Effect Of Nanoscale Confinement Research Articles

Boosting Osmotic Energy Harvesting from Organic Solutions by Ultrathin Covalent Organic Framework Membranes.

Extracting osmotic energy from waste organic solutions via reverse electrodialysis represents a promising approach to reuse such industrial wastes and helps to mitigate the ever-growing energy needs. Herein, a molecularly thin membrane of covalent organic frameworks is engineered via interfacial polymerization to investigate its ion transport behavior in organic solutions. Interestingly, a significant deviation from linearity between ion conductance and reciprocal viscosity is observed, attributed to the nanoscale confinement effect on intermolecular interactions. This finding suggests a potential strategy to modulate the influence of apprarent viscosity on transmembrane transport. The osmotic energy harvesting of the ultrathin membrane in organic systems was studied, achieving an unprecedented output power density of over 84.5 W m-2 at a 1000-fold salinity gradient with a benign conversion efficiency and excellent stability. These findings provide a meaningful stepping stone for future studies seeking to fully leverage the potentials of organic systems in energy harvesting applications.

Investigation on the flow behavior and mechanisms of water flooding and CO2 immiscible / miscible flooding in shale oil reservoirs

Shale reservoirs represent a significant untapped source of recoverable oil, and even a slight increase in recovery can yield substantial benefits. In recent years, there has been a growing interest in the development of shale reservoirs due to their vast potential. Shale reservoirs are characterized by their intricate pore structures, ultra-low porosity, and extremely low permeability. Consequently, fluid flow within shale formations is highly complex, and the distribution of shale oil is diverse. There is an urgent need to conduct research into the flow behavior of shale reservoirs and the modes of crude oil occurrence within them, in order to support effective shale oil extraction in the field. In this work, we established a MCMP-MRT-LBM model considering nano-scale confinement effects such as slip and adsorption. The model is employed to simulate single pore channels and blind-end pores to investigate the distinct mechanisms involved in water flooding, CO2 immiscible flooding, and CO2 miscible flooding. Subsequently, the research explores the fluid flow characteristics associated with these three development methods within porous media, as well as the distribution of remaining oil. Then we compared the oil displacement efficiency, swept volume, actual liquid injection volume and displacement front position of the three fluids in porous media. The results reveal that water flooding exhibits superior displacement performance in single pore channels, while CO2 miscible flooding proves to be the most effective method for exploiting oil in blind-end pores. In porous media, CO2 miscible flooding successfully mitigates fingering phenomena and efficiently recovers crude oil located at blind-end and corner regions of the pores. The recovery efficiency achieved through CO2 miscible flooding is approximately 30% higher than that of water flooding and about 10% greater than CO2 immiscible flooding.

Computational Analysis of the Effects of Nanoscale Confinement on the Structure of Low-k Dielectric Hybrid Organosilicate Materials

Computational Analysis of the Effects of Nanoscale Confinement on the Structure of Low-k Dielectric Hybrid Organosilicate Materials

Effects of nanoscale confinement on hydrogen in porous carbons

Effects of nanoscale confinement on hydrogen in porous carbons

Nanoscale Confinement Effects on Ionic Conductivity of Solid Polymer Electrolytes: The Interplay between Diffusion and Dissociation.

Solid polymer electrolytes (SPEs) are attractive for next-generation lithium metal batteries but still suffer from low ionic conductivity. Nanostructured materials offer design concepts for SPEs with better performance. Using molecular dynamics simulation, we examine SPEs under nanoscale confinement, which has been demonstrated to accelerate the transport of neutral molecules such as water. Our results show that while ion diffusion indeed accelerates by more than 2 orders of magnitude as the channel diameter decreases from 15 to 2 nm, the ionic conductivity does not increase significantly in parallel. Instead, the ionic conductivity shows a nonmonotonic variation, with an optimal value above, but on the same order as, its bulk counterparts. This trend is due to enhanced ion association with decreasing channel size, which reduces the number of effective charge carriers. This effect competes with accelerated ion diffusion, leading to the nonmonotonicity in ion conductivity.

