Millimeter-sized Particles Research Articles

Edible liquid marbles stabilized with millimeter-sized spherical particles

Liquid marbles (LMs) are millimeter-sized liquid droplets in a gaseous phase coated with solid particles. The LM technology allows liquid droplets to be treated as solid particles. As an LM stabilizer, edible particles are of particular interest, especially for applications in the food industry. However and surprisingly, there are limited numbers of reports describing LMs stabilized with edible particles. In this study, we utilize silver dragees, which are millimeter-sized spherical sugar beads coated by silver overlayers used for decorating cakes and cookies, as edible particles to stabilize LMs. The silver dragees surface was modified using stearic acid to work as an effective LM stabilizer by adsorbing at the gas-liquid interface. LMs with millimeter and centimeter sizes can be fabricated. Due to high adsorption energy and jamming effect of the modified dragees at gas-liquid interface, LMs with non-equilibrium shapes including intricate ones with varying curvatures can be prepared. Developing LMs with customizable shapes is crucial for expanding their potential applications and versatility as functional systems for food applications. We therefore show how these customizable-shaped LMs can be utilized as an edible decoration material for food applications.

Unsinkable, long-drifting, millimeter-sized pumice of the 2021 eruption of Fukutoku-Oka-no-Ba submarine volcano

Understanding the relationship between pumice formation and long-term floatability in seawater is becoming increasingly important in terms of eruption dynamics, material cycles, biological and environmental effects, and ocean hazards. Pumice rafts were produced during the 2021 eruption of the Fukutoku-Oka-no-Ba submarine volcano in the Pacific Ocean, far from the Japanese archipelago. The pumice rafts reached the Amami-Ōshima and Okinawa Islands approximately two months after the eruption and continued to cover the sea surface at several bays and ports, providing a great opportunity to study the characteristics of raft pumices. Sieve analysis of the floating pumice indicated that the pumice rafts characteristically contained several millimeter-sized particles with a peak at 2–4 mm. This evidence raises an important question why the millimeter-sized, Fukutoku-Oka-no-Ba 2021 pumice particles were able to float for over two months, which exceeds the floatation time shown in previous studies. To answer this question, a porosity measurement technique for millimeter-to-centimeter-sized pumice particles was established and applied to drifting pumice that erupted during the Fukutoku-Oka-no-Ba 2021 eruption. The total, connected, and isolated porosities (including errors) were acquired for floating and sunken pumice particles. As studied for the floating pumice from past submarine eruptions, most floating pumice particles contain a high amount of isolated porosity (> 30 vol%) and are thus unsinkable even when the pumice size is in the millimeter scale. This study emphasizes that skeletal density is a useful measure for the determination of pumice floatability (sinkable or unsinkable). As the particle size decreases, crystals are lost from the floating pumice particles, suggesting that the particle size of the floating pumice is affected by its petrological properties (crystal content and size). A comparison with natural pumices from subaerial eruptions and experimental pumices from magma decompression experiments suggests that the Fukutoku-Oka-no-Ba 2021 pumices contain abundant isolated pores due to the suppression of expansion after fragmentation by quenching in seawater, and that the relatively low to moderate crystal content in the magma (< 17 vol%) may contribute to favorable conditions to produce abundant, millimeter-sized, unsinkable pumice.Most floating pumices have lower saturation density than seawater due to abundant isolated porosity (> 30 vol%) and are thus unsinkable even when the pumice size is in the millimeter scale.

Design of Low-Cost Simulation Space Micro Debris Launch Device

The high cost and low emission frequency of microparticle launchers have resulted in a long lead time for the development of detectors for micro-debris in space. In this paper, two low-cost, high-emission-frequency, small-size, millimeter-sized particle launchers are designed using the principles of gas expansion and surge propulsion by a high-speed air stream. Electrostatic detection is utilized to determine the emission velocity of the microbeads and their deviation from a specific position on the flight trajectory. The emission rate and accuracy of both methods were experimentally evaluated, along with the deviation of the detection system. Both devices emitted microbeads to simulate micro-debris, providing experimental data for the development of a space debris detector and establishing research conditions for studying the impact of micro-debris.

