Space Confinement Research Articles

NiCo-MOFs derived carbon matrix composites: A promising electrode construction for high-performance supercapacitors

Metal-organic frameworks (MOFs) are great precursors and templates for preparing adsorbents, catalysts and electrodes due to the porous structure and high specific surface area. We report a promising approach to prepare nanocrystalline Co, Ni sulfides (CNS) embedded and N self-doped porous carbon (NPC) matrix composites derived from NiCo-MOFs. The CNS@NPC composite was investigated as electrodes for hybrid supercapacitors (HSCs). The prepared electrode achieved specific capacitance of 2789 F g−1 at 1 A/g, and high capacitance retention of 88.93% after 6000 galvanostatic charge–discharge (GCD) cycles under 10 A/g. The HSC structured with CNS@NPC//AC achieved an energy density of 46.79 Wh kg−1 at power density of 800 W kg−1. Meanwhile, specific capacitance of 131.56 F g−1 at 1 A/g and capacitance retention of 99.17% over 6000 GCD cycles under 3 A/g were obtained. Space confinement by the carbon skeleton effectively prevents the aggregation of the redox active nanocrystalline and improves the durability of the electrode. Meanwhile, the carbon skeleton provides abundant charge transfer channels to enhance the redox reaction. In other words, synergistic effect of the carbon skeleton and the active redox nanocrystalline significantly improves the electrochemical properties of the composite.

Integrating few-atom layer metal on high-entropy alloys to catalyze nitrate reduction in tandem

While high-entropy alloy (HEA) catalysts seem to have the potential to break linear scaling relationships (LSRs) due to their structural complexity, the weighted averaging of properties among multiple principal components actually makes it challenging to diverge from the symmetry dependencies imposed by the LSRs. Herein, we develop a ‘surface entropy reduction’ method to induce the exsolution of a component with weak affinity for others, resulting in the formation of few-atom-layer metal (FL-M) on the surface of HEAs. These exsolved FL-M surpass the confines of the original configurational space of conventional HEAs, and collaborate with the HEA substrate, serving as geometrically separated active sites for multiple intermediates in a complex reaction. This FL-M-covered HEA shows an outstanding performance for electrocatalytic reduction of nitrate to ammonia (NH3) with a Faradaic efficiency of 92.7%, an NH3 yield rate of 2.45 mmol h–1 mgcat.–1, and high long-term stability (>200 h). Our work achieves the precise manipulation of atomic arrangement, thereby expanding both the chemical space occupied by known HEA catalysts and their potential application scenarios.

Engendering carcerality: An introduction

AbstractReflecting the carceral turn in scholarship, this introduction to a special issue on engendering carcerality explores the difference that gender makes in the history of the carceral in its various forms over time and space. It considers the multiple meanings and spaces of imprisonment, surveillance, and confinement; incarceration of mothers; confinement of sex workers; imprisoning of political prisoners, and reforming of youths, taking account of intersectional identities, sexuality and resistance. It looks forward by looking back, engaging in a dialogue with abolitionist movements and current global struggles to encourage critical gendered histories of incarceration and resistance.

Interfacial space confinement engineering toward ultrastable all-climate aqueous zinc ion batteries

The interfacial instability, particularly uncontrollable Zn nucleation and deposition, significantly impeding the commercialization of aqueous zinc ion batteries (ZIBs). Herein, we propose an interfacial space confinement strategy to enable the dendrite-free anode, specifically through constructing a zincophilic buffer layer based on hollow Sn@C. The porous Sn@C contributes to modify the electrical double layer structure, which greatly alleviates the concentration polarization during high-rate plating. In-situ experimental results demonstrate the inhibited H2O-mediated parasitic side reactions and the absence of dendrite deposition morphology. Based on the improved thermodynamics and kinetics, zincophilic buffer layers can deliver low nucleation overpotential (20 mV), ultrastable cycle life (> 5000 h), and excellent zinc utilization rate (62.4%). Importantly, the full batteries with zincophilic buffer layer exhibit excellent electrochemical stability over -40 to 70 °C, pushing forward the construction of advanced all-climate ZIBs.

Nitrogen-doped amorphous monolayer carbon.

