Bulk Phase Research Articles

The synergistic effect of Cl doping and Bi coupling to promote the carrier separation of BiOBr for efficient photocatalytic nitrogen reduction

Photocatalytic nitrogen reduction reaction (NRR) is a sustainable process for ammonia synthesis under mild conditions. However, photocatalytic NRR activity and are generally limited by inefficient carrier separation and transfer. Therefore, parallel engineering of bulk phase doping and surface coupling is critical to achieving the goal of efficient NRR. In this study, Cl doped BiOBr nanosheet assemblies (BiOBr/Cl) were constructed in delicately designed deep eutectic solvents (DESs), combined with ionothermal methods at low temperatures and Bi3+ exsolution reduction strategy at high temperatures. The unique liquid state and reducibility of DESs induce the reduction of Bi3+ and the in situ coupling of Bi quantum dots at the surface of BiOBr/Cl nanosheets along with the construction of Bi-BiOBr/Cl nanosheet assemblies. The experimental results show that Cl doping could reduce the exciton dissociation energy and promote its dissociation to free carriers. Bi quantum dots could form tightly coupled Schottky junction with BiOBr/Cl enabling the efficient and unidirectional transmission of photogenerated electrons from BiOBr/Cl to metal Bi. The formed electron deficient region at Schottky interface promotes the adsorption and activation of N2. The hierarchical structure of Bi-BiOBr/Cl nanosheet assembly benefits to providing more N2 adsorption active sites. The DFT calculation shows that the accumulation of high concentration of active hydrogen in Bi-BiOBr/Cl leads to a significant decrease of energy barrier of the first step hydrogenation of N2. Bi-BiOBr/Clis more inclined to adsorb nitrogen for NRR in comparison with H* for hydrogen production. The synergistic effect of Cl doping and Bi coupling result in a high NRR activity of Bi-BiOBr/Cl photocatalyst of 6.67 mmol·g−1·h−1, which was 11.3 times higher than that of initial BiOBr. This study provides a promising strategy for designing highly active NRR photocatalysts with high efficiency carrier dissociation and transport.

Charge separation at liquid interfaces

We present a theory for phase-separated liquid coacervates with salt, taking into account spatial heterogeneities and interfacial profiles. We find that charged layers of alternating sign can form around the interface while the bulk phases remain approximately charge neutral. We show that the salt concentration regulates the number of layers and the amplitude of the layer's charge density and electrostatic potential. Such charged layers can either repel or attract single-charged molecules diffusing across the interface. Our theory could be relevant for artificial systems and biomolecular condensates in cells. Our work suggests that interfaces of biomolecular condensates could mediate charge-specific transport similar to membrane-bound compartments. Published by the American Physical Society 2024

Study on the minimum miscibility pressure and phase behavior of CO2–shale oil in nanopores

In recent years, CO2 enhanced oil recovery has gained traction in shale oil reservoirs. Shale oil reservoirs are characterized by numerous nanopores, where shale oil exhibits unique phase behavior due to nano–confinement effects. Traditional theoretical model and microfluidic experiment often fail to accurately depict the minimum miscible pressure (MMP) of CO2–shale oil in nanopores. In this study, nanofluidic experiments were conducted to investigate the MMP of CO2–alkanes in single pore channels and porous media channels with depths of 30 nm and 100 nm. Additionally, a novel thermodynamic model of gas–liquid–adsorbed phase equilibrium, which considers the capillary force and the shift in the critical property, was developed by integrating simplified local density functional theory. The feasibility of the method was determined by comparing the measured MMP with the MMP obtained using the newly established thermodynamic model, resulting in errors of 10.804 % and 5.545 %. Finally, phase behavior and MMP for two typical oil samples in block A in China were conducted using the newly established thermodynamic model. The results revealed that as the pore radius decreases, the area of the two–phase region enclosed by the phase envelope contracts progressively. In addition, the saturation pressure decreases gradually for shale oil with a higher content of light components as the molar fraction of the injected CO2 increases, whereas for shale oil with higher heavy component content, it increases as the CO2 molar fraction increases. The MMP of CO2–shale oil in 10 nm pores is 70.188 bar at 392.75 K of sample 1 and 83.007 bar at 374.72 K of sample 2. Compared to the bulk phase, the MMP was reduced by 63.76 % and 57.64 %.

