A Study on Hydrogen Bonding and Energy Variation during Bubble Nucleation in Water on a Grooved Substrate by Molecular Dynamics Simulation.

In this paper, the bubble nucleation process of water was studied by molecular dynamics (MD) simulation. The nucleation mechanism of water on a grooved substrate was revealed from the perspective of hydrogen bond and energy change, and the effect of system pressure on nucleation was studied. The results show that the process of bubble nucleation of water molecules is essentially a process in which the thermal motion of water molecules gradually intensifies and the hydrogen bond continues to break with the increase in kinetic energy. As the hydrogen bond breaks, the kinetic energy of the water molecules is continuously converted to intermolecular potential energy. By analyzing the composition of the hydrogen bond energy, it is found that the electrostatic energy is much greater than the van der Waals energy, so the water nucleation process mainly overcomes the electrostatic force between molecules. With the gradual increase of pressure, although the kinetic energy distribution of molecules does not change significantly, it will cause the potential energy of water molecules to decrease significantly and then lead to the increase of the energy barrier that needs to be crossed for nucleation. Meanwhile, the rise of the nucleation barrier may result in the absence of obvious initial vapor nuclei inside the liquid so that the number of hydrogen bonds cannot be rapidly reduced, which is not conducive to boiling nucleation. The results of this study provide important implications for further understanding of the nucleate boiling process of water.

Rational Design of Liquid-Liquid Microdispersion Droplet Microreactors for the Controllable Synthesis of Highly Uniform and Monodispersed Dextran Microspheres.

Hydrogel microspheres are biocompatible materials widely used in biological and medical fields. Emulsification and stirring are the commonly used methods to prepare hydrogels. However, the size distribution is considerably wide, the monodispersity and the mechanical intensity are poor, and the stable operation conditions are comparatively narrow to meet some sophisticated applications. In this paper, a T-shaped stepwise microchannel combined with a simple side microchannel structure is developed to explore the liquid-liquid dispersion mechanism, interfacial evolution behavior, satellite droplet formation mechanism and separation, and the eventual successful synthesis of dextran hydrogel microspheres. The effect of the operation parameters on droplet and microsphere size is comprehensively studied. The flow pattern and the stable operation condition range are given, and mathematical prediction models are developed under three different flow regimes for droplet size prediction. Based on the stable operating conditions, a microdroplet-based method combined with UV light curing is developed to synthesize the dextran hydrogel microsphere. The highly uniform and monodispersed dextran microspheres with good mechanical intensity are synthesized in the developed microfluidic platform. The size of the microsphere could be tuned from 50 to 300 µm with a capillary number in the range of 0.006-0.742. This work not only provides a facile method for functional polymeric microsphere preparation but also offers important design guidelines for the development of a robust microreactor.

Local hydrogen bonding environment induces the deprotonation of surface hydroxyl for continuing ammonia decomposition.

There is still a paucity of fundamental understanding about the reaction of ammonia decomposition over TiO2, especially the role of water. Herein, FPMD and DFT calculations were used to address this concern. The results reveal that ammonia decomposition in pure ammonia causes the hydroxylation of the surfaces and reduction of the proton acceptor sites, making proton transfer (PT) difficult, increasing the distances between the NH3 and Obr sites and changing the adsorption configurations of NH3, which are not favourable for accepting protons from NH3 dissociation. When water is introduced, the local hydrogen bonding environment, consisting of NH3 and H2O with the H2O dynamically close to the ObrH, promotes the increase of the positive charge of H atoms from 0.133 to 1.47 e, which increases the ObrH bond dipole moment from 1.136 to 1.400 Debye, resulting in the shortening of the H-bond distances between NH3 and ObrH (1.858 vs. 1.945 Å of only NH3) and enlarging the ObrH bonds (0.980 vs. 1.120 Å). This reduces the activation energy barriers of ObrH deprotonation and causes the surfaces to have low hydroxyl coverage from 0.425 to 0.382 eV. Our study reveals the role of water and provides new insights into ammonia decomposition on TiO2.

Molecular Dynamics Study on the Combined Effects of the Nanostructure and Wettability of Solid Surfaces on Bubble Nucleation.

