Confinement Effect Research Articles

Strong Dipole Moments from Ferrocene Methanol Clusters Boost Exciton Dissociation in Quantum-Confined Perovskite for CO2 Photoreduction.

Perovskite nanocrystals (PCNs) exhibit a significant quantum confinement effect that enhances multiexciton generation, making them promising for photocatalytic CO2 reduction. However, their conversion efficiency is hindered by poor exciton dissociation. To address this, we synthesized ferrocene-methanol-functionalized CsPbBr3 (CPB/FcMeOH) using a ligand engineering approach. By manipulating the electronic coupling between ligands and the PCN surface, facilitated by the increased dipole moment from hydrogen bonding in FcMeOH molecules, we effectively controlled exciton dissociation and interfacial charge transfer. Under 5 h of irradiation, the CO yield of CPB/FcMeOH reached 772.79 μmol g-1, 4.95 times higher than pristine CPB. This high activity is due to the formation of hydrogen-bonded FcMeOH clusters on the CPB surface. The nonpolar disruption and strong dipole moment of FcMeOH molecules enhance electronic coupling between the FcMeOH ligands and the CPB surface, reducing the surface barrier energy. Consequently, exciton dissociation and interfacial charge transfer are promoted, efficiently utilizing multiple excitons in quantum-confined domains. Transient absorption spectroscopy confirms that CPB/FcMeOH exhibits optimized exciton behavior with fast internal relaxation, trapping, and a short recombination time, allowing photogenerated charges to more rapidly participate in CO2 reduction.

Elucidating the selective adsorption of heavy rare earth by phosphate modified silica: The cooperation of pore confinement and surface structure regulating

Rare earths are considered strategic metals, with heavy rare earth elements of greater importance due to their supply and utilization field. However, efficient separation of heavy rare earth elements is a great challenge as the similar physicochemical properties between light and heavy rare earths. In this study, the highly efficient adsorbents with confinement effect are synthesized by the modification of MCM-41 materials with dimethyl clodronate (NP2) and methylene dichlorophosphate (NDP2). The adsorbents were characterized by XRD, TEM, SEM-EDS, N2 adsorption–desorption, FTIR, TG, 13C NMR, and XPS. It was discovered that the pore size of MCM-41 affected markedly the adsorption selectivity, and the cooperation of the organic adsorption center and pore confinement of MCM-41 support enabled the selective adsorption of heavy rare earth ion. The adsorbent modified by NP2 exhibited high adsorption selectivity toward heavy rare earth ions (Lu3+) with the increase in pore size of MCM-41. In contrast, the expanded pore of MCM-41 enhanced the selectivity of light rare earth ions for the NDP2 modified adsorbents. The distribution coefficient of Lu3+ adsorption over NP2-MCM-41(III) adsorbent reached 20,132 mL g−1 and the separation factor of Lu to La reached 82.17. DFT calculations revealed that a vital driving force for the selective adsorption of Lu was the gap of binding energy between Lu and La complexes with the surface NP2/NDP2 groups. The synergy of pore confinement and organic functional groups in adsorbents in this paper offers a valuable strategy for designing efficient materials in the separation of rare earth elements.

High coke resistance Ni-based CH4/CO2 reforming catalysts with strong spatial confinement effect: Effect of CeO2 shell thickness

Ni-based catalysts show promise as candidates for the dry reforming of methane (DRM), yet the susceptibility to sintering and carbon deposition is a major obstacle to industrialization. This work demonstrates a mesoporous Ni-based catalyst with a thickness-tailorable CeO2 shell for enhanced spatial confinement effect for the DRM. The Ni-MCM-41@xCeO2 catalysts are prepared at various CeO2 shell thickness through a two-step hydrothermal reaction. The kinetic studies have shown that the Ni-MCM-41@2CeO2 catalyst has the lowest activation energy, producing a high conversion of CH4 and CO2 as high as around 80 % at 700 °C. Our characterizations reveal that the Ni core is tightly confined in the mesoporous skeleton of MCM-41 and within a CeO2 shell. The Ni-MCM-41@2CeO2 catalyst is able to sustain high activity for more than 10 h of operation, with a remarkably reduced carbon deposition (0.28 %) as compared with a conventional Ni-Ce/MCM-41 catalyst (8.77 %). Furthermore, the density functional theory (DFT) calculation supports that the CeO2 shell layer significantly reduces dissociation potential barrier for CH4 and CO2, hence enhancing the catalytic activity of the DRM.