Growth of nanostructured molybdenum disulfide (MoS2) thin films on a nanohole-patterned substrate using plasma-enhanced atomic layer deposition (ALD)

Nanostructured molybdenum disulfide (MoS2) thin films were grown on a nanohole-patterned silicon substrate using plasma-enhanced atomic layer deposition. A nanoscale hole-patterned silicon substrate was fabricated for the growth of MoS2 film using the self-assembly-based nanofabrication method. The nanoscale holes can significantly increase the surface area of the substrate while the formation and growth of nanostructures normally start at the surface of the substrate. Hydrogen sulfide (H2S) gas was used as the S source in the growth of molybdenum disulfide (MoS2) while molybdenum (V) chloride (MoCl5) powder was used as the Mo source. The MoS2 film had a stoichiometric ratio of 1 (Mo) to 2 (S), and had peaks of E12g and A1g, which represent the in-plane and out-plane vibration modes of the Mo–S bond, respectively. It was found that the MoS2 film grown in the nanoscale hole, especially at the wall of the hole, has more hexagonal-like structures due to the effects of nanoscale space confinement and the nanoscale interface although the film shows an amorphous structure. Post-growth high-temperature annealing ranging from 800 to 900 °C produced local crystalline structures in the film, which are compatible with those reported by other researchers.

Single bubble nucleation in water-filled 59-nm nanochannel

Bubble nucleation, by surface heating, is simulated in a water-filled 59 nm height silicon-dioxide nanochannel using computational fluid dynamics. Disjoining pressure of water is integrated in the continuum-level simulations to capture the molecular effects of nanoscale confinement. Input parameters of imposed heat flux and phase-transition coefficient are widely varied to perform a set of 50 simulations. Bubble nucleation occurs within a narrow temperature range of 124.7 ± 2.5 °C, and in excellent agreement with prior experimental finding. Onset of bubble nucleation occurs at the center of the channel rather than at the surface due to the presence of disjoining pressure, i.e., no three-phase contact line forms and a water film is present between the bubble and the surface. Post nucleation, three distinct paths of bubble collapse, steady-state, and continuous growth are observed, with the last case leading to formation of three-phase contact line. Such behavior is attributed to a critical thickness of the water film and associated disjoining pressure. The present work sheds light on the importance of disjoining pressure and its dominance in governing the bubble onset and growth behavior. Such fundamental understanding can potentially advance the development of future thermal management devices, such as heat pipes.

Extreme hardness via nanoscale confinement effects in ultra-low density carbon matrix nanocomposites

Polymer-derived pyrolytic carbons (PyCs) are often desirable for low density high-temperature structural applications when they can be reinforced with high stiffness and strength fibers to address brittleness. Nanofibers, such as aligned carbon nanotubes (A-CNTs), can be an ideal reinforcement owing to their high mass-specific properties, and while modeling suggests that properties of A-CNTs at high volume fractions (i.e., 10–30 vol%) could yield significant enhancements, it is unknown how CNT confinement influences processing, as such materials have never been synthesized. Here, we report process development demonstrating the first successful fabrication of fully infused, void-free A-CNT carbon matrix nanocomposites (A/C-NCs) via polymer infiltration pyrolysis (PIP) that establishes a platform to study nanofiber-reinforced polymer-derived ceramics. The size of the average A/C-NC graphitic crystallites increases as CNT vol% increases up to 30 vol%, and the inter-layer separation of the PyC graphitic crystallites decreases, evidencing a nanoscale confinement effect observed in concert with increased mechanical performance. Vickers microhardness testing in the axial CNT direction of A/C-NCs shows agreement with prior data for low vol% CNTs in PyC and mechanical modeling, where specific hardness increases from ∼3.3 GPa/(g/cm3) for PyC to ∼6.7 GPa/(g/cm3) for 30 vol% A/C-NCs, demonstrating A/C-NCs as an advantaged superhard lightweight material.

Universal Behavior of Highly Confined Heat Flow in Semiconductor Nanosystems: From Nanomeshes to Metalattices

Nanostructuring on length scales corresponding to phonon mean free paths provides control over heat flow in semiconductors and makes it possible to engineer their thermal properties. However, the influence of boundaries limits the validity of bulk models, while first-principles calculations are too computationally expensive to model real devices. Here we use extreme ultraviolet beams to study phonon transport dynamics in a 3D nanostructured silicon metalattice with deep nanoscale feature size and observe dramatically reduced thermal conductivity relative to bulk. To explain this behavior, we develop a predictive theory wherein thermal conduction separates into a geometric permeability component and an intrinsic viscous contribution, arising from a new and universal effect of nanoscale confinement on phonon flow. Using experiments and atomistic simulations, we show that our theory applies to a general set of highly confined silicon nanosystems, from metalattices, nanomeshes, porous nanowires, to nanowire networks, of great interest for next-generation energy-efficient devices.

