Exploration of silver decoration concentration to enhance photocatalytic efficiency of titanium dioxide photocatalysts

Ag decoration on TiO₂ is favorable to absorption of visible light and wider absorption range. Ag nanoparticles playing the role of electron receivers on TiO₂ surface enhance photodegradation. However, excess Ag nanoparticles caused reduced specific surface area of photocatalysts and increased probability of charge recombination, resulting in lower photocatalytic efficiency. In this study, the influence of various Ag decoration concentrations on photocatalytic activity was investigated. Surface treatment by nitric acid after Ag decoration was performed to avoid excessive Ag deposition. The extent of Ag elimination and its impacts on photocatalytic activity were also explored. An optimum Ag content in the photocatalyst was achieved and photocatalytic efficiency was obviously improved. It was found that the number of calcination times affected the crystallinity and stability of photocatalysts. Better photocatalytic efficiency could be obtained after twice calcinations.     

Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post‐Synthetic Modification of a UiO‐66‐Type Metal–Organic Framework

The highly porous and stable metal–organic framework (MOF) UiO‐66 was altered using post‐synthetic modifications (PSMs). Prefunctionalization allowed the introduction of carbon double bonds into the framework through a four‐step synthesis from 2‐bromo‐1,4‐benzenedicarboxylic acid; the organic linker 2‐allyl‐1,4‐benzenedicarboxylic acid was obtained. The corresponding functionalized MOF (UiO‐66‐allyl) served as a platform for further PSMs. From UiO‐66‐allyl, epoxy, dibromide, thioether, diamine, and amino alcohol functionalities were synthesized. The abilities of these compounds to adsorb CO₂ and N₂ were compared, which revealed the structure–selectivity correlations. All synthesized MOFs showed profound thermal stability together with an increased ability for selective CO₂ uptake and molecular gate functionalities at low temperatures.     

Dynamics of water adsorption on TiO2 monitored by work function spectroscopy

Water adsorption dynamics on two TiO₂ (1 1 0) rutile surfaces at room temperature has been investigated using the work function (WF) change as a function of time. The first surface was prepared in a standard way using sputtering/annealing cycles, whereas the second one was long term annealed at 620 K in moderate vacuum conditions (the residual gas pressure of about 1 × 10⁻⁷ mbar) and cleaned afterwards. The WF change show striking difference as compared to those obtained for highly reduced TiO₂ (1 1 0) rutile or the (2 × 1) reconstructed surfaces. For the first kind of surface we show that the observed adsorption dynamics can be qualitatively explained by the present understanding of the water adsorption on non-reconstructed TiO₂ (1 1 0) rutile surface according to which the bridging oxygen vacancies and Ti rows are the main adsorption sites. Although generally similar to the former results, water adsorption dynamics on the second kind of the surface has an additional feature that can be only explained by a new adsorption site, which we suggest to be due to (2 × 1) reconstructed regions coexisting with the non-reconstructed TiO₂ (1 1 0) surface.     

Facile synthesis of poly(ether carbonate)s via copolymerization of CO2 and propylene oxide under combinatorial catalyst of rare earth ternary complex and double metal cyanide complex

Poly(ether carbonate)s (PPCs) with carbonate unit (CU) content ranging from 57.8 to 97.1% and number average molecular weight (M_n) around 100 kg/mol were conveniently prepared via copolymerization of CO₂ and propylene oxide under combinatorial catalyst of rare earth ternary (RET) complex and double metal cyanide (DMC) complex. Enhancement of catalytic activity and reduction of propylene carbonate byproduct were realized due to synergetic effect of the two metal catalysts, where DMC can be activated in the presence of RET. Solubility fractionation confirmed that the obtained PPCs were copolymers, not physical blends of each polymer. Thermal performances of the PPCs were closely related to their CU content, their glass transition temperatures (T_g) were tunable in the range of 6.7–36.3 °C, which decreased with decreasing CU content, while their thermal stabilities were enhanced significantly, an increase of 50.5 °C in 50% weight loss temperature was observed when CU content decreased from 97.1 to 57.8%. Both shear storage modulus and complex viscosity increased with increasing CU content, which became more obvious at lower frequency, featuring well with the CU content in the PPCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The effect of interfacial miscibility on the cell morphology of polyethylene terephthalate/bisphenol a polycarbonate blend foams