Superconductivity in TiZrNb and TiZrNbHf bulk equimolar alloys

We have prepared and investigated superconducting equimolar medium-entropy alloys of TiZrNb and TiZrNbHf. Their basic superconducting parameters, as the values of the critical temperature Tc, upper critical magnetic field Bc2 and the superconducting energy gap Δ have been studied with the use of magnetic susceptibility and point-contact Andreev reflection (PCAR) spectroscopy measurements. Although our samples have different critical temperatures, namely Tc ∼ 8.2 K for TiZrNb and Tc ∼ 6.3 K for TiZrNbHf, their zero-temperature critical magnetic field has the same value Bc2(0) = 12 T, from the vicinity of the Clogston limit. We have observed the presence of degraded phases on the surfaces of all the investigated samples using PCAR measurements. Still, we were able to show that the bulk phase in both systems exhibits BCS weakly coupled superconductivity with 2Δ(0)/kBTc ∼ 3.5.

Micro-encapsulated phase change material suspensions for heat and mass transfer: A thermo-physical characterization

Despite the growing popularity of phase change materials (PCM) and suspensions of micro-encapsulated phase change materials (mPCM) in both industrial and scientific applications, their properties characterization remains partial and mainly limited to thermal properties. The characterization of such suspension is a crucial aspect for comprehending their behavior and optimizing their performance. This paper is dedicated to a wide characterization of two suspensions containing micro-encapsulated phase change material. In pursuit of a thorough understanding, we also extend our characterization efforts to the bulk PCM encapsulated within the particles.Our primary focus is on determining the materials thermal properties such as latent heat and specific heat capacity using differential scanning calorimetry. Different cooling and heating rates have been employed in our measurements. Regarding our experiments, the bulk phase change material is predominantly identified as octadecane. Results obtained from calorimetry are then compared between the bulk PCM and the mPCM suspensions. By comparing the magnitudes of latent heat obtained for suspensions with the bulk material, we can accurately determine the mass fraction of PCM within each suspension. Noteworthy, during the solidification process an additional latent heat peak is observed only for the encapsulated PCM.The density of the materials is also measured. The phase change of PCM included in the capsules can be observed in densimetry: within the studied temperature range (283.15–306.15 K), the most significant density variations occur during intervals associated with phase change transitions. In ranges where the PCM, included in the capsules, is in a single-phase state (solid/liquid), we provide linear laws that account for density variations with temperature.Finally, our characterization work focuses on the rheological properties of the materials. While the bulk PCM in liquid phase exhibits a Newtonian viscosity, mPCM suspensions present a non-Newtonian viscosity. Both shear-thinning and shear-thickening behaviors are observed depending on the suspension particle volume fraction ϕ of mPCM. This paper concludes with a full comparison of our characterization results with models and correlations proposed in the literature.

Extraordinary phase transition revealed in a van der Waals antiferromagnet

While the surface-bulk correspondence has been ubiquitously shown in topological phases, the relationship between surface and bulk in Landau-like phases is much less explored. Theoretical investigations since 1970s for semi-infinite systems have predicted the possibility of the surface order emerging at a higher temperature than the bulk, clearly illustrating a counterintuitive situation and greatly enriching phase transitions. But experimental realizations of this prediction remain missing. Here, we demonstrate the higher-temperature surface and lower-temperature bulk phase transitions in CrSBr, a van der Waals (vdW) layered antiferromagnet. We leverage the surface sensitivity of electric dipole second harmonic generation (SHG) to resolve surface magnetism, the bulk nature of electric quadrupole SHG to probe bulk spin correlations, and their interference to capture the two magnetic domain states. Our density functional theory calculations show the suppression of ferromagnetic-antiferromagnetic competition at the surface is responsible for this enhanced surface magnetism. Our results not only show counterintuitive, richer phase transitions in vdW magnets, but also provide viable ways to enhance magnetism in their 2D form.

