Anion type-dependent confinement effect on glass transitions of solutions of LiTFSI and LiFSI

We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.

Dielectric Confinement Effect on Calculating the Band Gap of PbSe Quantum Dots

Considering the dielectric confinement effect on excitonics of PbSe quantum dots （QDs）, a correction factor in the wave function was introduced to propose a new band gap calculation model for QDs. The modified model showed great consistency with the experimental data, especially in small size range. According to the variation of confined barrier, the band gap calculation model of PbSe QDs was analyzed in different solvents. The calculating results showed that the modified model was almost solvent-independent, which was consistent with our experimental results and related reports.

Phonon Confinement Effect in Two-dimensional Nanocrystallites of Monolayer MoS_2 to Probe Phonon Dispersion Trends Away from Brillouin-Zone Center

The fundamental momentum conservation requirement q - 0 for the Raman process is relaxed in the nanocrystal- lites （NCs）, and phonons away from the Brillouin-zone center will be involved in the Raman scattering, which is well-known as the phonon confinement effect in NCs. This usually gives a downshift and asymmetric broadening of the Raman peak in various NCs. Recently, the A1 mode of 1L MoS2 NCs is found to exhibit a blue shift and asymmetric broadening toward the high-frequency side [Chem. Soc. Rev. 44 （2015） 2757 and Phys. Rev. B 91 （2015） 195411]. In this work, we carefully check this issue by studying Raman spectra of lL MoS2 NCs prepared by the ion implantation technique in a wide range of ion-implanted dosage. The same confinement coefficient is used for both E＇ and A＇1 modes in 1L MoS2 NCs since the phonon uncertainty in an NC is mainly determined by its domain size. The asymmetrical broadening near the A＇1 and E＇ modes is attributed to the appearance of defect-activated phonons at the zone edge and the intrinsic asymmetrical broadening of the two modes, where the anisotropy of phonon dispersion curves along Г-K and Г- M is also considered. The photoluminescence spectra confirm the formation of small domain size of 1L MoS2 nanocrystallites in the ion-implanted 1L MoS2. This study provides not only an approach to quickly probe phonon dispersion trends of 2D materials away from Г by the Raman scattering of the corresponding NCs, but also a reference to completely understand the confinement effect of different modes in various nanomaterials.

Solid-gas interface thermal conductance for the thermal barrier coating with surface roughness:The confinement effect

The yttria-stabilized zirconia(YSZ)is a famous thermal barrier coating material to protect hot-end components of an engine.As a characteristic feature of the YSZ,the surface roughness shall play an important role in the interface thermal conductance between the YSZ and gas,considering that the gas is typically at an extremely high temperature.We investigate the effect of the surface roughness on the thermal conductance of the YSZ-gas interface with surface roughness described by nanoscale pores on the surface of the YSZ.We reveal two competitive mechanisms related to the microstructure of the pore,i.e.,the actual contact area effect and the confinement effect.The increase of the pore depth will enlarge the actual contact area between the YSZ and gas,leading to enhancement of the solid-gas interface thermal conductance.In contrast to the positive actual contact area effect,the geometry-induced confinement effect greatly reduces the interface thermal conductance.These findings shall offer some fundamental understandings for the microscopic mechanisms of the YSZ-gas interface thermal conductance.

Analysis on porous Si PL from quantum confinement effect

We have measured the variation of photoluminescence(PL) in porous silicon with anodization(AO) time,HF soak time or natural oxidation time,and found that the peak value of PL spectrum will shift towards shorter value as above time is increased.The analyses in experiment and theory show that the quantum confined structures produced by the AO process may be responsible for the blue shift.

