Absence Of Energy Barrier Research Articles

Pickering Interfacial Catalysts with CO2 and Magnetic Dual Response for Fast Recovering in Biphasic Reaction.

Pickering interfacial catalysis provides an excellent platform for biphasic reactions, but the separation and recycling of nanocatalysts is a challenge because of high adsorption energy of nanocatalysts at the liquid-liquid interface. In this work, we represent a new type of versatile Pickering emulsion based on magnetic and CO2-responsive nanohybrids Fe3O4@SiO2@P(TMA-DEA). The smart nanoparticles can stabilize the water-in-oil Pickering emulsion in the biphasic system and achieve the subsequent demulsification by bubbling CO2 ascribed to their reversible switching surface. In the absence of energy barrier, the nanohybrids can be easily captured in situ by magnetic field in 2 min and showed excellent recyclability. In the Anelli system for alcohol oxidation, the nanocatalyst exhibited threefold enhancement in catalytic efficiency in comparison with an unemulsified two-phase and little loss on activity after five cycles. The conceptually novel dual-responsive system offers a green and energy-saving strategy for effective recycling of the nanocatalyst and intensification of biphasic reaction.

Applicability of Colloid Filtration Theory in Size-Distributed, Reduced Porosity, Granular Media in the Absence of Energy Barriers

The vast majority of colloid transport experiments use granular porous media with narrow size distribution to facilitate comparison with colloid filtration theory, which represents porous media with a single collector size. In this work we examine retention of colloids ranging in size from 0.21 to 9.1 μm in diameter, in columns packed with uniform and size-distributed borosilicate glass bead porous media with porosity ranging from 0.38 to 0.28. Conditions were favorable to attachment (absent a significant energy barrier). The goal was to determine the applicability of colloid filtration theory to colloid retention in these media. We also directly observed deposition at the pore scale in packed flow cells. The pore domain was characterized via high resolution computerized X-ray micro tomography (HRXMT). The flow field was examined using Lattice-Boltzmann flow simulation methods (LBM). The influence of preferential flow paths on colloid retention in the lowest porosity media was accounted for by correcting the fluid velocity. Straining in pore throats too small to pass was not a significant contributor to colloid retention despite colloid-to-collector size ratios up to 0.05. Mechanistic simulations via the Ma-Pedel-Fife-Johnson correlation equation (MPFJ) for colloid filtration predicted the experimentally observed trends in deposition with porosity when a number-based mean grain size was used.

Gravitational Settling Effects on Unit Cell Predictions of Colloidal Retention in Porous Media in the Absence of Energy Barriers

Laboratory column experiments for colloidal transport and retention are often carried out with flow direction oriented against gravity (up-flow) to minimize retention of trapped air. However, the models that underlie colloidal filtration theory (e.g., unit cell models such as the Happel sphere-in-cell and hemispheres-in-cell) typically set flow in the same direction as gravity (down-flow). We performed unit model simulations and experimental observations of retention of colloids with different size and density in porous media in the absence of energy barriers under both up-flow and down-flow conditions. Unit cell models predicted very different deposition (e.g., for large or dense colloids with gravity number N(G) > 0.01 at pore water velocity of 4 m/day) under down-flow versus up-flow conditions, which reflect underlying influences of gravity and flow on simulated colloid trajectories that resulted in very different distributions of attached colloids over the model surfaces. The Happel sphere-in-cell model showed greater sensitivity to flow orientation relative to gravity than the hemispheres-in-cell model. In contrast, experimental results were relatively insensitive to orientation of flow with respect to gravity, as a result of the variety of orientations of flow relative to gravity and to the porous media surface that exist in actual porous media. Notably, the down-flow simulations corresponded most closely to the experimental results (for near neutrally buoyant colloids); which justifies the common practice of comparing up-flow experiments to theoretical predictions developed for down-flow conditions.

Hemispheres-in-Cell Geometry to Predict Colloid Deposition in Porous Media

A "hemispheres-in-cell" geometry is provided for prediction of colloid retention during transport in porous media. This new geometry preserves the utilities provided in the Happel sphere-in-cell geometry; namely, the ability to predict deposition for a range of porosities, and representation of the influence of neighboring collectors on the fluid flow field. The new geometry, which includes grain to grain contact, is justified by the eventual goal of predicting colloid deposition in the presence of energy barriers, which has been shown in previous literature to involve deposition within grain to grain contacts for colloid:collector ratios greater than approximately 0.005. In order to serve as a platform for predicting deposition in the presence of energy barriers, the model must be shown capable of quantitatively predicting deposition in the absence of energy barriers, which is a requirement that was not met by previous grain to grain contact geometries. This paper describes development of the fluid flow field and particle trajectory simulations for the hemispheres-in-cell geometry in the absence of energy barriers, and demonstrates that the resulting simulations compare favorably to existing models and experiments. A correlation equation for predicting collector efficiencies in the hemispheres-in-cell model in the absence of energy barriers was developed via regression of numerical results to dimensionless parameters.

Relaxation in magnetic nanostructures

The damping of magnetization processes in nanostructures is investigated by Fokker–Planck-type model calculations and quantum-mechanical considerations based on Fermi’s golden rule. In the absence of energy barriers, the problem reduces to a magnetic diffusion equation with a particle-size-dependent diffusivity which is indirectly proportional to the relaxation-time parameter τo. For small particles, the relaxation time is proportional to the particle volume, but when the particle size reaches a few nanometers, it approaches a constant bulk value.

Quasiclassical and capture studies on the O ( 1D) + H 2 → OH + H reaction using a new potential energy surface for H 2O

In absence of energy barrier, the long-range interactions between reactants should play an important role on the dynamics of the reaction of O ( 1 D) with H 2 that mainly occurs in the ground state potential energy surface for H 2O. Quasiclassical and capture studies on a new potential energy surface that carefully reproduces these interactions are in close agreement with the most recent estimates for the thermal rate constant, when the effects of the excited surfaces are taken into account.

Reactive collision with excited states in a crossed beam experiment: O(1D)+H2(v)→OH(A 2Σ+)+H

At least for its most probable mechanisms, the reaction O(1D)+H2(X 1∑+g) →OH(A 2∑+)+H(1 2S) entirely takes place, from reagents to products, on electronically excited-state channels. Due to its endoergicity and to probable energy barriers (E*≊2.8 eV) encountered on these channels, the reaction can be produced in a crossed beam experiment only if the hydrogen molecule is excited on high vibrational levels (v≥5 or v≥7, according to the presence or the absence of energy barriers). This is obtained here by low-energy electron bombardment of the H2 molecular beam. The reaction is observed through the spontaneous fluorescence of the product OH. The measured spectrum corresponding to the 0–0 band of the A 2∑+→X 2Π transition is compared to simulated spectra, as obtained with a simple statistical model and with fitted rotational distribution for OH(A 2∑+,v=0): a broad rotational distribution and a strongly nonstatistical effect on the spin doublet populations are observed.