In this paper, molecular dynamics (MD) simulations are conducted to investigate the bubble nucleation process of liquid argon on surfaces with a nanostructure of different wettabilities. To account for the combined effects of the nanostructure and surface wettability on bubble nucleation, the variation of the bubble volume, the nucleation starting time, as well as the heat flux between the solid surface and fluid are examined. It is found that the position of bubble nucleation depends on the pillar wettability. Bubble nucleation occurs in the bulk of fluid when the pillar is hydrophilic, while it occurs on the pillar surface when the pillar is hydrophobic. Under an integrated influence of the free-energy barrier of nucleation and heat transfer, the nucleation occurs later as the wettability of the pillar gets weaker over surfaces with the hydrophilic pillar, while it occurs earlier as the wettability of the pillar gets weaker over surfaces with the hydrophobic pillar. Moreover, the peak heat flux decreases with the decrease of the pillar wettability over surfaces with the hydrophilic pillar, while it increases with the decrease of the pillar wettability over surfaces with the hydrophobic pillar, which can be explained from the perspective of the heat transfer efficiency and the timing of phase change occurrence. Finally, a new surface with mixed-wettable pillars is proposed, which is verified to be conducive to both bubble nucleation and heat transfer.

Convenient and large-scale fabrication of cost-effective superhydrophobic aluminum alloy surface with excellent reparability.

Superhydrophobic surfaces are widely used in industry and daily life, yet their practical application is limited by their complicated preparation process, high cost, and poor repairability. We propose a low-cost, facile process for preparing superhydrophobic surfaces to address this limitation. Through a simple three-step spraying process, the rough structure was first constructed on the aluminum alloy, and upon modification by modifier, the superhydrophobic aluminum alloy surface was successfully prepared. The effect of the process parameters on wettability was experimentally studied. The results showed that this method can obtain superhydrophobic surfaces with a contact angle of 156.2° and contact angle hysteresis of 7.4° by simply adjusting the etching time and modifier concentration. In addition, it was found that the prepared surface can keep the superhydrophobic property unchanged at 180 °C, showing good thermal stability. When immersed in acetic acid and sodium hydroxide solution, the prepared surface can maintain its superhydrophobicity for about 2 days, showing good chemical stability. Besides, the surface has excellent repairability and can compensate for the short-life defects caused by poor friction resistance. This superhydrophobic surface with a simple preparation process, low cost, and excellent repairable characteristics also has excellent self-cleaning, antifogging, and antifrosting applications.

Nanoparticle-Assisted Pool Boiling Heat Transfer on Micro-Pin-Fin Surfaces.

Boiling heat transfer intensification is of significant relevance to energy conversion and various cooling processes. This study aimed to enhance the saturated pool boiling of FC-72 (a dielectric liquid) by surface modifications and explore mechanisms of the enhancement. Specifically, circular and square micro pin fins were fabricated on silicon surfaces by dry etching and then copper nanoparticles were deposited on the micro-pin-fin surfaces by electrostatic deposition. Experimental results indicated that compared with a smooth surface, the micro pin fins increased the heat transfer coefficient and the critical heat flux by more than 200 and 65-83%, respectively, which were further enhanced by the nanoparticles up to 24% and more than 20%, respectively. Correspondingly, the enhancement mechanism was carefully explored by high-speed bubble visualizations, surface wickability measurements, and model analysis. It was quantitatively found that small bubble departure diameters with high bubble departure frequencies promoted high heat transfer coefficients. The wickability, which characterizes the ability of a liquid to rewet a surface, played an important role in determining the critical heat flux, but further analyses indicated that evaporation beneath bubbles was also essential and competition between the wicking and the evaporation finally triggered the critical heat flux.

Droplet Microfluidic Devices: Working Principles, Fabrication Methods, and Scale-Up Applications.