Numerical investigation of residual stress and strain in blades caused by foreign body impact. Comparison of impact modeling on real blade and flat surface

Damage caused by the impact of a foreign object on the turbine blades is caused by the entry of millimeter-sized foreign particles such as sand, stones, or small pieces of broken parts. Consequently, the remaining damage resulting from the impact of a foreign body on the blades is in the form of geometrical discontinuities such as craters or grooves on the blades, which create suitable conditions for the creation and growth of cracks and the complete failure of the blades. One of the most important aspects of foreign body impact damage is the study of the resulting residual stresses at the impact site, which plays a significant role in the creation and growth of cracks. In the present article, the main aim of this work was to analyze the residual stresses due to foreign object damage by expanding the simulation on the blades, considering a real blade model as well as the leading-edge curvature effect. To validate the numerical modeling, the impact of a spherical particle on a flat plate was modeled and the residual stresses and damages resulting from the modeling were compared to the experimental results available in the articles. Finally, the impact of the spherical foreign body on different places of the leading edge of a blade with different impact velocities was investigated. Moreover, the examined blade sample was replaced with a plate with the same material, and the impact of the foreign object on the flat surface was modeled for two different service temperatures. In this study, the resulting residual stresses and strains in three critical areas were compared.

Experimental investigation of a modified triboelectric charging device

Tribo-charging of plastic particles plays a critical role in the electrostatic separation industry, particularly for sorting millimeter-sized particles. The optimal charge/mass ratio can result in significant particle deviation in high intensity electric fields, making tribo-charging an important area of study. This work examines a modified tribo-electrostatic charging device that utilizes rotating propellers and an added air blower to increase particle charging. Through experimental analysis, the impact of air blower speed, rotating propeller speed, and sample mass was investigated using five different types of millimeter-sized particles. The results of the optimization study indicate a significant improvement in the charge/mass ratio, with the introduction of the air blower increasing the ratio by over 2.5 times.

Combustion characteristics of millimeter-sized aluminum particles in fluidized bed under various O2/CO2/H2O atmospheres

Aluminum is an attractive alternative fuel, but it burns very inefficiently due to the formation of a dense Al2O3 layer which prevents O2 from diffusion to the surface of Al particles. In previous experiments, the combustion of millimeter-sized Al (mAl) particles in the fluidized bed has achieved a substantial increase in the combustion efficiency, but further improvements are still needed. In this study, the effects of reaction atmosphere on the fluidized combustion of mAl particles were investigated. The experiments with different O2/H2O/CO2 concentrations were conducted. The experimental results indicate that the combustion efficiency of mAl particles in fluidized bed increases as the mole fraction of O2, H2O or CO2 increases, and the highest combustion efficiency can reach 38.7%. After the analysis of the oxide film on the surface of aluminum particles, it was found that it is easier to generate the unstable θ-Al2O3 under CO2 atmosphere, and it is easier to generate the unstable γ-Al2O3 and θ-Al2O3 under H2O atmosphere. The unstable Al2O3 film is more likely to be abraded in the fluidized bed, which leads to the effective improvement of the combustion efficiency.

Particle Clustering in Turbulence: Prediction of Spatial and Statistical Properties with Deep Learning

We investigate the utility of deep learning for modeling the clustering of particles that are aerodynamically coupled to turbulent fluids. Using a Lagrangian particle module within the Athena++ hydrodynamics code, we simulate the dynamics of particles in the Epstein drag regime within a periodic domain of isotropic forced hydrodynamic turbulence. This setup is an idealized model relevant to the collisional growth of micron- to millimeter-sized dust particles in early-stage planet formation. The simulation data are used to train a U-Net deep-learning model to predict gridded three-dimensional representations of the particle density and velocity fields, given as input the corresponding fluid fields. The trained model qualitatively captures the filamentary structure of clustered particles in a highly nonlinear regime. We assess model fidelity by calculating metrics of the density field (the radial distribution function) and of the velocity field (the relative velocity and the relative radial velocity between particles). Although trained only on the spatial fields, the model predicts these statistical quantities with errors that are typically <10%. Our results suggest that, given appropriately expanded training data, deep learning could complement direct numerical simulations in predicting particle clustering within turbulent flows.

