Water Condensation in the Nanoscale Pores of Pt/C Catalyst Particles and Its Impact on Catalyst Utilization: A Simulation Based on a Reconstructed Structure from Nanoimaging.

In polymer electrolyte membrane fuel cells, carbon-supported platinum (Pt/C) catalyst particles require sufficient water condensation within the nanoscale pores to effectively utilize the interior Pt catalysts. Since experimental visualizations with nanoscale precision of this phenomenon are not yet possible, we utilized a Pt/C catalyst particle reconstructed from segmented nanoimaging of a catalyst powder, which served as the computational domain for lattice density functional theory (LDFT) simulation of water condensation. Paired with experimental water uptake data, LDFT successfully simulated high-resolution water condensation, capturing both thin-film and capillary water condensation phenomena. Using a simple proton movement method within the water network, we reproduced the Pt utilization data from a CO stripping experiment. Our findings highlight that at low relative humidity (RH), Pt utilization is influenced by thin water film formations, mainly dictated by the wettability properties of surfaces within primary pores and the Pt/C catalyst particle's exterior. Conversely, at high RH, Pt utilization is attributed to capillary water condensation in medium-to-large sized pores. This approach contributes a qualitative and quantitative discussion on hypotheses regarding the mechanism of Pt utilization, supporting recent studies (e.g., Girod, R.; Nat. Catal. 2023, 6, (5), 383-391).

Quantitative Description of Bubble Formation in Response to Electrolyte Engineering.

The green hydrogen economy is expected to play a crucial role in carbon neutrality, but industrial-scale water electrolysis requires improvements in efficiency, operation costs, and capital costs before broad deployment. Electrolysis operates at a high current density and involves the substantial formation of gaseous products from the electrode surfaces to the electrolyte, which may lead to additional resistance and a resulting loss of efficiency. A detailed clarification of the bubble departure phenomena against the electrode surface and the surrounding electrolytes is needed to further control bubbles in a water electrolyzer. This study clarifies how electrolyte properties affect the measured bubble detachment sizes from the comparisons with analytical expressions and dynamic simulations. Bubble behavior in various electrolyte solutions and operating conditions was described using various physical parameters. A quantitative relationship was then established to connect electrolyte properties and bubble departure diameters, which can help regulate the bubble management through electrolyte engineering.

Gas Adsorption and Diffusion Behaviors in Interfacial Systems Composed of a Polymer of Intrinsic Microporosity and Amorphous Silica: A Molecular Simulation Study.

We investigate the adsorption and diffusion behaviors of CO2, CH4, and N2 in interfacial systems composed of a polymer of intrinsic microporosity (PIM-1) and amorphous silica using grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. We build model systems of mixed matrix membranes (MMMs) with PIM-1 chains sandwiched between silica surfaces. Gas adsorption analysis using GCMC simulations shows that gas molecules are preferentially adsorbed in microcavities distributed near silica surfaces, resulting in an increase in the solubility coefficients of CO2, CH4, and N2 compared to bulk PIM-1. In contrast, diffusion coefficients obtained from MD simulations and then calibrated using the dual-mode sorption model show different tendencies depending on gas species: CO2 diffusivity decreases in MMMs compared to PIM-1, whereas CH4 and N2 diffusivities increase. These differences are attributed to competing effects of silica surfaces: the emergence of larger pores as a result of chain packing disruption, which enhances gas diffusion, and a quadrupole-dipole interaction between gas molecules and silica surface hydroxyl groups, which retards gas diffusion. The former has a greater impact on CH4 and N2 diffusivities, whereas the latter has a greater impact on CO2 diffusivity due to the strong quadrupole-dipole interaction between CO2 and surface hydroxyls. These findings add to our understanding of gas adsorption and diffusion behaviors in the vicinity of PIM-1/silica interfaces, which are unobtainable in experimental studies.

Evaluation of gas permeability in porous separators for polymer electrolyte fuel cells: Computational fluid dynamics simulation based on micro-x-ray computed tomography images.

Pore structures and gas transport properties in porous separators for polymer electrolyte fuel cells are evaluated both experimentally and through simulations. In the experiments, the gas permeabilities of two porous samples, a conventional sample and one with low electrical resistivity, are measured by a capillary flow porometer, and the pore size distributions are evaluated with mercury porosimetry. Local pore structures are directly observed with micro-x-ray computed tomography (CT). In the simulations, the effective diffusion coefficients of oxygen and the air permeability in porous samples are calculated using random walk Monte Carlo simulations and computational fluid dynamics (CFD) simulations, respectively, based on the x-ray CT images. The calculated porosities and air permeabilities of the porous samples are in good agreement with the experimental values. The simulation results also show that the in-plane permeability is twice the through-plane permeability in the conventional sample, whereas it is slightly higher in the low-resistivity sample. The results of this study show that CFD simulation based on micro-x-ray CT images makes it possible to evaluate anisotropic gas permeabilities in anisotropic porous media.

