An alternative activation method for the enhancement of methane storage capacity of nanoporous aluminium terephthalate,MIL-53(Al)

An alternative solvent extraction method is reported for the activation of hydrothermally synthesized aluminium terephthalate, MIL-53(Al) eliminating the calcination step conventionally used for the removal of unreacted benzenedicarboxylic acid entrapped in the cavities/pores of as-synthesized MIL-53(Al). The surface area and micropore volume of the MIL-53(Al) activated by solvent extraction method (1235 m²/g) were higher than the MIL-53(Al) activated by conventional calcination method (1073 m²/g). Methane adsorption studies on MIL-53(Al) samples were carried out at 303 K up to 35 bar pressure. The solvent extracted MIL-53(Al) showed an enhanced methane storage capacity of 186 cm³/cm³ compared to the calcined MIL-53(Al) (158 cm³/cm³) at 303 K and 35 bar.     

Sorption studies of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, N<Subscript>2</Subscript>, CO,O<Subscript>2</Subscript> and Ar on nanoporous aluminum terephthalate [MIL-53(Al)]

Aluminum terephthalate, MIL-53(Al), metal–organic framework synthesized hydrothermally and purified by solvent extraction method was used as an adsorbent for gas adsorption studies. The synthesized MIL-53(Al) was characterized by powder X-Ray diffraction analysis, surface area measurement using N₂ adsorption–desorption at 77 K, FTIR spectroscopy and thermo gravimetric analysis. Adsorption isotherms of CO₂, CH₄, CO, N₂, O₂ and Ar were measured at 288 and 303 K. The absolute adsorption capacity was found in the order CO₂>CH₄>CO>N₂>Ar>O₂. Henry’s constants, heat of adsorption in the low pressure region and adsorption selectivities for the adsorbate gases were calculated from their adsorption isotherms. The high selectivity and low heat of adsorption for CO₂ suggests that MIL-53(Al) is a potential adsorbent material for the separation of CO₂ from gas mixtures. The high selectivity for CH₄ over O₂ and its low heat of adsorption suggests that MIL-53(Al) could also be a compatible adsorbent for the separation of methane from methane–oxygen gas mixtures.     

Selective Liquid Phase Adsorption and Separation of ortho-Xylene with the Microporous MIL-53(Al)

Metal-organic framework MIL-53(Al) pellets were tested for the selective adsorption and separation of xylene isomers, in liquid phase and using n-heptane as eluent. The objective of this work is to assess relevant data for a posterior xylene isomers separation process design. In order to complete this study, single and multi-component breakthrough experiments were performed at 313 K, in the presence of n-heptane. MIL-53(Al) presented a preference for o-xylene over m-xylene and p-xylene in all experiments. The selectivities of 2.0 were obtained for o-xylene over m-xylene and over p-xylene. It is concluded that MIL-53(Al) may be used for separating o-xylene from the other xylene isomers, using n-heptane as desorbent. Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science & Technology to view the free supplemental file.     

Separation of CO2/CH4 mixtures with the MIL-53(Al) metal–organic framework

Adsorptive separation of CH₄/CO₂ mixtures was studied using a fixed-bed packed with MIL-53(Al) MOF pellets. Such pellets of MIL-53(Al) were produced using a polyvinyl alcohol binder. As revealed by N₂ adsorption isotherms, the use of polyvinyl alcohol as binder results in a loss in overall capacity of 32%. Separations of binary mixtures in breakthrough experiments were successfully performed at pressures varying between 1 and 8 bar and different mixture compositions. The binary adsorption isotherms reveal a preferential adsorption of CO₂ compared to CH₄ over the whole pressure and concentration range. The separation selectivity was affected by total pressure; below 5 bar, a constant selectivity, with an average separation factor of about 7 was observed. Above 5 bar, the average separation factor decreases to about 4. The adsorption selectivity is affected by breathing of the framework and specific interaction of CO₂ with framework hydroxyl groups. CO₂ desorption can be realised by mild thermal treatment.     

