甲烷在层状石墨烯和活性炭上的吸附平衡

以吸附式天然气（ANG）吸附剂的工程应用为目的,以0-10 MPa、283.15-303.15 K甲烷在层状石墨烯（GS（3D）,比表面积2062 m²/g）和活性炭SAC-01（比表面积1507 m²/g）上的吸附平衡数据作分析。首先,在77.15 K下由氮气吸附表征样品的孔径大小及分布（PSD）和比表面积。其次,选择极低压力下的吸附平衡数据标定亨利定律常数,确定甲烷在两吸附剂上的极限吸附热,并由维里方程和10-4-3势能函数计算甲烷与两吸附剂壁面之间的相互作用势。最后,依据测试的甲烷在吸附剂上的高压吸附平衡数据,比较了Langmuir系列方程的关联数据后的拟合精度,并由绝对吸附量计算了甲烷的等量吸附热。结果表明,甲烷在GS（3D）和活性炭SAC-01上的平均极限吸附热为23.07、20.67 kJ/mol;283.15 K下甲烷分子与GS（3D）和活性炭SAC-01之间的交互作用势ε_sf/k为67.19、64.23 K,与洛伦混合法则的计算值64.60 K相近;Toth方程关联甲烷在活性炭SAC-01和GS（3D）上吸附平衡数据的拟合累计相对误差为0.25%和2.29%;甲烷在活性炭SAC-01和GS（3D）上的等量吸附热平均值为16.8和18.3 kJ/mol。相对于活性炭SAC-01,比表面积和微孔容积均较高的GS（3D）对甲烷的吸附更具有优势。     

Adsorption of uranium from aqueous solution by graphene oxide nanosheets supported on sepiolite

Adsorptive behavior of uranium from aqueous solution on graphene oxide supported on sepiolite composites (GO@sepiolite composites) as a function of pH, ionic strength, temperature and initial uranium concentration was carried out by the batch techniques. GO@sepiolite composites was synthesized and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and potentiometric acid–base titration. According to XRD patterns and SEM images, the graphene oxide nanosheets were grafted on sepiolite surface successfully. The macroscopic results showed that the adsorption of uranium on GO@sepiolite composites was significantly depended on pH, whereas no effect of ionic strength on uranium adsorption at high pH and high ionic strength conditions was observed. The uptake equilibrium is best described by Langmuir adsorption isotherm, and the maximum adsorption capacity (Q_e) of GO@sepiolite composites at pH 5.0 and T = 298 K were calculated to be 161.29 mg/g. Thermodynamic results indicated that the adsorption of uranium on GO@sepiolite composites is the spontaneous and exothermic process.     

Adsorption of carbon dioxide on tantalum oxide coated with palladium chloride

Isotherms of adsorption of CO₂ on a Ta₂O₅ surface and the same surface coated with a 0.5 monolayer of PdCl₂ were measured over temperature and pressure ranges of 293–473 K and 0.015–1.5 Pa, respectively. It was established that, in the presence of PdCl₂, the adsorption becomes greater in value and reversible. The isotherms were S-shaped, which was explained by the association of adsorbed CO₂ molecules due to the change in their polarization caused by rising CO₂ pressure. The influence of the temperature and PdCl₂ on the adsorbate-adsorbate and adsorbate-adsorbent interaction constants were analyzed using the Kiselev isotherm and an isotherm that takes into account the interaction between the electrons of the semiconductor oxide and adsorbate molecules.     

Adsorption of nitrogen oxides on graphene and graphene oxides: insights from density functional calculations

The interactions of nitrogen oxides NO(x) (x = 1,2,3) and N(2)O(4) with graphene and graphene oxides (GOs) were studied by the density functional theory. Optimized geometries, binding energies, and electronic structures of the gas molecule-adsorbed graphene and GO were determined on the basis of first-principles calculations. The adsorption of nitrogen oxides on GO is generally stronger than that on graphene due to the presence of the active defect sites, such as the hydroxyl and carbonyl functional groups and the carbon atom near these groups. These active defect sites increase the binding energies and enhance charge transfers from nitrogen oxides to GO, eventually leading to the chemisorption of gas molecules and the doping character transition from acceptor to donor for NO(2) and NO. The interaction of nitrogen oxides with GO with various functional groups can result in the formation of hydrogen bonds OH???O (N) between -OH and nitrogen oxides and new weak covalent bonds C???N and C???O, as well as the H abstraction to form nitrous acid- and nitric acidlike moieties. The spin-polarized density of states reveals a strong hybridization of frontier orbitals of NO(2) and NO(3) with the electronic states around the Fermi level of GO, and gives rise to the strong acceptor doping by these molecules and remarkable charge transfers from molecules to GO, compared to NO and N(2)O(4) adsorptions on GO. The calculated results show good agreement with experimental observations.     

