Rapid Transfer Research Articles

An Improved Detail-Enhancement CycleGAN Using AdaLIN for Facial Style Transfer

The rise of comics and games has led to increased artistic processing of portrait photos. With growing commercial demand and advancements in deep learning, neural networks for rapid facial style transfer have become a key research area in computer vision. This involves converting face photos into different styles while preserving content. Face images are more complex than regular images, requiring extensive modification. However, current methods often face issues such as unnatural color transitions, loss of detail in highlighted areas, and noticeable artifacts along edges, resulting in low-quality stylized images. In this study, an enhanced generative adversarial network (GAN) is proposed, which is based on Adaptive Layer Instance Normalization (AdaLIN) + Laplacian. This approach incorporates the AdaLIN normalization method, allowing for the dynamic adjustment of Instance Normalization (IN) and Layer Normalization (LN) parameters’ weights during training. By combining the strengths of both normalization techniques, the model selectively preserves and alters content information to some extent, aiming to strike a balance between style and content. This helps address problems such as unnatural color transitions and loss of details in highlights that lead to color inconsistencies. Furthermore, the introduction of a Laplacian regularization term aids in denoising the image, preventing noise features from interfering with the color transfer process. This regularization also helps reduce color artifacts along the face’s edges caused by noise while maintaining the image’s contour information. These enhancements significantly enhance the quality of the generated face images. To compare our method with traditional CycleGAN and recent algorithms such as XGAN and CariGAN, both subjective and objective evaluations were conducted. Subjectively, our method demonstrates more natural color transitions and superior artifact elimination, achieving higher scores in Mean Opinion Score (MOS) evaluations. Objectively, experiments using our method yielded better scores across three metrics: FID, SSIM, and MS-SSIM. The effectiveness of the proposed methods is validated through both objective and subjective evaluations.

Ultrasensitive electrochemiluminescence biosensing from Cobalt single atom embedded high crystalline g-carbon nitride nanorod

Here, cobalt single-atom (Co SA) was introduced into the structure of the crystalline g-C3N4 nanorod (cry-CNN), which showed rapid electron transfer rate and excellent redox activity, thereby resulting in high electrochemiluminescence (ECL) emission. Compared to bulk g-C3N4, the cry-CNN had higher ECL intensity due to increasing the crystallinity to change the charge transport of electrons in the layer. Besides, benefiting from the unique electronic structure and catalytic activity of Co SA, the obtained Co SA@cry-CNN represented enhanced ECL intensity at a lower negative potential than that of cry-CNN, owing to the Co SA not only accelerated the electron transfer of the cry-CCN in heptazine cavity, but also promoted the co-reactive S2O82- to produce more active intermediate SO4•–. Interestingly, the experimental results showed that the ECL emission of Co SA@cry-CNN was about 23 times higher than that of BCN, and was 5 times higher than that of cry-CNN. Furthermore, using Co SA@cry-CNN as luminophore, a compact and efficient HCR-link-CHA(HLC) cascade amplification strategy was designed to construct a biosensor for detection of microRNA-222, which converted a certain amount of target to a DNA nanonet with plenty of quencher via N cycle of HCR and CHA reaction. The constructed biosensor had good monitoring performance and the limit of detection was as low as 40.0 amol/L. The proposed strategy integrated luminous structural adjustment and co-reaction efficiency improvement could be effectively extended to exploration of other novel ECL materials, and also provided new ideas for the early diagnosis of diseases.

Multiscale Simulation of Laser-Based Direct Energy Deposition (DED-LB/M) Using Powder Feedstock for Surface Repair of Aluminum Alloy.

Laser-based direct energy deposition (DED-LB/M) has been a promising option for the surface repair of structural aluminum alloys due to the advantages it offers, including a small heat-affected zone, high forming accuracy, and adjustable deposition materials. However, the unequal powder particle size during powder-based DED-LB/M can cause unstable flow and an uneven material flow rate per unit of time, resulting in defects such as pores, uneven deposition layers, and cracks. This paper presents a multiscale, multiphysics numerical model to investigate the underlying mechanism during the powder-based DED-LB/M surface repair process. First, the worn surfaces of aluminum alloy components with different flaw shapes and sizes were characterized and modeled. The fluid flow of the molten pool during material deposition on the worn surfaces was then investigated using a model that coupled the mesoscale discrete element method (DEM) and the finite volume method (FVM). The effect of flaw size and powder supply quantity on the evolution of the molten pool temperature, morphology, and dynamics was evaluated. The rapid heat transfer and variation in thermal stress during the multilayer DED-LB/M process were further illustrated using a macroscale thermomechanical model. The maximum stress was observed and compared with the yield stress of the adopted material, and no relative sliding was observed between deposited layers and substrate components.