Monoatomic-layered carbon materials, such as graphene1 and amorphous monolayer carbon2,3, have stimulated intense fundamental and applied research owing to their unprecedented physical properties and a wide range of promising applications4,5. So far, such materials have mainly been produced by chemical vapour deposition, which typically requires stringent reaction conditions compared to solution-phase synthesis. Herein, we demonstrate the solution preparation of free-standing nitrogen-doped amorphous monolayer carbon with mixed five-, six- and seven-membered (5-6-7-membered) rings through the polymerization of pyrrole within the confined interlayer cavity of a removable layered-double-hydroxide template. Structural characterizations and first-principles calculations suggest that the nitrogen-doped amorphous monolayer carbon was formed by radical polymerization of pyrrole at the α, β and N sites subjected to confinement of the reaction space, which enables bond rearrangements through the Stone-Wales transformation. The spatial confinement inhibits the C-C bond rotation and chain entanglement during polymerization, resulting in an atom-thick continuous amorphous layer with an in-plane π-conjugation electronic structure. The spatially confined radical polymerization using solid templates and ion exchange strategy demonstrates potential as a universal synthesis approach for obtaining two-dimensional covalent networks, as exemplified by the successful synthesis of monolayers of polythiophene and polycarbazole.

Epitaxial Growth of Cs3Cu2I5 Single‐Crystal Arrays for UV‐Responsive Neuromorphic Devices

Copper‐based halides, a type of perovskite derivative, inherit their excellent optoelectronic properties and solution processability and also have the advantages of being nontoxic and stable. Despite the tremendous achievements of microfabrication in conventional halide perovskites, reports on copper‐based halide array devices are rare due to their difficult high‐quality crystallization. Here, by introducing single‐crystal thin films grown by space confinement method as substrates, reliable photolithography based on their single crystals is successfully achieved and controllable homoepitaxial single‐crystal arrays is demonstrated. By adjusting the substrate, angle, and growth time, the orientation, arrangement, and size of arrays could be controlled. Temperature and time are used to regulate the growth stage to obtain clean and appropriately sized arrays. ITO/Cs3Cu2I5/ITO neuromorphic device based on homoepitaxial arrays is developed. The variation of synaptic plasticity could be controlled by the number and frequency of light pulses. The device successfully simulated the process of “learning, forgetting, and relearning” in the human brain, demonstrating the potential of application in sensing‐storage‐computing‐integrated devices.

Prediction of human initial operation situation in confined space with a multi-task deep neural network

Most large manufacturing fields still rely on manual operations, requiring operators to enter the Confined Space (CS) to conduct assembly and maintenance tasks. The ergonomics analysis combined with the Digital Human Model (DHM) can provide valuable suggestions and guidance for product structure design and process planning. Due to the particularity of CS, the current algorithms applied to DHM operation planning are not suitable for CS operations. To address this challenge, we introduce a novel approach to predict the initial operation situation in CS. The Restriction State Expression Model for Bi-Directional Confined Space (RSEMfBDCS) is introduced to quantify the restricted degree, and a novel multi-task deep neural network, as the Human Operation Situation Prediction Network in CS (HOSPNiCS) is developed to predict the initial operation situation in CS, which includes operation reachability, the initial OPI, and the initial OPII of the operators. Training and Verifying by the data collected from the real operation cases, HOSPNiCS distinguishes whether the manual operation is reachable with an average accuracy of 0.996, and the average accuracy for initial OPI prediction can reach 0.957. For initial OPII prediction, HOSPNiCS has an average distance error of 0.036 m and an average angle error of 0.395°. Based on the proposed approach, the engineering designers can swiftly ascertain operation reachability and get the initial OPI and OPII of DHM with the help of the prediction results. In light of this, the human operation simulation would be more practical for future human factor analysis.