Selectivity Descriptors of Methanol‐to‐Aromatics Process over 3‐Dimensional Zeolites

AbstractThe zeolite‐catalyzed methanol‐to‐aromatics (MTA) process is a promising avenue for industrial decarbonization. This process predominantly utilizes 3‐dimensional 10‐member ring (10‐MR) zeolites like ZSM‐5 and ZSM‐11, chosen for their confinement effect essential for aromatization. Current research mainly focuses on enhancing selectivity and mitigating catalyst deactivation by modulating zeolites′ physicochemical properties. Despite the potential, the MTA technology is at a low Technology Readiness Level, hindered by mechanistic complexities in achieving the desired selectivity towards liquid aromatics. To bridge this knowledge gap, this study proposes a roadmap for MTA catalysis by strategically combining controlled catalytic experiments with advanced characterization methods (including operando conditions and “mobility‐dependent” solid‐state NMR spectroscopy). It identifies the descriptor‐role of Koch‐carbonylated intermediates, longer‐chain hydrocarbons, and the zeolites′ intersectional cavities in yielding preferential liquid aromatics selectivity. Understanding these selectivity descriptors and architectural impacts is vital, potentially advancing other zeolite‐catalyzed emerging technologies.

Confinement Effect and Application in Catalytic Oxidation–Reduction Reaction of Confined Single-Atom Catalysts

Confinement Effect and Application in Catalytic Oxidation–Reduction Reaction of Confined Single-Atom Catalysts

Triphasic heterostructured Zn–Sn–S hollow nanoboxes encapsulated by N, S-codoped carbon as anodes for high-performance sodium-ion batteries

Metal sulfides have been expected huge practical potential for sodium-ion batteries (SIBs), which are mainly owing to their admirable merits of natural abundance, low price, and high theoretical capacity. However, the inferior electrical conductivity and enormous volume variation originating from sodiation/desodiaziton reactions usually result in unsatisfied rate and cycling properties. In this work, a coprecipitation with a following sulfurization method has been rationally designed to prepare the triphasic heterostructured hollow Zn–Sn–S nanoboxes encapsulated by N, S-codoped carbon (ZSS@NCS) as anodes for SIBs. The coexistence of triphasic ZSS heterostructures that consist of ZnS, SnS2, and Sn2S3 effectively facilitates the fast Na + diffusion. The N, S-codoped carbon (NSC) derived from the polydopamine is coated outside of the ZSS heterostructures, which provides infinite affinity between ZSS and NSC that efficiently accelerates the electron transport and maintains the structural stability via the confinement effect. The synergistic effects of the heterostructured ZSS and NSC endow the ZSS@NSC anode with favorable sodium storage properties including decent discharge capacity (683.8 mAh g−1 at 0.1 A g−1), satisfying rate (232.6 mAh g−1 at 10.0 A g−1) and cycling properties (402.2 mAh g−1 over 150 cycles).

The effect of quantum confinement and the role of electron-phonon interaction on the band gap shrinkage of some II-VI semiconductors

The role of electron-phonon interaction in band gap shrinkage for some II-VI bulk and low-dimensional semiconductors is investigated in this work. The variation of the energy band gap is studied as a function of temperature using Varshni's, Vina's, and Passler's relations. It is observed that the change in the energy band gap is affected due to the quantum confinement as the dimensionality of these semiconductors is decreased.

