Air invasion into three-dimensional foam induces viscous fingering instabilities.

We conducted an experimental investigation to examine the immiscible radial displacement flows of air invading three-dimensional foam in a Hele-Shaw cell. Our study successfully identified three distinct flow regimes. In the initial regime, characterized by relatively low fingertip velocities, the foam underwent a slow displacement through plug flow. During this process, the three-phase contact lines slipped at the cell walls. Notably, we discovered that the air injection pressure exhibited a proportional relationship with the power of the fingertip velocity. This relationship demonstrated excellent agreement with a power law, where the exponent was determined to be 2/3. Transitioning to the second regime, we observed relatively high velocities, resulting in the displacement of the foam as a plug within single layers of foam bubbles. The movement of these bubbles near the cell walls was notably slower. Similar to the first regime, the behavior in this regime also adhered to a power law. In the third regime, which manifested at higher air injection pressures, the development of air fingers occurred through narrow channels. These channels had the potential to isolate the air fingers as they underwent a process of "healing." Furthermore, our results unveiled a significant finding that the width of the air fingers exhibited a continuous scaling with the air injection pressure, irrespective of the flow regimes being observed.

Investigation of enhanced geothermal system in the Basal Cambrian Sandstone Unit, Alberta, Canada.

Given the climate challenge, society is seeking low greenhouse gas emission energy sources. In jurisdictions such as Alberta, Canada where power is largely generated through the combustion of natural gas, geothermal offers a compelling option but it remains unclear as to its economic and technical viability. Here, we examine the potential for an enhanced geothermal system in the Basal Cambrian Sandstone Unit in Alberta, Canada. Prior to geothermal operation, hydraulic fracturing is conducted to enhance the permeability of the thermal reservoir. This lowers the pressure drop required for circulating fluids through the system. The results show that the open-loop enhanced geothermal system realizes an energy produced to energy invested ratio from 4 to 9 depending on different operating rate. The results also suggest that applying hydraulic fracturing can accelerate energy harvesting and energy efficiency over the early stages of the process but the greater the injection rate, the smaller is this benefit of hydraulic fracturing stimulation.

Why copper catalyzes electrochemical reduction of nitrate to ammonia.

Electrochemical reduction of nitrate (NO3RR) has drawn significant attention in the scientific community as an attractive route for ammonia synthesis as well as alleviating environmental concerns for nitrate pollution. To improve the efficiency of this process, the development of catalyst materials that exhibit high activity and selectivity is of paramount importance. Copper and copper-based catalysts have been widely investigated as potential catalyst materials for this reaction both computationally and experimentally. However, less attention has been paid to understanding the reasons behind such high activity and selectivity. Herein, we use Density Functional Theory (DFT) to identify reactivity descriptors guiding the identification of active catalysts for the NO3RR, establish trends in activity, and explain why copper is the most active and selective transition metal for the NO3RR to ammonia among ten different transition metals, namely Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Ru, and Co. Furthermore, we assess NO3RR selectivity by taking into account the competition between the NO3RR and the hydrogen evolution reaction. Finally, we propose various approaches for developing highly active catalyst materials for the NO3RR.

A descriptor for the structural stability of organic-inorganic hybrid perovskites based on binding mechanism in electronic structure.

The poor stability of organic-inorganic hybrid perovskites hinders its commercial application, which motivates a need for greater theoretical insight into its binding mechanism. To date, the binding mode of organic cation and anion inside organic-inorganic hybrid perovskites is still unclear and even contradictory. Therefore, in this work based on density functional theory (DFT), the binding mechanism between organic cation and anion was systematically investigated through electronic structure analysis including an examination of the electronic localization function (ELF), electron density difference (EDD), reduced density gradient (RDG), and energy decomposition analysis (EDA). The binding strength is mainly determined by Coulomb effect and orbital polarization. Based on the above analysis, a novel 2D linear regression descriptor that Eb = - 9.75Q2/R0 + 0.00053 V∙EHL - 6.11 with coefficient of determination R2 = 0.88 was proposed to evaluate the binding strength (the units for Q, R0, V, and EHL are |e|, Å, bohr3, and eV, respectively), revealing that larger Coulomb effect (Q2/R0), smaller volume of perovskite (V), and narrower energy difference (EHL) between the lowest unoccupied molecular orbital (LUMO) of organic cation and the highest occupied molecular orbital (HOMO) of anion correspond to the stronger binding strength, which guides the design of highly stable organic-inorganic hybrid perovskites.