Operation characteristics and limitations of small-diameter two-phase closed thermosyphon

Two-phase closed thermosyphon (TPCT) is a latent heat-based, high-efficiency heat transfer device primarily utilized in heat pipe heat exchangers in waste heat recovery (WHR) applications. Recently, there has been increasing interest in small-diameter TPCT due to thermal confinement issues and space and cost limitations of heat transfer devices. The nature of the two-phase flow and the resulting thermal performance of a small-diameter thermosyphon differ from that of a large-diameter thermosyphon, which is called the “confinement effect” of TPCT. In the present study, we experimentally explored the internal flow and heat transfer characteristics of TPCT with a very small inner diameter of 5 mm. Based on the Laplace length, which means the characteristic bubble size, four working fluids were considered: water, acetone, ethanol, and the HFE-7000. As a result, except for a specific condition where the degree of confinement and heat flux were very low, the shear force between the falling liquid condensate and upward vapor prevented the smooth circulation of working fluid inside the small-diameter channel. This caused local dry-out of the evaporator, resulting in the effective thermal conductivity of the TPCT being lower than that of the copper block.

Regulating Li+ transport behavior by cross-scale synergistic rectification strategy for dendrite-free and high area capacity polymeric all-solid-state lithium batteries

The inability to effectively inhibit the lithium (Li) dendrite growth is identified as the real culprit hindering the practical application of polyethylene oxide (PEO)-based electrolytes. Herein, a novel PEO composite electrolyte with ion rectifier is developed based on the cross-scale synergistic rectification strategy. At the micro-scale, the array structure of the ion rectifier suppresses the growth of PEO crystals and their distribution in the non-ionic conduction direction through space confinement, alleviating ion-migration crosstalk and enabling polymer chain rectification. Furthermore, the matrix contains abundant copper ions and oxygen-containing groups that inhibit anion conduction and accelerate Li+ migration at the nanoscale, respectively, to achieve ion flow rectification. Implementing this strategy results in a uniform, fast, and stable Li+ migration/diffusion behavior from the electrolyte to anode interface. The critical current density of the PEO electrolyte is increased to 2.5 mA cm−2, indicating a significant improvement in dendrite growth inhibition. Impressively, the composite electrolytes exhibit long-term stability (>4000 h at 0.2 mA cm−2) and ultra-high current-density tolerance (>200 h at 1 mA cm−2). Moreover, the composite electrolytes enable stable cycling of high-area-capacity (3.11 mAh cm−2, 20 mg cm−2) LiFePO4/Li pouch cells, highlighting the importance of this strategy for the practical application of PEO electrolytes.

Sub-nanometer size level regulation of biomimetic channels in porous membrane for high-capacity removal of toxic dye contaminants

Organic dyes are an important chemical with a market demand of millions of tons. However, their massive emissions, especially alkaline dye contaminants, have caused serious disruption of the ecosystem and even cancers. Inspired by bionic mass transfer, several amino acid fragments (carboxylic acid, γ-aminobutyric acid, and glutamic acid) are introduced into the 2.5 nm-pore size cavity through in-situ polymerization. The flexible amino acid chains facilitate the transport of guest molecules into the channels, accelerating their movement within the porous framework. These flexible chains are implanted into a 2.5 nm pore cavity, forming a 0.8–1.5 nano-meter-sized confinement space, bringing about the strong absorption capability for alkaline contaminants. Notably, LNU-74-glutamic acid achieves an ultra-fast absorption rate for toxic dye contaminants (4.74 g g−1h−1), as well as the highest capacity per unit area among all reported porous adsorbents, including porous carbons, metal–organic frameworks, porous polymers. After encapsulation in commercial polymer, the mixed-matrix membrane reveals (LNU-74-glutamic acid@MMM) a rejection rate greater than 98 % in various real water environments at permeation flux of ∼320 L m−2h−1, including strong acid/alkali, river water, and seawater.

Curvature strain tunes electron transfer accelerates peroxymonosulfate activation to achieve high-efficiency advanced oxidation

