In this paper, the ethylene adsorption capacities of the nano-sized carbon hollow spheres (CNB) and active carbon (AC), the
Pd (PdCl2) impregnated CNB or AC (Pd/CNB, Pd/AC) and heat treatment under various conditions, were studied at different ethylene concentrations
from 64 to 1060 ppm. The results indicated that AC had a good ethylene adsorption capacity at high ethylene concentration.
Pd impregnation decreased the ethylene adsorption capacity of AC. Heat treatment and H2 activation could increase the ethylene adsorption capacity, but also lowered than AC itself. CNB had lower ethylene adsorption
capacity than AC, but heat treatment and H2 activation could increase its ethylene adsorption capacity markedly. With activating condition from heat treatment in N2 at 300 °C to activation in H2/N2 at 100 °C, to activation in H2 at 200 °C, and to activation in H2 at 300 °C, the ethylene adsorption capacity of Pd/CNB was increased regularly. At low ethylene concentration, viz., 64 ppm,
the ethylene adsorption quantities (qa) by Pd/CNB activated in H2 at 200 or 300 °C were higher than any other adsorbents. So, activated in H2 atmosphere at higher than 100 °C, Pd/CNB is particularly advantaged for adsorbing low concentration of ethylene. Amongst
all the adsorbents used, Pd/CNB activated in H2 atmosphere at 300 °C for 2 h has the highest ethylene adsorption capacity at lower concentration than 125 ppm. In addition,
all the CNB, Pd/CNB, AC, and Pd/AC samples can be easily regenerated in airflow for more than 3 h. 相似文献
Hydrogen adsorption and absorption at thin palladium deposits of 0.8-10 monolayers (ML) on Au(1 1 1) was studied in 0.1 M H2SO4 and HClO4 using cyclic voltammetry, ac voltammetry, and impedance spectroscopy in the absence and in the presence of poison, crystal violet. Hydrogen adsorption on palladium is more reversible in sulfuric acid than in perchloric acid but it occurs at potentials 30 mV more positive in latter. The charge-transfer resistance exhibits a minimum at ∼0.27 V versus RHE and decreases with increasing in Pd deposit thickness in both acids. Adsorption capacitance at 0.8 ML Pd reaches maximum at the same potential. At other deposits the pseudo-capacitance starts to increase at lower overpotentials indicating the beginning of absorption, even at 2 ML Pd. The double layer capacitance is similar for all the deposits in sulfuric acid and it has a sharp maximum at 0.27 V versus RHE. In perchloric acid a broad maximum is observed. Crystal violet inhibits hydrogen adsorption but makes hydrogen absorption more reversible. The results suggest a fast direct hydrogen absorption mechanism that proceeds in parallel with slower hydrogen adsorption and indirect absorption. 相似文献
The effect of high temperature reduction (HTR) in hydrogen (up to 1180 K) on the microstructure of 9 wt.-% Pd/CeO2 catalyst was studied by HRTEM and XRD methods. Reduction of the catalyst at or above 973 K caused severe recrystallization of CeO2 and Pd with simultaneous strong interaction between the two components appearing as three phenomena: epitaxial growth of small Pd particles on CeO2 (most frequently with [111]Pd[111]CeO2); decoration of large Pd particles with ordered CeO2 overlayer and expansion of the lattice parameter of Pd (by 2.1%). The origin of the Pd lattice expansion is discussed and diffusion of Ce species into the Pd lattice seems to be the most probable one. HTR caused also phase transformations in the ceria support. At 973 K and 1100 K, whole CeO2 was transformed into oxygen deficient CeOx phase exhibiting the same or similar structure but with expanded lattice parameter (by 2.8%). At 1180 K most ceria was transformed into hexagonal A-Ce23. The CeOx phase appeared to be stable in hydrogen and in vacuum at room temperature, but upon exposure to air at room temperature it rapidly reoxidised to CeO2. Ce2O3 also reoxidised to CeO2 but much slower. Another consequence of HTR at or above 773 K was formation of pits in CeO2 crystallites, mainly on (112)-type crystal faces. The pits (1–10 nm) exhibited well defined walls parallel to CeO2 lattice fringes and they could possibly constitute nucleation sites for strongly bonded, epitaxial oriented Pd particles. 相似文献
The role of La2O3 loading in Pd/Al2O3-La2O3 prepared by sol–gel on the catalytic properties in the NO reduction with H2 was studied. The catalysts were characterized by N2 physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.
The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La2O3 inclusion. The selectivity depends on the NO/H2 molar ratio (GHSV = 72,000 h−1) and the extent of interaction between Pd and La2O3. At NO/H2 = 0.5, the catalysts show high N2 selectivity (60–75%) at temperatures lower than 250 °C. For NO/H2 = 1, the N2 selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H2O vapor. The high N2 selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdOx phase interacting with La2O3. The formation of this phase is favored by the spreading of PdO promoted by La2O3. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al2O3 the O2 uptake is consistent with the oxidation of PdO to PdO2, and when La2O3 is present the O2 uptake exceeds that amount (1.5 times). La2O3 in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N2. 相似文献
The different low temperature coordination modes of ethylene and butadiene on a platinum (111) face, (110) face and on a palladium (111) face are compared on the basis of extended Hückel calculations. The nature of the chemical interaction between the olefin and the surface is detailed and the electronic factors that govern the coordination mode of the hydrocarbon are underlined. The different surfaces are modelled by a 49 or a 44 atoms cluster. A correction is applied in the calculation in order to minimize the artefact introduced by this cluster representation of an extended surface. For the adsorption, the respective importance of two electrons interactions and four electrons repulsions is the key point for the determination of the preferred mode. The di- coordination is more stable on platinum (111) but on the platinum (110) face the coordination yields the same adsorption energy than the di- one. This is roughly the same result for the palladium (111) face. The mode is there favored by a decrease of the four electrons repulsions caused either by a smaller number of metal neighbours for the surface atom (Pt(110)) or by a reduced radial expansion of the metal orbitals (Pd(111)). This coordination is associated with a smaller hybridization of the ethylene molecule. The results are extended to the adsorption of butadiene and this allows a qualitative explanation of the better selectivity for butadiene partial hydrogenation on palladium compared with platinum. 相似文献