Intermetallic Nanoarchitectures for Efficient Electrocatalysis.

Intermetallic structures whose regular atomic arrays of constituent elements present unique catalytic properties have attracted considerable attention as efficient electrocatalysts for energy conversion reactions. Further performance enhancement in intermetallic catalysts hinges on constructing catalytic surfaces possessing high activity, durability, and selectivity. In this Perspective, we introduce recent endeavors to boost the performance of intermetallic catalysts by generating nanoarchitectures, which have well-defined size, shape, and dimension. We discuss the beneficial effects of nanoarchitectures compared with simple nanoparticles in catalysis. We highlight that the nanoarchitectures have high intrinsic activity owing to their inherent structural factors, including controlled facets, surface defects, strained surfaces, nanoscale confinement effects, and a high density of active sites. We next present notable examples of intermetallic nanoarchitectures, namely, facet-controlled intermetallic nanocrystals and multidimensional nanomaterials. Finally, we suggest the future research directions of intermetallic nanoarchitectures.

Noncanonical DNA Cleavage by BamHI Endonuclease in Laterally Confined DNA Monolayers Is a Step Function of DNA Density and Sequence.

Cleavage of DNA at noncanonical recognition sequences by restriction endonucleases (star activity) in bulk solution can be promoted by global experimental parameters, including enzyme or substrate concentration, temperature, pH, or buffer composition. To study the effect of nanoscale confinement on the noncanonical behaviour of BamHI, which cleaves a single unique sequence of 6 bp, we used AFM nanografting to generate laterally confined DNA monolayers (LCDM) at different densities, either in the form of small patches, several microns in width, or complete monolayers of thiol-modified DNA on a gold surface. We focused on two 44-bp DNAs, each containing a noncanonical BamHI site differing by 2 bp from the cognate recognition sequence. Topographic AFM imaging was used to monitor end-point reactions by measuring the decrease in the LCDM height with respect to the surrounding reference surface. At low DNA densities, BamHI efficiently cleaves only its cognate sequence while at intermediate DNA densities, noncanonical sequence cleavage occurs, and can be controlled in a stepwise (on/off) fashion by varying the DNA density and restriction site sequence. This study shows that endonuclease action on noncanonical sites in confined nanoarchitectures can be modulated by varying local physical parameters, independent of global chemical parameters.

Confinement of Luminescent Guests in Metal-Organic Frameworks: Understanding Pathways from Synthesis and Multimodal Characterization to Potential Applications of LG@MOF Systems.

This review gives an authoritative, critical, and accessible overview of an emergent class of fluorescent materials termed “LG@MOF”, engineered from the nanoscale confinement of luminescent guests (LG) in a metal–organic framework (MOF) host, realizing a myriad of unconventional materials with fascinating photophysical and photochemical properties. We begin by summarizing the synthetic methodologies and design guidelines for representative LG@MOF systems, where the major types of fluorescent guest encompass organic dyes, metal ions, metal complexes, metal nanoclusters, quantum dots, and hybrid perovskites. Subsequently, we discuss the methods for characterizing the resultant guest–host structures, guest loading, photophysical properties, and review local-scale techniques recently employed to elucidate guest positions. A special emphasis is paid to the pros and cons of the various methods in the context of LG@MOF. In the following section, we provide a brief tutorial on the basic guest–host phenomena, focusing on the excited state events and nanoscale confinement effects underpinning the exceptional behavior of LG@MOF systems. The review finally culminates in the most striking applications of LG@MOF materials, particularly the “turn-on” type fluorochromic chemo- and mechano-sensors, noninvasive thermometry and optical pH sensors, electroluminescence, and innovative security devices. This review offers a comprehensive coverage of general interest to the multidisciplinary materials community to stimulate frontier research in the vibrant sector of light-emitting MOF composite systems.

Manipulation of the crystalline phase diagram of hydrogen through nanoscale confinement effects in porous carbons.