The development of high performance and stable heterogeneous catalysts is conducive to promoting the advanced oxidation process (AOPs) to promote the degradation of organic pollutants efficiently, low-cost and environmentally friendly. Here nitrogen-doped hollow carbon spheres (NHCSs) and rigid organic molecule were used to create space confinement and complexation confinement conditions, respectively, and an advanced single-atom catalyst capable of strongly activating peroxymonosulfate (PMS) to degrade organic pollutants was finally constructed. The AOPs system driven by CoNC/NHCSs (20 mg) combined with PMS (20 mg) can degrade nearly 100 % of 20 mg/L (100 mL) bisphenol A (BPA, a microplastic) pollutant within 30 min, and the mineralization rate is up to 70.5 %. Face the complex water environment, such as sewage containing coexisting anions and cations, or acidic or alkaline sewage, the CoNC/NHCSs/PMS system still has high catalytic stability, and universality for other organic pollutants. The filter column with CoNC/NHCSs as the core also realizes the continuous purification of organic pollutants, which shortens the distance between laboratory research and practical application. Radical quenching and electron paramagnetic resonance techniques confirmed that CoNC/NHCSs activated PMS to SO4·−, ·OH, and 1O2, and these reactive oxygen species combined to eliminate organic pollutants. Density functional theory (DFT) calculations jointly confirm that the strong activation of PMS by CoNC/NHCSs is the key to achieving efficient degradation of organic pollutants, and the activity of CoNC/NHCSs is derived from high exposure rate of active sites and curvature effect caused by structural bending.

Proton transfer induced persistent triplet charge transfer phosphorescence in molecule-doped polymer systems

The intermolecular interactions between small molecules and the matrix in a highly polar environment could easily lead to non-radiative transitions, which significantly hampers the development of high-performance persistent room-temperature phosphorescence (pRTP) materials in such condition. Herein, we introduce a novel strategy that integrates consecutive proton transfer and photo-induced charge transfer to facilitate triplet charge transfer emission in highly polar polymer matrix. In particular, doping aza-arene guests including 1,10-phenanthroline (1,10-Phen), 2,9-dimethyl-1,10-phenanthroline (DM-Phen), and 7,8-benzoquinoline (7,8-BQ) into polyacrylic acid (PAA) resulted in superior pRTP properties compared to other polymer hosts. Spectroscopic investigations and theoretical calculations elucidate that this is attributed to the proton transfer and triplet charge transfer characteristics between the host and guest. Moreover, due to the rigid environment and space confinement provided by PAA, pRTP with the lifetime up to 841 ms is achieved. Capitalizing on the excellent water solubility of the doped PAA films, the inkjet printings have been executed, and showcasing the promising the potential applications of these pRTP materials in the field of information encryption.

Structure, Dynamics, and Reactivity of Encapsulated Molecules in Restricted Spaces: Arylazoisoxazoles within an Octa Acid Capsule.

In this study, a well-defined organic capsule assembled from two octa acid (OA) molecules acting as host and select arylazoisoxazoles (AAIO) acting as guests were employed to demonstrate that confined molecules have restricted freedom that translates into reaction selectivity in both ground and excited states. The behavior of these AAIO guests in confined capsules was found to be different from that found in both crystals, where there is very little freedom, and in isotropic solvents, where there is complete freedom. Through one-dimensional (1D) and two-dimensional (2D) 1H NMR spectroscopic experiments, we have established a relationship between structure, dynamics and reactivity of molecules confined in an OA capsule. Introduction of CF3 and CH3 substitution at the 4-position of the aryl group of AAIO reveals that in addition to space confinement, weak interactions between the guest and the OA capsule control the dynamics and reactivity of guest molecules. 1H NMR studies revealed that there is a temperature-dependence to guest molecules tumbling (180° rotation along the capsular short axis) within an OA capsule. While 1H NMR points to the occurrence of tumbling motion, MD simulations and simulation of the temperature-dependent NMR signals provide an insight into the mechanism of tumbling within OA capsules. Thermal and photochemical isomerization of AAIO were found to occur within an OA capsule just as in organic solvents. The observed selectivity noted during thermal and photo induced isomerization of OA encapsulated AAIOs can be qualitatively understood in terms of the well-known concepts due to Bell-Evans-Polanyi (BEP principle), Hammond and Zimmerman.

Sustainable urban road planning under the digital twin-MCDM-GIS framework considering multidisciplinary factors

Sustainable urban road planning necessitates the formulation of functional, economic, people-friendly, eco-friendly, and engineering-reasonable road schemes within the confines of limited urban space. It is challenging to meet traffic demands, stimulate economic growth, foster social progress, and minimize adverse impacts on the social and natural environment. This study proposes a comprehensive approach for sustainable urban road planning, employing the Digital Twin-MCDM-GIS framework. Digital twins play a pivotal role in converting diverse factors into comprehensible expressions. MCDM (multi-criteria decision making) evaluates and assigns weights to these multidisciplinary factors. GIS (geographic information system) offers an integrated digital space for analysis. Various digitalisation and parsing methods, including direct assignment methods, spatial analysis methods, and complex professional methods, are introduced for traffic, development, cost, social, environmental, and engineering factors. By assigning distinct weights to these factors, diverse raster data are established to generate multiple road schemes using the least-cost wide path analysis. To validate the proposed approach, a case study was conducted in the London Borough of Bromley, resulting in the generation of 14 road schemes with varying widths and factor considerations in limited urban space.