Bitumen and asphaltene derived nanoporous carbon and nickel oxide/carbon composites for supercapacitor electrodes.

Asphaltenes from bitumen are abundant resource to be transformed into carbon as promising supercapacitor electrodes, while there is a lack of understanding the impact from different fractions of bitumen and asphaltenes, as well as the presence of transition metals. Here, nanoporous carbon was synthesized from bitumen, hexane-insoluble asphaltenes and N,N-dimethylformamide (DMF)-fractionated asphaltenes by using Mg(OH)2 nanoplates as the template with in-situ KOH activation, and used as an supercapacitor electrode material. All of the carbon exhibited large surface area (1500-2200 m2 g-1) with a distribution of micro and mesopores except for that derived from the DMF-soluble asphaltenes. The pyrolysis of asphaltenes resulted in the formation of nickel oxide/carbon composite (NiO/C), which demonstrated high capacitance of 380 F g-1 at 1 A g-1 discharge current resulting from the pseudocapacitance of NiO and the electrochemical double layer capacitance of the carbon. The NiO/C composite obtained from the DMF-insoluble portion had low NiO content which led to lower capacitance. Meanwhile, the specific capacitance of NiO/C composite from the DMF-soluble part was lower than the unfractionated asphaltene due to the higher NiO content resulting in lower conductivity. Therefore asphaltenes derived from nickel-rich crude bitumen is suitable for the synthesis of nanoporous NiO/C composite material with high capacitance.

A Sulfur-Tolerant MOF-Based Single-Atom Fe Catalyst for Efficient Oxidation of NO and Hg0.

Catalytic oxidation of NO and Hg0 is a crucial step to eliminate multiple pollutants from emissions from coal-fired power plants. However, traditional catalysts exhibit low catalytic activity and poor sulfur resistance due to low activation ability and poor adsorption selectivity. Herein, a single-atom Fe decorated N-doped carbon catalyst (Fe1 -N4 -C), with abundant Fe1 -N4 sites, based on a Fe-doped metal-organic framework is developed to oxidize NO and Hg0 . The results demonstrate that the Fe1 -N4 -C has ultrahigh catalytic activity for oxidizing NO and Hg0 at low and room temperature. More importantly, Fe1 -N4 -C exhibits robust sulfur resistance as it preferably adsorbs reactants over sulfur oxides, which has never been achieved before with traditional catalysts. Furthermore, SO2 boosts the catalytic oxidation of NO over Fe1 -N4 -C through accelerating the circulation of active sites. Density functional theory calculations reveal that the Fe1 -N4 active sites result in a low energy barrier and high adsorption selectivity, providing detailed molecular-level understanding for its excellent catalytic performance. This is the first report on NO and Hg0 oxidation over single-atom catalysts with strong sulfur tolerance. The outcomes demonstrate that single-atom catalysts are promising candidates for catalytic oxidation of NO and Hg0 enabling cleaner coal-fired power plant operations.

Exploring the Effects of Ionic Defects on the Stability of CsPbI3 with a Deep Learning Potential.