Nickel nanocatalyst on lanthanum aluminate: Optimizing preparation and evaluating performance in glycerol dry reforming for syngas production

In this study, mesoporous nanocrystalline Ni/La-Al catalysts with varying nickel (Ni) loadings (5, 10, 15, and 20 wt.%) were synthesized using a solid-state method for the glycerol dry reforming (GDR) reaction. The effects of different Ni loadings and the addition of steam on the structural and catalytic performance of the catalysts were investigated. Characterization techniques, including Brunauer-Emmett-Teller (BET) surface area analysis, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), and X-ray diffraction (XRD) were employed to analyze the catalysts' properties. Results showed that increasing Ni loading to 10 wt.% improves the catalytic properties. However, by increasing the Ni loading, a decrease in catalytic properties due to increasing particle size, creating NiO bulk phase and surface pore blockage is obvious. A series of experiments were performed to investigate the effect of steam usage on catalytic properties. TPO analysis revealed that steam addition reduces the carbon deposition and shifts oxidation peaks to lower temperatures; consequently, the activity and stability of the catalyst will be enhanced. Although the 5 - 7.5 vol.% of steam in the feed composition significantly stabilizes the catalyst, it is possible to produce H2-rich synthesis gas, and conversely, increasing the temperature reduces the H2/CO ratio. Various examinations were conducted under different conditions, including varying gas hourly space velocity (GHSV), carbon-to-glycerol ratio (CGR), and temperature, to obtain more comprehensive data on the catalysts.

Harvesting nucleating structures in nanoparticle crystallization: The example of gold, silver, and iron.

The thermodynamics and kinetics of nanoparticle crystallization, as opposed to bulk phases, may be influenced by surface and size effects. We investigate the importance of such factors in the crystallization process of gold, silver, and iron nanodroplets using numerical simulations in the form of molecular dynamics combined with path sampling. This modeling strategy is targeted at obtaining representative ensembles of structures located at the transition state of the crystallization process. A structural analysis of the transition state ensembles reveals that both the average size and location of the critical nucleation cluster are influenced by surface and nanoscale size effects. Furthermore, we also show that transition state structures in smaller nanodroplets exhibit a more ordered liquid phase, and differentiating between a well-ordered critical cluster and its surrounding disordered liquid phase becomes less evident. All in all, these findings demonstrate that crystallization mechanisms in nanoparticles go beyond the assumptions of classical nucleation theory.

Multifunctional surface modification to enhance the electrochemical performance of lithium-rich manganese-based cathode materials

The preparation of high-performance lithium-rich manganese-based cathode materials (LLOs) require attention to the redox of anions and the migration of transition metals (TM) during the cycling process. In this study, Ce ion-doped Li-rich cathode coated with La0.2Ce0.8O2, which has abundant oxygen vacancies on its surface, was prepared. The presence of the oxygen storage material La0.2Ce0.8O2 can effectively absorb the irreversible oxygen generated during cycling, preventing it from reacting with the electrolyte to form thick cathode electrolyte interface (CEI) coatings. These coatings hinder the relative activity of lattice oxygen in the bulk phase, reducing the specific capacity of the material. Additionally, the 5d metal ion Ce carries a large nuclear charge, causing a 'pinning effect' when it integrates into the LLOs structure. This effect reduces thermal oscillation in the lattice, impedes TM migration during battery charging and discharging, and effectively prevents voltage decay. Results indicate that after 100 cycles at 1C and 25 °C, the surface-coated materials maintain a discharge-specific capacity of 194 mAh/g, compared to 158 mAh/g for uncoated material. Voltage decay decreased from 4.4 mV/cycle to 1.8 mV/cycle, with an ICE of 91.5 % versus the original material's 82.8 %. The modified material also exhibits improved rate performance, retaining a specific capacity of 162 mAh/g at 3C, in contrast to the original material's 123 mAh/g.

Thiocarbonyl Pseudohalides - The Curious Case of Thiocarbonyl Dithiocyanate.

Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn-anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X-ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kinetic reaction products by a lower transition states opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof-of-principle study we show that it in turn can be used for the complexation of nickel to yield (4).