Research on Electric Field Confinement Effect in Silicon LED Fabricated by Standard CMOS Technology

The wedge-shaped and leaf-type silicon light-emitting devices(LED)are designed and fabricated with the Singapore Chartered Semi Inc.'s dual-gate standard 0.35μm CMOS process.The basic structure of the two devices is N well-P+ junction.P+ area is the wedge-shaped structure,which is embedded in N well.The leaf-type silicon LED device is a combination of the three wedge-shaped LED devices.The main difference between the two devices is their different electrode distribution,which is mainly in order to analyze the application of electric field confinement(EFC).The devices' micrographs were measured with the Olympus IC test microscope.The forward and reverse bias electrical characteristics of the devices were tested.Light measurements of the devices show that the electrode layout is very important when the electric field confinement is applied.

Ultrasensitive detection of micro RNA-21 in human serum based on the confinement effect enhanced chemical etching of gold nanorods

Natural enzymes,such as horseradish peroxidase(HRP),are a class of important biocatalysts with the high specificity,but their catalytic efficiency is usually unsatisfactory.Thus,the higher catalytic efficiency induced by the confinement effect is promising in optical sensing systems.In this work,a dark-field light scattering sensing platform was fabricated by the confinement effect of HRP from hybridization chain reaction(HCR)and then released to solution by the toehold-mediated strand displacement reaction(TSDR).Then,HRP catalyzed the 3,3,5,5-tetramethylbenzidine(TMB)to TMB^(2+)with the assistance of hydrogen peroxide,which etched the gold nanorods(Au NRs)with the weakened light scattering.The single-particle assay was established based on the decreased light scattering intensity of AuNRs under dark-field microscope.The proposed assay revealed excellent analytical performance within a linear range from 25 pmol/L to 600 pmol/L,and a low limit of detection of 3.12 pmol/L.Additionally,it also manifested satisfactory recovery of mi RNA-21 in human serum samples.The high sensitivity,excellent specificity,and universal applicability make this sensing platform promising for disease diagnosis.

Evaluating the quantum confinement effects modulating exciton and electronic band structures of two-dimensional layered MoSSe films and their photodetection potentials

Emerging two-dimensional ternary transition metal dichalcogenide alloys have attracted much attention for their unique optical and optoelectronic properties,making them ideal candidates for optoelectronic applications.However,a comprehensive understanding of their quantum confinement effects and photoelectronic response characteristics remains crucial for device optimization and performance enhancement.In this study,we employed various spectroscopic techniques to investigate the optical properties and electronic band structures of molybdenum sulfide selenide(MoSSe)films with different layer numbers(4–11 layers).Our results revealed the splitting of Raman modes and shifting of phonon vibrational frequencies with increasing thickness,suggesting that MoSSe has strong interactions within the lattice.The A1g and E2g 1 modes were mainly shifted by internal strain and dielectric screening effect versus thickness,respectively.The redshift phenomenon of A and B excitons with increasing thickness was attributed to the leading effect of quantum confinement on exciton properties and optical band gaps.We observed a strong decrease in the direct bandgap spectral weight in photoluminescence(PL)when the layer number increased from 4 to 5.In addition,we have fabricated MoSSe photodetectors that exhibit a broadband response in the visible wavelength band of 350–800 nm.Furthermore,the observed enhancement in photocurrent and responsivity with increasing film thickness underscored the potential of MoSSebased devices for practical optoelectronic applications.This research contributes to advancing our fundamental understanding of MoSSe materials and paves the way for the design and development of high-performance optoelectronic devices.

Efficient oxygen reduction reaction by a highly porous,nitrogen-doped carbon sphere electrocatalyst through space confinement effect in nanopores

A highly porous nitrogen-doped carbon sphere(NPC)electrocatalyst was prepared through the carbonization of biomass carbon spheres mixed with urea and zinc chloride in N_(2) atmosphere.The sample carbonized at.1000℃ demonstrates a superior oxygen reduction reaction(ORR)performance over the Pt/C electrocatalyst,while its contents of pyridinic nitrogen and graphitic nitrogen are the lowest among samples synthesized at the same or lower carbonization temperatures.This unusual result is explained by a space confinement effect from the microporous and mesoporous structures in the microflakes,which induces the further reduction of peroxide ions or other oxygen species produced in the first step reduction to water to have the preferred overall four electron reduction ORR process.This work demonstrates that in addition to the amount or species of its aptive sites,the space confinement can be a new approach to enhance the ORR performance of precious-metal-free,nitrogen-doped carbon electrocatalysts.