Inorganic metal halide perovskites, such as CsPbI3 , have recently drawn extensive attention due to their excellent optical properties and high photoelectric efficiencies. However, the structural instability originating from inherent ionic defects leads to a sharp drop in the photoelectric efficiency, which significantly limits their applications in solar cells. The instability induced by ionic defects remains unresolved due to its complicated reaction process. Herein, to explore the effects of ionic defects on stability, we develop a deep learning potential for a CsPbI3 ternary system based upon density functional theory (DFT) calculated data for large-scale molecular dynamics (MD) simulations. By exploring 2.4 million configurations, of which 7,730 structures are used for the training set, the deep learning potential shows an accuracy approaching DFT-level. Furthermore, MD simulations with a 5,000-atom system and a one nanosecond timeframe are performed to explore the effects of bulk and surface defects on the stability of CsPbI3 . This deep learning potential based MD simulation provides solid evidence together with the derived radial distribution functions, simulated diffraction of X-rays, instability temperature, molecular trajectory, and coordination number for revealing the instability mechanism of CsPbI3 . Among bulk defects, Cs defects have the most significant influence on the stability of CsPbI3 with a defect tolerance concentration of 0.32 %, followed by Pb and I defects. With regards to surface defects, Cs defects have the largest impact on the stability of CsPbI3 when the defect concentration is less than 15 %, whereas Pb defects act play a dominant role for defect concentrations exceeding 20 %. Most importantly, this machine-learning-based MD simulation strategy provides a new avenue to explore the ionic defect effects on the stability of perovskite-like materials, laying a theoretical foundation for the design of stable perovskite materials.

High throughput screening of promising lead-free inorganic halide double perovskites via first-principles calculations.

Perovskite solar cells (PSCs) have been intensively investigated and made great progress due to their high photoelectric conversion efficiency and low production cost. However, poor stability and the toxicity of Pb limit their commercial applications. It is particularly important to search for new non-toxic, high-stability perovskite materials. In this study, 760 Cs2B2+B'2+X6 (X = F, Cl, Br, I) inorganic halide double perovskites are screened based on high-throughput first-principles calculations to obtain an ideal perovskite material. The band gaps of this type of double perovskite are mainly determined by the elements X and B2+, decreasing monotonously with the increase in the atomic number of X (from F to I). We obtain 14 optimal and unreported materials with suitable band gaps as potential alternative materials for Pb-based photovoltaic absorbers in PSCs. This theoretical investigation can provide theoretical guidance for developing novel lead-free PSC materials.

A novel Fe-Co double-atom catalyst with high low-temperature activity and strong water-resistant for O3 decomposition: A theoretical exploration.

Developing catalysts with high activity, durability, and water resistance for ozone decomposition is crucial to regulate the pollution of ozone in the troposphere, especially in indoor air. To overcome the shortcomings of metal oxide catalysts with respect to their durability and water resistance, Fe-Co double-atom catalyst (DAC) is proposed as a novel catalyst for ozone decomposition. Here, through a systematic study using density functional theory (DFT) calculations and microkinetic modeling, the adsorption and catalytic decomposition of O3 on Fe-Co DAC have been examined based on adsorption configuration, orbital hybridization, and electron transfer. Based on Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) reaction mechanisms, the mechanisms of ozone decomposition on Fe-Co DAC were explored by analyzing reaction paths and energy variations. To confirm the water-resistant of Fe-Co DAC, competitive adsorption behavior between O3 and dominant environmental gases was discussed through ab initio molecular dynamic (AIMD) simulation. The dominant reaction mechanism of ozone decomposition is L-H and the rate-determining step is the desorption of the first oxygen molecule from the surface of Fe-Co DAC which has an energy barrier of 0.78 eV. Due to this relatively low energy barrier and high turnover frequency (TOF), the optimal operation window of catalytic O3 decomposition on Fe-Co DAC is <500 K suggesting that catalytic decomposition of O3 on Fe-Co DAC can occur at room temperature. This theoretical study provides new insights for designing novel catalysts for ozone decomposition and fundamental guidance for subsequent experimental research.

Methane activation on dual-atom catalysts supported on graphene.