Compared with the conventional emulsification method, droplets generated within microfluidic devices exhibit distinct advantages such as precise control of fluids, exceptional monodispersity, uniform morphology, flexible manipulation, and narrow size distribution. These inherent benefits, including intrinsic safety, excellent heat and mass transfer capabilities, and large surface-to-volume ratio, have led to the widespread applications of droplet-based microfluidics across diverse fields, encompassing chemical engineering, particle synthesis, biological detection, diagnostics, emulsion preparation, and pharmaceuticals. However, despite its promising potential for versatile applications, the practical utilization of this technology in commercial and industrial is extremely limited to the inherently low production rates achievable within a single microchannel. Over the past two decades, droplet-based microfluidics has evolved significantly, considerably transitioning from a proof-of-concept stage to industrialization. And now there is a growing trend towards translating academic research into commercial and industrial applications, primarily driven by the burgeoning demands of various fields. This paper comprehensively reviews recent advancements in droplet-based microfluidics, covering the fundamental working principles and the critical aspect of scale-up integration from working principles to scale-up integration. Based on the existing scale-up strategies, the paper also outlines the future research directions, identifies the potential opportunities, and addresses the typical unsolved challenges.

Acoustofluidic one-step production of plasmonic Ag nanoparticles for portable paper-based ultrasensitive SERS detection of bactericides.

SERS measurements for monitoring bactericides in dairy products are highly desired for food safety problems. However, the complicated preparation process of SERS substrates greatly impedes the promotion of SERS. Here, we propose acoustofluidic one-step synthesis of Ag nanoparticles on paper substrates for SERS detection. Our method is economical, fast, simple, and eco-friendly. We adopted laser cutting to cut out appropriate paper shapes, and aldehydes were simultaneously produced at the cutting edge in the pyrolysis of cellulose by laser which were leveraged as the reducing reagent. In the synthesis, only 5 µL of Ag precursor was added to complete the reaction, and no reducing agent was used. Our recently developed acoustofluidic device was employed to intensely mix Ag+ ions and aldehydes and spread the reduced Ag nanoparticles over the substrate. The SERS substrate was fabricated in 1 step and 3 min. The standard R6G solution measurement demonstrated the excellent signal and prominent uniformity of the fabricated SERS substrates. SERS detection of the safe concentration of three bactericides, including tetracycline hydrochloride, thiabendazole, and malachite green, from food samples can be achieved using fabricated substrates. We take the least cost, time, reagents, and steps to fabricate the SERS substrate with satisfying performance. Our work has an extraodinary meaning for the green preparation and large-scale application of SERS.

Multi-Physics Simulation of Tar-Rich Coal In Situ Pyrolysis with a Multiregion Homogenization Treatment.

The macroscopic multi-physics simulation of tar-rich coal in situ pyrolysis (TCISP) is conducted, in the fractured porous zone, by coupling heat transfer, fluid flow, and chemical reaction. A novel TCISP pattern of gas injection between fractured zones is proposed by treating the fractured porous zone as a homogeneous porosity gradient descending region. In this case, nearly 11,500 kg of oil can be produced within 6 months from a 10*10*1 m3 area. The influence of the fractured zone and porosity are investigated. The results indicated that gas injection between fractured zones is more conducive to rapid production, compared with the traditional case where the gas injection is in the center. The temperature field is more uniform, which is conducive to maintaining the same reaction conditions and producing appropriate products. Inlet velocity has a positive effect on the increase of heat transfer rate but has a negative effect on heat transfer uniformity. There is an optimal inlet temperature of 973 K for the fastest heating rate. With the increase in temperature, the heat transfer uniformity gets worse. Increasing the height of the fractured zone is beneficial for the heating rate and heat transfer uniformity.

Effect of Polymer Drag Reducer on Rheological Properties of Rocket Kerosene Solutions.

Adding drag reduction agent (DRA) to rocket kerosene is an effective way to reduce the pipeline resistance of rocket kerosene transportation systems. However, so far, there have been few research reports on the effect of DRA on the rheological properties of rocket kerosene solution, especially from a microscopic perspective. In this study, coarse-grained molecular dynamics simulations were conducted to investigate the rheological properties of rocket kerosene solutions with DRAs of different chain lengths and concentrations. The results showed that the viscosity of DRA-kerosene solution is generally higher than that of pure kerosene at a low shear rate, while with an increase in shear rate, the viscosity of DRA-kerosene solution decreases rapidly and finally tends to become similar to that of pure kerosene. The shear viscosity of DRA-kerosene solution increases with an increase in chain length and concentration of polymers. Through observing the morphologic change of DRA molecules and analyzing the radius of gyration and the mean-squared end-to-end distance of polymers, it was confirmed that the rheological properties of DRA-kerosene solutions are strongly related to the degree of entanglement of polymer chains. The simulation results provide microscopic insights into the rheological behavior of DRA-kerosene solutions and clarify the intrinsic relation between the morphologic change of polymer molecules and the rheological properties of DRA-kerosene solutions.