Quantum confinement effect of two-dimensional all-inorganic halide perovskites

Quantum confinement effect（QCE）, an essential physical phenomenon of semiconductors when the size becomes comparable to the exciton Bohr radius, typically results in quite different physical properties of low-dimensional materials from their bulk counterparts and can be exploited to enhance the device performance in various optoelectronic applications. Here, taking Cs Pb Br3 as an example, we reported QCE in all-inorganic halide perovskite in two-dimensional（2D） nanoplates. Blue shifts in optical absorption and photoluminescence spectra were found to be stronger in thinner nanoplates than that in thicker nanoplates, whose thickness lowered below -7 nm. The exciton binding energy results showed similar trend as that obtained for the optical absorption and photoluminescence. Meanwile, the function of integrated intensity and full width at half maximum and temperature also showed similar results, further supporting our conclusions. The results displayed the QCE in all-inorganic halide perovskite nanoplates and helped to design the all-inorganic halide perovskites with desired optical properties.

Photoluminescence of carbon quantum dots:coarsely adjusted by quantum confinement effects and finely by surface trap states

Photoluminescence(PL) mechanism of carbon quantum dots(CQDs) remains controversial up to now even though a lot of approaches have been made. In order to do that, herein a PL color ladder from blue to near infrared of CQDs with the absolute quantum yields higher than 70% were prepared via a one-pot hydrothermal synthesis route and separated by silica gel column.Time-correlated single photon counting measurements suggest that the electron transition takes in effect in the PL progress of the crystalline core-shell structured CQDs, and the PL properties could be coarsely adjusted by tuning the size of the crystalline carbon core owing to quantum confinement effects, and finely adjusted by changing the surface functional groups consisted shell owing to surface trap states,respectively. Both coarse and fine adjustments of PL, as optical and photoelectrical characterizations and density-functional theory(DFT) calculations have demonstrated, make it possible for top-level design and precise synthesis of new CQDs with specific optical properties.

Lamella-like electrode with high Br_(2)-entrapping capability and activity enabled by adsorption and spatial confinement effects for brominebased flow battery

Bromine-based flow batteries(Br-FBs)are well suitable for stationary energy storage owing to their high energy density and low cost.However,their power density and lifespan are limited by relatively low reaction kinetics of Br_(2)/Br-couple and serious self-discharge caused by bromine migration.Herein,lamella-like porous carbon nitride nanosheets(PCNS)with adsorption and spatial confinement effects are used to modify cathodes for Br-FBs.The large specific surface area and plentiful N-containing groups enable PCNS with excellent adsorption capacity,which captures bromine species into the pores on PCNS layers.The captured bromine species is subsequently confined in PCNS interlayers due to the strong interaction between bromine species and N-containing groups,thus effectively depressing bromine diffusion/migration.Moreover,the strong bromine adsorption capacity significantly improves the electrochemical activity of PCNS.Consequently,a zinc-bromine flow battery(ZBFB)employing PCNS-modified cathode achieves a high current density of 180 m A cm^(-2),with an ultra-high coulombic efficiency of 99.22%.It also exhibits better self-discharge performance and a long cycle life of 500 cycles.Furthermore,a complexing agent-free ZBFB is successfully realized based on the superior bromineentrapping/retaining capacity of the PCNS-modified cathode.Consequently,this work provides a promising strategy toward electrode modifications for high-performance and long-lifespan Br-FBs.