Copolymerization of carbon dioxide and propylene oxide with supported diethylzinc catalysts

Diethylzinc was allowed to react with various metal oxides in n-heptane at 60°C, and the copolymerization of propylene oxide and carbon dioxide was investigated at 60°C in solution in dioxane with reaction products as catalysts. An alternate copolymer was obtained with every catalyst, but the yield of copolymer and the number-average molecular weight depended significantly on the supporting materials. In a kinetic study of the copolymerization we found that the catalytic efficiency (number of propagating species per number of zinc supported) was only a few percent with every catalyst. The copolymerization was also examined by using several kinds of silica, whose pore diameters are markedly different, as supports. The results obtained strongly suggested that only the active species existing in large pores act as the propagating species.     

Oxidative dehydrogenation of ethane with carbon dioxide over sulfated zirconia supported metal oxides catalysts

Several metal oxides supported on sulfated zirconia catalysts were tested for the oxidative dehydrogenation of ethane into ethylene by carbon dioxide. It is found that the catalytic behavior of supported oxide catalysts differ depending on the nature of metal oxides. Chromium oxide-sulfated zirconia exhibits the highest ethane conversion and medium level of ethylene selectivity, producing 38% ethylene yield at 50% ethane conversion at 650°C.     

Adsorption of carbon dioxide on microporous carbon adsorbents

Adsorption isotherms of carbon dioxide on microporous carbon adsorbents prepared by activation with potassium sulfide in water vapor were measured. The measurements were carried out in the pressure interval from 1 Pa to 0.1 MPa at temperatures from 216.2 to 293.15 K. Based on the theory of volumetric filling of micropores, the main structural and energetic parameters of the microporous carbon adsorbents were calculated. The adsorption isosters of carbon dioxide were calculated from the adsorption isotherms in the same pressure and temperature ranges and approximated by linear dependences. The plots of the differential mole isosteric heats of adsorption vs amount adsorbed were constructed by using the adsorption isosters.     

Copolymerization of carbon dioxide and propylene oxide under inorganic oxide supported rare earth ternary catalyst

Recently, rare earth ternary coordination catalyst represented as Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ has been used for producing poly(propylene carbonate) (PPC, an alternating copolymer of carbon dioxide and propylene oxide) in industry scale, but its catalytic activity needs further improvement. One reason for the relatively low catalytic activity lied in that only 11.7% of active center was efficient due to possible embedding of active center in the heterogeneous catalyst. In this report, supporting strategy was developed, where Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ was supported on various inorganic oxides. Two supporting methods were carried out. One way was to mix Y(CCl₃OO)₃‐Glycerin with inorganic oxide first and then ZnEt₂ was dropped to form the supported catalyst, and the other was to make Y(CCl₃OO)₃‐Glycerin‐ZnEt₂ at first and then mixing with inorganic oxides. The former showed decreasing catalytic activity compared with corresponding unsupported rare earth ternary catalyst, while an improvement of 16–36% in catalytic activity was realized in the latter. PPC with an average number molecular weight (M_n) of over 100 kg/mol and carbonate unit (CU) content of higher than 96% was prepared by both supported catalysts. The catalytic activity of the supported catalyst depended significantly on the supports, which increased in the following order: α‐Al₂O₃ < MgO < ZnO ≈ SiO₂ <γ‐Al₂O₃. γ‐Al₂O₃ was the best support for rare earth ternary catalyst, which showed a remarkable 36% increase in catalytic activity, corresponding to the utilization of 17% of active center. Although MgO supported catalyst gave only an 8% increase in catalytic activity, the M_n and CU content of PPC were raised to about 143 kg/mol and 99%, whereas the PPC from common rare earth ternary catalyst was about 108 kg/mol and 97%, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Coupling dehydrogenation of isobutane in the presence of carbon dioxide over chromium oxide supported on active carbon