Modulation of hair growth by topical drug delivery enhanced by STAR particles

Topical treatments to modulate hair growth are generally limited by low drug bioavailability due to poor skin permeability. Here, we studied the use of STAR particles, which are millimeter-sized ceramic particles with protruding microneedles, to form micropores in the skin to increase skin permeability to hair growth-modulating drugs. STAR particle design and fabrication were optimized, and the resulting STAR particles were shown to reduce lag time and increase skin permeability to minoxidil and acyclovir by more than three-fold compared to no treatment in pig skin ex vivo. In rats, STAR particles also improved topical delivery of minoxidil and acyclovir, which resulted in an increase or a decrease in the number, length and/or thickness of hairs and/or the number of anagen-phase hair follicles after minoxidil or acyclovir treatment, respectively. Clinical exam and histological evaluation showed no evidence of skin irritation or other adverse effects of the treatments. We conclude that STAR particles can increase topical delivery of minoxidil and acyclovir to improve modulation of hair growth promotion and inhibition, respectively.

Combustion characteristics of millimeter-sized aluminum particles in fluidized bed

Al is an attractive alternative fuel, but it has very low combustion efficiency because of the dense Al2O3 layer that formed during combustion. This layer blocks O2 diffusion, which hinders Al combustion. To solve this problem, many methods have been adopted, such as nano/μm-sized particles, alloys, additives. But these methods are expensive, complicated and unfeasible for large-scale production. In this study, a method that adopts fluidized bed has been proposed. The fluidized bed has attrition characteristics, which may destroy the oxide layer during combustion. A fluidized bed reactor was used to investigate the combustion characteristics of Al particles. The results indicate that the combustible particle size can increase to 0.5 mm with the help of fluidization, and the combustion efficiency can be increased by about three times. The combustion mode of millimeter-sized Al particles in fluidized bed is layer-by-layer combustion, but the agglomeration still exists and hinders the complete combustion.

Numerical simulation of the coupled multiphysics fields and reactions during the microwave pyrolysis of wood particles

Microwave heating has gained significant attention as an alternative to conventional methods for biomass pyrolysis. To investigate the electromagnetic-thermal-hydraulic-chemical processes during biomass pyrolysis under microwave irradiation, a three-dimensional comprehensive pyrolysis model was developed. The model numerically described the physicochemical processes of the electromagnetic wave propagation in the reactor, heat transfer and fluid flow inside porous wood particles, pyrolysis reactions, and phase changes. The model was validated by comparing the temperature profiles of biomass samples under varying microwave powers against literature data. The modeling results demonstrated that there was a strong interaction between the distributions of the microwave electromagnetic fields in the cavity and that inside the wood particles; these distributions changed with the size, shape, and location of the biomass sample in the cavity. Using the model, the thermal response of wood particles to microwave radiation was determined. The predicted results showed that a millimeter-sized wood particle was large enough to straddle multiple high-energy microwave regions in the cavity, resulting in more than one intraparticle hotspots. The transient dielectric loss inside wood particles is nonuniform due to the enhancement of the local relative permittivity by the local hotspots. The maximum permeability within the wood particles increases by an order of magnitude during microwave pyrolysis at 1 kW. The hotspots have a considerable influence on the structural homogeneity and stability of biochar due to the formation of large thermal and expansion stresses around the hotspot locations. Moreover, the energy efficiency (ηe) of converting microwave electromagnetic energy into the thermal energy of wood particles is sensitive to the input microwave power and particle shape. For instance, ηe ranges from 12.44% to 36.15% under the microwave powers of 0.8–1 kW for the pyrolysis of a cylindrical wood particle with aspect ratios of 0.25–2. This work provides the fundamental technical support for the industrial application of microwave pyrolysis.

Investigation into the Hydration Behavior of K2CO3 Packed Beds: An NMR Study

K2CO3 is seen as a promising heat storage material, available for applications in the domestic sector. For practical purposes, the material is hereby often employed in a packed bed containing millimeter-sized particles. To gain more insight into the hydration behavior of these packed beds, quantitative NMR measurements, capable of following the in-situ hydration behavior, are presented for the first time. It is found that hydration behavior varies significantly, depending on the specific hydration conditions that are chosen. At low airflows hydration is found to proceed via a hydration front, while higher airflows cause the hydration front to widen. Since an increase in flow rate coincided with an increase in the supplied water vapor, hydration is eventually found to proceed in a uniform manner. A comparison between TGA and NMR measurements shows that the overall packed bed hydration kinetics hereby transition to the reaction kinetics of single K2CO3 particles.Graphical

