Confinement Effect Research Articles

Silver nanoparticles (AGNPs): A review on properties and behavior of silver at the nanoscale level

Silver nanoparticles (AgNPs) have garnered significant interest due to their unique and enhanced properties compared to bulk silver. These nanoparticles exhibit remarkable chemical, physical, and biological characteristics, primarily attributed to their high surface area-to-volume ratio and nanoscale dimensions. Key properties include superior antibacterial, antiviral, and antifungal activities, potent catalytic capabilities, and distinctive optical properties, such as localized surface plasmon resonance (LSPR). These enhanced properties stem from the increased surface reactivity and quantum effects at the nanoscale. AgNPs are extensively applied across various fields. In medicine, they are utilized for their antimicrobial properties in wound dressings, coatings for medical devices, and as components in drug delivery systems. In environmental science, they serve as effective agents in water treatment processes due to their potent antimicrobial action. Additionally, AgNPs are employed in electronics for conductive inks, in catalysis for chemical reactions, and in textiles for producing antibacterial fabrics. The improved properties of silver nanoparticles over bulk silver are mainly due to the increased proportion of surface atoms, which leads to higher surface energy and reactivity. Furthermore, the nanoscale dimensions allow for quantum confinement effects, enhancing their optical and electronic properties. These unique characteristics enable AgNPs to perform more effectively and efficiently in various applications, making them a vital component in advancing technology and healthcare solutions.

Quantum Prism-Nano Source of Light with Dispersive Spectrum and Optical Upconversion.

A quantum prism, a new structure, consisting of many quantum wires with a diameter that gradually decreases from the base to the top, is the focus of our research. This distribution of quantum wires leads to a dispersive emitted spectrum. The red edge of the spectrum is determined by the band gap width of the bulk semiconductor, and the blue edge is determined by the quantum size of the excitons at the top of the prism. The PL spectrum of the silicon prismatic sample was excited by weak and strong light absorption. At weak absorption (hνex = 1.2 eV), the PL spectrum is located in the visible part of the spectrum, from 1.4 eV to 1.9 eV, with an energy higher than the band gap of the Si crystal. Such a "blue shift" of PL spectra by 0.7 eV is characteristic of the quantum confinement effect. It is a rainbow spectrum with an optical upconversion. The quantum prism is a new type of nano light source, as it replaces two elements in a conventional spectrometer: a light source and a dispersive element. These features enable to create a nano-spectrometer for measuring the absorption spectrum of individual molecules or viruses.

Circular concrete-filled double-skin steel tubular short columns under axial compression: An improved theoretical model and design

Existing theoretical analysis methods for concrete-filled double-skin steel tubular (CFDST) short columns generally ignore the reduction of concrete strength due to brittleness. As a result, these methods cannot accurately capture full range behavior for CFDST columns containing high-strength concrete. By focusing on the reduction effect of concrete strength in CFDST columns due to concrete brittleness, this paper proposes a reduction factor for use in design, for the first time. Based on this reduction factor, a theoretical model for axially compressed circular CFDST short columns considering non-uniform confinement effect of the sandwiched concrete is established. A substantial experimental database of 168 CFDST columns with carbon circular steel tubes is then compiled. By comparing with this database, the proposed theoretical model is shown to achieve greater accuracy than existing approaches. Utilizing this model, the influence of column parameters on the performance of the studied CFDST members are investigated and the results are discussed. It is shown that concrete strength, hollow ratio, yield strength of the outer tube, and the diameter-to-thickness ratio of the outer and inner tubes are influential to the ultimate strength and ductility of CFDST columns. However, the yield strength of the inner tube only affects the ultimate strength of CFDST columns but has a negligible influence on the ductility. Finally, utilizing the experimental and theoretical data presented, the accuracy of existing design codes for concrete-filled steel tubes for the design of CFDST members with or without considering the reduction effect of concrete strength is assessed. The results indicate that Eurocode 4 provides a more reasonable prediction result.

