydrogen supply to the anode is disrupted, a reverse voltage is generated. This phenomenon, which seriously degrades the anode catalyst, is referred to as cell reversal. To prevent its occurrence, iridium oxide (IrO₂) particles were added to the anode in the membrane-electrode assembly of the PEMFC single-cells. After 100 cell reversal cycles, the single-cell voltage profiles of the anode with Pt/C only and the anodes with Pt/C and various IrO₂ contents were obtained. Additionally, the cell reversal-induced degradation phenomenon was also confirmed electrochemically and physically, and the use of anodes with various IrO₂ contents was also discussed.     

Effective factors improving catalyst layers of PEM fuel cell

Cathode catalyst layer has an important role on water management across the membrane electrode assembly (MEA). Effect of Pt percentage in commercial catalyst and Pt loading from the viewpoint of activity and water management on performance was investigated. Physical and electrochemical characteristics of conventional and hydrophobic catalyst layers were compared. Performance results revealed that power density of conventional catalyst layers (CLs) increased from 0.28 to 0.64 W/cm² at 0.45 V with the increase in Pt amount in commercial catalyst from 20% to 70% Pt/C for H₂/Air feed. In the case of H₂/O₂ feed, power density of CLs increased from 0.64 to 1.29 W/cm² at 0.45 V for conventional catalyst layers prepared with Tanaka. Increasing Pt load from 0.4 to 1.2 mg/cm², improved kinetic activity at low current density region in both feeding conditions. Scattering electron microscopy (SEM) images revealed that thickness of the catalyst layers (CLs) increases by increasing Pt load. Electrochemical impedance spectroscopy (EIS) results revealed that thinner CLs have lower charge transfer resistance than thicker CLs. Inclusion of 30 wt % Polytetrafluoroethylene (PTFE) nanoparticles in catalyst ink enhanced cell performance for the electrodes manufactured with 20% Pt/C at higher current densities. However, in the case of 70% Pt/C, performance enhancement was not observed. Cyclic voltammetry (CV) results revealed that 20% Pt/C had higher (77 m²/g) electrochemical surface area (ESA) than 70% Pt/C (65 m²/g). In terms of hydrophobic powders, ESA of 30PTFE prepared with 70% Pt/C was higher than 30PTFE prepared with 20 %Pt/C. X-Ray Diffractometer (XRD) results showed that diameter of Pt particles of 20% Pt/C was 2.5 nm, whereas, it was 3.5 nm for 70% Pt/C, which confirms CV results. Nitrogen physisorption results revealed that primary pores of hydrophobic catalyst powder prepared with 70% Pt/C was almost filled (99%) with Nafion and PTFE.     

Lab scale optimization of various factors for photocatalytic hydrogen generation over low cost Cu0.02Ti0.98O2-δ photocatalyst under UV/Visible irradiation and sunlight

We have demonstrated earlier that maximum H₂ generated @ 1.167 l/h/m² over Cu_0.02Ti_0.98O_2-δ photocatalyst with apparent quantum efficiency, AQE of 7.5% and solar fuel efficiency, SFE of 3.9% under sunlight. With an aim to scale-up the solar photocatalytic hydrogen process to pilot plant, optimization studies at lab scale as well as in upscaled photoreactors were performed over Cu_0.02Ti_0.98O_2-δ, photocatalyst under UV/visible and sunlight. Cu_0.02Ti_0.98O_2-δ was synthesized by facile sol-gel route and characterized by relevant techniques. Several operational parameters were investigated in order to finalize the conditions which are most favourable for photocatalytic hydrogen yield. Factors such as photocatalyst loadings, v/v concentration of sacrificial reagent, replacement of methanol by industrial waste glycerol, role of different configuration of light source with reactor, effect of stirring during the photocatalytic reaction, effect of fluctuations of solar flux at hourly basis, illumination area on hydrogen yield were studied. Contribution of each factor in determining the hydrogen yield was quantified. Relative standard deviation in hydrogen yield as a function of each factor was estimated. Our findings suggest that in addition to catalyst loadings and sacrificial reagent, improved dispersion of photocatalyst obtained by stirring the reaction mixture in horizontal geometry resulted in enhanced H₂ yield. Hydrogen yield obtained at lab scale can be appropriately extrapolated with respect to illumination area instead of weight of photocatalyst. A relative standard deviation (RSD) of ± 3.82% and ± 4.53% in H₂ yield was calculated for sunny and cloudy days in time zone of 10.30–16.30 h IST. Deviation of H₂ yield was more on cloudy days and beyond 16:30 h. These studies have provided a daily window of 11:00–15:00 h to be utilized throughout the year for a commercial scaled up process, prohibiting the illumination during less productive hours of the day for shaping the improved economics of solar hydrogen generation. Our results obtained at lab scale would be useful to perform sunlight driven scaled –up photocatalytic process using low cost visible light efficient photocatalyst, Cu_0.02Ti_0.98O_2-δ.     