Confinement effect of geocell on the mechanical characteristics of reinforced sand subgrade

Geocell has a confinement effect, limiting the deformation of soil and enhancing the strength of reinforced soil, and has a wide range of application prospects in traffic transportation subgrade engineering. To investigate the confinement effect of geocell on the mechanical characteristics of reinforced sand subgrade, this paper analyzes the macro-mechanical properties of reinforced sand subgrade using triaxial tests, investigates the micro-reinforcement mechanism employing discrete element method (DEM)-based simulations. The potential macro–micro linkages are studied. The experimental results revealed that the volumetric strain of the geocell-reinforced samples increased with the material’s elastic modulus, exhibiting a shear shrinkage phenomenon. The deformation pattern of the reinforced samples presented “segmental deformation,” which differed from that of the unreinforced sand samples. The geocell enhanced the cohesion intercept of the sand samples while having a minimal impact on friction angle. Through the analysis of numerical simulation results, it was found that the geocell constrained the displacement of the soil particles, altering the shear band development trend of the sample and resulting in “segmental deformation”. The geocell facilitated the concentration of force chains, enhancing their stability and resulting in improving the strength in the macro. Additionally, it was observed that the confinement effect of the geocell significantly reduced the fabric and force anisotropy of the granular soil, promoting consistent vertical alignment of force chains. This, in turn, enhanced the vertical force transmission capacity of the sample, explaining the micro-mechanism by which the confinement effect of the geocell increases the peak shear strength of the samples.

CONTRASTING A MODEL MODELLING OF PERCEPTION COVID-19

Mitigation policies, as their objective is the informative control of the pandemic in terms of its effects on public health, stand out because they consider risks as inherent to social communication. In this sense, the objective of this work was modelling the social perception of the risks associated with the SARS CoV-2 and Covid-19 pandemics. Axes, trajectories and relationships between categories were established that explain and anticipate the effects of confinement and social distancing strategies, alluding to the extension of the study in confinement and high-risk settings such as hospitals, the adoption of self-care and adherence to treatment. from the impact of the pandemic on the parties involved.

The Impact of Metal Centers in the M-MOF-74 Series on Formic Acid Production.

The confinement effect of porous materials on the thermodynamical equilibrium of the CO2 hydrogenation reaction presents a cost-effective alternative to transition metal catalysts. In metal-organic frameworks, the type of metal center has a greater impact on the enhancement of formic acid production than the scale of confinement resulting from the pore size. The M-MOF-74 series enables a comprehensive study of how different metal centers affect HCOOH production, minimizing the effect of pore size. In this work, molecular simulations were used to analyze the adsorption of HCOOH and the CO2 hydrogenation reaction in M-MOF-74, where M = Ni, Cu, Co, Fe, Mn, Zn. We combine classical simulations and density functional theory calculations to gain insights into the mechanisms that govern the low coverage adsorption of HCOOH in the surrounding of the metal centers of M-MOF-74. The impact of metal centers on the HCOOH yield was assessed by Monte Carlo simulations in the grand-canonical ensemble, using gas-phase compositions of CO2, H2, and HCOOH at chemical equilibrium at 298.15-800 K, 1-60 bar. The performance of M-MOF-74 in HCOOH production follows the same order as the uptake and the heat of HCOOH adsorption: Ni > Co > Fe > Mn > Zn > Cu. Ni-MOF-74 increases the mole fraction of HCOOH by ca. 105 times compared to the gas phase at 298.15 K, 60 bar. Ni-MOF-74 has the potential to be more economically attractive for CO2 conversion than transition metal catalysts, achieving HCOOH production at concentrations comparable to the highest formate levels reported for transition metal catalysts and offering a more valuable molecular form of the product.

Polymer Free Volume-Controlled Molecular Clock and Emitter for Multicolored Transient Data Display in Advanced Photonic Cryptography.

The booming demand on data security has aroused great interest for developing smart materials with temporal display feature and dynamic multicolor fluorescence. However, it remains challenging to implement both features on most responsive molecules. Herein, we construct a polymer free volume-controlled "molecular clock and emitter" via covalently embedding a multi-stimuli responsive molecular switch (i.e., spiropyran) into a polymer network (i.e., poly(pentafluorophenyl acrylate)) with programmable crosslink density and free volume. By the aminolysis of pentafluorophenyl ester with different amount of diamine crosslinkers, pPFPA-co-SP networks with controllable crosslink densities are generated, which have different confinement effects on the rate constant of SP/MC isomerization, thus leading to time-dependent photochromism. In addition, PTF1, a fluorescent probe that is sensitive to polymer rigidity, is introduced to further endow pPFPA-co-SP system with phototunable dynamic full-color emission. Therefore, relying on their synergistical responses to the rigidity of the polymer network, we have successfully developed a versatile molecular clock and emitter via an "one stone two birds" manner, which shows time-dependent data display along with dynamic multicolor fluorescence switching, providing great potential for advanced encryption and anticounterfeiting with a high security level.