Hollow g-C3N4@Ag3PO4 Core-Shell Nanoreactor Loaded with Au Nanoparticles: Boosting Photothermal Catalysis in Confined Space.

Low solar energy utilization efficiency and serious charge recombination remain major challenges for photocatalytic systems. Herein, a hollow core-shell Au/g-C3N4@Ag3PO4 photothermal nanoreactor is successfully prepared by a two-step deposition method. Benefit from efficient spectral utilization and fast charge separation induced by the unique hollow core-shell heterostructure, the H2 evolution rate of Au/g-C3N4@Ag3PO4 is 16.9 times that of the pristine g-C3N4, and the degradation efficiency of tetracycline is increased by 88.1%. The enhanced catalytic performance can be attributed to the ordered charge movement on the hollow core-shell structure and a local high-temperature environment, which effectively accelerates the carrier separation and chemical reaction kinetics. This work highlights the important role of the space confinement effect in photothermal catalysis and provides a promising strategy for the development of the next generation of highly efficient photothermal catalysts.

Study of the immune disorder and metabolic dysregulation underlying mental abnormalities caused by exposure to narrow confined spaces

Prolonged confinement in cramped spaces can lead to derangements in brain function/structure, yet the underlying mechanisms remain unclear. To investigate, we subjected mice to restraint stress to simulate long-term narrow and enclosed space confinement, assessing their mental state through behavioral tests. Stressed mice showed reduced center travel and dwell time in the Open Field Test and increased immobility in the Tail Suspension Test. We measured lower hippocampal brain-derived neurotrophic factor levels and cortical monoamine neurotransmitters (5-HT and NE) in the stressed group. Further examination of the body’s immune levels and serum metabolism revealed immune dysregulation and metabolic imbalance in the stressed group. The results of the metabolic network regulation analysis indicate that the targets affected by these differential metabolites are involved in several metabolic pathways that the metabolites themselves participate in, such as the “long-term depression” and “purine metabolism” pathways. Additionally, these targets are also associated with numerous immune-related pathways, such as the TNF, NF-κB, and IL-17 signaling pathways, and these findings were validated using GEO dataset analysis. Molecular docking results suggest that differential metabolites may regulate specific immune factors such as TNF-α, IL-1β, and IL-6, and these results were confirmed in experiments. Our research findings suggest that long-term exposure to confined and narrow spaces can lead to the development of psychopathologies, possibly mediated by immune system dysregulation and metabolic disruption.

In Situ Universal Construction of Thiophosphite/MXene Hybrids via Lewis Acidic Etching for Superior Sodium Storage

AbstractMetal thiophosphite has demonstrated promising application potential as an anode material for sodium‐ion batteries. Nevertheless, the intrinsic low electrical conductivity and drastic volume expansion impede its commercialization. Herein, a series of metal thiophosphite/Ti3C2Tx (metal = Fe, Ni, Co, and Cd) composites are constructed via Lewis acidic molten salt etching followed by synchronous phospho‐sulfurization. The Ti3C2Tx substrate endows the thiophosphite/Ti3C2Tx hybrids with high electrical conductivity. Importantly, thiophosphite grown on the MXene layers exhibits a 3D cross‐linked structure, which not only facilitates electron/ion transport, but also maintains robust structural stability owing to the space confinement effect. As a proof of concept, FePS3/Ti3C2Tx demonstrates remarkable rate performance (827.4 and 598.1 mAh g−1 at 0.1 and 10 A g−1, respectively) along with long‐term cycling stability (capacity retention of 93.7% after 2000 cycles at 5 A g−1). Impressively, the FePS3/Ti3C2Tx//NVPO full cell exhibits a high reversible capacity of 396.8 mAh g−1 over 1350 cycles at 2 A g−1. The sodium storage mechanism of FePS3/Ti3C2Tx anode is further unveiled through in situ XRD/ex situ HRTEM characterizations and theoretical calculations. This work provides a fresh perspective on enhancing the electrochemical performance of thiophosphite through the in situ construction of thiophosphite/Ti3C2Tx hybrids.