The dehydrogenation of isobutane （IB） to produce isobutene coupled with reverse water gas shift in the presence of carbon dioxide was investigated over the catalyst Cr2O3 supported on active carbon （Cr2O3/AC）. The results illustrated that isobutane conversion and isobutene yield can be enhanced through the reaction coupling in the presence of carbon dioxide. Moreover, carbon dioxide can partially eliminate carbonaceous deposition on the catalyst and keep the active phase （Cr2O3）, which are then helpful to alleviate the catalyst deactivation.     

Synthesis of layered double hydroxides/graphene oxide nanocomposite as a novel high-temperature CO_2 adsorbent

In this contribution, a novel high-temperature CO2 adsorbent consisting of Mg-Al layered double hydroxide(LDH) and graphene oxide(GO)nanosheets was prepared and evaluated. The nanocomposite-type adsorbent was synthesized based on the electrostatically driven self-assembly between positively charged Mg-Al LDH single sheet and negatively charged GO monolayer. The characteristics of this novel adsorbent were investigated using XRD, FE-SEM, HRTEM, FT-IR, BET and TGA. The results showed that both the CO2 adsorption capacity and the multicycle stability of LDH were increased with the addition of GO owing to the enhanced particle dispersion and stabilization. In particular, the absolute CO2 capture capacity of LDH was increased by more than twice by adding 6.54 wt% GO as support. GO appeared to be especially effective for supporting LDH sheets. Moreover, the CO2 capture capacity of the adsorbent could be further increased by doping with 15 wt%K2CO3. This work demonstrated a new approach for the preparation of LDH-based hybrid-type adsorbents for CO2 capture.     

Layered assembly of graphene oxide and Co-Al layered double hydroxide nanosheets as electrode materials for supercapacitors

An innovative strategy of fabricating electrode material by layered assembling two kinds of one-atom-thick sheets, carboxylated graphene oxide (GO) and Co-Al layered double hydroxide nanosheet (Co-Al LDH-NS) for the application as a pseudocapacitor is reported. The Co-Al LDH-NS/GO composite exhibits good energy storage properties.     

Dehydrogenation of isobutane in the presence of carbon dioxide over supported vanadium oxide catalysts

Summary The dehydrogenation of isobutane to isobutene in the presence of carbon dioxide was carried out over supported vanadium oxide catalysts. The influence of the support on the catalytic performance was investigated. The isobutane conversion and isobutene selectivity in the presence of carbon dioxide were compared with the results obtained during the dehydrogenation reaction in the presence of helium (inert gas). The catalysts were characterized by temperature-programmed techniques (TPR, TPD-NH₃, TPD-CO₂).     

Adsorption of carbon dioxide on microporous carbon adsorbent PAU-10

Carbon dioxide adsorption on the microporous carbon adsorbent PAU-10 within the 177.8—423 K temperature and 0.1—5.13·10⁶ Pa pressure intervals was studied. The isosteres of absolute adsorption are well approximated by straight lines, which do not change their slope on going to temperatures higher than the critical temperature of CO₂. An increase in the differential molar isosteric heat of adsorption (q _st) at 0 < a < 1 mmol g^–1 is explained by the influence of the endothermic effect of adsorption expansion of the adsorbent. In the region of high pressures and nonideal gas phase, q _st is temperature-dependent.     

Adsorption properties of Ni-Pd catalysts supported on aluminum oxide

The surface composition of Ni-Pd/Al₂O₃ catalysts has been studied using XPES and adsorption methods. The bimetallic catalysts differ from the single-metal Ni and Pd catalysts in the dispersivity of the metal phase which depends on the method of preparation and the presence of K⁺ promoter. A catalyst produced by the immersion method is strongly enriched in Pd compared with impregnated catalysts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1746–1751, August, 1991.     