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。     

Facile synthesis of amine-functionalized MIL-53(Al) by ultrasound microwave method and application for CO<Subscript>2</Subscript> capture

An amine functional MIL-53(Al) material was prepared through a clean, rapid, energy-efficient method of microwave and ultrasound irradiation. The pure phase NH₂-MIL-53(Al) can be formed in 25 min, utilizing the synergistic effect of microwave and ultrasound irradiation. The dramatic acceleration in reaction rates suggested that the removal of a passivation coating on the substrate particles and the resultant enhancement in mass and heat transfer. The porous MOFs exhibited a high thermal and chemical stability, decomposing at temperatures above 410 °C in air. The NH₂-MIL-53(Al) performed an excellent adsorption for CO₂. The CO₂ capacities up to 33.86 cm³ g^?1 at 298 K at low pressures, which suggests chemisorption between CO₂ and pendan amine groups. Measurement of CO₂ adsorption cycles proved that the functionalized materials show good regenerability and stability.     

Metal organic framework Cu/MIL-53(Ce)-mediated synthesis of highly active and stable CO oxidation catalysts

The highly dispersed CuO@CeO₂ catalysts were produced from Cu/MIL-53(Ce) through encapsulated copper in a matrix of metal organic framework MIL-53(Ce), serving as a catalyst for CO oxidation. Comparison on the catalytic performance between the CuO@CeO₂ and the (CuO or MIL-53(Ce)) catalytic material has been conducted to understand the catalytic behavior of the catalysts. The CuO@CeO₂ catalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), N₂ adsorption-desorption, and the hydrogen temperature-programmed reduction (H₂-TPR). The analyses indicated that the unique CuO@CeO₂ spatial confinement in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation. Indeed, the heterogeneous catalytic composite materials CuO@CeO₂ catalyst exhibited excellent activity in CO oxidation test, with 100% conversion at 79–95 °C and the catalytic activity were stable after reaction 300 h.     

Hydrothermal preparation of Sn3O4/TiO2 nanotube arrays as effective photocatalysts for boosting photocatalytic dye degradation and hydrogen production

The efficient TiO₂ NTs/Sn₃O₄ photocatalysts were synthesized by the hydrothermal deposition of Sn₃O₄ on TiO₂ nanotube arrays (TiO₂ NTs), and the morphology, microstructure and photocatalytic property were adjusted by changing the alkali kind. The TiO₂ NTs/Sn₃O₄ prepared with NaOH exhibited the outstanding photoelectric conversion and photocatalytic environment remediation/H₂ evolution. The methylene blue (MB) dye and Cr(VI) could be removed by the as-prepared photocatalysts under visible light irradiation, and ?O₂^?/?OH radicals were the main active species for MB photodegradation. Furthermore, the high photocatalytic H₂ evolution rate was as high as 6.49 μmol cm^?2 h^?1. The outstanding photocatalytic activity and stability of TiO₂ NTs/Sn₃O₄ photocatalysts would exhibit attractive prospect in the wastewater remediation and electric energy/hydrogen generation.     

Photocatalytic Decomposition of Formic Acid Under Visible Light Irradiation Over V-ion-implanted TiO2 Thin Film Photocatalysts Prepared on Quartz Substrate by Ionized Cluster Beam (ICB) Deposition Method

Unique visible-light-responsive TiO₂ photocatalysts (λ>450 nm) were successfully developed by implantation of V ions into the TiO₂ thin films prepared on a quartz substrate by an ionized cluster beam (ICB) deposition method. After V ions implantation into TiO₂ thin film, the photocatalytic activity of the thin films for the decomposition of formic acid into CO₂ and H₂O was found to proceed efficiently under visible light irradiation longer than 450 nm. The TiO₂ thin film photocatalysts were characterized by XRD, UV-vis, XPS, FE-SEM and AFM.     