Dual-atom Fe catalysts supported by three nitrogen atom doped graphene (Fe-TM/GP, where TM = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) are explored for methane adsorption and activation. The addition of the second metal significantly tunes the properties of the catalysts. The main factor influencing methane adsorption is electron transfer. The second metal promotes methane adsorption by altering the electronic properties such as the band structure and charge transfer. A volcano-shaped relationship is found between the absolute value of adsorption energy and energy barrier at the heteroatom Fe-TM/GP. Fe-Ni/GP has the lowest energy barrier. Heteroatom Fe-TM/GP has a lower energy barrier than Fe-Fe/GP.

Ultrastretchable, Adhesive, and Antibacterial Hydrogel with Robust Spinnability for Manufacturing Strong Hydrogel Micro/Nanofibers.

The ultrastretchable (over 12 400%) hydrogel with long-lasting adhesion, strong antibacterial activity, and robust spinnability is developed based on the oxidative decarboxylation and quinone-catechol reversible redox reaction induced by Ag-lignin nanoparticles in a precursor solution containing citric acid (CA), acrylic acid (AA), and poly (acrylamide-co-acrylic acid) (P(AAm-co-AA)). With massive reversible interactions including hydrogen bonds and electrostatic forces, such hydrogel exhibits promising injectability and is facilely spun via manual drawing, draw-spinning, and electrospinning for manufacturing strong hydrogel micro/nanofibers. The resulting fibers exhibit excellent mechanical properties, including tensile stress of 422.0 MPa, strain of 86.5%, Young's modulus of 8.7 GPa, and toughness of 281.6 MJ m-3 . The hydrogel microfibers obtained from a house-built spinner are scaled-up fabricated while retaining promising mechanical properties, as evidenced by lifting a load (317.2 g) using the spun fibers of ≈33 000 times lighter weight (9.5 mg), indicating their great potentials in the applications such as net and safety cord which require robust mechanical properties. Moreover, assisted by a commercial electrospinning machine, nanosized hydrogel fibers are facilely spun on personal protective equipment such as a mask to offer an antiseptic coating with near 100% killing efficiency against airborne bacteria aerosols, demonstrating the capability of spun hydrogel fibers on disinfection-related applications.

A Facile Strategy to Prepare Small Water Clusters via Interacting with Functional Molecules.

Although small water clusters (SWCs) are important in many research fields, efficient methods of preparing SWCs are still rarely reported, which is mainly due to the lack of related materials and understanding of the molecular interaction mechanisms. In this study, a series of functional molecules were added in water to obtain small water cluster systems. The decreasing rate of the half-peak width in a sodium dodecyl sulfate (SDS)-water system reaches ≈20% at 0.05 mM from 17O nuclear magnetic resonance (NMR) results. Based on density functional theory (DFT) and molecular dynamics (MD) simulation calculation, it can be concluded that functional molecules with stronger negative electrostatic potential (ESP) and higher hydrophilicity have a stronger ability to destroy big water clusters. Notably, the concentrations of our selected molecule systems are one to two magnitudes lower than that of previous reports. This study provides a promising way to optimize aqueous systems in various fields such as oilfield development, protein stability, and metal anti-corrosion.

Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst.

Electrochemically converting nitrate, a widespread water pollutant, back to valuable ammonia is a green and delocalized route for ammonia synthesis, and can be an appealing and supplementary alternative to the Haber-Bosch process. However, as there are other nitrate reduction pathways present, selectively guiding the reaction pathway towards ammonia is currently challenged by the lack of efficient catalysts. Here we report a selective and active nitrate reduction to ammonia on Fe single atom catalyst, with a maximal ammonia Faradaic efficiency of ~ 75% and a yield rate of up to ~ 20,000 µg h-1 mgcat.-1 (0.46 mmol h-1 cm-2). Our Fe single atom catalyst can effectively prevent the N-N coupling step required for N2 due to the lack of neighboring metal sites, promoting ammonia product selectivity. Density functional theory calculations reveal the reaction mechanisms and the potential limiting steps for nitrate reduction on atomically dispersed Fe sites.

