Exciton binding energy has been regarded as a crucial parameter for mediating charge separation in polymeric photocatalysts. Minimizing the exciton binding energy of the polymers can increase the ...yield of charge‐carrier generation and thus improve the photocatalytic activities, but the realization of this approach remains a great challenge. Herein, a series of linear donor–acceptor conjugated polymers has been developed to minimize the exciton binding energy by modulating the charge‐transfer pathway. The results reveal that the reduced energy loss of the charge‐transfer state can facilitate the electron transfer from donor to acceptor, and thus, more electrons are ready for subsequent reduction reactions. The optimized polymer, FSO‐FS, exhibits a remarkable photochemical performance under visible light irradiation.
Modulating the charge‐transfer pathway in a series of linear donor–acceptor conjugated polymers controls their ability to minimize the exciton binding energy. A low exciton binding energy promotes the photoreaction for artificial photosynthesis
We experimentally, numerically and theoretically investigate the nonlinear interaction between a cavitation bubble and the interface of two immiscible fluids (oil and water) on multiple time scales. ...The underwater electric discharge method is utilized to generate a cavitation bubble near or at the interface. Both the bubble dynamics on a short time scale and the interface evolution on a much longer time scale are recorded via high-speed photography. Two mechanisms are found to contribute to the fluid mixing in our system. First, when a bubble is initiated in the oil phase or at the interface, an inertia-dominated high-speed liquid jet generated from the collapsing bubble penetrates the water–oil interface, and consequently transports fine oil droplets into the water. The critical standoff parameter for jet penetration is found to be highly dependent on the density ratio of the two fluids. Furthermore, the pinch-off of an interface jet produced long after the bubble dynamics stage is reckoned as the second mechanism, carrying water droplets into the oil bulk. The dependence of the bubble jetting behaviours and interface jet dynamics on the governing parameters is systematically studied via experiments and boundary integral simulations. Particularly, we quantitatively demonstrate the respective roles of surface tension and viscosity in interface jet dynamics. As for a bubble initiated at the interface, an extended Rayleigh–Plesset model is proposed that well predicts the asymmetric dynamics of the bubble, which accounts for a faster contraction of the bubble top and a downward liquid jet.
Large-scale photochemical synthesis of high value chemicals under mild conditions is an ideal method of green chemical production. However, a scalable photocatalytic process has been barely reported ...due to the costly preparation, low stability of photosensitizers and critical reaction conditions required for classical photocatalysts. Here, we report the merging of flow chemistry with heterogeneous photoredox catalysis for the facile production of high value compounds in a continuous flow reactor with visible light at room temperature in air. In the flow reactor system, polymeric carbon nitrides, which are cheap, sustainable and stable heterogeneous photocatalysts, are immobilized onto glass beads and fibers, demonstrating a highly flexible construction possibility for devices of the photocatalytic materials. As an example of the production of high value chemicals, important chemical structures such as cyclobutanes, which are basic building blocks for many pharmaceutical compounds, like magnosalin, are synthesized in flow with high catalytic efficiency and stability.
Covalent triazine frameworks (CTFs) have attracted a great deal of attention as an attractive new class of visible light-active, metal-free, and polymer-based heterogeneous photocatalysts. CTFs have ...demonstrated promising characteristics such as synthetic diversity, stability, nontoxicity, pure organic nature, and enhanced ordered structure. In this review, we aim to summarize the recent developments in CTFs ranging from novel preparation methods to critical factors that directly impact their photocatalytic efficiency. Various physical and chemical design strategies for morphology, band structure, charge separation, and transfer optimization described in the literature are discussed. Emphasis is placed on the enhancement and maximization of photocatalytic efficiencies of specific applications such as photoredox organosynthesis, water splitting, CO2 photoreduction, H2O2 generation, etc.