Hybrid Amino Acid Ligand-Regulated Excited Dynamics of Highly Luminescent Perovskite Quantum Dots for Bright White Light-Emitting Diodes.

Organic-inorganic hybrid perovskite quantum dots (QDs) have garnered significant research interest owing to their unique structure and optoelectronic properties. However, their poor optical performance in ambient air remains a significant limitation, hindering their advancement and practical applications. Herein, three amino acids (valine, threonine and cysteine) were chosen as surface ligands to successfully prepare highly luminescent CH3NH3PbBr3 (MAPbBr3) QDs. The morphology and XRD results suggest that the inclusion of the amino acid ligands enhances the octahedral structure of the QD solutions. Moreover, the observed blue-shifted phenomenon in the photoluminescence (PL) aligns closely with the blue-shifted phenomenon observed in the ultraviolet-visible (UV-Vis) absorption spectra, attributed to the quantum confinement effect. The time-resolved spectra indicated that the introduction of the amino acid ligands successfully suppressed non-radiative recombination, consequently extending the fluorescence lifetime of the MAPbBr3 QDs. The photoluminescence quantum yields (PLQYs) of the amino acid-treated MAPbBr3 QDs are increased by 94.8%. The color rendering index (CRI) of the produced white light-emitting diode (WLED) is 85.3, with a correlated color temperature (CCT) of 5453 K. Our study presents a novel approach to enhancing the performance of perovskite QDs by employing specially designed surface ligands for surface passivation.

Electrokinetic properties of NaCl solution via molecular dynamics simulations with scaled-charge electrolytes.

Scaling ionic charges has become an alternative to polarizable force fields for representing indirect charge transfer effects in molecular simulations. In our work, we apply molecular dynamics simulations to investigate the properties of NaCl aqueous solutions in homogeneous and confined media. We compare classical integer- and scaled-charge force fields for the ions. In the bulk, we validate the force fields by computing equilibrium and transport properties and comparing them with experimental data. Integer-charge ions overestimate dielectric saturation and ionic association. Both force fields present an excess in ion-ion correlation, which leads to a deviation in the ionic conductivity at higher ionic strengths. Negatively charged quartz is used to simulate the confinement effect. Electrostatic interactions dominate counter-ion adsorption. Full-charge ions have stronger and more defined adsorption planes. We obtain the electroosmotic mobility of the solution by combining the shear plane location from non-equilibrium simulations with the ionic distribution from equilibrium simulations. From the Helmholtz-Smoluchowski equation, the zeta potential and the streaming potential coupling coefficient are computed. From an atomic-scale perspective, our molecular dynamics simulations corroborate the hypothesis of maximum packing of the Stern layer, which results in a stable and non-zero zeta potential at high salinity. The scaled-charge model representation of both properties is in excellent qualitative and quantitative agreement with experimental data. With our work, we demonstrate how useful and precise simple scaled-charge models for electrolytes can be to represent complex systems, such as the electrical double layer.

Dual-enhanced enzyme cascade hybrid hydrogel for the construction of optical biosensor

The biomimetic enzyme cascade system plays a key role in biosensing as a sophisticated signal transduction and amplification strategy. However, constructing a regulated enzyme cascade sensing system remains challenging due to the mismatch of multiple enzyme activities and poor stability. Herein, we design an efficient dual-enhanced enzyme cascade hybrid system (UFD-DEC) containing DNA-controlled nanozymes (Fe-cdDNA) and enzyme (urease) via combining the electrostatic contact effect with the hydrogel-directed confinement effect. Precise modulation of Fe-cdDNA nanozyme by DNA offers a means to control its catalytic efficiency. This regulated UFD-DEC system accelerates the reaction rate and provides remarkable stability compared with the free enzyme system. Benefiting from the plasticity properties of hydrogels, a “lab-in-a-tube” platform was constructed by encapsulating UFD-DEC in a microcentrifuge tube. Such a UFD-DEC-based hydrogel tube exhibits sufficient adaptability to profile urea when used in conjunction with a smartphone-assisted image processing algorithm, which on-site delivers urea information with a detection limit of 0.12 mmol L−1. This customizable and inexpensive miniaturized biosensor platform for monitoring urea may facilitate point-of-care testing applications.