Advances in Frazil Ice Evolution Mechanisms and Numerical Modelling in Rivers and Channels in Cold Regions

Frazil ice comprises millimeter-sized ice crystal particles or flocculations in water, and its generation and evolution primarily occur during the initial stage of the river ice process. Meanwhile, ice damage caused by frazil ice is common, so it is crucial to determine its generation and evolution mechanisms to develop a full understanding of the river ice processes, the prediction of ice development, and ice damage prevention. The recent developments in frazil ice research and modeling are summarized in this article. From the perspectives of field measurements and laboratory experiments, the techniques and methods for observing frazil ice are reviewed, including the flow generation, temperature control, and observation techniques necessary for laboratory observations of frazil ice, as well as the challenging observation techniques used for field measurements. Frazil ice’s evolution mechanisms (nucleation, thermal growth, secondary nucleation, collisional fragmentation, and flocculation) are affected by water temperature processes. Work on the movement and distribution of frazil ice is also presented. A review of the current numerical models used to assess frazil ice evolution is conducted. Moreover, the open issues and potential future research topics are suggested.

τ Herculid meteor shower in the night of 30/31 May 2022 and the meteoroid properties

Context. A τ Herculid meteor outburst or even storm was predicted to occur by several models around 5 UT on 31 May 2022 as a consequence of the break-up of comet 73P/Schwassmann-Wachmann 3 in 1995. The multi-instrument and multi-station experiment was carried out within the Czech Republic to cover possible earlier activity of the shower between 21 and 1 UT on 30/31 May. Aims. We report meteor shower activity that occurred before the main peak and provide a comparison with the dynamical simulations of the stream evolution. The physical properties of the meteoroids are also studied. Methods. Multi-station observations using video and photographic cameras were used to calculate the atmospheric trajectories and heliocentric orbits of the meteors. Their arrival times were used to determine the shower activity profile. The physical properties of the meteoroids were evaluated using various criteria based on meteor heights. The evolution of the spectra of three meteors were studied as well. Results. This annual but poor meteor shower was active for the whole night many hours before the predicted peak. A comparison with dynamical models shows that a mix of older material ejected after 1900 and fresh particles originating from the 1995 comet fragmentation event was observed. The radiant positions of both groups of meteors were identified and were found to agree well with the simulated radiants. Meteoroids with masses between 10 mg and 10 kg were recorded. The mass distribution index was slightly higher than 2. The study of the physical properties shows that the τ Herculid meteoroids belong to the most fragile particles observed ever, especially among higher masses of meteoroids. The exceptionally bright bolide observed during the dawn represents a challenge for the dynamical simulations as it is necessary to explain how a half-metre body was transferred to the vicinity of the Earth at the same time as millimetre-sized particles.

Grain Size Effects on Visible and Near-infrared (0.35–2.5 μm) Laboratory Spectra of Ordinary Chondrite and HED Meteorites

Remote spectral characterization of near-Earth asteroids (NEAs) relies on laboratory spectral calibration to constrain their surface composition, including mineral chemistry and relative mineral abundances. Often these calibrations are based on fine meteorite powders that are representative of regolith observed on large NEAs such as (433) Eros. However, spacecraft observations of smaller NEAs such as (25143) Itokawa, (101955) Bennu, and (162173) Ryugu show surfaces devoid of a thick layer of regolith and instead find variegated landscapes with millimeter-sized particles to meter-scale boulders. Here we present the results of a laboratory study to understand the effects of grain size on the spectral properties of meteorites and how this can impact ground-based characterization of NEAs. Our study focuses on ordinary chondrites (H, L, LL) and HED meteorites, as they comprise ∼90% of all meteorites that fall on Earth. Compared to ordinary chondrites, the spectral band parameters of HED meteorites are less affected by changing grain size. Among the ordinary chondrites, LL chondrites are least affected, but the spectral band parameters and mineral chemistries and abundances for H and L chondrites are most affected by changing grain size. Grain size does not seem to have any significant effect on the taxonomic classification of our meteorite spectra. We also used the Hapke model to investigate trends in single-scattering albedo as a function of grain size and present equations to recover the grain size from a spectrum.