Boosted photo-Fenton-like process for selective degradation of emerging contaminants by dehydrated Fe-based metal–organic framework with thermodynamically-favorable center metal electron density and confinement effect

The Heterogeneous Fenton reaction has long stood out as a highly effective technology for water purification. However, it is nowadays facing challenges such as low selectivity, sluggish Fe(III) reduction, and limited H2O2 conversion efficiency. Herein, dehydrated MIL-100(Fe)-250 was synthesized through thermal treatment, demonstrating superior efficiency in removing emerging contaminants, with a three-fold efficiency higher than undehydrated sample. The dehydrated MIL-100(Fe)-250 exhibited selective acceleration in the removal of quinolones and phenolic organics, rendering the system resistant to interference from coexisting matter. Through in-situ diffuse reflectance infrared Fourier-transform spectroscopy and density functional theory calculation, it was manifested that dehydration process regulates the steric hindrance and local electron density of Fe ions. This adjustment enhances charge transfer, thereby facilitating Fe(III) reduction and promoting the H2O2 activation and conversion efficiency. Moreover, the quasi-steady-state concentrations of hydroxyl radical in MIL-100(Fe)-250 were found to be 2.2 times higher than that those in undehydrated sample. Impressively, the dehydrated MIL-100(Fe)-250 displayed adaptability across a broad pH range of 5.0–9.0. The present study underscores the significant potential of porous MIL-100(Fe)-250 with spatial confinement, which imparts a clear size exclusion effect. As a result, this catalyst emerges as a promising candidate for eliminating contaminants in real water matrices, offering a viable strategy for water pollution control.

Polymer Free Volume‐Controlled Molecular Clock and Emitter for Multicolored Transient Data Display in Advanced Photonic Cryptography

AbstractThe booming demand on data security has aroused great interest for developing smart materials with temporal display feature and dynamic multicolor fluorescence. However, it remains challenging to implement both features on most responsive molecules. Herein, we construct a polymer free volume‐controlled “molecular clock and emitter” via covalently embedding a multi‐stimuli responsive molecular switch (i.e., spiropyran) into a polymer network (i.e., poly(pentafluorophenyl acrylate)) with programmable crosslink density and free volume. By the aminolysis of pentafluorophenyl ester with different amount of diamine crosslinkers, pPFPA‐co‐SP networks with controllable crosslink densities are generated, which have different confinement effects on the rate constant of SP/MC isomerization, thus leading to time‐dependent photochromism. In addition, PTF1, a fluorescent probe that is sensitive to polymer rigidity, is introduced to further endow pPFPA‐co‐SP system with phototunable dynamic full‐color emission. Therefore, relying on their synergistical responses to the rigidity of the polymer network, we have successfully developed a versatile molecular clock and emitter via an “one stone two birds” manner, which shows time‐dependent data display along with dynamic multicolor fluorescence switching, providing great potential for advanced encryption and anticounterfeiting with a high security level.

Aggravated NBTI reliability due to hard-to-detect open defects

FinFET technology has become an attractive candidate for high-performance and power-efficient applications. In the other hand, the behavior of FinFET devices is influenced by self-heating effect (SHE) due to its 3D structure, low thermal coupling and quantum confinement effect, among others. SHE degrades the device’s performance and could worsen reliability mechanisms like NBTI. In addition, some hard-to-detect open defects in FinFET based-circuits using logic gates designed with multi-fin and multi-finger techniques may escape the test and present abnormal static currents, which may increase the impact of self-heating effect and make the NBTI degradation more severe. Hence, it is crucial to accurately determine the temperature profiles of those chips passing the test and presenting abnormal static currents. This paper investigates the reliability of chips passing the test with abnormal static currents using Sentaurus Technology Computer-Aided Design (TCAD). FinFET transistors are calibrated with Intel 14-nm FinFET technology. Our TCAD simulation framework determines accurately the temperature and NBTI degradation. Using the TCAD information, the device degradation over time can be predicted. Moreover, the delay penalization of a critical logic path of an ISCAS benchmark circuit is investigated. The delay penalization of logic paths, attributed to the defect and NBTI, is analyzed with varying logic depths, emphasizing the importance of addressing critical paths with different logic depths. Our study leads to new considerations for improving the prediction of circuit reliability and taking countermeasures.