A multiaxial thermo-mechanical damage model for concrete including Load Induced Thermal Strain (LITS)

In the current study, a multiaxial LITS model of concrete was innovatively developed. This model can predict the behavior of concrete subjected to wide applied load level ranges from 20 % to 80 % and temperatures up to 800 °C. A 3D LITS model is developed through a triaxial compression stress confinement implementation and Poisson's ratio. Considering the water evaporation of concrete under high temperature, a third order polynomial LITS derivative function and an exponential derivative function were proposed to characterize the effects of the stress confinement and thermal effect. In order to comprehensively predict the performance of concrete subjected to multiaxial compressive loads in fire, an orthotropic triaxial compression thermo-mechanical damage model for concrete is developed. The effect of LITS on the multiaxial stress-strain response was considered in the multiaxial model. The coupling thermo-mechanical contributions containing the development of LITS among thermal effect, stress confinement, damage and plastic hardening evolution were creatively considered in the potential function within thermodynamics framework. The numerical calculations of this proposed model were conducted for validation. The effect of LITS on the multiaxial stress-strain response was studied. The nonlinear stress-strain responses of concrete were accurately captured at temperatures ranges from 20 °C to 1000 °C through the comparative study with test results in literatures, which indicates the accuracy and applicability of the proposed model.

Improving the performance of cutting fluids by using ZnO and ZrO2 nanoparticles

Sustainability is nowadays a global research priority, especially in machining, where optimizing production processes for increased productivity, profits, and efficiency is key. Addressing this need, the adoption of nanofluids in minimum quantity lubrication machining has surged, aligning with environmental concerns and regulatory demands. In this study, sustainable zinc oxide (ZnO) and zirconium dioxide (ZrO2) nanoparticles fabricated using plant extracts have been incorporated into conventional cutting fluids to enhance their machinability performance under minimum quantity lubrication for turning process. The microstructural analysis confirms the successful synthesis of the targeted nanoparticles with excellent purity and size distribution. The addition of nanoparticles significantly enhanced thermal conductivity from 0.5916 W/(m⋅K) for the base fluid to 0.6286 W/(m⋅K) for ZnO and to 0.6242 W/(m⋅K) for ZrO2. Further, nanofluids exhibited an increased dynamic viscosity, 1.435 mPa.s for ZrO2 and 1.125 mPa.s for ZnO as compare to 0.7644 mPa.s of base fluid, attributed to the nanoparticle confinement effect whereas contact angle measurements indicated an improved wettability for all nanofluids. Machining experiments validate the efficacy of nanofluids, demonstrating reduced cutting temperatures and enhanced surface finish. Notably, ZrO2-based nanofluids exhibit improved tribological response, while ZnO-based nanofluids showcase exceptional heat transfer ability, offering promising solutions to key technical challenges in machining processes. In conclusion, this study underscores the potential of green, sustainable ZnO and ZrO2 nanoparticles as additives in cutting fluids, poised to revolutionize metalworking and manufacturing processes, thereby enhancing product quality and sustainability.

The luminescent Nb2C MXene nanosheet-based whispering gallery mode-enhanced ECL strategy for miRNA-214 detection

MiRNA-214 can regulate the expression of their downstream target genes after post-transcriptional and are involved in the biological processes of triple negative breast cancer (TNBC). In this work, the small-sized luminescent Nb2C nanosheet-based whispering gallery mode-enhanced electrochemiluminescence (ECL) strategy was successfully constructed to detect miRNA-214 in TNBC. Firstly, we have synthesized small-sized luminescent Nb2C nanosheets from Nb2AlC MXene. The Nb2C nanosheets not only exhibited more stable chemical properties and reduced the defects of the large sheet structures, but also possessed the quantum confinement effect with the discrete energy level. As a result, the prepared small-sized Nb2C nanosheets had unique luminescent and electrochemical properties. Furthermore, in order to improve the ECL performance of Nb2C nanosheets, SiO2 microspheres were self-assembled on the electrode surface by gas-liquid interface method to form whispering gallery mode structure. Because the light was continuously reflected at the interface of the microcavity in the whispering gallery mode, the ECL signal of Nb2C luminescent nanosheets was amplified largely. Finally, the whispering gallery mode-based ECL sensing platform was established. The results showed that the biosensor had a good linear correlation between the ECL intensity and the logarithm of concentration of miRNA-214 in the range of 10 fM to 100 nM with a limit of detection of 2.5 fM. The actual detection of miRNA-214 content in clinical TNBC tissue samples was realized successfully.