Synthesis of magnetically separable core–shell structured Ni<Subscript>x</Subscript>Fe<Subscript>1−x</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>@TiO<Subscript>2</Subscript> nanoparticles photocatalysts for the degradation of organic dyes

In this paper, the core–shell structured NiFe₂O₄@TiO₂ nanoparticles and nanochains as photocatalysts were successfully prepared through hydrothermal and hydrolysis method. The as-prepared core–shell structure was composed of a magnetic NiFe₂O₄ core and photocatalytic titanium oxide coating shell. SEM and TEM images characterized the morphology of NiFe₂O₄@TiO₂ nanoparticles. Moreover, the results of XRD patterns proved that the TiO₂ coating shell consisted of anatase. The VSM measurements showed that the saturation magnetization values of NiFe₂O₄ and NiFe₂O₄@TiO₂ nanoparticles was 65 and 53 emu/g, respectively. The photocatalyst of NiFe₂O₄@TiO₂ nanoparticles exhibited the outstanding recyclable performance for RhB. And, the photo_degradation ration of maintained 69 % after the photocatalyst experienced ten photocatalysis experiments, which is better than that of Fe₃O₄@TiO₂ photocatalysts.     

Selective coordination activation regulating the selectivity for photocatalytic hydrogenation of α, β-unsaturated aldehyde over Pd/MIL-100(FeaCub)

Here, the mixed metal nodes MOFs, Pd/MIL-100(Fe_aCu_b), were constructed as photocatalysts for hydrogenation of α, β-unsaturated aldehyde (UAL) under visible light. 1 wt% Pd/MIL-100(Fe_0.81Cu_0.19) can convert a range of UAL to saturated aldehydes (SAL) with a high efficiency (≈ 100 %) and selectivity (≈ 98 %). The results of XPS and in situ DRIFTS reveal that UAL can be selectively activated via a coordination of -CC- on Cu²⁺ sites, determining the high selectivity of the photocatalytic reaction. The mixed metal nodes and Pd clusters can improve the transformation and separation of photogenerated electrons-holes. EPR result suggests that photogenerated carriers can facilitate the generation of H·on Pd/MIL-100(Fe_0.81Cu_0.19), enhancing the catalytic activity. A possible mechanism is proposed for elucidating the catalytic processes at the molecular level. This work provides a valuable strategy for tailoring the selectivity of photocatalytic hydrogenation via selective coordination activation.     

Porous MOFs supported palladium catalysts for phenol hydrogenation: A comparative study on MIL-101 and MIL-53

Two metal organic frameworks (MOFs), chromium benzenedicarboxylates MIL-101 and MIL-53, have been synthesized and used as the support of palladium catalysts. The palladium catalysts were characterized by XRD, TEM, and CO chemisorption. MIL-101 is highly hydrophilic and beneficial as support for fine Pd nanoparticles with an average size of 2.3 nm. Microporous MIL-53 is relatively hydrophobic and larger Pd particles with an average size of 4.3 nm were formed on the external surface. Pd/MIL-101 showed better phenol selective hydrogenation activity to cyclohexanone (> 98%) under mild reaction conditions because of its smaller particle size.     

Preparation of transparent PVA/TiO2 nanocomposite films with enhanced visible-light photocatalytic activity

Polymer/semiconductor oxide nanocomposite films have been intensively investigated for various applications. In this work, we reported a simple hydrothermal method to fabricate highly transparent poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposite films with enhanced visible-light photocatalytic activity. The as-prepared PVA/TiO₂ nanocomposite films showed high optical transparency in the visible region even at a high TiO₂ content (up to 40 wt.%). The determination of photocatalytic activity by photodegradation of methyl orange (MO) and colorless phenol showed that PVA/TiO₂ nanocomposite films exhibited enhanced visible-light photocatalytic activity and excellent recycle stability. This work provided new insights into fabrication of polymer/TiO₂ nanocomposites as high performance photocatalysts in waste water treatment.     

Construction of Au/TiO2 Heterojunction with high photocatalytic performances under UVA illumination

Anatase TiO₂ nanoparticles (NPs) were successfully prepared through a hydrothermal approach, and Au NPs at various Au (0.1–2 wt%) contents were photodeposited onto the TiO₂ NPs surface. The photocatalytic efficiency for the Au/TiO₂ NPs for resorcinol photodegradation throughout UVA illumination was assessed. The TEM images and XPS findings indicated that the Au NPs are highly distributed onto TiO₂ surface in the metallic state. The 0.1%Au/TiO₂ NPs exhibited the highest photocatalytic efficiency of about 95.34%; however, 72.36% is given by pure TiO₂ NPs. It was found that the photodegradation rate of 0.1% Au/TiO₂ NPs exhibited 1.5 times of magnitude higher than pure TiO₂ NPs. 0.1%Au/TiO₂ NPs was considered to be the outstanding photoactive due to the ultimate efficient charge-carriers separation through charge transfer between Au and TiO₂ NPs. The Au NPs sizes, its dispersity on TiO₂ surface and surface plasmon resonance (SPR) were believed the critical factors for the higher photocatalytic performance of 0.1% Au/TiO₂ NPs. The prepared photocatalysts are found to be the promising materials for toxic organic compounds remediation and solar conversion.     