Effect of the Addition of Graphene Nanoplatelets on the Thermal Conductivity of Rocket Kerosene: A Molecular Dynamics Study.

Rocket kerosene plays an important role in the regenerative cooling process of rocket thrust chambers. Its thermal conductivity determines the cooling efficiency and the tendency to coke in rocket kerosene engines. In this paper, graphene nanoplatelets (GNPs) were introduced into rocket kerosene to improve its thermal conductivity. Molecular dynamics simulation was used to investigate the thermal conductivity of the composite system and its underlying thermal conductivity mechanism. Firstly, by studying the effect of the mass fraction of GNPs, it was found that, when the graphene mass fraction increases from 1.14% to 6.49%, the thermal conductivity of the composite system increases from 4.26% to 17.83%, which can be explained by the percolation theory. Secondly, the influence of the size of GNPs on the thermal conductivity of the composite system was studied. Basically, the thermal conductivity was found to increase by increasing the aspect ratio of GNPs, indicating that GNPs with a higher aspect ratio are more conducive to improving the thermal conductivity of rocket kerosene. By carefully analyzing the effect of the size of GNPs on thermal conductivity, it was concluded that the thermal conduction enhancement by adding GNPs is determined by the combined effect of the percolation theory and the Brownian motion. The results of the temperature effect study showed that the ratio of thermal conductivity to rocket kerosene increased from 1.16 to 1.26 and from 1.07 to 1.11 for the composite systems, with graphene sizes of 41.18 Å × 64.00 Å and 24.14 Å × 17.22 Å in the temperature range of 293 K to 343 K, respectively. It is further proved that the Brownian motion of GNPs has a non-negligible effect on the thermal conductivity of the composite system. This work provides microscopic insights into the thermal conduction mechanism of GNPs in nanofluids and will offer practical guidance for improving the thermal conductivity of rocket kerosene.

Thermally-enhanced sono-photo-catalysis by defect and facet modulation of Pt-TiO2 catalyst for high-efficient hydrogen evolution.

Sono-photo-catalysis (SPC) has been regarded as a promising route for hydrogen evolution from water splitting due to the sono-photo-synergism, whereas its current performance (∼µmol g-1 h-1) is yet far from expectation. Herein, we give the first demonstration that the intrinsically coupled thermal effects of light and ultrasound, which is normally underestimated or neglected, can simultaneously reshape the photo- and sono-catalytic activities for hydrogen evolution and establish a higher degree of synergy between light and ultrasound in SPC even on the traditional Pt-TiO2 catalyst. A high-efficient hydrogen evolution rate of 225.04 mmol g-1 h-1 with light-to­hydrogen efficiency of 0.89% has been achieved in thermally-enhanced SPC, which is an order of magnitude higher than that without thermal effects. More impressively, the increase of synergy index up to 53% has been achieved. Through experiments and theoretical calculations, the thermally-enhanced sono-photo-synergism is attributed to the sono-photo-thermo-modulated structural optimization of defect-rich TiO2 support and deaggregated Pt species with functional complementary lattice facets, which optimizes not only the thermodynamic properties by enhancing light harvesting and the charge redox power, but also the kinetic properties by accelerating the net efficiency of charge separation and the whole processes of water splitting, including the dissociation of water molecules on high-index (200) Pt facets and production of H∗ intermediates on defect-rich TiO2-x support and low-index (111) Pt facets. This study exemplifies that coupling light- and ultrasonic-induced thermal effects in SPC system could enhance the synergy between light and ultrasound by modulating catalyst structure to achieve double optimization of thermodynamic and kinetic properties of SPC hydrogen evolution.

Dynamics and Structure Formation of Confined Polymer Thin Films Supported on Solid Substrates.