Controlled growth of MPA-capped ZnS quantum dots through concentration-modulated single injection hydrothermal method

This study presents the controlled growth of 3-Mercaptopropionic acid (MPA)-capped ZnS quantum dots (QDs) using a concentration-modulated single injection hydrothermal method. Employing the Concentration optimization by optical spectra (COOS) method, we optimized the MPA:Zn:S ratios to investigate the influence of the capping agent, cation, and anion for exceptional properties suitable for optoelectronic and sensor applications. CMSIH operates as a single-step synthesis process, reducing processing time and complexity. This streamlined approach not only enhances efficiency but also minimizes the risk of contamination and ensures batch-to-batch consistency in QD production. Its moderate operating conditions, compared to other high-energy methods, also contribute to reduced energy consumption and environmental impact, aligning with sustainable manufacturing practices. Further, X-ray diffraction (XRD) confirmed the Zinc blend (cubic) phase of ZnS, and Fourier-transform infrared spectroscopy (FTIR) validated MPA capping. The QDs exhibited strong quantum confinement, causing a blue shift in absorption peaks compared to bulk ZnS. Higher MPA concentrations ranging from 0.02 M to 0.1 M induced a red shift in the absorption edge due to prolonged reaction times and strong cation binding by MPA. Variations in cation Zn and anion S ratios from 0.02 M to 0.1 M caused blue and red shifts in the absorption edge, respectively. For instance, Zn:S = 0.04:0.01 M increased cation concentrations, reducing QD size up to 0.67 nm, while enhanced anion concentrations Zn:S = 0.04:0.04 M enlarged the QDs size up to 2.35 nm. Remarkably, calculated QD sizes using Brus’ equation were smaller than the Bohr radius, even at an elevated temperature of 95 °C, indicating significant quantum confinement. Luminescence studies revealed reduced luminescence with higher MPA concentrations, increased luminescence intensity with higher cation Zn+ concentrations, and a red shift in the luminescence peak with higher anion S concentrations. As the temperature rises, there is an observable decrease in luminescence intensity. Furthermore, the investigation into the relationship between chemical composition and optical properties of MPA-capped ZnS QDs at elevated temperatures expands understanding of quantum confinement effects. The synthesised unique ultra small ZnS QDs can be used in advanced quantum sensors mainly as radiation detectors.

Size dependent dual functionality of CeO2 quantum dots: A correlation among parameters for hydrogen gas sensor and pollutant remediation

The metal oxide-based nanostructures of variable size and shape are found effective in optimizing the gas sensing ability and pollutant degradation. The size induced lattice strain and large band gap in 3nm CeO2 quantum dots evolved the ability towards hydrogen gas sensing and dye degradation compared to nanopebbles and nanoparticles of sizes 15 ± 3, and 30 ± 12 nm. The smaller CeO2 quantum dots than Debye length was found underlying reason for nearly four times sensor response and selectivity towards reducing hydrogen gases than the oxidizing gases at 1–10 ppm level. The lattice strain calculated by Rietveld refinement and W–H analysis was found in-line with the size of CeO2 nanostructures. The enhancement in lattice strain and optical band gap (2.66, 2.78, and 2.89 eV) with decrease in size are found critical for determining the overall efficiency of CeO2 nanostructures for photocatalytic activity, attributed to the strong quantum confinement effect. The higher catalytic activity of 98 % was achieved CeO2 quantum dots in comparison to the 95 % and 94 % obtained for CeO2 nanopebbles and nanoparticles. The impact of change in degradation efficacy and gas sensing ability of different CeO2 nanomaterials is discussed in detail. This work offers a novel and simplistic method to produce CeO2 quantum dots as an efficient sensor for selective detection of H2 gas and photocatalyst. The correlation between size, Debye length, band gap, and lattice strain gives an insight for understanding the underlying detection mechanism for selective detection of reducing gas molecules and efficient pollutant remediation.