Efficient visible-light photocatalysts from Gd–La codoped TiO2 nanotubes

Robust visible-light Gd–La codoped TiO₂ nanotubes were successfully synthesized via an ultrasonic hydrothermal method and the photocatalytic activities were evaluated by photodegrading Rhodamine B (RB). The calcined Gd–La codoped TiO₂ nanotubes have significantly enhanced photocatalytic activities than the uncalcined ones. The La³⁺ and Gd³⁺ in the lattices of rare earth oxides may be substituted by Ti⁴⁺, creating abundant oxygen vacancies and surface defects for electron trapping and dye adsorption, accelerating the separation of photogenerated electron–hole pairs and RB photodegradation. The formation of an excitation energy level below the conduction band of TiO₂ from the binding of electrons and oxygen vacancies decreases the excitation energy of Gd–La codoped TiO₂ nanotubes, resulting in robust photocatalysts. The results suggest that Gd–La codoped TiO₂ nanotubes calcined at 500 °C are very promising for enhancing the photocatalytic activity of photocatalysts in visible-light region.     

Bi and Al co-doped anatase titania for photosensitized degradation of Rhodamine B under visible-light irradiation

Although TiO₂ is a wide band gap semiconductor, it demonstrates photodegradation activity under visible light irradiation after dye sensitization. Compared with esterification between the surface hydroxyl group of TiO₂ and the carboxylic group of dyes, electrostatic interaction between TiO₂ and dye shows better photosensitized performance. In this work, Bi/Al co-doping anatase titania (Ti_1-xBi_2x/3Al_2x/3O₂ (0 ≤ x ≤ 0.3)) is designed to enhance the electrostatic interaction. The effect of Al ions is to enhance the solubility of Bi³⁺ into titania nanocrystals. A new band gap is generated after high concentration of Bi element doping, which not only promotes the absorption of visible light, but also improves the utilization of photogenerated carriers. Based on the results of transmission electron microscopy, light absorption, photodegradation activity and density functional theory calculations, it is found that bismuth dopant is the electron capture site. It first accumulates electrons through photocatalytic degradation reaction to enhance electrostatic adsorption between the catalyst and the positively charged dye molecules, and finally realizes high-efficiency photosensitization degradation of Rhodamine B. In addition, the sensitized titania has excellent photodegradation recyclability.     

Characterization of metal (Ba, Al, Si, V, and W)-incorporated TiO2 and toluene photodecomposition in the presence of H2O

This study focused on toluene photodecomposition in the presence of H₂O over metal (Ba, Al, Si, V, and W)-incorporated TiO₂. The nanometer-sized, metal-TiO₂ photocatalyst samples, including Ba²⁺, Al³⁺, Si⁴⁺, V⁵⁺, and W⁶⁺ ions, were prepared by using the solvothermal method. The X-ray photoelectron spectroscopy (XPS) results showed that the Ti-OH peak, which indicates hydrophilicity, increased with increasing Al and Si ion components but decreased with increasing Ba, V, and W ion components. The contact angles were distributed over the range of 0–10° on almost all films (200-nm thick) after irradiation for 2 h, and in particular approached 0° on the Al-TiO₂ and Si-TiO₂ nanometer-sized films after just 30 min. The toluene (100 ppm) photodecomposition in the continuous system increased in the order of Al-TiO₂>Si-TiO₂>pure TiO₂>W-TiO₂>Ba-TiO₂>V-TiO₂, and the maximum toluene conversion rate achieved was 45% over Al-TiO₂ film after 120 min. The toluene conversion remarkably increased; however, over all photocatalysts, with H₂O addition during the toluene photo-decomposed reaction, and in particular, the conversion reached up to 90% after 120 min over Al-TiO₂ and Si-TiO₂ with increased hydrophilicity. After photoreaction for 24 h, minimal carbon was deposited on the photocatalyst under both reaction conditions, with and without H₂O addition, although the deposited carbon amounts were smaller for the former. These results confirmed that the hydrophilicity of the photocatalyst had a greater effect on toluene decomposition, while the photocatalytic deactivation could be retarded by H₂O supplementation during toluene decomposition.     

