Porous niobium oxide films prepared by anodization in HF/H3PO4

Ordered porous niobium oxide with the diameter of less than 10 nm and the aspect ratio of more than 20 is prepared by anodization of niobium foils at 2.5 V in the mixture of 1 wt% HF and 1 M H₃PO₄ for 1 h. In this study, the effects of the mixed electrolytes, anodic potential and anodization time on the preparation of porous niobium oxide are described based on the current-time transients during anodization and morphological observations. It is founded that a single HF electrolyte leads to the formation of pores as well as the fast dissolution of formed pores at the surface. The dissolution of the formed oxide is significantly retarded by the addition of appropriate amount of H₃PO₄.     

Structures of H3PO4/SiO2 catalysts and catalytic performance in the hydration of ethene

The hydration of ethene was carried out over H₃PO₄/SiO₂ having various amounts of H₃PO₄. The rate of the ethanol formation increased markedly with the increasing H₃PO₄ loadings, in particular above 60–70 wt%. By X-ray diffraction (XRD), and

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MAS NMR methods, it was revealed that various silicon phosphates were produced in the preparation of the catalysts. The structures of the phosphates depended on the H₃PO₄ loadings. It was suggested that Si(HPO₄)₂·H₂O species which formed at higher H₃PO₄ loadings were hydrolyzed to H₃PO₄ and SiO₂ during the course of the reaction, yielding the catalysts with high performance. The bulk phase of the H₃PO₄ was involved in the reaction.     

Photocatalytic activities of NH3-treated titanias modified with other elements

Nanocrystalline titanias were obtained by thermal reaction of titanium tetraisopropoxide in 1,4-butanediol (glycothermal reaction). In this study, titanias modified with various elements (B, Mg, Al, P, Zn, and Ga) were prepared by the glycothermal method. The obtained samples were nitrified and their physical and photocatalytic properties were investigated. Among the six modifiers examined, addition of P was the most effective for photocatalytic decomposition of acetaldehyde under visible-light irradiation. After nitrification and annealing, the P-modified titania showed a strong absorption in the visible region (400–550 nm). It was found that the photocatalytic activity was related to the amount of nitrogen atoms doped in the anatase structure.     

Influence of the morphology and microstructure on the photocatalytic properties of titanium oxide films obtained by sparking anodization in H3PO4

The aim of this paper is to investigate changes in morphology and microstructure of TiO₂ films, prepared by sparking anodization of Ti in a H₃PO₄ solution, by applying different formation charges. We show that although films obtained by this technique are rarely used in photocatalytic applications, the morphological and microstructural changes during sparking anodization produce TiO₂ films that can be used as photocatalysts. In contrast to qualitative analysis commonly found in the literature, we used quantitative methods of analysis to quantify average pore diameter and pore density from the morphology and structural parameters from X-ray diffraction (XRD) patterns using the Rietveld refinement. The results indicated that changes in both the morphology and crystalline structure have a strong influence on the photoactivity of the films. From this investigation, we concluded that, for films prepared in early stages of anodization, the morphology had the biggest influence on photoactivity, and after applying 72C of charge, crystalline properties dominated the photocatalytic characteristics of the films.     

Curing temperature effect on smokeless fuel briquettes prepared with molasses and H3PO4

Chars from the co-carbonisation of a low-rank coal and olive stones have been used to prepare environmental acceptable smokeless fuel briquettes. The blend was a mixture of char, molasses and H₃PO₄. This acid was added to favour the polymerisation of the binder. The effect of the curing temperature on the physico-chemical features of the briquettes was studied by Fourier Transform Infrared Spectroscopy and Temperature Programmed Decomposition followed by Mass Spectrometry. The presence of H₃PO₄ as well as the curing process at 200 °C of temperature, contribute to the formation of carboxylic acids which lead to the production of briquettes with adequate mechanical properties.     

Studies on proton conductivity of polyimide/H3PO4/imidazole blends

A new anhydrous proton conducting material based on polyimide(PI)/H₃PO₄/imidazole(Imi) Blends was prepared. FTIR spectrum shows the existence of hydrogen bonds between protonated and unprotonated imidazole units. The addition of phosphoric acid can accelerate the degradation process of PIs, while the addition of imidazole in PI/H₃PO₄ blends can improve their chemical oxidation stability enormously. The proton conductivity of PI/H₃PO₄ blends increases significantly with increasing content of imidazole. Proton conductivity of PI/xH₃PO₄/yImi membranes increases with increasing temperature and content of phosphoric acid. The experimental results show that it is possible to significantly improve the operating temperature of PEM fuel cell system by replacing water with imidazole as proton solvent in the polymer membrane. Hydrogen bond seems to play an important role in the proton conductivity of this system. The decrease of proton conductivity of imidazolium phosphate shows in some degree that the interaction between imidazole and phosphoric acid is not the main reason for the conductivity increment of imidazole doped PI/H₃PO₄ system.     