SP-SAT: DEVELOPMENT OF AN EDUCATIONAL SATELLITE

n Bolivia, as in several other Latin American nations, there is a growing trend of burgeoning space projects and a rising interest among young students in the aerospace domain. Consequently, there arises an imperative to cultivate a new generation of space professionals. However, the exorbitant costs associated with the equipment utilized in these projects render them inaccessible to a vast majority of inter- ested students, including CubeSat kits, educational satellites, satellite kits, among others. Consequently, alternatives like educational sat- ellites have emerged to simulate the satellite design, construction, testing, launch, and operation processes on a scale conducive to student involvement. The primary challenge faced by students lies in integrating the essential subsystems of a satellite, encompassing power supply, sensors, and communication systems, within the confines of limited space. Considering this, the design and construction of an educational satellite with its respective signal reception equipment was developed. The equipment designed and manufactured is a low-cost one so that universities and educational centers could acquire it. This equipment educational kit is called SP-SAT (Space Program — educational satellite kit). This real satellite simulator offers a wide variety of educational activities. The kit’s equipment is distributed in two systems: 1) Space Segment, which consists of an Onboard Computer (OBC), Electrical Power System (EPS), Communications System (COMM), Experiment Plate (PYL), Complete PLA plastic structure (3D printed), rods, bolts, and nuts. 2) Ground segment: This segment includes all the equipment that is part of the ground station, which will receive data from the satellite.

Phase behavior of ionic fluid in charged confinement: An associating polymer density functional theory study

AbstractWith the rapid advancement of the new energy industry, porous electrode materials and complex electrolytes have gained widespread usage. Electrolytes exhibit distinctive phase behavior when subjected to the combined influence of confined space and electric fields. However, the measurement and prediction of such phase behavior encounter significant challenges. Consequently, numerous theoretical tools have been employed to establish models for phase equilibrium calculations. Nevertheless, current research in this field has notable limitations and fails to address the confinement of space or complex polymer electrolytes. Considering these shortcomings, an associating polymer density functional theory (PDFT) was developed by modifying excess free energy. This study examines the phase behavior of electrolytes with various chain lengths within diverse confined slits, revealing that the confinement effect and fluid tail chains can narrow the phase diagram. Additionally, a linear correlation between the electric field strength and the phase equilibrium offset has been identified, and a quantitative relationship is derived. The results of this investigation contribute to a deeper comprehension of complex fluid phase behavior and guide the design of electrochemical devices.

Assessment of the macrovascular contribution to resting-state fMRI functional connectivity at 3 Tesla

Abstract In resting-state functional magnetic resonance imaging (rs-fMRI) functional connectivity (FC) mapping, temporal correlation is widely assumed to reflect synchronized neural-related activity. Although a large number of studies have demonstrated the potential vascular effects on FC, little research has been conducted on FC resulting from macrovascular signal fluctuations. Previously, our study found (Tong, Yao, et al., 2019) a robust anti-correlation between the fMRI signals in the internal carotid artery and the internal jugular vein (and the sagittal sinus). The present study extends the previous study to include all detectable major veins and arteries in the brain in a systematic analysis of the macrovascular contribution to the functional connectivity of the whole-gray matter (GM). This study demonstrates that: (1) The macrovasculature consistently exhibited strong correlational connectivity among itself, with the sign of the correlations varying between arterial and venous connectivity; (2) GM connectivity was found to have a strong macrovascular contribution, stronger from veins than arteries; (3) FC originating from the macrovasculature displayed disproportionately high spatial variability compared to that associated with all GM voxels; and (4) macrovascular contributions to connectivity were still evident well beyond the confines of the macrovascular space. These findings highlight the extensive contribution to rs-fMRI blood-oxygenation level-dependent (BOLD) and FC predominantly by large veins, but also by large arteries. These findings pave the way for future studies aimed at more comprehensively modeling and thereby removing these macrovascular contributions.