Magnetism of Otherwise Nonmagnetic Elements: From Clusters to Monolayers.

Atomic clusters are known to exhibit properties different from their bulk phase. However, when assembled or supported on substrates, clusters often lose their uniqueness. For example, uranium and coinage metals (Cu, Ag, Au) are nonmagnetic in their bulk. Herein, we show that UX6 (X= Cu, Ag, Au) clusters, unlike their nonmagnetic bulk, are not only magnetic but also retain their magnetic character and structure when assembled into a two-dimensional (2D) material. The magnetic moment remains localized at the U site and is found to be 3μB in clusters and about 2μB in the 2D structure. In 2D UX4 (X = Cu, Ag, Au) monolayers, U atoms are found to be coupled antiferromagnetically through an indirect exchange coupling mediated by the coinage metal atoms. Furthermore, hydrogenation of these monolayers can induce a transition from the antiferromagnetic to the ferromagnetic phase. These results, based on density functional theory, have predictive capability and can motivate experiments.

First-principles predictions of HfO2-based ferroelectric superlattices

The metastable nature of the ferroelectric phase of HfO2 is a significant impediment to its industrial application as a functional ferroelectric material. In fact, no polar phases exist in the bulk phase diagram of HfO2, which shows a dominant non-polar monoclinic ground state. As a consequence, ferroelectric orthorhombic HfO2 is stabilized either kinetically or via epitaxial strain. Here, we propose an alternative approach, demonstrating the feasibility of thermodynamically stabilizing polar HfO2 in superlattices with other simple oxides. Using the composition and stacking direction of the superlattice as design parameters, we obtain heterostructures that can be fully polar, fully antipolar or mixed, with improved thermodynamic stability compared to the orthorhombic polar HfO2 in bulk form. Our results suggest that combining HfO2 with an oxide that does not have a monoclinic ground state generally drives the superlattice away from this non-polar phase, favoring the stability of the ferroelectric structures that minimize the elastic and electrostatic penalties. As such, these diverse and tunable superlattices hold promise for various applications in thin-film ferroelectric devices

Influence of the temperature-induced ordered-disordered phases for iron difluoride on the electrochemical performance

Iron difluoride (FeF2) is one of the promising cathodes to achieve high energy-density lithium-ion batteries (LIBs). However, the sluggish ion transportation kinetics in the FeF2 bulk phase may cause large voltage hysteresis and lower cell efficiency, which hinders its commercial adoption. Introducing a disordered phase into the ordered bulk FeF2 is proposed to promote ion transportation and increase ion diffusion channels. Here, varying ratios of the disordered phase are incorporated into the ordered matrix of FeF2 by adjusting the annealed temperatures. The ion transportation is improved due to the optimal ratio of the disordered to ordered (RDO) phase. Among four electrodes, the RDO25% electrode demonstrates the least electrochemical polarization of 1.22 V and the lowest voltage hysteresis of about 1.0 V, in addition to delivering a discharge capacity of 128 mAh g−1 after 100 cycles in the carbonate-type electrolyte. The introduction of the disordered phase enables FeF2 to exhibit a distinct intercalation and conversion dual-mechanism cathode. Additionally, appropriate ratios of the disordered-ordered phase can mitigate nanoparticle agglomeration, establish a conformal cathode electrolyte interface (CEI), reduce interfacial resistance, and thereby enhance ion transport.

Impact of Nuclear Quantum Effects on the Structural Properties of Protonated Water Clusters.

Nuclear quantum effects (NQEs) play a crucial role in hydrogen-bonded systems due to quantum tunneling and proton fluctuation. Our understanding of how NQEs affect microstructures mainly focuses on bulk phases of liquids and solids but remains deficient for water clusters, including their hydrogen nuclei, hydrogen-bonded configurations, and temperature dependence. Here, we conducted ab initio molecular dynamics (MD) and path integral MD simulations to investigate the influence of NQEs on the structural properties of protonated water clusters H+(H2O)n (n = 3, 6, 9, 12). The results reveal that the NQEs become less evident as the cluster size increases due to the competition between NQEs and electrostatic interactions. Simulations of several H+(H2O)6 isomers at different temperatures indicate that the effect of elevated temperature on proton transfer is related to the initial structure. Interestingly, the process of proton transfer also involves the interconversion between Zundel-type and Eigen-type isomers. These findings significantly deepen our understanding of ion-water and water-water interactions, opening new avenues for the study of hydrated ion clusters and related systems.