Dynamic behavior of compound droplets with millimeter-sized particles impacting substrates with different wettabilities

The dynamic behavior of compound droplets, which are made up of a millimeter-sized particle and distilled water, impacting substrates of different wettabilities is investigated via high-speed photography. The effects of the size of the particle within the compound droplet, substrate contact angle, and impact height on the deformation of the droplets and the characteristics of the impact are analyzed. It is found that the collisions of compound droplets with substrates can be classified into four categories based on the observed experimental phenomena that occur during the impact. These categories are referred to as adhesion collision, rebound collision, daughter-droplet collision (or partial rebound collision), and breakup collision. We consider both the impact of water droplets and compound droplets (with one of two different-sized particles) on substrates of different wettabilities. The effects of inertia, surface tension, and adhesion between the substrate and the liquid droplet, and adhesion between the particle and the liquid droplet are considered to explain the different collision phenomena of compound droplets and reveal the evolution mechanism of the droplet morphologies in the experiments. Furthermore, the effects of the height from which the droplet is released and the contact angle of the substrate (i.e., its wettability) on the maximum spreading diameter and maximum jet height of the droplet are presented quantitatively. The effect of the size of the particle within the compound droplet and the substrate contact angle on the dynamic behavior of the compound droplet subject to impact with the substrate is also described.

Thermochemical conversion of millimeter-sized single char particle in steam dominated environments under varying temperature, reactant composition and flux—Experimental and numerical analysis

This work reports experimental and numerical investigations of biomass char conversion in H2O-dominated thermal environment. Temperature parametric analysis establishes 730 °C as the temperature beyond which char conversion rate becomes practically relevant — 0.4 mg min−1 °C−1. The mass loss rate of char particles of different sizes (8–20 mm) is studied under a wide range of temperatures (800–1000 °C), H2O concentrations (10%–100%, bal. N2/H2/CO, at varying ratios), and combinations thereof. Increasing the temperature/reactant concentration by 10% reduces the conversion time scales by up to 2 times. Temperature and reactant concentration in combination control the conversion regime (kinetic limit to diffusion limit) and can be used as control parameters. It is observed that the presence of H2 inhibits the char–steam reaction, attributed to adsorption of H2 on the char surface: 25% H2 in feed reduces the reaction rate by 50%. The CO+H2O reaction is found to play a pivotal role in controlling the char conversion by virtue of being the source of both H2 (blocking active sites) and CO2 (curtailing the forward reaction rate), and the sink for H2O (reduced reactant concentration). A novel method to identify the conversion regime based on temperature and reactant concentration is hypothesized and validated.

Particle-size segregation in self-channelized granular flows

Geophysical mass flows such as debris flows, dense pyroclastic flows and snow avalanches can self-channelize on shallow slopes. The confinement afforded by formed levees helps to maintain the flow depth, and hence mobility, allowing self-channelized flows to run out significantly farther than unconfined, spreading flows. Levee formation and self-channelization are strongly associated with particle-size segregation, but can also occur in monodisperse flows. This paper uses the monodisperse depth-averaged theory of Rochaet al.(J. Fluid Mech., vol. 876, 2019, pp. 591–641), which incorporates a hysteretic friction law and second-order depth-averaged viscous terms. Both of these are vital for the formation of a travelling wave that progressively deposits a pair of levees just behind the front. The three-dimensional velocity field is reconstructed in a frame moving with the front assuming Bagnold flow. This enables a bidisperse particle-size segregation theory to be used to solve for the large and small particle concentrations and particle paths in three-dimensions, for the first time. The model shows that the large particles tend to segregate to the surface of the flow, forming a carapace that extends over the centre of the channel, as well as along the external sides and base of the levee walls. The small particles segregate downwards, and are concentrated in the main channel and in the inner levee walls. This supports the contention that a low-friction channel lining provides a secondary mechanism for run-out enhancement. It is also shown that the entire theory scales with particle diameter, so experiments with millimetre-sized particles provide important insights into geophysical-scale flows with boulders and smaller rock fragments. The model shows that self-channelization does not need particle-size segregation to occur, but supports the hypothesis that particle-size segregation and the associated frictional feedback can significantly enhance both the flow mobility and the levee strength.