High Heat Flux Evaporation of Low Surface Tension Liquids from Nanoporous Membranes.

Water is often considered as the highest performance working fluid for liquid-vapor phase change due to its high thermal conductivity and large enthalpy of vaporization. However, a wide range of industrial systems require using low surface tension liquids where heat transfer enhancement has proved challenging for boiling and evaporation. Here, we enable a new paradigm of phase change heat transfer, which favors high volatility, low surface tension liquids rather than water. We utilized a nanoporous membrane of ≈600 nm thickness and <140 nm pore diameters supported on efficient liquid supply architectures, decoupling capillary pumping from viscous loss. Proof-of-concept devices were microfabricated and tested in a custom-built environmental chamber. We used R245fa, pentane, methanol, isopropyl alcohol, and water as working fluids with devices of total membrane area varying from 0.017 to 0.424 cm2. We realized a device-level pure evaporation heat flux of 144 ± 6 W/cm2 for water, and the highest evaporation heat flux was obtained with pentane at 550 ± 90 W/cm2. We developed a three-level model to understand vapor dynamics near the interface and thermal conduction within the device, which showed good agreement with experiments. We then compared pore-level heat transfer of different fluids, where R245fa showed approximately 10 times the performance of water under the same working conditions. Finally, we illustrate the usefulness of a figure of merit extracted from the kinetic theory for evaporation. The current work provides fundamental insights into the evaporation of low surface tension liquids, which can impact various applications such as refrigeration and air conditioning, petroleum and solvent distillation, and on-chip electronics cooling.

A unified relationship for evaporation kinetics at low Mach numbers.

We experimentally realized and elucidated kinetically limited evaporation where the molecular gas dynamics close to the liquid-vapour interface dominates the overall transport. This process fundamentally dictates the performance of various evaporative systems and has received significant theoretical interest. However, experimental studies have been limited due to the difficulty of isolating the interfacial thermal resistance. Here, we overcome this challenge using an ultrathin nanoporous membrane in a pure vapour ambient. We demonstrate a fundamental relationship between the evaporation flux and driving potential in a dimensionless form, which unifies kinetically limited evaporation under different working conditions. We model the nonequilibrium gas kinetics and show good agreement between experiments and theory. Our work provides a general figure of merit for evaporative heat transfer as well as design guidelines for achieving efficient evaporation in applications such as water purification, steam generation, and thermal management.

Mutual influence of molecular diffusion in gas and surface phases.

We develop molecular transport simulation methods that simultaneously deal with gas- and surface-phase diffusions to determine the effect of surface diffusion on the overall diffusion coefficients. The phenomenon of surface diffusion is incorporated into the test particle method and the mean square displacement method, which are typically employed only for gas-phase transport. It is found that for a simple cylindrical pore, the diffusion coefficients in the presence of surface diffusion calculated by these two methods show good agreement. We also confirm that both methods reproduce the analytical solution. Then, the diffusion coefficients for ink-bottle-shaped pores are calculated using the developed method. Our results show that surface diffusion assists molecular transport in the gas phase. Moreover, the surface tortuosity factor, which is known to be uniquely determined by physical structure, is influenced by the presence of gas-phase diffusion. This mutual influence of gas-phase diffusion and surface diffusion indicates that their simultaneous calculation is necessary for an accurate evaluation of the diffusion coefficients.

An Ultrathin Nanoporous Membrane Evaporator.

Evaporation is a ubiquitous phenomenon found in nature and widely used in industry. Yet a fundamental understanding of interfacial transport during evaporation remains limited to date owing to the difficulty of characterizing the heat and mass transfer at the interface, especially at high heat fluxes (>100 W/cm2). In this work, we elucidated evaporation into an air ambient with an ultrathin (≈200 nm thick) nanoporous (≈130 nm pore diameter) membrane. With our evaporator design, we accurately monitored the temperature of the liquid-vapor interface, reduced the thermal-fluidic transport resistance, and mitigated the clogging risk associated with contamination. At a steady state, we demonstrated heat fluxes of ≈500 W/cm2 across the interface over a total evaporation area of 0.20 mm2. In the high flux regime, we showed the importance of convective transport caused by evaporation itself and that Fick's first law of diffusion no longer applies. This work improves our fundamental understanding of evaporation and paves the way for high flux phase-change devices.