Ag3PO4的制备及其复合材料研究进展

能源与环境已成为当前亟需解决的问题,半导体光催化技术因具有氧化降解有机污染物完全、不产生二次污染、易操作等优点,在环境治理和新能源开发领域成为热点研究课题之一。Ag3PO4因具有高量子效率、可见光响应及较高的光催化效率等特点而引起了广大研究者的关注,并具有广泛的应用前景。本文总结了Ag3PO4的制备方法、不同形貌Ag3PO4的可控合成及其复合材料的研究进展。     

Analysis of the microporosity shrinkage upon thermal post-treatment of H3PO4 activated carbons

Starting from a commercial pelletized phosphoric acid based activated carbon, with a typical opened and developed micro and mesoporosity, a post-heat-treatment in KOH, at different KOH/activated carbon ratios, has been studied. In all the cases, a pore size shrinkage has been observed. To find an explanation for the reason of this micropore size distribution shrinkage different factors have been studied, among them: (a) effect of the presence of impurities coming from the activation process with phosphoric acid; (b) effect of the KOH post-treatment temperature; (c) heat-treatment temperature of the precursor (without chemical agent); (d) effect of the reagent nature (NaOH, NaCl and KCl vs. KOH). The variable that produces the most intense shrinkage effect, and the disappearance of the mesoporosity, is the heat-treatment in presence of hydroxide, which affects even using a low hydroxide/activated carbon ratio. Such a low hydroxide/activated carbon ratio does not produce activation, nor porosity development of the starting activated carbon during the treatment. This shrinkage phenomenon, which seems to be independent of the method of preparation used to prepare the activated carbon, can be understood considering our previous studies about the reactions involved during chemical activation by hydroxides.     

Physical and chemical properties of carbons synthesized from xylan, cellulose, and Kraft lignin by H3PO4 activation

Physical and chemical properties of activated carbons produced from commercial xylan, cellulose, and Kraft lignin by H₃PO₄ activation at various process conditions were studied. The results show that the more reactive the precursor under acidic conditions, the easier the porosity development, particularly mesoporosity. In addition, Boehm titration and Fourier Transform Infrared Spectroscopy (FTIR) characterization results demonstrated that the functional groups on the surfaces of these carbons consist of both temperature-sensitive and temperature-insensitive components. The temperature-sensitive component is primarily caused by the hydrolysis of raw materials under acidic conditions at low temperature, and the reaction between activation mixture and oxygen in the process of activation, particularly at low impregnation ratio. These surface groups decompose at high temperature. The temperature-insensitive contribution is mainly composed of phosphorus-containing groups arising from the reaction of H₃PO₄ (or pyro- and polyphosphoric acids) with precursor, and carbonyl-containing groups. This part of surface functional group is stable, even at high activation temperatures. This study also confirmed that the nature of precursor, impregnation ratio between H₃PO₄ and precursor, and activation temperature are important factors affecting the properties of final activated carbon products.     

Texture, surface acidic and catalytic properties of niobium phosphate

The texture and surface acidic properties on niobium phosphate and its catalytic activities for isomerization of 1-butene, dehydration of 2-butanol and polymerization of propylene were studied as a function of pretreatment temperature. The surface of niobium phosphate showed strong acid sites of H_o - 8.2, for temperatures between 100 and 500°C; the acid sites were ascribed as Lewis and Bronsted sites on the basis of IR spectra of adsorbed pyridine. The activity for dehydration of 2-butanol was higher for samples pretreated at 150°C and activities for isomerization of 1-butene and polymerization of propylene were higher for samples pretreated at 250 and 300°C repectively.     