Numerical Modeling of Steel Fiber Reinforced Recycled Concrete Filled Steel Tube Column Under Cyclic Loading

A finite element model (FEM) was created with the aim of analyzing the behavior of steel fiber reinforced recycled concrete (SFRRC)-filled steel tube columns under combined cyclic loading and monotonic axial load. The FEM considered the effect of steel tube confinement on the inner concrete behavior under cyclic loading. The numerical model was described in detail, with a focus on modeling the materials involved (normal concrete, SFRRC, and steel) under cyclic loading. A constitutive concrete model - with and without considering confinement - was based on utilizing a concrete damaged plasticity (CDP) model. The steel tube - concrete core interface was modeled by a surface-to-surface contact. A stress-strain constitutive concrete model, confined by circular steel tubes, was implemented, and validated using experimental results from the literature. The developed FEM considered various parameters: steel tube thickness, volume ratios of steel fibers, besides strengths of both concrete core and the steel tube. The FEM results showed great similarity to the under- cyclic- loading tested columns. The results indicated that the concrete confining pressure must be considered in CDP model. A good correlation between numerical and experimental findings was obvious, including failure modes, and hysteretic curves of load-displacement.

Assessing Subsurface Gas Storage Security for Climate Change Mitigation and Energy Transition

AbstractSubsurface gas storage is crucial for achieving a sustainable energy future, as it helps to reduce CO2 emissions and facilitates the provision of renewable energy sources. The confinement effect of the nanopores in caprock induces distinctive thermophysical properties and fluid dynamics. In this paper, we present a multi‐scale study to characterize the subsurface transport of CO2, CH4, and H2. A nanoscale‐extended volume‐translated Cubic‐Plus‐Association equation of state was developed and incorporated in a field‐scale numerical simulation, based on a full reservoir‐caprock suite model. Results suggest that in the transition from nanoscale to bulk‐scale, gas solubility in water decreases while phase density and interfacial tension increase. For the first time, a power law relationship was identified between the capillary pressure within nanopores and the pore size. Controlled by buoyancy, viscous force and capillary pressure, gases transport vertically and horizontally in reservoir and caprock. H2 has the maximum potential to move upward and the lowest areal sweep efficiency; in short term, CH4 is more prone to upward migration compared to CO2, while in long term, CH4 and CO2 perform comparably. Thicker caprock and larger caprock pore size generally bring greater upward inclination. Gases penetrate the caprock when CH4 is stored with a caprock thickness smaller than 28 m or H2 is stored with a caprock pore size of 2–10 nm or larger than 100 nm. This study sheds light on the fluid properties and dynamics in nanoconfined environment and is expected to contribute to the safe implementation of gigatonne scale subsurface gas storage.

Fabrication Techniques for a Tuneable Room Temperature Hybrid Single-electron Transistor and Field-effect Transistor