Comparison between acetonitrile-water separation by betaine and betaine hydrochloride

Acetonitrile and water are miscible solvents. This study compares their separation by betaine and betaine hydrochloride. Acetonitrile is a hydrogen (H) bond acceptor and so is betaine, because of its -CO and -CO- groups. Therefore, betaine competes with acetonitrile for interactions with the hydrogens of water molecules, as indicated by attenuated total reflectance - Fourier transform infrared spectroscopy (ATR-FTIR). Therefore, when added to acetonitrile-water mixtures, betaine displaces acetonitrile. Separation into bulk phases occurs with 5–10 wt% betaine (relative to water), for acetonitrile concentrations between 50 and 80 wt% (relative to the aqueous phase). At lower acetonitrile concentrations (e.g., 1 wt%), betaine separates acetonitrile from water to yield emulsified acetonitrile droplets, detected by light scattering. With 1 wt% acetonitrile and betaine, acetonitrile droplets in water are negatively charged due to the -CO- group of betaine, as shown by electrophoretic measurements. In the case of betaine hydrochloride, the negative charge of the -CO- group is shielded by a proton, and interactions with water are weaker. As a result, bulk separation is not observed. Nonetheless, betaine hydrochloride also competes against acetonitrile for interactions with hydrogen atoms of water molecules, albeit not as effectively as betaine. This is shown by ATR-FTIR. Therefore, betaine hydrochloride emulsifies acetonitrile in water into sub-micron droplets. These droplets are positively charged, owing to the positively charged nitrogen atom of betaine hydrochloride. Acidifying mixtures of betaine, acetonitrile and water (with HCl) impedes bulk separation. This result confirms the importance of electrostatic interactions between the hydrogens of water and the unshielded, negative -CO- group of betaine.

Chitosan nanocoatings N-acylated with decanoic anhydride: Hydrophobic, hygroscopic and structural properties

Thin (ca. 340 nm) chitosan coatings were deposited onto glass substrates via dip-coating, then modified with the methanol solution of decanoic anhydride (0.17–56 mM). NMR, FTIR and XPS measurements confirmed that the acylation degree increased from 18 % to 45 %, and at the highest degree, the whole layer was acylated homogeneously by the reagent molecules. The coating thickness increased (up to 60 %), and the refractive index decreased (from 1.541 to 1.532) due to the acylation, that was determined by UV–visible spectroscopy. The AFM did not reveal morphological changes, but wetting tests showed that the acylation rendered the coating hydrophobic (water contact angle increased from ca. 75° to 100°). The contact angle, however, decreased to 85° due to the development of a second molecular layer of the decanoic acid by-product at the highest (over 25 mM) reagent concentrations. XRD studies showed a self-assembling structuring of the alkyl-chains in the bulk phase, which occurred in the case of the highest degree of acylation. This also manifested itself in a significant decrease of the layer hygroscopicity: the swelling degree decreased from 40 % to 8 % in a saturated water atmosphere monitored by spectroscopic ellipsometry.

Thermal effects of organic porous media on absorption and desorption behaviors of carbon dioxide

