Pores in nanoporous materials can be interconnected in different ways; preliminary evidence exists that connecting channels can affect the overall hydrophobicity of the material thus providing an additional parameter in designing applications that require controlled wetting properties. In this work, we show that the length of secondary channels is a key parameter to tune the overall hydrophobicity of the material: short secondary channels make the main pore effectively more hydrophilic than a simple cylindrical pore, while long secondary channels enhance its hydrophobicity, producing the macroscopic effect of superhydrophobic textures. This rich behavior is rooted in the spontaneous filling of the secondary channels, which is unexpected based on classical capillarity. This length-dependent filling is explained by the formation of hydrogen bonds bridging the main pores which becomes less frequent with longer channels. These findings could be useful for designing nanoporous materials with tailored wetting properties. The intrusion and extrusion of non-wetting liquids has many industrial applications and understanding how the underlying dynamics that govern the interaction of a given liquid and a nanoporous material can help refine performance. Here, using molecular dynamics simulations, the authors consider the impact of pore connectivity on the water intrusion of hydrophobic nanopores finding that the depth of small interconnecting secondary channels plays a crucial role for the wetting/dewetting properties.
Establishing molecular mechanisms of wetting and drying of hydrophobic porous materials is a general problem for science and technology within the subcategories of the theory of liquids, chromatography, nanofluidics, energy storage, recuperation, and dissipation. In this article, we demonstrate a new way to tackle this problem by exploring the effect of the topology of pure silica nanoparticles, nanotubes, and zeolites. Using molecular dynamics simulations, we show how secondary porosity promotes the intrusion of water into micropores and affects the hydrophobicity of materials. It is demonstrated herein that for nano-objects, the hydrophobicity can be controlled by changing the ratio of open to closed nanometer-sized lateral pores. This effect can be exploited to produce new materials for practical applications when the hydrophobicity needs to be regulated without significantly changing the chemistry or structure of the materials. Based on these simulations and theoretical considerations, for pure silica zeolites, we examined and then classified the experimental database of intrusion pressures, thus leading to the prediction of any zeolite's intrusion pressure. We show a correlation between the intrusion pressure and the ratio of the accessible pore surface area to total pore volume. The correlation is valid for some zeolites and mesoporous materials. It can facilitate choosing prospective candidates for further investigation and possible exploitation, especially for energy storage, recuperation, and dissipation.
Controlling the pressure at which liquids intrude (wet) and extrude (dry) a nanopore is of paramount importance for a broad range of applications, such as energy conversion, catalysis, chromatography, separation, ionic channels, and many more. To tune these characteristics, one typically acts on the chemical nature of the system or pore size. In this work, we propose an alternative route for controlling both intrusion and extrusion pressures via proper arrangement of the grains of the nanoporous material. To prove the concept, dynamic intrusion-extrusion cycles for powdered and monolithic ZIF-8 metal-organic framework were conducted by means of water porosimetry and in operando neutron scattering. We report a drastic increase in intrusion-extrusion dynamic hysteresis when going from a fine powder to a dense monolith configuration, transforming an intermediate performance of the ZIF-8 + water system (poor molecular spring) into a desirable shock-absorber with more than 1 order of magnitude enhancement of dissipated energy per cycle. The obtained results are supported by MD simulations and pave the way for an alternative methodology of tuning intrusion-extrusion pressure using a macroscopic arrangement of nanoporous material.
Intrusion (wetting)/extrusion (drying) of liquids in/from lyophobic nanoporous systems is key in many fields, including chromatography, nanofluidics, biology, and energy materials. Here we demonstrate that secondary topological features decorating main channels of porous systems dramatically affect the intrusion/extrusion cycle. These secondary features, allowing an unexpected bridging with liquid in the surrounding domains, stabilize the water stream intruding a micropore. This reduces the intrusion/extrusion barrier and the corresponding pressures without altering other properties of the system. Tuning the intrusion/extrusion pressures via subnanometric topological features represents a yet unexplored strategy for designing hydrophobic micropores. Though energy is not the only field of application, here we show that the proposed tuning approach may bring 20-75 MPa of intrusion/extrusion pressure increase, expanding the applicability of hydrophobic microporous materials.
In this article, we review some recent theoretical results about intrusion and extrusion of non-wetting liquids in and out of cavities of nanotextured surfaces and nanoporous materials. Nanoscale confinement allows these processes to happen at conditions which significantly differ from bulk phase coexistence. In particular, the pressure at which a liquid penetrates in and exits from cavities is of interest for many technological applications such as energy storage, dissipation, and conversion, materials with negative compressibility, ion channels, liquid chromatography, and more. Notwithstanding its technological interest, intrusion/extrusion processes are difficult to understand and control solely via experiments: the missing step is often a simple theory capable of providing a microscopic interpretation of the results, e.g., of liquid porosimetry or other techniques used in the field, especially in the case of complex nanoporous media. In this context, simulations can help shedding light on the relation between the morphology of pores, the chemical composition of the solids and liquids, and the thermodynamics and kinetics of intrusion and extrusion. Indeed, the intrusion/extrusion kinetics is determined by the presence of free energy barriers and special approaches, the so-called rare event techniques, must be used to study these processes. Usually, rare event techniques are employed to investigate processes occurring in relatively simple molecular systems, while intrusion/extrusion concerns the collective dynamics of hundreds to thousands of degrees of freedom, the molecules of a liquid entering in or exiting from a cavity, which, from the methodological point of view, is itself a challenge.