Performance degradation studies on PBI/H3PO4 high temperature PEMFC and one-dimensional numerical analysis

Five hundred hours continuous aging test at constant discharge current (640 mA cm⁻²) was performed on PBI/H₃PO₄ high temperature PEMFC unit cell, electrochemical techniques-linear sweep voltammetry (LSV) and AC impedance measurement were used to investigate the changes of electrochemical surface area (ESA) and high frequency resistance (internal resistance) with time. Initial experimental results showed that during 500 h continuous aging test the main reason for cell performance degradation is the decrease of ESA caused by sintering. In addition, a one-dimensional mathematical model was constructed, the concentration distributions of cathode reactant gases (O₂ and gaseous H₂O) were calculated and polarization curves recorded during aging test were simulated based on the model, the simulated polarization curves compare well with the experimental results.     

Preparation of activated carbons from olive-tree wood revisited. I. Chemical activation with H3PO4

In the conditioning tasks of olive-tree a large amount of a woody residue is generated. Such a residue has been traditionally used as a domestic fuel. In the last decades, however, this kind of use has lost importance and the preparation of activated carbons from olive-tree wood appears as an attractive alternative to valorize this by-product. In this study, the optimization of the chemical activation method with phosphoric acid for the production of activated carbon has been analyzed. The results obtained clearly show that samples prepared at 350 and 400 °C exhibit a discrete porous development. On the contrary, when the carbonization temperature increases above 450 °C the presence of a well-developed mesoporosity is observed. The mercury intrusion curves indicate that the samples exhibit a noticeably developed mesopore volume as well as a wide variety of mesopores ranging from 40 up to 1100 Å of diameter. If the appropriate conditions are used, it is possible to prepare activated carbons showing tailored properties in terms of micro- or mesoporous texture and surface area.     

Influence of preparation conditions on porous structures of olive stone activated by H3PO4

An olive factory residue was used as a precursor in the preparation of granular activated carbon by chemical activation with H₃PO₄. Effects of final activation temperature, time, and H₃PO₄ concentration used in the impregnation stage on the porous development were investigated. SO₂ adsorption experiments were also performed for some of the activated carbon samples to represent their adsorption performance. Activation at low temperature represented that micropores were developed first at early stages of the temperatures. Mesoporosity developed at around 250 °C, enhanced up to 400 °C, and then started to decrease due to possibly shrinking of pores. The optimum temperature for olive stone was found to be around 400 °C on the basis of total pore volume and BET surface area. It was clearly demonstrated that H₃PO₄ concentration used in the impregnation stage was not only effective for development of surface area and pore volumes but also an effective tool for tailoring the pore structure and size distribution.     

磷酸/活性炭催化剂的制备及其在乙二醇脱水制1,4-二氧六环中的应用

以处理过的活性炭为载体,采用浸渍法制备了不同负载量的磷酸/活性炭催化剂。采用XRD、XRF、SEM、EDS、TEM、NH_3-TPD和N_2吸附-脱附等对催化剂进行表征分析,并将制备的催化剂应用于乙二醇脱水制1,4-二氧六环的反应。表征分析表明,制备的催化剂具有良好的微观形貌、孔道结构和酸性质;反应结果表明,磷酸负载质量分数为8%的催化剂反应效果最好,在此条件下,乙二醇转化率100%,1,4-二氧六环选择性达到90.6%,具有良好的应用前景。     

O2 reduction at the Pt/Nafion interface in 85% concentrated H3PO4

The kinetics of oxygen electroreduction have been studied on a smooth platinum electrode coated with Nafion® in concentrated 85% H₃PO₄. The effects of Nafion® coatings of different thickness on O₂ electroreduction at a smooth Pt rotating disk electrode with 85% phosphoric acid as the bulk electrolyte were examined. The kinetic current increases with increasing Nafion® film thickness while the diffusion limiting current decreases with increasing Nafion® film thickness. A O₂ concentration profile model for the Pt/Nafion®/bulk electrolyte has been established, and this model can be used to explain the O₂ reduction polarization results. The performance of Nafion®-modified, high surface area Pt/carbon air cathodes for use in the H₂–air concentrated phosphoric acid fuel cell was also studied.     

Characterization of surface chemistry and pore structure of H3PO4-activated poly(vinyl alcohol) coated fiberglass

H₃PO₄-activated poly(vinyl alcohol) coated fiberglass mats (PAPCF) were prepared in air at temperatures below 400 °C. The surface chemistry and pore structure of PAPCF were characterized by using N₂ adsorption at 77 K, XPS, DRIFTS, TGA, NaOH uptake and Ag⁺ adsorption. PAPCF prepared at 300 °C yields a high BET surface area (up to 1745 m²/g of coating) with a structure composed mainly of micropores. Some oxygen-containing functional groups, such as carboxylic, phenolic hydroxyl groups, and phosphorus species, are incorporated into the PVA-based char coating, with higher activation temperatures leading to increased formation of these groups. Post-treatment with sulfuric acid decreases the content of phosphorus species, but increases that of oxygen-containing groups in the coating. NaOH uptake and Ag⁺ adsorption show substantial cationic exchange capacity with the PAPCF or acid-treated PAPCF. TGA data show that PAPCF is more thermally stable in air than acid-treated PAPCF. Furthermore, PAPCF activated at 300 °C can be regenerated at least 5 times with no change in ion exchange capacity.     