Size and morphology-controlled synthesis of mesoporous hydroxyapatite nanocrystals by microwave-assisted hydrothermal method

We report the rapid microwave-assisted hydrothermal synthesis of mesoporous hydroxyapatite (HAp) nanocrystals with controlled size, morphology, and surface area using various organic modifiers as regulators. The products were analyzed for their crystalline nature, phase purity, morphology, particle size and pore size distribution. Results indicated that ascorbic acid, cetyltrimethyl ammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) play an important role to obtain needle like, rod like and fiber like mesoporous HAp nanocrystals with different specific surface area by controlling growth habit of HAp along c-axis. In addition, the prepared samples were B-type carbonated HAp similar to bone minerals. Therefore, the present approach can be a promising way to obtain precursor for making tissue engineering scaffolds, drug/protein delivery carriers and bone fillers with tunable characteristics.     

来瓦希尔骨架材料MIL-53(Al)填充PEBA膜渗透汽化分离水中苯胺

将来瓦希尔骨架材料MIL-53(Al)引入到聚醚共聚酰胺（PEBA-2533）高分子相中制备了不同填充量的PEBA/MIL-53(Al)杂化膜并用于渗透汽化分离水中微量苯胺。X-射线衍射结果证实MIL-53(Al)被成功合成。扫描电镜和激光粒度分析结果表明所制备MIL-53(Al)颗粒粒径在纳米尺度范围内。采用扫描电镜、红外光谱、X-射线衍射、差示扫描量热和水接触角对杂化膜进行了表征，并考察了杂化膜的溶胀行为和分离性能。结果表明，所得杂化膜的热稳定性较好。当MIL-53(Al)质量分数小于20%时，MIL-53(Al)在高分子相中分散均匀，继续增大填充量出现团聚现象。杂化膜的结晶度随MIL-53(Al)填充量的增加而降低。MIL-53(Al)的引入增强了杂化膜的疏水性和溶胀度。在料液温度为60℃、膜下游压力400Pa、料液苯胺质量分数为3.6%时，MIL-53(Al)质量分数为20%的杂化膜（M-20）综合分离性能最优，渗透通量达到2.15kg/(m²·h)，分离因子为264。12天的稳定性测试结果表明所得杂化膜分离性能无显著变化，能够满足渗透汽化应用要求。     

超高性能混凝土国内外研究与应用进展*

介绍了超高性能混凝土（UHPC）的制备原理和性能特点，对UHPC国内外研究和应用情况进行了综述，指出了我国UHPC研究和应用中存在的问题。结果表明：UHPC是一种具有优异的力学性能、耐久性能和环保效益的新型水泥基复合材料。国外在UHPC理论研究和应用研究方面都取得了大量成果，在实际工程中已经获得了广泛的应用；近年来我国在理论研究和应用方面也得到了快速发展；如何简化UHPC制备工艺、降低生产成本、补偿自收缩是今后的主要研究方向，完善相关规范标准以更好地指导UHPC现浇工程应用是目前首要解决的问题。随着环保和可持续发展理念的日益重视，UHPC这种低碳环保材料将有广阔的发展前景。     