Nonempirical Prediction of the Length-Dependent Ionization Potential in Molecular Chains.

The ionization potential of molecular chains is well-known to be a tunable nanoscale property that exhibits clear quantum confinement effects. State-of-the-art methods can accurately predict the ionization potential in the small molecule limit and in the solid-state limit, but for intermediate, nanosized systems prediction of the evolution of the electronic structure between the two limits is more difficult. Recently, optimal tuning of range-separated hybrid functionals has emerged as a highly accurate method for predicting ionization potentials. This was first achieved for molecules using the ionization potential theorem (IPT) and more recently extended to solid-state systems, based on an ansatz that generalizes the IPT to the removal of charge from a localized Wannier function. Here, we study one-dimensional molecular chains of increasing size, from the monomer limit to the infinite polymer limit using this approach. By comparing our results with other localization-based methods and where available with experiment, we demonstrate that Wannier-localization-based optimal tuning is highly accurate in predicting ionization potentials for any chain length, including the nanoscale regime.

Real-time monitoring of fast gas dynamics with a single-molecule resolution by frequency-comb-referenced plasmonic phase spectroscopy

Surface plasmon resonance (SPR) sensors are based on photon-excited surface charge density oscillations confined at metal-dielectric interfaces, which makes them highly sensitive to biological or chemical molecular bindings to functional metallic surfaces. Metal nanostructures further concentrate surface plasmons into a smaller area than the diffraction limit, thus strengthening photon-sample interactions. However, plasmonic sensors based on intensity detection provide limited resolution with long acquisition time owing to their high vulnerability to environmental and instrumental noises. Here, we demonstrate fast and precise detection of noble gas dynamics at single molecular resolution via frequency-comb-referenced plasmonic phase spectroscopy. The photon-sample interaction was enhanced by a factor of 3,852 than the physical sample thickness owing to plasmon resonance and thermophoresis-assisted optical confinement effects. By utilizing a sharp plasmonic phase slope and a high heterodyne information carrier, a small atomic-density modulation was clearly resolved at 5 Hz with a resolution of 0.06 Ar atoms per nano-hole (in 10–11 RIU) in Allan deviation at 0.2 s; a faster motion up to 200 Hz was clearly resolved. This fast and precise sensing technique can enable the in-depth analysis of fast fluid dynamics with the utmost resolution for a better understanding of biomedical, chemical, and physical events and interactions.

Stabilization of δ-like Bi2O3 Phase at Room Temperature in Binary and Ternary Bismuthate Glass Systems with Al2O3, SiO2, GeO2, and B2O3.

Recently, it was shown that the nanocrystallization of Bi2O3 glasses with the addition of SiO2 and Al2O3 leads to the stabilization of the δ-like Bi2O3 phase at least down to room temperature, which is significantly below its stability range in bulk form. In this research, we investigated the properties of bismuthate glasses synthesized with various glass-forming agents such as SiO2, GeO2, B2O3, and Al2O3. It was demonstrated that vitrification of all these systems is possible using a standard melt quenching route. Furthermore, we investigated the crystallization processes in pristine glasses upon increasing the temperature and the thermal stability of arising phases using thermal analysis and high-temperature XRD in situ experiments. It was shown that it is possible to stabilize crystallites' isostructures with δ-Bi2O3 embedded in a residual glassy matrix down to room temperature. The temperature range of the appearance of the δ-like phase strongly depended on the nominal composition of the glasses. We postulate that the confinement effect depends on the local properties of the residual glassy matrix and its ability to introduce sufficient force to stretch the structure of the δ-like Bi2O3 phase in the nanocrystallites.

