The condensation and desorption of nickel tetra-carbonyl (Ni(CO)4) on Cu(1 1 0) has been studied by thermal desorption spectroscopy. A quite unusual evolution of the desorption spectra is observed. First a desorption peak appears at around 140 K, which disappears with increasing coverage and merges into a clearly separated new desorption peak at around 150 K. This transformation takes place at a coverage of about 10% of a monolayer. It is suggested that the low temperature peak is due to desorption of monomers. With increasing coverage nucleation and growth of multilayer islands starts, from which the desorption energy is higher due to the higher coordination of the carbonyl molecules, compared to that of the monomers. Evaluation of the multilayer desorption spectra yields a desorption energy of 57.9 kJ/mol (0.60 eV) and an unusually high frequency factor of 1.6 × 1019 s−1. 相似文献
A novel crosslinked poly(acrylic acid-copolymer-Kryptofix-22-DM) superabsorbent copolymer, poly(AA-co-Kry22-DM), was synthesised by the reaction of 4,13-dimethylacryloyl-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (Kyrptofix-22-DM) and acrylic acid (AA). Characterisation of the polymers was achieved by FTIR and 1H NMR techniques. Sorption capacity of the crosslinked poly(AA-co-Kry22-DM) superabsorbent copolymer was investigated for Pb2+, Cu2+, Cr3+, Cd2+, Mn2+, Zn2+, and Ni2+ heavy metal ions at different pH values using Freundlich and Langmuir isotherms. Swelling ratio, qv, and distribution ratio, log D, values of the crosslinked poly(AA-co-Kry22-DM) superabsorbent copolymer were calculated at various pH values. 相似文献
1. INTRODUCTION Nowdays the volatile organic compounds (VOCs) have become important pollutants to air [1]. The source of these wastes is very wide. The leakage of the VOCs from chemical and pharmaceutical manufacturing, printing processes, paint and adhesive manufacturing and applications, composites and fiberglass molding etc. is the source of the pollutants. A number of adsorbents are capable of capturing a wide range of VOCs. However, the conventional process of regenerating … 相似文献
Surfactants appear in multiphase fluid systems in which the interface and the adjacent bulk phase have been removed from equilibrium. Here, a new method is described for the measurement of rate constants of desorption of surface-active materials from fluid/fluid interfaces and the extent to which adsorption is reversible: the coaxial capillary pendant drop experimental technique.
Kinetic constants are determined by desorption experiments in pendant drops in which the interface adjacent to a surfactant solution is removed from equilibrium by replacing the subphase of the drop with pure water. Further, we demonstrate that although the rate of subphase exchange is comparatively slow with respect to the desorption timescale, it is possible to resolve desorption processes which occur under local equilibrium with the adjacent bulk phase from those that are determined in part by sorption kinetics. Experiments which measure the desorption kinetic coefficient, , using a homologous series of n-alkyl (C8, C10, C12, C14) dimethyl phosphine oxides are presented. 相似文献
In this work we are concerned with the study of long-term relaxation phenomena in dipalmitoyl phosphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) monolayers spread at the air–water interface as a function of the surface pressure and the aqueous phase pH (pH 5, 7, and 9). Long-term relaxation phenomena were determined in an automated Langmuir-type film balance at constant temperature (20 °C). Two kinds of experiments were performed to analyze relaxation mechanisms. In one, the surface pressure (π) was kept constant, and the area (A) was measured as a function of time (θ). In the second, the area was kept constant at monolayer collapse and the surface pressure was decreased. This decrease was measured as a function of time. Various relaxation mechanisms, including monolayer molecular loss by dissolution, collapse, and/or organization/reorganization changes, can be fitted to the results derived from these experiments. These relaxation mechanisms are pH and phospholipid dependent. In the discussion, special attention will be given to the effect of the relaxation phenomena on the hysteresis in π–A isotherms before and after the relaxation experiment. At π lower than the equilibrium spreading pressure (πe) the relaxation phenomena are mainly due to the loss of DPPC or DOPC molecules by desorption into the bulk aqueous phase. The formation of interfacial macroscopic vesicles, which are dissolved into the bulk phase, makes the phospholipid monolayer molecular loss irreversible. At the collapse point (at π > πe), the relaxation phenomena may be due either to collapse for DPPC and/or to a complex mechanism including competition between desorption and monolayer collapse for DOPC. 相似文献