Degradation of chlorophenol by photocatalysts with various transition metals

In this research, the photocatalytic degradation of 4-chlorophenol (4-CP) in TiO₂ aqueous suspension was studied. TiO₂ photocatalysts were prepared by sol-gel method. The dominant anatase-structure on TiO₂ particles was observed after calcining the TiO₂ gel at 500 °C for 1 hr. Photocatalysts with various transition metals (Fe, Cu, Nd, Pd and Pt) loading were tested to evaluate the effect of transition metal impurities on photodegradation. The photocatalytic degradation in most cases follows first-order kinetics. The maximum photodegradation efficiency was obtained with TiO₂ dosage of 0.4 g/L, retention time of 1 min and air flow rate of 2,500 cc/min. The photodegradation efficiency with Pt-TiO₂ or Pd-TiO₂ is higher than pure TiO₂ powder. The optimal content value of Pt and Pd is 2 wt%. However, the photodegradation efficiency with Fe(1.0 wt%)-TiO₂ and Cu(1.0 wt%)-TiO₂ is lower than pure TiO₂ powder. This paper was prepared at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4, 2004.     

Photodegradation of benzene,toluene, ethylbenzene and xylene by fluidized bed gaseous reactor with TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> photocatalysts

The photodegradation of BTEX (benzene, toluene, ethylbenzene and xylene) in a photocatalytic fluidized bed reactor with TiO₂/SiO₂ was investigated. The TiO₂ film was prepared using the sol-gel method and coated onto silica-gel powder. The effects of the superficial gas velocity and SiO₂ size on the photodegradation of BTEX were examined in a fluidized bed reactor. At steady-state operation, above 79, 79, 99, 98, and 98% removal efficiencies were achieved for benzene, toluene, ethylbenzene, m, p-xylene and o-xylene, respectively, under optimal conditions (2.0 U _mf of superficial gas velocity and 1.43 of height/diameter ratio). The reaction product such as CO₂ was detected and intermediate products such as benzaldehyde, malonic acid, acetaldehyde, and formic acid were identified from the photocatalytic reaction. Also, small amounts of benzoic acid and benzyl alcohol were found through analyzing the intermediate species adsorbed on the photocatalysts. The experimental results can lead to the development of an efficient photocatalytic treatment system that utilizes solar energy and TiO₂/SiO₂ photocatalysts.     

A unique Cu2O/TiO2 nanocomposite with enhanced photocatalytic performance under visible light irradiation

A unique Cu₂O/TiO₂ nanocomposite with high photocatalytic activity was synthesized via a two-step chemical solution method and used for the photocatalytic degradation of organic dye. The structure, morphology, composition, optical and photocatalytic properties of the as-prepared samples were investigated in detail. The results suggested that the Cu₂O/TiO₂ nanocomposite is composed of hierarchical TiO₂ hollow microstructure coated by a great many Cu₂O nanoparticles. The photocatalytic performance of Cu₂O/TiO₂ nanocomposite was evaluated by the photodegradation of methylene blue (MB) under visible light, and compared with those of the pure TiO₂ and Cu₂O photocatalysts synthesized by the identical synthetic route. Within 120 min of reaction time, nearly 100% decolorization efficiency of MB was achieved by Cu₂O/TiO₂ photocatalyst, which is much higher than that of pure TiO₂ (26%) or Cu₂O (32%). The outstanding photocatalytic efficiency was mainly ascribed to the unique architecture, the extended photoresponse range and efficient separation of the electron-hole pairs in the Cu₂O/TiO₂ heterojunction. In addition, the Cu₂O/TiO₂ nanocomposite also retains good cycling stability in the photodegradation of MB.