As a result of global warming, people are increasingly concerned about greenhouse gas emissions, particularly carbon dioxide (CO2). Many countries have been promoting carbon capture, storage (CCS) projects in order to alleviate climate degradation and achieve net zero carbon emissions. To study the thermal effects of organic porous media on CO2 absorption and desorption, molecular dynamics coupled with Monte Carlo (MDMC) were used in this study. A part of the CO2 molecules will be trapped within kerogen matrix due to its complex porous structure. The affinity of kerogen to CO2 facilitates CO2′s adsorption within the kerogen porous media, resulting in a heterogeneous distribution of CO2. The kerogen forms high potential energy peaks and low potential energy wells in the matrix, which provide preferred adsorption sites for CO2 in the porous space. The low stress state of CO2 also indicates that it prefers adsorption in the matrix as CO2 performs a lower potential energy state in the kerogen matrix than in the bulk phase. This study examines different thermal effects of kerogen, and results indicate that increasing CO2 thermal motion facilitates its absorption, while a high temperature matrix promotes CO2 desorption. Adsorbed layer provides resistance for CO2′s diffusion behaviors. The free energy of CO2′s diffusion is analyzed in relation to its mechanism, revealing that irregular thermal motion causes uncertainty in the adsorption capacity.

Determining interfacial tension and critical micelle concentrations of surfactants from atomistic molecular simulations

HypothesisAtomistically-detailed models of surfactants provide quantitative information on the molecular interactions and spatial distributions at fluid interfaces. Hence, it should be possible to extract from this information, macroscopical thermophysical properties such as interfacial tension, critical micelle concentrations and the relationship between these properties and the bulk fluid surfactant concentrations.Simulations and ExperimentsMolecular-scale interfacial of systems containing n-dodecyl β-glucoside (APG12) are simulated using classical molecular dynamics. The bulk phases and the corresponding interfacial regions are all explicitly detailed using an all-atom force field (PCFF+). During the simulation, the behaviour of the interface is analyzed geometrically to obtain an approximated value of the critical micelle concentration (CMC) in terms of the surfactant area number density and the interfacial tension is assessed through the analysis of the forces amongst molecules.New experimental determinations are reported for the surface tension of APG12 at the water/air and at the water/n-decane interfaces.FindingsWe showcase the application of a thermodynamic framework that inter-relates interfacial tensions, surface densities, CMCs and bulk surfactant concentrations, which allows the in silico quantitative prediction of interfacial tension isotherms.

Evaluating The Thickness Of A Cyclopentane Hydrate Film Over A Sessile Water Drop Using PLIF And PIV

The accumulation of hydrates presents an important flow-assurance challenge. Herein, we performed an experimental study to quantify the thickness of a hydrate layer growing laterally along the interface of a water drop submerged in the bulk phase of cyclopentane at sub-zero temperatures. Spatially-resolved velocity and temperature measurements in both liquid phases were taken independently using particle image velocimetry, one- or two-color planar laser-induced fluorescence. We found that the appearance of hydrates leads to a displacement of the temperature maximum away from the phase boundary, which is typically observed very close to the interface due to the recirculating motion of water inside the drop. Making an assumption that, when hydrates are absent, this recirculating motion is retained in time and the maximum position is, thus, unchanged, we conclude that this shift should indicate the hydrate layer should mostly protrude into the drop, and its thickness was evaluated to be around 0.38 mm.

Single-Dye Multispectral PLIF (SDMS-PLIF) For Quantitative Thermographic Visualisation Of Nucleate Boiling

The boiling of dielectric fluids in miniaturised channels has emerged as one of the most promising solutions to high- density electronics cooling. Although significant breakthroughs have been made, a fundamental understanding of the hydrodynamic and thermal performance in relevant flows is still lacking, which calls for further development of state-of-the-art measurement techniques and their deployment for the provision of high-quality, detailed experimental information. To this end, we conducted an experimental investigation of flow boiling in a miniaturised vertical square channel with a hydraulic diameter of 5 mm, using HFE-7100 as the working fluid. A whole-field thermographic imaging approach referred to as single-dye multispectral planar laser-induced fluorescence (SDMS-PLIF) was developed and applied to measure spatiotemporally-resolved temperature fields. For its implementation, Nile Red, a thermosensitive lipophilic dye, was dissolved in HFE-7100 as a fluorophore. The measurements were taken at selected conditions to achieve a nucleate boiling regime in a laminar flow. Time-lapse temperature maps provided direct evidence for bubble-induced mixing observed as thermal plumes, where a portion of hot fluid is advected above the thermal boundary layer at the heated wall and penetrates the colder bulk phase in the flow core.