Effect of capillary condensation on gas transport properties in porous media.

We investigate the effect of capillary condensation on gas diffusivity in porous media composed of randomly packed spheres with moderate wettability. To simulate capillary phenomena at the pore scale while retaining complex pore networks of the porous media, we employ density functional theory (DFT) for coarse-grained lattice gas models. The lattice DFT simulations reveal that capillary condensations preferentially occur at confined pores surrounded by solid walls, leading to the occlusion of narrow pores. Consequently, the characteristic lengths of the partially wet structures are larger than those of the corresponding dry structures with the same porosities. Subsequent gas diffusion simulations exploiting the mean-square displacement method indicate that while the effective diffusion coefficients significantly decrease in the presence of partially condensed liquids, they are larger than those in the dry structures with the same porosities. Moreover, we find that the ratio of the porosity to the tortuosity factor, which is a crucial parameter that determines an effective diffusion coefficient, can be reasonably related to the porosity even for the partially wet porous media.

Construction of non-Markovian coarse-grained models employing the Mori-Zwanzig formalism and iterative Boltzmann inversion.

We propose a new coarse-grained (CG) molecular simulation technique based on the Mori-Zwanzig (MZ) formalism along with the iterative Boltzmann inversion (IBI). Non-Markovian dissipative particle dynamics (NMDPD) taking into account memory effects is derived in a pairwise interaction form from the MZ-guided generalized Langevin equation. It is based on the introduction of auxiliary variables that allow for the replacement of a non-Markovian equation with a Markovian one in a higher dimensional space. We demonstrate that the NMDPD model exploiting MZ-guided memory kernels can successfully reproduce the dynamic properties such as the mean square displacement and velocity autocorrelation function of a Lennard-Jones system, as long as the memory kernels are appropriately evaluated based on the Volterra integral equation using the force-velocity and velocity-velocity correlations. Furthermore, we find that the IBI correction of a pair CG potential significantly improves the representation of static properties characterized by a radial distribution function and pressure, while it has little influence on the dynamic processes. Our findings suggest that combining the advantages of both the MZ formalism and IBI leads to an accurate representation of both the static and dynamic properties of microscopic systems that exhibit non-Markovian behavior.

Hyperthermal molecular beam source using a non-diaphragm-type small shock tube.

We have developed a hyperthermal molecular beam source employing a non-diaphragm-type small shock tube for gas-surface interaction studies. Unlike conventional shock-heated beam sources, the capability of repetitive beam generation without the need for replacing a diaphragm makes our beam source suitable for scattering experiments, which require signal accumulation for a large number of beam pulses. The short duration of shock heating alleviates the usual temperature limit due to the nozzle material, enabling the generation of a molecular beam with higher translational energy or that containing dissociated species. The shock-heated beam is substantially free from surface-contaminating impurities that are pronounced in arc-heated beams. We characterize the properties of nitrogen and oxygen molecular beams using the time-of-flight method. When both the timing of beam extraction and the supply quantity of nitrogen gas are appropriately regulated, our beam source can generate a nitrogen molecular beam with translational energy of approximately 1 eV, which corresponds to the typical activation energy of surface reactions. Furthermore, our beam source can generate an oxygen molecular beam containing dissociated oxygen atoms, which can be a useful probe for surface oxidation. The dissociation fraction along with the translational energy can be adjusted through the supply quantity of oxygen gas.

Molecular Dynamics Study for Channel Size Dependence of Shear Stress Between Droplet and Wall.

In this study, the channel size dependence of the shear stress between water droplets and solid walls in nm-order channel was analyzed. We considered a several different-sized and highly hydrophobic channel whose macroscopic contact angle was about 150 degrees. We have evaluated the shear stress and the normal pressure by molecular dynamics simulation. Analyzing shear stress and normal pressure based on the macroscopic model, we have discussed the difference between the macroscopic model based on hydrodynamics and the microscopic model. As a result, in the high hydrophobic case, it became clear that the shear stress depends on the channel size due to the large Laplace pressure. Furthermore, in the case that the channel size was less than 50 A, the normal pressure by the molecular simulation didn't agree with the expected value from the Young-Laplace equation. From this study it was clear that molecular simulation is needed when the channel size is less than 40 A.

Molecular beam study of the scattering behavior of water molecules from a graphite surface.