Condensed phases of molecular hydrogen (H2) are highly desired for clean energy applications ranging from hydrogen storage to nuclear fusion and superconductive energy storage. However, in bulk hydrogen, such dense phases typically only form at exceedingly low temperatures or extremely high (typically hundreds of GPa) pressures. Here, confinement of H2 within nanoporous materials is shown to significantly manipulate the hydrogen phase diagram leading to preferential stabilization of unusual crystalline H2 phases. Using pressure and temperature-dependent neutron scattering at pressures between 200-2000 bar (0.02-0.2 GPa) and temperatures between 10-77 K to map out the phase diagram of H2 when confined inside both meso- and microporous carbons, we conclusively demonstrate the preferential stabilisation of face-centred cubic (FCC) solid ortho-H2 in microporous carbons, at temperatures five times higher than would be possible in bulk H2. Through examination of nanoconfined H2 rotational dynamics, preferential adsorption and spin trapping of ortho-H2, as well as the loss of rotational energy and severe restriction of rotational degrees of freedom caused by the unique micropore environments, are shown to result in changes to phase behaviour. This work provides a general strategy for further manipulation of the H2 phase diagram via nanoconfinement effects, and for tuning of anisotropic potential through control of confining material composition and pore size. This approach could potentially provide lower energy routes to the formation and study of more exotic non-equilibrium condensed phases of hydrogen that could be useful for a wide range of energy applications.

Confined crystallization in the binary blends of diblock copolymers bearing stereoisomeric isotactic and syndiotactic polypropylene

The morphology and crystallization behavior of the binary blends of two crystalline-amorphous diblock copolymers bearing stereoisomeric crystalline blocks have been investigated. A polystyrene-block-isotactic polypropylene (S-iPP) and a polystyrene-block-syndiotactic polypropylene (S-sPP) were used to prepare a series of blends forming lamellar morphology. In the melt state, the PS blocks from these two diblock copolymers mixed intimately in the PS lamellar microdomains; meanwhile, the iPP and sPP blocks were found to form a miscible mixture in the PP domains. Under the effects of nanoscale confinement and the constraint imposed by the junction points, the iPP and sPP blocks exhibited the crystallization behavior greatly deviated from that in the neat diblock copolymers. A local demixing between a fraction of iPP and sPP chains was found to occur in the S-sPP-rich blend at low crystallization temperatures, which yielded the defective crystalline domains composed of alternately intervened iPP and sPP crystallites. This crystalline species displayed a significant depression of melting point located at the temperature around 10°C higher than the corresponding Tc due to an excess surface free energy at the interface between the alternately intervened iPP and sPP crystallites.

Effect of Nanoscale Confinement on Polymer-Infiltrated Scaffold Metal Composites

Most research on polymer composites has focused on adding discrete inorganic nanofillers to a polymer matrix to impart properties not found in polymers alone. However, properties such as ion conductivity and mechanical reinforcement would be greatly improved if the composite exhibited an interconnected network of inorganic and polymer phases. Here, we fabricate bicontinuous polymer-infiltrated scaffold metal (PrISM) composites by infiltrating polymer into nanoporous gold (NPG) films. Polystyrene (PS) and poly(2-vinylpyridine) (P2VP) films are infiltrated into the ∼43 nm diameter NPG pores via capillary forces during thermal annealing above the polymer glass transition temperature (Tg). The infiltration process is characterized in situ using spectroscopic ellipsometry. PS and P2VP, which have different affinities for the metal scaffold, exhibit slower segmental dynamics compared to their bulk counterparts when confined within the nanopores, as measured through Tg. The more attractive P2VP shows a 20 °C increase in Tg relative to its bulk, while PS only shows a 6 °C increase at a comparable molecular weight. The infiltrated polymer, in turn, stabilizes the gold nanopores against temporal coarsening. The broad tunability of these polymer/metal hybrids represents a unique template for designing functional network composite structures with applications ranging from flexible electronics to fuel cell membranes.

Ultrathin Ti3C2 nanowires derived from multi-layered bulks for high-performance hydrogen evolution reaction

One-dimensional ultrathin nanowires (NWs) offer a great deal of promising properties for electrochemical energy storage and conversion due to their nanoscale confinement effect and high surface-to-volume ratios. It is highly desirable to precisely design and synthesize ultrathin Ti3C2 NWs in the aspect of size, crystalline structure and composition. Here, we report a simple alkalization strategy to design the ultrathin Ti3C2 NWs for hydrogen evolution reaction (HER) by modulating the surface-active sites. The design principle can well improve the amount of the defect sites and ion accessibility to increase the interactions between Ti3C2 NWs and H*. The optimized Ti3C2 NWs achieve an overpotential of 476 mV at the current density of 10 mA/cm2 and a Tafel slope of 129 mV/dec for HER catalysis, which are superior to that of Ti3C2 nanosheets and m-Ti3C2. It paves an avenue for the rational transformation of MXene bulks to one-dimensional NWs catalysts for HER.