The stability/instability behavior of polystyrene (PS) films with tunable thickness ranging from higher as-cast to lower residual made on Si substrates with and without native oxide layer was studied in this paper. For further extraction of residual PS thin film (hresi) and to investigate the polymer-substrate interaction, Guiselin's method was used by decomposing the polymer thin films in different solvents. The solvents for removing loosely adsorbed chains and extracting the strongly adsorbed irreversible chains were selected based on their relative desorption energy difference with polymer. The PS thin films rinsed in chloroform with higher polarity than that of toluene showed a higher decrease in the residual film thickness but exhibited earlier growth of holes and dewetting in the film. The un-annealed samples with a higher oxide film thickness showed a higher decrease in the PS residual film thickness. The effective viscosity of PS thin films spin-coated on H-Si substrates increased because of more resistance to flow dynamics due to the stronger polymer-substrate interaction as compared to that of Si-SiOx substrates. By decreasing the film thickness, the overall effective mobility of the film increased and led to the decrease in the effective viscosity, with matching results of the film morphology from atomic force microscopy (AFM). The polymer film maintained low viscosity until a certain period of time, whereupon further annealing occurred, and the formation of holes in the film grew, which ultimately dewetted the film. The residual film decrement, growth of holes in the film, and dewetting of the polymer-confined thin film showed dependence on the effective viscosity, the strength of solvent used, and various involved interactions on the surface of substrates.

Micro-pin-finned Surfaces with Fractal Treelike Hydrophilic Networks for Flow Boiling Enhancement.

Due to its outstanding heat transfer performance, flow boiling has a wide range of applications in many fields, especially for cooling of electronic devices. Previous studies have shown that the liquid replenishment on the downstream of the heating surface is the critical restriction of the increase of the critical heat flux (CHF). In this work, we designed a series of heterogeneous surfaces with fractal treelike hydrophilic networks for flow boiling enhancement. The micro-pin-finned surface structures are expected to increase the CHF and reduce the superheat by its high wickability. Moreover, by virtue of the efficient transport capacity of treelike networks, the fractal hydrophilic paths are designed to serve as the liquid delivery channels for the liquid replenishment on the downstream of the heating surface. The heterogeneous surfaces improve the comprehensive boiling heat transfer performance, especially the CHF, which is 82.2% higher than that of the smooth surface and 5.4% higher than the surface homogeneously covered by the microstructure with twice of the extended surface area. This work provides reference for the design of heterogeneous surfaces with both smooth and structured parts to increase the flow boiling CHF to some extent.

Can Steam- and CO-Rich Streams Be Produced Sequentially in the Isothermal Chemical Looping Super-Dry Reforming Scheme?

Super-dry reforming of methane (CH4 + 3CO2 → 2H2O + 4CO) is a very promising route for CO2 utilization. To maximize the yield of CO, a water-gas shift reaction (CO + H2O → CO2 + H2) should be circumvented. Combination of dry reforming of methane, redox reactions (metal oxide is reduced by CO and H2 in one step and then oxidized by CO2 in the next step), and CO2 sorption in a fixed-bed reactor was proposed as a potential approach to suppress the water-gas shift reaction. It was demonstrated that this isothermal operation can produce two separate streams, one is rich in steam and the other in CO, in a redox cycle at 750 °C. However, both the thermodynamic analysis and experimental investigations suggest that steam- and CO-rich streams may not be produced sequentially in the redox mode at 750 °C.

Visible-Light Activation of Photocatalytic for Reduction of Nitrogen to Ammonia by Introducing Impurity Defect Levels into Nanocrystalline Diamond.

Nitrogen impurity has been introduced in diamond film to produce a nitrogen vacancy center (NV center) toward the solvated electron-initiated reduction of N2 to NH3 in liquids, giving rise to extend the wavelength region beyond the diamond's band. Scanning electron microscopy and X-ray diffraction demonstrate the formation of the nanocrystalline nitrogen-doped diamond with an average diameter of ten nanometers. Raman spectroscopy and PhotoLuminescence (PL) spectrum show characteristics of the NV0 and NV- charge states. Measurements of photocatalytic activity using supraband (λ < 225 nm) gap and sub-band gap (λ > 225 nm) excitation show the nitrogen-doped diamond significantly enhanced the ability to reduce N2 to NH3 compared to the polycrystalline diamond and single crystal diamond (SCD). Our results suggest an important process of internal photoemission, in which electrons are excited from negative charge states into conduction band edges, presenting remarkable photoinitiated electrons under ultraviolet and visible light. Other factors, including transitions between defect levels and processes of reaction, are also discussed. This approach can be especially advantageous to such as N2 and CO2 that bind only weakly to most surfaces and high energy conditions.