Preparation of fibrous porous materials by chemical activation 2. H3PO4 activation of polymer coated fibers

Fibrous porous materials (FPMs) have been prepared by coating a glass fiber with an aqueous solution of poly(vinyl alcohol) (PVA) and H₃PO₄, followed by stabilization and heat treatment in air. The H₃PO₄ was then removed by washing with deionised water and NaOH. The results show that H₃PO₄ acts as a dehydration agent to promote pyrolytic and thermal crosslinking of PVA at a much lower temperature of 170 °C, leading to FPMs having much higher char yields and surface areas. The activation in air is of benefit to achieve higher surface areas as compared to using N₂. Utilizing a fiberglass mat to support coatings of PVA activated with H₃PO₄ results in much higher specific surface areas. The activation temperature, activation time and concentration of H₃PO₄ have strong effects on the surface area, pore size distribution and coating content of FPMs.     

Adsorption and inhibition effect of vanillin on cold rolled steel in 3.0 M H3PO4

The adsorption and inhibition effect of vanillin (4-hydroxy-3-methoxy-benzaldehyde) on cold rolled steel (CRS) in 3.0 M H₃PO₄ at 30–60 °C was investigated by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods. The results show that inhibition efficiency increases with the inhibitor concentration, while decreases with temperature. The adsorption of vanillin obeys Temkin adsorption isotherm. The thermodynamic parameters (adsorption enthalpy ΔH_ads, adsorption free energy ΔG_ads and adsorption entropy ΔS_ads) have been calculated and discussed in detail. Polarization curves show that vanillin acts as a mixed-type inhibitor. EIS shows that charge transfer resistance increases while the capacitance of double layer decreases with the inhibitor concentration, confirming the adsorption process mechanism. The adsorbed film on CRS surface containing vanillin was examined by atomic force microscope (AFM). Quantum chemical calculation was applied to elucidate the adsorption mode of the inhibitor molecule onto steel surface. Depending on the results, the inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

Electrical properties of niobium doped Bi4Ti3O12-SrBi4Ti4O15 intergrowth ferroelectrics

Nb-doped Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ intergrowth ceramics have been prepared by modified oxalate route. XRD phase analysis confirmed the formation of single phase compound. Nb-doping does not affect the basic crystal structure of the intergrowth. SEM micrographs showed that the grain size of the ceramics decreases with Nb-doping. The temperature dependence of dielectric constant and losses was investigated in the temperature range 30–800 °C and frequency range 1 kHz–1 MHz. With Nb-doping, the T_c of the ferroelectrics reduces and peak permittivity increases. Doping also introduces small relaxor behavior in the ferroelectrics. The dc conductivity of the ceramics decreases with doping. The remnant polarization (P_r) of the intergrowth ferroelectrics is increased with Nb doping.     

Degradation of high temperature MEA with PBI-H3PO4 membrane in a life test

The article reports on the results of a 780 h life test of high temperature MEA with PBI-H₃PO₄ membrane. The MEA was loaded by current density 0.2 A cm⁻² for 763 h at 160 °C in hydrogen-air feed. The load was discontinued 14 times during the life test including three complete shut downs. In the course of the life test MEA characteristics were studied by electrochemical methods. Pt particle size growth was evaluated by ex situ measurements of electrochemical hydrogen adsorption/desorption with the cathode catalyst sampled after the life test and with pristine catalyst. Possible changes of electrochemically active surface area (ESA) of carbon support were monitored by electrochemical impedance studies (EIS) performed in the course of the MEA life test. Average Pt particle diameter was found 3.8 and 7.8 nm for pristine catalyst and for catalyst sampled after the life test, respectively. ESA of carbon support remained unchanged, membrane resistance decreased by ∼20%, hydrogen crossover increased by a factor of 14, although remained insignificant. Voltage loss rate in the life test was ∼25 μV h⁻¹. The major cause of the MEA degradation was identified as a loss of Pt ESA by particle size growth.