Dual Stimuli-Responsive Pickering Emulsions from Novel Magnetic Hydroxyapatite Nanoparticles and Their Characterization Using a Microfluidic Platform.

Stimuli-responsive emulsifiers have emerged as a class of smart agents that can permit regulated stabilization and destabilization of emulsions, which is essential for food, cosmetic, pharmaceutical, and petroleum industries. Here, we report the synthesis of novel "smart" hydroxyapatite (HaP) magnetic nanoparticles and their corresponding stimuli-responsive Pickering emulsions and explore their movement under confined spaces using a microfluidic platform. Pickering emulsions prepared with our magnetic stearic acid-functionalized Fe2O3@HaP nanoparticles exhibited pronounced pH-responsive behavior. We observed that the diameter of emulsion droplets decreases with an increase in pH. Swift demulsification was achieved by lowering the pH, whereas the reformation of emulsions was achieved by increasing the pH; this emulsification-demulsification cycling was successful for at least ten cycles. We used a microfluidic platform to test the stability of the emulsions under flowing conditions and their response to a magnetic field. We observed that the emulsion stability was diminished and droplet coalescence was enhanced by the application of the magnetic field. The smart nanoparticles we developed and their HaP-based emulsions present promising materials for pharmaceutical and petroleum industries, where responsive emulsions with controlled stabilities are required.

Lipase-Immobilized Cellulosic Capsules with Water Absorbency for Enhanced Pickering Interfacial Biocatalysis.

Lipase-immobilized cellulosic capsules consisting of hydrophobic ethyl cellulose (EC) and hydrophilic carboxymethyl cellulose (CMC) were developed with a promising interfacial activity and water absorbency for the enhanced Pickering interfacial biocatalysis. Lipase was physically immobilized with water-absorbent materials (CMC) via hydrogen bonding and electrostatic interactions and acted as the interior catalytic core of the capsule. The interfacially active EC worked as the exterior shell, enabling capsules to stabilize the oil-in-water Pickering emulsion for the subsequent Pickering interfacial catalysis. The capsules with CMC created interior water-rich conditions to improve the conformational and enzymatic activity of the immobilized lipase. Compared with capsules without water-absorbent materials, the capsules with CMC enhanced the efficiency of the Pickering interfacial catalysis for the esterification of oleic acid and 1-octanol by 12%. Immobilized with a small amount of lipase (0.0625 g/g), the cellulosic capsules with water absorbency could convert 50.8% of the reactants after 10 h under room temperature, significantly higher than that by the same amount of free lipase in the biphasic system (15%) and a Pickering emulsion (24.1%) stabilized by empty capsules (without lipase). Moreover, the cellulosic capsules could be recycled by simple centrifugation while retaining their high relative catalytic activity for at least eight cycles, demonstrating their sustainable catalytic performance.

Apparent Contact Angle around the Periphery of a Liquid Drop on Roughened Surfaces.

The wetting of roughened surfaces is complicated since not all of the surface of the irregular surface is wetted and thus, the three-phase contact line for the liquid drop is a complex, three-dimensional line that varies according to the dimensions of the roughness and its spatial heterogeneity. This can cause the contact line to not sit within a constant height horizontal plane especially when air is trapped underneath the liquid layer. Here, we explore the effect of roughness on the effective contact angle of a water droplet on a roughened hydrophobic surface. The results show that the apparent contact angle varies around the periphery of the droplet due to the roughness of the surface on first contact. Also, repeated wetting of the droplet on the surface reveals that the apparent contact angle changes due to residual liquid remaining on the roughened surface. The results also show that the Wenzel and Cassie-Baxter models tend to overestimate the apparent contact angle on the roughened surfaces.

Bayesian biclustering by dynamics: Algorithm testing, comparison against random agglomeration, and calculation of application specific prior information.