Ag(0) nanocatalyst stabilized with networks of p(SPA-co-AMPS) for the hydrogen generation process from ethylenediamine bisborane hydrolysis

In this study, the hydrogen generation from the catalytic hydrolysis of the ethylenediamine bisborane (EDAB) was performed. For this purpose, the p(sulfopropyl acrylate potassium salt-co-2-acrylamido-2-methylpropansulfonic acid sodium salt)@Ag(0) (p(SPA-co-AMPS)@Ag) catalyst was prepared. Later the p(SPA-co-AMPS)@Ag containing Ag(0) particles with nanodimensions was used as catalyst in EDAB hydrolysis. Our study is the first in the literature from this aspect, and investigated in detail the effect of catalyst amount, reactive concentration, temperature and dry or swollen nature of the catalyst on the EDAB hydrolysis. At the end of the reaction series, the hydrolysis reaction of EDAB with p(SPA-co-AMPS)@Ag catalyst was determined to have activation energy (E_a) of 43.24 kJmol^-1. Additionally, the turn over frequency (TOF) was 0.560 mol H₂(mol Ag(0).min)⁻¹ at 30 °C. The p(SPA-co-AMPS)@Ag catalyst had perfect reusability with 95% of initial activity after the 5th use for the hydrogen generation from EDAB.     

Influence of carbonation on the low-temperature consolidation by Spark Plasma Sintering of carbonated calcium phosphate bioceramics

Calcium phosphates (CaP) such as biomimetic nanocrystalline apatite or amorphous calcium phosphate are hydrated bioactive compounds particularly suitable for bone repair applications due to their similarity with bone mineral. However, their consolidation in ceramic parts deserves special attention as they are thermodynamically metastable and can decompose into less bioactive phases upon heating. Adapted strategies are needed to obtain bulk bioceramics. Spark Plasma Sintering (SPS) has been shown to allow cold sintering of such compounds at temperatures like 150 °C while preserving the hydrated character and nanosized dimensions of the precursor powders. To this date, however, the role of the degree of carbonation of these precursors on the densification of CO₃-bearing CaP compounds via SPS has not been explored despite the natural carbonation of bone. In this work, several carbonated CaP hydrated compounds were prepared and consolidated by SPS and the characteristics of the obtained ceramics was scrutinized with respect to the starting powders. Two carbonation routes were carried out: via volume carbonation during powder synthesis or via subsequent surface ion exchange. All samples tested led to apatitic compounds after SPS, including amorphous CaP. We show that the degree of carbonation negatively affects the densification rate and propose possible hypotheses explaining this behavior. Evolution in the nature of the carbonate sites (apatitic A-, B-types and labile surface carbonates) before and after SPS is also noticed and commented. The consolidation of such compounds is however proven possible, and gives rise to bone-like apatitic compounds with great potential as bioactive resorbable ceramics for bone regeneration.     

Influence of Impurities and Oxidation on Hydroconversion of Waste Cooking Oil into Bio-jet Fuel

The influences of impurities and oxidation evolution of waste cooking oil on the preparation of bio-jet fuel via hydroconversion were studied. The hydrogenation active sites and acid sites were covered by heavy metals, sulfides, and basic nitrogen compounds, resulting in the increase of selectivity for bio-jet fuel by decreasing the selectivity of diesel, aromatics, and iso-alkanes. The effects of impurities, oxidation on the reaction pathway, and product distribution became more distinct with higher catalyst acidity. The evolution and variation of naphthalene, indan, and phenanthrene obtained from cyclic fatty acids influenced the properties of fuel or evoked the catalyst deactivation. This work will help to design new catalysts for selective conversion of waste cooking oil into bio-jet fuel.