Hybrid room-temperature (RT) silicon single-electron – field effect transistors (SET-FETs) provide a means to switch between ‘classical’, high current FET, and low-power SET operation, using a gate voltage. While operating as a SET, charge on a silicon quantum dot (QD) within the current channel, can be controlled at the one-electron level using the Coulomb blockade effect. This paper investigates nanofabrication methods for sub-10 nm ‘fin’ channel hybrid RT SET-FETs, and their influence on the energy band diagram, and formation of tunnel barriers and QDs, along the channel. Devices are fabricated in heavily n-doped SOI material using electron beam lithography, with thermal oxidation to reduce the as-defined fin width. Effective channel dimensions, following oxidation and excluding Si/SiO2 interface dopant deactivation, are ∼2.4 nm × 32 nm × 20 nm. Dopant disorder, fin width variation at the nanometre scale, and quantum confinement effects are considered as mechanisms for the formation of tunnel barriers and QDs, with dopant disorder the most likely reason. Arrhenius plots of Ids vs. 1/T allow extraction of a potential barrier energy ∼0.2 eV along the fin channel. For 180devices fabricated on four chips, 37% show RT SET-FET operation, ∼3 times higher than the corresponding yield observed in previous work on point-contact silicon SETs.

Electrochemical identification of reductive enantiomers in wood channels: A low-cost and scalable platform for chiral sensing

Chirality, an inherent characteristic of natural substances (such as sugars, peptides, proteins, and nucleic acid), plays a vital role in human metabolism and exerts substantial impacts. In general, chiral drugs can display diverse pharmacological and pharmacokinetic properties. One enantiomer may exhibit therapeutic effects, while the other could cause adverse reactions. Selective recognition of enantiomers is thus a significant task in the biomolecular and pharmaceutical fields. Despite the development of several chiral identification techniques, low-cost enantioselective sensing methods remain highly desirable. Here, we designed and developed an electrochemical sensing device for reductive enantiomer identification using natural wood channels as the substrate. The wood channels were endowed with oxidase-like activity through the in-situ growth of cerium oxide nanoparticles (CeO2). Chiral recognition capability was further introduced by incorporating a layer of chiral ZIF-8 (L-ZIF) as the chiral selector. To demonstrate the enantioselective sensing performance, 3,4-dihydroxyphenylalanine (DOPA) enantiomers were employed as model analytes. Due to the oxidase-like activity and the confinement effect of the proposed channels, the captured DOPA enantiomers were effectively oxidized to their quinone structure, and the Ce(IV) in CeO2 was reduced to Ce(III). These changes led to alterations in the surface charge of the channels, thereby modulating their ionic transport properties. This sensing mechanism also proved useful for the identification of other reductive enantiomers. The limits of detection for l-DOPA and d-DOPA were determined as 2.41 nM and 1.56 nM, respectively. The resulting wood channel-based sensing device not only can be used for the recognition and detection of reductive enantiomers, but also is expected to be applied to the non-electochemically active substances. Moreover, this study offers a novel type of solid-state channel material with low cost, reproducibility, and easy accessibility for electrochemical chiral sensing.

3D numerical study of axial compression behavior of concrete-filled steel tubular columns from mesoscopic perspective

This study investigates the axial compression behavior of Concrete-Filled Steel Tubular (CFST) short columns from a mesoscopic perspective. Concrete is regarded as a three-phase composite material consisting of aggregates, mortar, and interfacial transition zones (ITZs). The Concrete Damaged Plasticity (CDP) model was employed to simulate the nonlinear mechanical response and fracture characteristics of concrete. Verified against experimental results, the numerical model excels in realistically simulating the uniaxial compression behavior of CFST short columns. Subsequently, factors influencing the macroscopic behavior of CFST short columns were investigated. Results indicate that the random aggregate model adopted for concrete enables a more realistic prediction of the behavior of CFST short columns. Additionally, circular section steel tubes demonstrate a stronger confinement effect compared to square ones. With increasing lateral confinement, the properties of CFST short columns, such as bearing capacity and ductility, are significantly enhanced.

Experimental and theoretical investigation on flexural behavior of concrete-filled tubular flange girders

Concrete-filled tubular flange (CFTF) girders offer superior torsional stiffness compared to traditional I-shaped plate girders, providing enhanced flexural performance. To accurately assess the flexural capacity of CFTF girders, both flexural tests and theoretical analyses were conducted on specimens with and without concrete decks. The experimental data were meticulously analyzed to understand the flexural mechanism, yielding sequence, interface slip, strain distribution, and confinement effect of CFTF girders. Subsequently, finite element models were then utilized to analyze the influence of cross-section dimensions and material optimization on the flexural behavior of CFTF girders. Comparative analyses with I-shaped girders were also performed to highlight the structural advantages of CFTF girders. The proposed flexural calculation formulas were validated against both experimental and analytical results, demonstrating a fitting accuracy between 95 % and 98 % for the yield moment and between 96 % and 98 % for the ultimate moment. The method proposed in this paper provides a reliable and accurate approach for evaluating the flexural capacity of CFTF girders, significantly contributing to the advancement of design and analysis practices in structural engineering.