Interfacial Interaction Enhanced Rheological Behavior in PAM/CTAC/Salt Aqueous Solution-A Coarse-Grained Molecular Dynamics Study.

Interfacial interactions within a multi-phase polymer solution play critical roles in processing control and mass transportation in chemical engineering. However, the understandings of these roles remain unexplored due to the complexity of the system. In this study, we used an efficient analytical method-a nonequilibrium molecular dynamics (NEMD) simulation-to unveil the molecular interactions and rheology of a multiphase solution containing cetyltrimethyl ammonium chloride (CTAC), polyacrylamide (PAM), and sodium salicylate (NaSal). The associated macroscopic rheological characteristics and shear viscosity of the polymer/surfactant solution were investigated, where the computational results agreed well with the experimental data. The relation between the characteristic time and shear rate was consistent with the power law. By simulating the shear viscosity of the polymer/surfactant solution, we found that the phase transition of micelles within the mixture led to a non-monotonic increase in the viscosity of the mixed solution with the increase in concentration of CTAC or PAM. We expect this optimized molecular dynamic approach to advance the current understanding on chemical-physical interactions within polymer/surfactant mixtures at the molecular level and enable emerging engineering solutions.

T-Nb2O5 nanoparticle enabled pseudocapacitance with fast Li-ion intercalation.

Orthorhombic Nb2O5 (T-Nb2O5) nanocrystallites are successfully fabricated through an evaporation induced self-assembly (EISA) method guided by a commercialised triblock copolymer - Pluronic F127. We demonstrate a morphology transition of T-Nb2O5 from continuous porous nanofilms to monodisperse nanoparticles by changing the content of Pluronic F127. The electrochemical results show that the optimized monodisperse Nb-2 with a particle size of 20 nm achieves premier Li-ion intercalation kinetics and higher rate capability than mesoporous T-Nb2O5 nanofilms. Nb-2 presents an initial intercalation capacity of 528 and 451 C g-1 at current densities of 0.5 and 5 A g-1 and exhibited a stable capacity of 499 C g-1 after 300 charge/discharge cycles and 380 C g-1 after 1000 cycles, respectively. We would expect this copolymer guided monodispersion of T-Nb2O5 nanoparticles with high Li+ intercalation performance to open up a new window for novel EES technologies.

Anchoring Tailored Low-Index Faceted BiOBr Nanoplates onto TiO2 Nanorods to Enhance the Stability and Visible-Light-Driven Catalytic Activity.

In this work, a fantastic one-dimensional (1D) BiOBr/TiO2 nanorod (NR) heterojunction composite was rationally proposed and designed from the perspective of molecular and interface engineering. The fabricated intimately connected interfacial heterojunction between two-dimensional BiOBr nanoplates and 1D TiO2 NRs acts as an interfacial nanochannel to promote efficient interfacial charge migration and separation of photogenerated electron-hole pairs. As a result, 1D BiOBr/TiO2 NR heterojunctions exhibited outstanding visible-light photocatalytic activities and sustained cycling performance. Under visible-light irradiation for 120 min, the reduction efficiency of Cr(VI) over the TB-2 sample (molar ratio: n(Ti)/n(Bi) = 2:1) is as high as 95.4% without adding any scavengers. Furthermore, the sample also shows excellent photodegradation activity of RhB with a much higher apparent rate constant of 0.49 min-1 and 88.5% total organic carbon removal ratio. Furthermore, the corresponding mechanism of enhanced photocatalytic activity is proposed according to comprehensively investigated results from photoluminescence spectroscopy, photoelectrochemical measurement analysis, and radical trapping experiments. This study provides an attractive avenue to design and fabricate highly efficient 1D NR heterojunction photocatalysts, which possessed a high application value in the field of environmental remediation, especially for wastewater purification.