Engineering nanoparticle (NP) functions at the molecular level requires a detailed understanding of the dynamic processes occurring at the NP surface. Herein we show that a combination of dark‐state exchange saturation transfer (DEST) and relaxation dispersion (RD) NMR experiments on gel‐stabilized NP samples enables the accurate determination of the kinetics and thermodynamics of adsorption. We used the former approach to describe the interaction of cholic acid (CA) and phenol (PhOH) with ceria NPs with a diameter of approximately 200 nm. Whereas CA formed weak interactions with the NPs, PhOH was tightly bound to the NP surface. Interestingly, we found that the adsorption of PhOH proceeds via an intermediate, weakly bound state in which the small molecule has residual degrees of rotational diffusion. We believe the use of aqueous gels for stabilizing NP samples will increase the applicability of solution NMR methods to the characterization of nanomaterials. 相似文献
Worldwide, arsenic contamination has become a matter of extreme importance owing to its potential toxic, carcinogenic and mutagenic impact on human health and the environment. The magnetite-loaded biochar has received increasing attention for the removal of arsenic (As) in contaminated water and soil. The present study reports a facile synthesis, characterization and adsorption characteristics of a novel magnetite impregnated nitrogen-doped hybrid biochar (N/Fe3O4@BC) for efficient arsenate, As(V) and arsenite, As(III) removal from aqueous environment. The as-synthesized material (N/Fe3O4@BC) characterization via XRD, BET, FTIR, SEM/EDS clearly revealed magnetite (Fe3O4) impregnation onto biochar matrix. Furthermore, the adsorbent (N/Fe3O4@BC) selectivity results showed that such a combination plays an important role in targeted molecule removal from aqueous environments and compensates for the reduced surface area. The maximum monolayer adsorption (Qmax) of developed adsorbent (N/Fe3O4@BC) (18.15 mg/g and 9.87 mg/g) was significantly higher than that of pristine biochar (BC) (9.89 & 8.12 mg/g) and magnetite nano-particles (MNPs) [7.38 & 8.56 mg/g] for both As(III) and As(V), respectively. Isotherm and kinetic data were well fitted by Langmuir (R2 = 0.993) and Pseudo first order model (R2 = 0.992) thereby indicating physico-chemical sorption as a rate-limiting step. The co-anions (PO43-) effect was more significant for both As(III) and As (V) removal owing to similar outer electronic structure. Mechanistic insights (pH and FTIR spectra) further demonstrated the remarkable contribution of surface groups (OH–, –NH2 and –COOH), electrostatic attraction (via H- bonds), surface complexation and ion exchange followed by external mass transfer diffusion and As(III) oxidation into As(V) by (N/Fe3O4@BC) reactive oxygen species. Moreover, successful desorption was achieved at varying rates up to 7th regeneration cycle thereby showing (N/Fe3O4@BC) potential practical application. Thus, this work provides a novel insight for the fabrication of novel magnetic biochar for As removal from contaminated water in natural, engineering and environmental settings. 相似文献
The desorption of Br adatoms from Br-saturated Si(1 0 0)-(2 × 1) was studied with scanning tunneling microscopy as a function of dopant type, dopant concentration, and temperature for 620-775 K. Analysis yields the activation energies and prefactors for desorption, and the former correspond to the energy separation between the Fermi level and Si-Br antibonding states. Thus, electron capture in long-lived states results in Br expulsion via a Franck-Condon transition. Analysis of the prefactors reveals that optical phonons provide the energy needed for the electronic excitation. These results show that desorption induced by an electronic transition can occur in closed system without external stimulus, and they indicate that thermally-excited charge carriers may play a general role in surface reactions. 相似文献