Lattice contraction and Surface stress investigation in nanoparticles of zinc sulfide

Nanostructured zinc sulfide was synthesized through controlled chemical precipitation method using zinc chloride and sodium sulfide as starting materials. Zinc sulfide nanoparticle with different average grain sizes were obtained by annealing the as prepared sample at different temperatures in inert atmosphere. The samples were characterized using XRD, TEM, and SAED. The lattice contraction, which have significant impact on the electrical and mechanical properties of nanomaterials were studied using Hall-Williamsons analysis. The lattice contraction present in nanoparticles of zinc sulfide with different average particle size at different planes was studied. The observed lattice contraction in nanoparticles of zinc sulfide seems to have contributions from micro strain over and above the contribution from quantum confinement effect due to small particle size and it follows an inverse proportional relationship with the particle size.The present paper discusses the reduced unit cell size in ZnS nanoparticles, along with their diminutive particle size, and its contribution to the broadening of X-ray diffraction peaks.

Maneuvering magic-sized transition metal chalcogenides nanoclusters for Solar-to-Hydrogen conversion

Magic-sized nanoclusters (MSCs) have recently deemed as a novel and crucial sector of nanomaterials on account of their large absorption coefficient for light harvesting, peculiar quantum confinement effect, and abundant active. Nevertheless, precise control of photoinduced charge carriers over MSCs has so far not yet been reported because of the ultra-short carrier lifetime and intrinsic instability of MSCs, which renders the complexity of MSCs photosystems with photoredox mechanism remaining blank. Herein, we for the first time conceptually demonstrate the grafting of amino-containing organic molecular onto the L-cysteine (L-Cys) ligand of CdSe@L-Cys MSCs as charge transport mediator, and the amino functional group acts as an efficient electron-withdrawing trap, which markedly boosts the charge separation and prolongs the charge lifetime of CdSe@L-Cys MSCs, resulting in the significantly improved photocatalytic hydrogen generation performances under visible light irradiation along with favorable stability. Our work will provide sparking ideas for fine tuning of photoinduced charge separation and transfer over transition metal chalcogenides MSCs photosystems for solar-to-hydrogen energy conversion.

Fe based MOF encapsulating triethylenediamine cobalt complex to prepare a FeN3-CoN3 dual-atom catalyst for efficient ORR in Zn-air batteries

Single-atom catalysts show good oxygen reduction reaction (ORR) performance in metal-air battery. However, the symmetric electron distribution results in discontented adsorption energy of ORR intermediates and a lower ORR activity. Herein, Fe-Co dual-atom catalyst with FeN3-CoN3 configuration was prepared by encapsulating nitrogen-rich ion (triethylenediamine cobalt complex, [Co(en)3]3+) in Fe based MOF cage to greatly enhance ORR performance. Due to the confinement effect of the MOF cage, the encapsulated [Co(en)3]3+ is closer to Fe of MOF, thus easily generating FeN3-CoN3 sites. The FeN3-CoN3 sites can break the symmetric electron distribution of single-atom sites, optimizing adsorption energy of oxygen intermediate. Thus, FeCo-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.915 V and 0.789 V in alkaline and acidic electrolyte, respectively, while it was 0.874 V and 0.79 V for Pt/C. The liquid and solid Zn-air batteries with FeCo-NC as cathode show higher peak power density and specific capacity. DFT results indicate that FeN3-CoN3 site can reduce the reaction energy barrier of the rate-determining step resulting in an excellent ORR performance.