Bayesian Biclustering by Dynamics (BBCD) is a new clustering algorithm for Steam-Assisted Gravity Drainage (SAGD) oil recovery time series data [1]. In this companion paper the BBCD algorithm is tested on synthetic data, demonstrating use of the algorithm, as well as its robustness, and performance accuracy against Random Agglomeration. Supplementary information includes formulae to calculate analytical steam and oil volume data used as background knowledge for the SAGD application. Advantages of the BBCD algorithm are listed below. •It includes background knowledge directly into the clustering process.•It finds similarity between series and over time.•It allows a user-specified definition for behaviour of interest, which relaxes dependency on series shape. This is important when similar behavioural events do not necessarily occur in the same temporal order.

The effect of coordination environment on the kinetic and thermodynamic stability of single-atom iron catalysts.

The stability of a single-atom catalyst is directly related to its preparation and applications, especially for high-loading single-atom catalysts. Here, the effect of a coordination environment induced by nitrogen (N) atoms coordinated with iron on the kinetic and thermodynamic stabilities of single-atom iron catalysts supported with carbon-based substrates (FeSA/CS) was investigated by density functional theory (DFT) calculations. Five FeSA/CS with different numbers of N atoms were modelled. The kinetic stability was evaluated by analyzing the migration paths of iron atoms and energy barriers. The thermodynamic stability was studied by calculating the adsorption and formation energies. Our results indicated that the coordination environment induced by N can promote the kinetic and thermodynamic stability of FeSA/CS. N atoms on the substrate promote the kinetic stability by raising the energy barrier for iron migration and not only increase the thermodynamic stability, but also contribute to catalyst synthesis. Doping N on the substrate enhances charge transfer between the iron atoms and substrates simultaneously improving the kinetic and thermodynamic stabilities. This theoretical research provides guidance for synthesizing stable and high loading single-atom catalysts by tuning the coordination environment of single-atom elements.

Release of sugars and fatty acids from heavy oil biodegradation by common hydrolytic enzymes.

In response to recent advances in understanding relating to the remarkable persistence of soil organic matter during burial and diagenesis, we examine the extent to which bitumen compositionally reflects the soil organic matter from which it was derived. Through a simple set of experiments, exposure of bitumen to lipase and cellulase, two enzymes effective in the biodegradation of soil organic matter, resulted in the release of glycerin, palmitic and oleic fatty acids from lipase digestion in addition to the release of glucose, alkylphenols and acyclic polyols from fermentation with cellulase, consistent with the products expected these enzymes. These results are significant in that they suggest that heavy oils are more similar to their soil precursor than previously thought, that biodegradation of bitumen can be accelerated using common over the counter enzymes in aerobic conditions and that heavy oils, which are 1000 times more abundant than coal, can release similar biomolecules as those generated in bioreactor culture or biomass harvest, using two of the most abundantly produced enzymes presently available.

A working method for estimating dynamic shear velocity in the montney formation.

In this paper, we present a customized method for estimating sonic shear velocity (Vs) from compressional velocity (Vp) logs in the Montney Formation, in wells lacking dipole sonic data. Following a multi-scenario analysis that comprised of assessing empirical Vs estimation relations [including lithology, porosity (Ø), and volume of clay (Vsh)-based Vs estimation techniques], bivariate statistics, and machine learning, we found that the Greenberg & Castagna (1992) shale lithology constants yield Vs log estimates that best match the measured Montney Formation Vs in our study area, with a regional correlation coefficient of 0.8. We have therefore customized the Vs estimation method in our study to use the Greenberg & Castagna (1992) shale lithology constants. Our working method: •Improves the efficacy of Vs log estimation from Vp logs in the study area•Demonstrates the importance of calibrating empirical relations for Vs estimation to a specific formation, and•Provides a more accurate complementary Vs log dataset for subsequent regional reservoir characterization studies.