High-performance flexible asymmetric supercapacitor utilizing hierarchical NiCo2O4 nanosheets supported on porous carbonized Verbena leaves

This study employed three-dimensional porous carbon with high surface area as the conductive substrate for composite electrode materials, aiming to facilitate rapid charge transfer and ion diffusion to increase the specific capacitance of pseudo-capacitive materials. We employed an in-situ hydrothermal method to anchor NiCo2O4 onto the porous carbonized verbena leaves, yielding nanostructured VC@NiCo2O4-8 composite electrode materials. At a current density of 1.0 A g-1, VC@NiCo2O4-8 exhibited a high specific capacitance of up to 2061.8 F g−1 and remarkable cycling stability (with only 7.8 % capacitance loss after 10000 cycles). Additionally, we assembled VC@NiCo2O4-8//VC asymmetric all-solid-state flexible supercapacitors, attaining a significant energy density of 54.0 Wh kg−1 at a power density of 695 W kg−1, while maintaining good flexibility and stability. This study provides a simple and effective method for the design and construction of high-performance electrode materials for flexible energy storage devices.

Eosin Y Post-Decorated Metal-Organic Framework as a Selectivity Regulator for the Alcohols Oxidation.

The selective oxidation of alcohols into aldehydes is a basic and significant procedure, with great potential for scientific research and industrial applications. However, as an important factor in the C(sp3)-H activation process, high selectivity is generally difficult to achieve due to the fact that the more easily activated properties of aldehydes are compared to alcohols. Herein, by the ingenious decoration of eosin Y into a Zr-based metal-organic framework (MOF-808), EY@MOF-808 was prepared as a selectivity regulator for the aerobic oxidation of the benzyl alcohols into corresponding aldehydes, possessing applicability for the benzylic alcohols with various substituents. By anchoring eosin Y on Zr6O4(OH)4 clusters of MOF-808 and maintaining open metal nodes with selective binding effects, the benzyl alcohol substrates were selectively coordinated to the unsaturated metal clusters adjacent to eosin Y, which ensured that the excited eosin Y rapidly activated substrates to generate carbon radicals by the hydrogen atom transfer (HAT) process. The rapid electron transfer (ET) simultaneously produced reactive oxygen species (O2•-) and then a combination of both to further promote the generation of benzaldehydes. The weak interaction of benzaldehydes with the skeleton allowed it to dissociate rapidly, thus preventing overoxidation. Under the catalysis of EY@MOF-808, the selectivity of various benzaldehydes was more than 99%. In contrast, eosin Y gave only benzoic acid products under the same conditions, which demonstrated the superiority of regulatory selectivity of EY@MOF-808. Taking advantage of the heterogeneity of the MOF, EY@MOF-808 was recycled four times without a decrease in its selectivity and avoided the quenching effect of eosin Y. The organic functional units postdecorated MOF-based photocatalyst strategy exhibits a promising new perspective approach to sustainably regulating the selectivity of inert oxidation.

Rapid Exciton Dissociation and Charge Transfer Endowed by Reinforced Interfacial Interaction in a Mixed-Dimensional 2D/3D Heterojunction Nanocatalyst for High-Efficiency Photocatalysis

Rapid Exciton Dissociation and Charge Transfer Endowed by Reinforced Interfacial Interaction in a Mixed-Dimensional 2D/3D Heterojunction Nanocatalyst for High-Efficiency Photocatalysis