Quantum confinement effect in β-SiC nanowires

The quantum confinement effect is important in nanoelectronics and optoelectronics applications; however, there is a discrepancy between the theory of quantum confinement, which indicates that band-gap widening occurs only at small sizes, and experimental observations of band-gap widening in large-diameter nanowires （NWs）. This paper reports an obvious blue shift of the absorption edge in the UV-visible absorption spectra of SiC NWs with diameters of 50-300 nm. On the basis of quantum confinement theory and high-resolution transmission electron microscopy images of SiC NWs, band-gap widening in SiC NWs with diameters of up to hundreds of nanometers is fully explained; the results could help to explain similar band-gap widening in other NWs with large diameters.

Mechanistic investigation on Ag-Cu_(2)O in electrocatalytic CO_(2) to CH_(4) by in situ/operando spectroscopic and theoretical analysis

Silver-copper electrocatalysts have demonstrated effectively catalytic performance in electroreduction CO_(2) toward CH_(4),yet a revealing insight into the reaction pathway and mechanism has remained elusive.Herein,we construct chemically bonded Ag-Cu_(2)O boundaries,in which the complete reduction of Cu_(2)O to Cu has been strongly impeded owing to the presence of surface Ag shell.The interfacial confinement effect helps to maintain Cu^(+)sites at the Ag-Cu_(2)O boundaries.Using in situ/operando spectroscopy and theoretical simulations,it is revealed that CO_(2) is enriched at the Ag-Cu_(2)O boundaries due to the enhanced physisorption and chemisorption to CO_(2),activating CO_(2) to form the stable intermediate^(*)CO.The boundaries between Ag shell and the Cu_(2)O mediate local^(*)CO coverage and promote^(*)CHO intermediate formation,consequently facilitating CO_(2)-to-CH_(4) conversion.This work not only reveals the structure-activity relationships but also offers insights into the reaction mechanism on Ag-Cu catalysts for efficient electrocatalytic CO_(2) reduction.

High-performance Si-Containing anode materials in lithium-ion batteries: A superstructure of Si@Co-NC composite works effectively

To mitigate the massive volume expansion of Si-based anode during the charge/discharge cycles,we synthesized a superstructure of Si@Co±NC composite via the carbonization of zeolite imidazolate frameworks incorporated with Si nanoparticles.The Si@Co±NC is comprised of Sinanoparticle core and N-doped/Co-incorporated carbon shell,and there is void space between the core and the shell.When using as anode material for LIBs,Si@Co±NC displayed a super performance with a charge/discharge capacity of 191.6/191.4 mA h g^(-1)and a coulombic efficiency of 100.1%at 1000 mA g^(-1)after 3000 cycles,and the capacity loss rate is 0.022%per cycle only.The excellent electrochemical property of Si@Co±NC is because its electronic conductivity is enhanced by doping the carbon shell with N atoms and by incorporating with Co particles,and the pathway of lithium ions transmission is shortened by the hollow structure and abundant mesopores in the carbon shell.Also,the volume expansion of Si nanoparticles is well accommodated in the void space and suppressed by the carbon host matrix.This work shows that,through designing a superstructure for the anode materials,we can synergistically reduce the work function and introduce the confinement effect,thus significantly enhancing the anode materials’electrochemical performance in LIBs.

Exploiting quasi-one-dimensional confinement for proficient hydrogen production from formic acid at room temperature

We describe herein that the quasi-one-dimensional confinement effect of functionalized nanoporous supports is particularly advantageous for boosting formic acid(FA)dehydrogenation efficiency over palladium nanoparticles(NPs).Benefiting from their unique structural merits that lead to significant lowering of the entropic barrier for FA activation,the Pd NPs interiorly located on the amino-modified MCM-41 offer the promise of more than an order of magnitude speedup of the initial activity in H2 production from FA over their exterior analogs.Under mild and additive-free conditions,ultrafine Pd NPs confined in aminomodified MCM-41 channels exhibit an initial turnover frequency as high as 46,677 h-1 and a turnover number up to 1,060,000 at 60℃.In conjunction with the enhancement and robust performance for efficient regeneration of FA via CO2 hydrogenation,the presented approach greatly contributes to the development of FA-based hydrogen storage and related technologies as viable means of enabling sustainable future energy prospects.