Particle-scale heat and mass transfer processes during the pyrolysis of millimeter-sized lignite particles with solid heat carriers

• Devolatilization kinetics is coupled with the heat and mass transfer processes. • Evolution of pore structure in coal pyrolysis with solid heat carrier is included. • Multi-physical fields inside a lignite particle during pyrolysis is elaborated. • The intraparticle mass transfer mechanism influences the secondary reaction. The study of mesoscale solid fuel pyrolysis behavior is a key bridge between the microscopic reaction kinetics and macroscopic multiphase reaction flow in a reactor. In this work, a one-dimensional nonstationary model was developed in spherical coordinate system for the pyrolysis of millimeter-scale lignite particles with solid heat carriers, in which a modified multistep kinetic model (MSM) was coupled with a series of correlative transient heat and mass conservation equations in conjunction with the dusty gas model (DGM). The MSM for coal pyrolysis was modified by adding a set of kinetic equations of pseudo-elementary secondary reactions, making the kinetic model comparable to the Chemical Percolation Devolatilization model in terms of accuracy. In addition, a semiempirical submodel for the evolution of pore structure parameters (porosity, pore size, and permeability) was incorporated to obtain the precise mechanism of volatile species transport in the porous coal matrix. The modified MSM and pore evolution submodel were validated against literature data. The coupling effects between intraparticle transport processes and transient devolatilization kinetics were investigated. It was concluded that notable multiphysical fields (pressure, concentration, and velocity) emerged within lignite particles during pyrolysis, governed by the heating history. In addition, it should be noted that the direction and mechanism of volatiles transfer within porous lignite particles varied during pyrolysis, which can significantly affect secondary reactions. Flow reversal and shifts in the dominant mass transfer mode influenced the secondary reaction pathway, in addition to the impact of volatiles flow velocity on the reaction degree.

A coupled SPH-DEM approach for modeling of free-surface debris flows

A Lagrangian mesh-less model is proposed to simulate fluid–solid flows with multiple-sized solids, i.e., millimeter-sized particle and larger-sized debris. Considering the difference in the size of solid phases, a hybrid resolved and unresolved model is established based on the coupling method of smoothed particle hydrodynamics (SPH) and discrete element method (DEM). SPH is used to model fluid, and the locally averaged Navier–Stokes equations are adopted as governing equations. DEM is used to model the particle–particle interactions, and the unresolved description of hydrodynamic forces including drag and buoyancy is established. The large-sized debris is modeled as the rigid body, which is discretized by particle elements having both SPH and DEM characteristics, where SPH particle elements are involved in the closure of the SPH fluids, and DEM particle elements interact with the solid particles following the contact law. The numerical model is validated and verified by several examples, including single-particle sedimentation, collapse of cylinder columns, and debris dam break. Results show that the present model reproduces general features of the complex fluid–solid flow with free surfaces. The advantage of the hybrid model is that it can deal with the fluid–solid flow problem with both small particles and large objects at a suitable resolution, and it is especially good at dealing with the free surface flow problem. A discretization for the modeling of debris flows is proposed based on the coupled SPH-DEM method. The novelty of the work is a coupled resolved–unresolved scheme for the free surface flow with multi-sized solids. The present scheme allows using a uniform resolution by bridging the size difference between small-scale solid particles and large-scale debris. The unresolved model of fluid-particle flow is efficient because the fluid resolution can be configured comparably to the particle size. The unified nature of the model allows the combination of resolved and unresolved simulations in the same computational domain.

A supraparticle-based biomimetic cascade catalyst for continuous flow reaction

Robust millimeter-sized spherical particles with controlled compositions and microstructures hold promises of important practical applications especially in relation to continuous flow cascade catalysis. However, the efficient fabrication methods for producing such particles remain scare. Here, we demonstrate a liquid marble approach to fabricate robust mm-sized porous supraparticles (SPs) through the bottom-up assembly of silica nanoparticles in the presence of strength additive or surface interactions, without the need for the specific liquid-repellent surfaces used by the existing methods. As the proof of the concept, our method was exemplified by fabricating biomimetic cascade catalysts through assembly of two types of well-defined catalytically active nanoparticles. The obtained SP-based cascade catalysts work well in industrially preferred fixed-bed reactors, exhibiting excellent catalysis efficiency, controlled reaction kinetics, high enantioselectivity (99% ee) and outstanding stability (200~500 h) in the cascades of ketone hydrogenation-kinetic resolution and amine racemization-kinetic resolution. The excellent catalytic performances are attributed to the structural features, reconciling close proximity of different catalytic sites and their sufficient spatial isolation.