Alternating copolymerization of propylene oxide and carbon dioxide with an alumina supported diethylzinc catalyst

Diethylzinc was allowed to react with γ-alumina in n-heptane at 50°C, and the copolymerization of propylene oxide and carbon dioxide was investigated in some detail at 30–90°C by using the reaction product as a catalyst. From an analysis of the catalyst it was found that diethylzinc reacted with the surface hydroxyl groups of γ-alumina mainly to give the following A-type species by evolving ethane: The catalyst showed considerably high activity for the copolymerization. The polymer obtained was a white solid with a high molecular weight soluble in benzene, acetone, dioxane, and methylene chloride and insoluble in diethyl ether and water. It was confirmed as an alternate copolymer of propylene oxide and carbon dioxide. The copolymerization was also conducted with a reaction mixture of the catalyst and catechol in which the molar ratio of catechol to the A-type species was varied. The copolymerization activity decreased linearly with an increase in the molar ratio and disappeared completely at the molar ratio of unity. On the basis of these results it has been concluded that the A-type is the true active species for the copolymerization.     

Stabilization of high-performance oxygen reduction reaction pt electrocatalyst supported on reduced graphene oxide/carbon black composite

Oxygen reduction reaction (ORR) catalyst supported by hybrid composite materials is prepared by well-mixing carbon black (CB) with Pt-loaded reduced graphene oxide (RGO). With the insertion of CB particles between RGO sheets, stacking of RGO can be effectively prevented, promoting diffusion of oxygen molecules through the RGO sheets and enhancing the ORR electrocatalytic activity. The accelerated durability test (ADT) demonstrates that the hybrid supporting material can dramatically enhance the durability of the catalyst and retain the electrochemical surface area (ECSA) of Pt: the final ECSA of the Pt nanocrystal on the hybrid support after 20?000 ADT cycles is retained at >95%, much higher than the commercially available catalyst. We suggest that the unique 2D profile of the RGO functions as a barrier, preventing leaching of Pt into the electrolyte, and the CB in the vicinity acts as active sites to recapture/renucleate the dissolved Pt species. We furthermore demonstrate that the working mechanism can be applied to the commercial Pt/C product to greatly enhance its durability.     

Methanol decomposition on copper and manganese oxides supported on activated carbon

Copper and manganese oxides supported on activated carbon have been studied in the reaction of methanol decomposition to H₂ and CO. XRD, EPR, TPR with CO and magnetic measurements have been used for their characterization. The nature of the catalytically active complex is also discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

铝基类水滑石和复合氧化物负载Pt催化剂的制备及对甲基苯酚加氢脱氧反应的催化性能

采用共沉淀法制备了多种铝基类水滑石,焙烧后得到对应的复合氧化物;以水滑石或复合氧化物为载体,制备了系列Pt基催化剂,研究了该催化剂对甲基苯酚加氢脱氧反应的催化性能。结果表明,Pt基催化剂的性能与载体的组分组成和结构相关;当以不经焙烧的类水滑石做载体时,所制备的Pt基催化剂具有较高的活性。其中,Pt-Ni-Al-H催化剂的加氢脱氧活性最高,对甲基苯酚转化率达到99.8%,甲苯选择性为1.4%,而Pt-Zn-Al-H催化剂的直接脱氧活性最高,在275℃和氢压2MPa下反应1h后,甲苯选择性达到84.1%。研究发现,反应过程中所生成的甲基环己烷可进一步发生脱氢反应转化为甲苯,说明所制备的Pt基催化剂具有较好的脱氢活性,可节省脱氧过程中的氢气消耗量。     

High-performance supercapacitor based on tantalum iridium oxides supported on tungsten oxide nanoplatelets

Here we report on a novel supercapacitor electrode based on IrO₂–Ta₂O₅ nanoparticles supported on WO₃ nanoplatelets. The nanoplatelets were directly grown on a W plate using a facile hydrothermal method, whereas the IrO₂–Ta₂O₅ nanoparticles were formed via a thermal decomposition technique which can be easily scaled up. The structural, morphological, and electrochemical properties of the WO₃ nanoplatelets and the formed trimetallic oxide nanocomposite have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), cyclic voltammetry (CV), and charging/discharging techniques. The fabricated trimetallic oxide nanocomposite exihibited rectangular cyclic voltamograms even tested at high potential scan rates, a high specific capacitance and high charging/discharging stability, promising utilization in the design of high-performance devices for energy storage.