Gas flow in nanospaces is greatly affected by the scattering behavior of gas molecules on solid surfaces, resulting in unique mass transport properties. In this paper, the molecular beam scattering experiment of water molecules on a graphite surface was conducted to understand their scattering dynamics in an incident energy range that corresponds to their thermal velocity distribution at room temperature (35-130 meV). Because of the large adsorption energy (∼100 meV), the scattering behavior is quite sensitive to the incident energy even within this narrow energy range. For relatively large incident energies, the direct-inelastic and trapping-desorption channels have comparable contributions to the scattering process on the surface at 300 K. In contrast, when the incident energy decreases well below the adsorption energy on the surface, the trapping-desorption channel becomes dominant, changing the scattering pattern from directional to diffusive scattering. As a result, the tangential momentum accommodation coefficient (TMAC), which significantly impacts the mass transport in nanospaces, largely depends on the incident energy. A decrease in the incident energy from 130 to 35 meV doubles the TMAC (0.42 to 0.86). In addition to the incident energy, the TMAC shows a strong dependence on the surface temperature. With increasing the surface temperature from 300 to 500 K, the scattering becomes more directional because of the increasing contribution of the direct-inelastic channel, which reduces the TMAC for the incident beam energy of 35 meV to 0.48.

Bottom-up construction of interaction models of non-Markovian dissipative particle dynamics.

We derive the equation of motion for non-Markovian dissipative particle dynamics (NMDPD) by introducing the history effects on the time evolution of the system. Our formulation is based on the generalized Langevin equation, which describes the motions of the centers of mass of clusters comprising microscopic particles. The mean, friction, and fluctuating forces in the NMDPD model are directly constructed from an underlying molecular dynamics (MD) system without any scaling procedure. For the validation of our formulation, we construct NMDPD models from high-density Lennard-Jones systems, in which the typical time scales of the coarse-grained particle motions and the fluctuating forces are not fully separable. The NMDPD models reproduce the temperatures, diffusion coefficients, and viscosities of the corresponding MD systems more accurately than the dissipative particle dynamics models based on a Markovian approximation. Our results suggest that the NMDPD method is a promising alternative for simulating mesoscale flows where a Markovian approximation is not valid.

A non-diaphragm type small shock tube for application to a molecular beam source.

A non-diaphragm type small shock tube was developed for application to a molecular beam source, which can generate beams in the energy range from 1 to several electron volts and beams containing dissociated species such as atomic oxygen. Since repetitive high-frequency operation is indispensable for rapid signal acquisition in beam scattering experiments, the dimensions of the shock tube were miniaturized to reduce the evacuation time between shots. The designed shock tube is 2-4 mm in diameter and can operate at 0.5 Hz. Moreover, a high shock Mach number at the tube end is required for high-energy molecular beam generation. To reduce the shock attenuation caused by the wall boundary layer, which becomes significant in small-diameter tubes, we developed a high-speed response valve employing the current-loop mechanism. The response time of this mechanism is about 100 µs, which is shorter than the rupture time of conventional diaphragms. We show that the current-loop valve generates shock waves with shorter formation distances (about 200-300 mm) than those of conventional shock tubes. In addition, the converging geometry efficiently accelerates shock wave in the small-diameter tubes. The optimal geometry of the shock tube yields shock Mach number around 7, which indicates that the translation energy of molecular beams can exceed 1 eV even in the presence of the real gas effect.

Inhomogeneous decomposition of ultrathin oxide films on Si(100): application of Avrami kinetics to thermal desorption spectra.

Thermal decomposition of ultrathin oxide layers on silicon surface was investigated with temperature programed desorption. Oxide layers were formed on Si(100) at 400 degrees C by exposure to O(2) molecular beam. Desorption spectrum for oxygen coverages between 1.7 and 2.6 ML exhibits a single dominant peak with an additional broad peak at lower temperatures. The former peak corresponds to stable binding states of O atoms at dimer bridge sites and dimer backbond sites. The high peak intensity indicates that most O atoms are at stable states. The latter peak corresponds to an unstable binding state, where O atoms are presumably trapped at dangling bonds. The SiO desorption rate from the stable binding states is well described by Avrami kinetics, suggesting that the decomposition process is spatially inhomogeneous with void formation and growth. The rate-determining step is the reaction at void perimeter even if the overlap between voids becomes quite large. The Avrami exponents determined from our experiment indicate that the increase in the initial coverage makes the oxide layer more stable and suppresses the rate of void formation at the potential nucleation sites.