Non-reflecting boundary conditions (NRBCs) play an important role in computational fluid dynamics (CFD). A novel NRBC based on the method of characteristics using timeline interpolations is proposed ...for fluid dynamics solved by smoothed particle hydrodynamics (SPH). It is performed by four layers of particles whose pressures and velocities are obtained through the Lagrange interpolation in the time domain which is derived from the propagation of characteristic waves between particles. The proposed NRBC can allow outward travelling pressure and velocity messages to pass through the boundary without obvious reflection. That is, with the implementation of the NRBC, the solution in a finite computational domain of interest is close to that in an infinite domain. Several numerical tests show that this NRBC is robust and applicable for a broad variety of hydrodynamics ranging from low to high speed.
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•Four types of new refractory HEAs are designed.•These HEAs mainly consist of a simple BCC solid solution.•The formation mechanism of β-Ti is proposed.•Oxidation resistance is ...improved by adding Ti and Si, but reduced by adding V.
High-entropy alloys (HEAs) are defined as the alloys composed of at least five principal elements in equimolar or near equimolar ratios, which can facilitate the formation of simple solid solutions during solidification. Recent studies suggested that the refractory HEAs exhibited great promise for high temperature structural materials. However, their oxidation behavior had received little attention. In the present study, Cr, Al and Si elements were added to improve the oxidation resistance, four types of new refractory HEAs were designed and synthesized, including NbCrMoTiAl0.5 (H-Ti), NbCrMoVAl0.5 (H-V), NbCrMoTiVAl0.5 (H-TiV) and NbCrMoTiVAl0.5Si0.3 (H-TiVSi0.3). Their microstructures and oxidation behavior were studied. As expected, these refractory HEAs mainly consist of a simple body-centred cubic (BCC) refractory metal solid solution (RMss) due to the high mixing entropy effect. Solidification process and thermodynamic analysis were investigated to explain the formation mechanism of their microstructures. For all the refractory HEAs, the oxidation kinetics at 1300°C follows a linear behavior. The oxidation resistance of the HEAs is significantly improved with Ti and Si addition, but reduced with V addition.
This paper is concerned with the dynamics of large bubbles subject to various strengths of buoyancy effects, which are associated with applications for underwater explosion. The bubble is produced by ...electric discharge in a low-pressure tank to enhance the buoyancy effects. Experiments are carried out for a bubble in an infinite field, below a free surface and above a rigid boundary. The effects of buoyancy are reflected by the dimensionless parameter
${\it\delta}=\sqrt{{\it\rho}gR_{m}/(p_{amb}-p_{v})}$
, where
$R_{m}$
,
$p_{amb}$
,
$p_{v}$
,
${\it\rho}$
and
$g$
are the maximum bubble radius, ambient pressure, saturated vapour pressure, density of water and the acceleration of gravity respectively. A systematic study of buoyancy effects is carried out for a wide range of
${\it\delta}$
from 0.034 to 0.95. A series of new phenomena and new features is observed. The bubbles recorded are transparent, and thus we are able to display and study the jet formation, development and impact on the opposite bubble surface as well as the subsequent collapsing and rebounding of the ring bubble. Qualitative analyses are carried out for the bubble migration, jet velocity and jet initiation time, etc. for different values of
${\it\delta}$
. When a bubble oscillates below a free surface or above a rigid boundary, the Bjerknes force due to the free surface (or rigid boundary) and the buoyancy are in opposite directions. Three situations are studied for each of the two configurations: (i) the Bjerknes force being dominant, (ii) the buoyancy force being dominant and (iii) the two forces being approximately balanced. For case (iii), we further consider two subcases, where both the balanced Bjerknes and buoyancy forces are weak or strong. When the Bjerknes and buoyancy forces are approximately balanced over the pulsation, some representative bubble behaviours are observed: the bubble near free surface is found to split into two parts jetting away from each other for small
${\it\delta}$
, or involutes from both top and bottom for large
${\it\delta}$
. A bubble above a rigid wall is found to be subject to contraction from the lateral part leading to bubble splitting. New criteria are established based on experimental results for neutral collapses where there is no dominant jetting along one direction, which correlate well with the criteria of Blake et al. (J. Fluid Mech., vol. 170, 1986, pp. 479–497; J. Fluid Mech., vol. 181, 1987, pp. 197–212) but agree better with the experimental and computational results.