Annealing polyethylene terephthalate (PET)/polycarbonate (PC) blends enhance the transesterification reaction and increase the amount of copolymer at the interface of both polymers. The copolymer enhances the compatibility of PET with PC, because it contains both PET and PC blocks, which causes the interface between PET and PC to become fuzzy. When the PET/PC undergoes batch physical foaming with CO₂, the copolymer significantly changes the resulting cell morphology, that is, the annealing time. Before annealing or in the absence of the copolymer, bubble nucleation occurs and dominates growth at the interface. When the PET/PC blends are annealed, the interface impedes bubble nucleation and growth. The polymer is stretched at the interface by bubble growth, forming fibril‐like structures connecting two polymer domains at the interface. Increased annealing time causes the interface to become more homogeneous and makes heterogeneous bubble nucleation difficult. At higher copolymer concentrations, the interface of PET and PC becomes fuzzy and the cell morphology becomes like those of foamed homogeneous polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

The First Catalytic Synthesis of an Acrylate from CO2 and an Alkene—A Rational Approach

For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C₁ building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO₂, ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.     

An Experimental Study on Heat Transfer Coefficients of a CO2-Filled Thermosyphon

Abstract

Because carbon dioxide is ozone friendly and has negligible global warming potential, it has received renewed interest in recent years as an important alternative refrigerant. In this article, the heat transfer characteristics of a carbon dioxide-filled two-phase closed thermosyphon were investigated experimentally, and the empirical heat transfer correlations are reported. The heat transfer data were analyzed, and heat transfer coefficients were compared with conventional heat transfer correlations. The results represent that heat transfer correlation of the heated section can be expressed with Kutatelatze's correlation, and heat transfer coefficients of the condenser section are found to be in reasonable agreement with the Nusselt equation.     

Infrared evidence for the folded-chain model of trans-1,4-polybutadiene

The influence of the first-order crystalline transformation at about 60°C on the infrared bands of trans-1,4-polybutadiene yields microscopic information that supports the two-component microcrystalline model of a folded chain having loose and tight end loops at the lamellar surfaces. The temperature dependence of the band parameters of the 908-cm^?1 vinyl band indicates that 1,2-(side vinyl) units are not easily taken into the crystalline component, thus forming long loops at the crystal surface that account for the micro-Brownian motion detected in the low-temperature phase. The results argue that infrared band parameters are excellent probes for details of the thermodynamics and morphology of polymers.     

Synthesis of Cyclohexene Carbonate Catalyzed by Polymer-Supported Catalysts

A series of polystyrene-divinylbenzene cross-linked resin (PS)–supported zinc chloride catalysts were prepared in this study. They can efficiently catalyze the solventless cycloaddition of cyclohexene oxide with carbon dioxide in the presence of tetrabutylammonium bromide (TBAB) as cocatalyst under relatively mild reaction conditions. The catalyst is composed of carrier, connecting arm, ligand, and active ingredient. The connecting arms of different lengths can significantly affect the catalytic activity. Among these catalysts, the one using diethylene glycol as connecting arm and 2-aminopyridine as ligand, named PS-DEG-2ap-ZnCl₂, showed the optimal catalytic performance. The yield of cyclohexene carbonate was 95.18% calculated by gas chromatographic analysis under the optimal conditions (393 K, 5 MPa, 6 h). Moreover, the catalyst showed good stability and reusability. From the viewpoint of industrial application, the catalyst is attractive because of its excellent catalytic efficiency on the synthesis of cyclohexene carbonate.