CONFINING PRESSURE EFFECT ON ACOUSTIC EMISSIONS IN ROCK FAILURE

Based on the phenomenon that acoustic emissions (AE) generated by rock mass increase suddenly because of underground excavation, time sequence of AE rate in rock failure has been discussed by using statistical damage theory. It has been demonstrated that how the influence of confining pressure on the deformation behavior and AE characteristics in rocks can be inferred from a simple mechanics model. The results show that loading confining pressure sharply brings out increasing of AE. On the other hand, few AE emits when confining pressure is loaded sharply, and AE occurs again when axial pressure keeps on increasing. These results have been well simulated with computer and show close correspondence with directly measured curves in experiments.

Inorganic Halide Perovskite Quantum Dots:A Versatile Nanomaterial Platform for Electronic Applications

Metal halide perovskites have generated significant attention in recent years because of their extraordinary physical properties and photovoltaic performance.Among these,inorganic perovskite quantum dots(QDs)stand out for their prominent merits,such as quantum confinement effects,high photoluminescence quantum yield,and defect-tolerant structures.Additionally,ligand engineering and an all-inorganic composition lead to a robust platform for ambient-stable QD devices.This review presents the state-of-the-art research progress on inorganic perovskite QDs,emphasizing their electronic applications.In detail,the physical properties of inorganic perovskite QDs will be introduced first,followed by a discussion of synthesis methods and growth control.Afterwards,the emerging applications of inorganic perovskite QDs in electronics,including transistors and memories,will be presented.Finally,this review will provide an outlook on potential strategies for advancing inorganic perovskite QD technologies.

Recent Progress of Layered Perovskite Solar Cells Incorporating Aromatic Spacers

Layered two dimensional(2D) or quasi-2D perovskites are emerging photovoltaic materials due to their superior environment and structure stability in comparison with their 3D counterparts. The typical 2D perovskites can be obtained by cutting 3D perovskites along < 100 > orientation by incorporation of bulky organic spacers, which play a key role in the performance of 2D perovskite solar cells(PSCs). Compared with aliphatic spacers, aromatic spacers with high dielectric constant have the potential to decrease the dielectric and quantum confinement effect of 2D perovskites, promote efficient charge transport and reduce the exciton binding energy, all of which are beneficial for the photovoltaic performance of 2D PSCs. In this review, we aim to provide useful guidelines for the design of aromatic spacers for 2D perovskites. We systematically reviewed the recent progress of aromatic spacers used in 2D PSCs. Finally, we propose the possible design strategies for aromatic spacers that may lead to more efficient and stable 2D PSCs.

Tailoring microenvironment for efficient CO_(2)electroreduction through nanoconfinement strategy

The electrocatalytic conversion of CO_(2)to produce fuels and chemicals holds great promise,not only to provide an alternative to fossil feedstocks,but also to use renewable electricity to convert and recycle the greenhouse gas CO_(2)to mitigate climate problems.However,the selectivity and reaction rates for the conversion of CO_(2)into desirable carbon-based products,especially multicarbon products with high added value,are still insufficient for commercial applications,which is attributed to insufficiently favourable microenvironmental conditions in the vicinity of the catalyst.The construction of catalysts/electrodes with confined structures can effectively improve the reaction microenvironment in the vicinity of the electrodes and thus effectively direct the reaction towards the desired pathway.In this review,we firstly introduce the effects of the microenvironment at the electrode-electrolyte interface including local pH,local intermediate concentration,and local cation concentration on CO_(2)reduction reaction(CO_(2)RR)as well as the mechanism of action,and then shed light on the microenvironmental modulation within the confined space,and finally and most importantly,introduce the design strategy of CO_(2)RR catalyst/electrode based on the confinement effect.