The construction of multiple heteroatom-doped porous carbon with unique nanoarchitectures and abundant heteroatom active sites is promising for reversible oxygen-involving electrocatalysis. However, ...most of the synthetic methods required the use of templates to construct precisely designed nanostructured carbon. Herein, we introduced an ultrasound-triggered route for the synthesis of a piperazine-containing covalent triazine framework (P-CTF). The ultrasonic energy triggered both the polycondensation of monomers and the assembly into a nanoflower-shaped morphology without utilizing any templates. Subsequent carbonization of P-CTF led to the formation of nitrogen, phosphorus, and fluorine tri-doped porous carbon (NPF@CNFs) with a well-maintained nanoflower morphology. The resultant NPF@CNFs showed high electrocatalytic activity and stability toward bifunctional electrolysis, which was better than the commercial Pt/C and IrO2 electrocatalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. As a further demonstration, employing NPF@CNFs as air electrode materials resulted in an excellent performance of liquid-state and solid-state Zn-air batteries, showing great potentials of the obtained multiple heteroatom-doped porous carbon electrocatalysts for wearable electronics.
•Delta-SPH model is extended for simulating strongly-compressible multiphase flows.•A new Volume Adaptive Scheme is proposed.•Governing equations are discretized with corrected SPH operators.•Strict ...numerical validations are carried out using challenging benchmarks.
In the present work, the single-phase and weakly-compressible δ-SPH model is further extended to simulate multiphase and strongly-compressible flows. This is motivated by the fact that traditional SPH models can meet some difficulties when modeling strongly-compressible flows with large volume variations (e.g. expansion and collapse of cavitation bubbles). Due to the strong compressibility of the fluid, the energy equation should be considered in the governing equations. In that case, the pressure is solved based on both density and internal energy. To stabilize the pressure field, density and energy diffusive terms should be applied. Large variations of particle volumes in the compressible phase would result in large variations of particle spacing. Therefore, particle smoothing lengths are adjusted in time to maintain appropriate neighboring particles. To ensure good properties of accuracy and conservation when particles with different smoothing lengths interact, corrected SPH operators are utilized to discretize the governing equations. Moreover, in order to limit the particle volume variations and maintain a homogeneous volume distribution in the entire flow field, especially near the interface between different phases of different compressibility, a new volume adaptive scheme is proposed to control particle volumes. The volumes which are over-expanded or over-compressed will be split or merged with others, maintaining a small particle volume variation in the flow. Finally, the proposed SPH model is validated with several challenging benchmarks including expansion and collapse of underwater-explosion bubbles or cavitation bubbles. All the SPH results are compared with other numerical solutions with good agreements.
The search for metal‐free organic photocatalysts for H2 production from water using visible light remains a key challenge. Reported herein is a molecular structural design of pure organic ...photocatalysts, derived from conjugated polybenzothiadiazoles, for photocatalytic H2 evolution using visible light. By alternating the substitution position of the electron‐withdrawing benzothiadizole unit on the phenyl unit as a comonomer, various polymers with either one‐ or three‐dimensional structures were synthesized and the effect of the molecular structure on their catalytic activity was investigated. Photocatalytic H2 evolution efficiencies up to 116 μmol h−1 were observed by employing the linear polymer based on a phenyl‐benzothiadiazole alternating main chain, with an apparent quantum yield (AQY) of 4.01 % at 420 nm using triethanolamine as the sacrificial agent.
Bring to light: Conjugated polybenzothiadiazoles were introduced as a new family of organic photocatalysts for H2 evolution from water in the presence of electron donors with visible‐light irradiation. The molecular engineering of the electron‐withdrawing benzothiadiazole unit on the phenyl unit allows the construction of either one‐ or three‐dimensional polybenzothiadiazoles, and the effect of the structure on the photocatalytic H2 evolution activity was investigated.
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