Mechanistic insight into gold nanorod transformation in nanoscale confinement of ZIF-8

Core-shell hybrid nanomaterials have shown new properties and functions that are not attainable by their single counterparts. Nanoscale confinement effect by porous inorganic shells in the hybrid nanostructures plays an important role for chemical transformation of the core nanoparticles. However, metal-organic frameworks (MOFs) have been rarely applied for understanding mechanical insight into such nanoscale phenomena in confinement, although MOFs would provide a variety of properties for the confining environment than other inorganic shells such as silica and zeolite. Here, we examine chemical transformation of a gold nanorod core enclosed by a zeolitic imidazolate framework (ZIF) through chemical etching and regrowth, followed by quantitative analysis in the core dimension and curvature. We find the nanorod core shows template-effective behavior in its morphological transformation. In the etching event, the nanorod core is spherically carved from its tips. The regrowth on the spherically etched core inside the ZIF gives rise to formation of a raspberry-like branched nanostructure in contrast to the growth of an octahedral shape in bulk condition. We attribute the shell-directed regrowth to void space generated at the interfaces between the etched core and the ZIF shell, intercrystalline gaps in multi-domain ZIF shells, and local structural deformation from the acidic reaction conditions.

The effects of nanoscale confinement on the behavior of metal laminates

By reducing the layer thickness, h, in metal multilayers from micrometer- to nanometer-levels, scale-dependent transitions in behavior are observed. The role of interface properties in these transitions has been extensively investigated. However, reducing h to the nanoscale regime also imposes a physical geometric confinement on defect-related processes occurring within the layers, an effect that is less explored. We present illustrative examples of the influence of nanoconfinement on the strength, structure, and radiation response of multilayers. These examples show that nanoconfinement and interface structure and topology act cooperatively in the nanoscale limit, affecting behaviors that cannot be explained based on either factor alone.

Nanoscale Bubble Dynamics Induced by Damage of Graphene Liquid Cells.

Graphene liquid cells provide the highest possible spatial resolution for liquid-phase transmission electron microscopy. Here, in graphene liquid cells (GLCs), we studied the nanoscale dynamics of bubbles induced by controllable damage in graphene. The extent of damage depended on the electron dose rate and the presence of bubbles in the cell. After graphene was damaged, air leaked from the bubbles into the water. We also observed the unexpected directional nucleation of new bubbles, which is beyond the explanation of conventional diffusion theory. We attributed this to the effect of nanoscale confinement. These findings provide new insights into complex fluid phenomena under nanoscale confinement.

Synthesis and resistivity of topological metal MoP nanostructures

Due to the increased surface to volume ratios, topological nanomaterials can enhance contributions from the topological surface states in transport measurements, which is critical for device applications that exploit the topological properties. It is particularly important for topological semimetals in which bulk carriers are unavoidable to make them into nanostructures to reveal the nature of the topological surface states, such as the Fermi arcs or nodal lines. Here, we report the nanostructure synthesis of the recently discovered triple-point topological metal MoP by direct conversion of MoO3 nanostructures and study their transport properties. We observe that the initial size of the MoO3 templates critically determines the crystalline quality of the resulting MoP nanostructures: large MoO3 flakes lead to porous MoP flakes, while narrow MoO3 nanowires lead to MoP nanowires without pores. The size-dependent porosity observed in MoP nanostructures is attributed to the volume change during the conversion reaction and nanoscale confinement effects. For MoO3 nanowires with diameters less than 10 nm, the resulting MoP nanowires are single crystalline. The resistivity values of MoP nanostructures are higher than the reported values of MoP bulk crystals owing to the porous nature. However, despite the high porosity present in MoP flakes, the residual resistance ratio is ∼2 and the temperature-dependent resistivity curves do not show any strong surface or grain-boundary scattering. Demonstration of the facile synthesis of MoP nanostructures provides opportunities for careful investigations of the surface states in transport measurements and exploration of future electronic devices, including nanoscale interconnects.