Clathrate Hydrates as a Kind of Promising Ice Nanoreactors.

Since their discovery, clathrate hydrates (CHs) have received great attention both from theoretical and experimental aspects due to their great potential for gas storage and prospective applications as icy crystal materials. However, there has been limited research on the decomposition, reduction or other reactions of gases enclosed in CHs. Thanks to their unique hydrogen bonding network and cavity structures, CHs can serve as the promising nanoreactors to achieve chemical conversions, e. g. reducing greenhouse gases. In this review-type article, we characterize the potential performance of such CHs nanoreactors by discussing their multiple functions including important roles of hydrogen bonds in CHs, e. g. the confinement effect and proton source, and then discuss the enhanced electron-binding ability of guest molecules and the structures and properties of trapped electrons in the stacked nanocages, which contribute to our understanding of chemical reactions occurring in CHs. Finally, we provide detailed analyses of representative reaction mechanisms underwent in CH nanoreactors and effective calculational and molecular dynamics simulation methods. This review-type article aims to provide a detailed summary about the functional characteristics of CHs and reactivity in CHs, which make CHs a kind of promising icy nanoreactors.

High Electron Mobility in Si-Doped Two-Dimensional β-Ga2O3 Tuned Using Biaxial Strain.

Two-dimensional (2D) semiconductors have attracted much attention regarding their use in flexible electronic and optoelectronic devices, but the inherent poor electron mobility in conventional 2D materials severely restricts their applications. Using first-principles calculations in conjunction with Boltzmann transport theory, we systematically investigated the Si-doped 2D β-Ga2O3 structure mediated by biaxial strain, where the structural stabilities were determined by formation energy, phonon spectrum, and ab initio molecular dynamic simulation. Initially, the band gap values of Si-doped 2D β-Ga2O3 increased slightly, followed by a rapid decrease from 2.46 eV to 1.38 eV accompanied by strain modulations from -8% compressive to +8% tensile, which can be ascribed to the bigger energy elevation of the σ* anti-bonding in the conduction band minimum than that of the π bonding in the valence band maximum. Additionally, band structure calculations resolved a direct-to-indirect transition under the tensile strains. Furthermore, a significantly high electron mobility up to 4911.18 cm2 V-1 s-1 was discovered in Si-doped 2D β-Ga2O3 as the biaxial tensile strain approached 8%, which originated mainly from the decreased quantum confinement effect on the surface. The electrical conductivity was elevated with the increase in tensile strain and the enhancement of temperature from 300 K to 800 K. Our studies demonstrate the tunable electron mobilities and band structures of Si-doped 2D β-Ga2O3 using biaxial strain and shed light on its great potential in nanoscale electronics.

Confinement strength prediction of corroded rectangular concrete columns using BP neural networks and support vector regression

The application of machine learning in predicting the mechanical performance of reinforced concrete columns subjected to reinforcement corrosion was investigated in this study. Traditional models, often relying on empirical formulas or simplified assumptions, are known to struggle in capturing all variables and relationships in complex problems, leading to inadequate prediction accuracy. Through theoretical analysis, the confinement effect of stirrups on core concrete and its performance deterioration caused by reinforcement corrosion were determined. To improve the prediction accuracy and generalization ability, the error Back Propagation Neural Network (BPNN) and Support Vector Regression (SVR) models were employed. Parameter effects in the BPNN model were interpreted using the SHapley Additive exPlanations (SHAP) and compared with traditional parameter sensitivity analyses. The investigation indicates that the machine learning models have a high degree of fit and low error levels, particularly within the training set. After analyzing using the SHAP approach, it is found that the corrosion ratio of the stirrup and longitudinal reinforcement have a significant effect on the confinement strength of the concrete, whereas the effects of the stirrup configuration and size effect are negligible, which is different from conventional parametric sensitivity analysis. As to the stability analysis of model predictions, the SVR model shows lower volatility and higher prediction stability compared with the BPNN model, despite the latter occasionally providing superior generalization ability. This research underscores the significant advantages offered by machine learning models in addressing longstanding challenges associated with strength prediction, and thus presents new perspectives for future study.