Molecular Dynamics-Based Study of Graphene/Asphalt Mechanism of Interaction

This study employed molecular dynamics simulation to investigate the mechanism of action of graphene-modified asphalt. A series of molecular models of graphene-modified asphalt were constructed and validated using thermodynamic parameters. The impact of the graphene (PGR) size and number of layers on its interaction with asphalt components were examined, and the self-healing process and mechanism of action of PGR-modified asphalt were analyzed. The results demonstrated that the size and number of layers of PGR significantly influenced its interaction with asphalt components, with polar components demonstrating a stronger affinity for PGR. When the size and number of layers of PGR were held constant, the interfacial binding energy between it and ACR-modified asphalt was the highest, followed by SBS-modified asphalt, and 70# matrix asphalt exhibited the lowest interfacial binding strength. This interfacial binding strength is primarily attributed to intermolecular van der Waals interactions. Furthermore, the incorporation of multi-layer PGR can markedly enhance the mechanical properties of matrix asphalt, whereas small-sized PGR is more efficacious in improving the low-temperature performance of polymer-modified asphalt. PGR can act as a bridge between asphalt molecules through rapid heat transfer and π-π stacking with aromatic ring-containing substances, which markedly increases the free diffusion ability of asphalt molecules, shortens the healing time of asphalt, and enhances the collective self-healing performance of asphalt. This study provides an essential theoretical basis for understanding the mechanism and application of PGR in asphalt modification.

Anchoring NiSx (x=0, 1, 2) on porous g-C3N4 (PCN) to enhance photocatalytic H2 production: The effect of S element on H2 evolution

Constructing effective active sites on photocatalysts is key to promoting H2 evolution activity. Although nickel sulfides are found to be non-noble cocatalysts with high cocatalytic performance, the effect of the S element on H2 evolution still needs to be clarified. Herein, NiSx (x = 0, 1 and 2) cocatalysts are successfully anchored respectively on the surface of porous g-C3N4via the same solid-state method. The combined experimental and theoretical calculations reveal that an intimate Schottky junction constructed between metallic NiSx and PCN impels the rapid transfer of electrons from PCN to NiSx., which promotes a charge separation efficiency and enhances photocatalytic activity. Furthermore, the introduction of the S in the NiSx lattice regulates the adsorption and desorption energies of reactant (H+) and product (H2), determining the H2-evolving performance. Among the Ni, NiS and NiS2 cocatalysts, the S element in the NiS adjusts the equilibrium of adsorption and desorption for H+/H2, resulting in the most favorable thermodynamics of H2 evolution. The maximum H2-rate of NiS/PCN reaches 142.9 μmol h−1, which is 4.3 and 1.6 times of Ni/PCN and NiS2/PCN. Our results gain a deeper understanding of the mechanism that transition metal dichalcogenide based cocatalysts promote photocatalytic activity.

Elemental doping tailoring photocatalytic hydrogen evolution of InP/ZnSeS/ZnS quantum dots

Photocatalytic water splitting for hydrogen production has garnered considerable attention as an effective method to alleviate energy shortages. In comparison to cadmium-based quantum dots (QDs) photocatalysts, InP QDs possess a smaller bandgap, larger exciton radius, broader absorption range, and are environmentally friendly. Although InP/ZnS core/shell QDs exhibit immense potential in photocatalysis, they suffer from rapid electron-hole recombination owing to interface defects and lattice mismatch. To address these issues, this study introduces an intermediate ZnSeS shell to reduce defects and tailor QD redox properties through transition metals (manganese and copper) doping. The characterization of QDs was performed from various perspectives, including morphology, element distribution, band structure, and charge transport efficiency. Notably, the photoelectrochemical properties of doped QDs were superior to those of the undoped QDs, while Mn-doped QDs showed inferior catalytic performance compared to the undoped ones. The mechanism of different photoelectrochemical and photocatalytic performances has been studied more intensely. The Mn-doped QDs undergo a process where Mn4+ is converted to Mn2+, consuming electrons in competition with the photocatalytic hydrogen evolution process. Conversely, InP/ZnSeS:Cu/ZnS QDs introduced an additional energy level into the original band structure, capturing some holes and slowing down the electron-hole recombination, thereby providing positive feedback for photocatalytic hydrogen production. Profiting from both the synergies of energy level structure and doping metal state, effective electron-hole separation, and rapid electron transfer to the surface of Cu-doped QDs accomplish the efficient hydrogen generation. The present study offers more possibilities for exploiting the required photocatalytic performance of QD catalysts via elemental doping.

An efficient NiS-ReS2/CdS nanoparticles with dual cocatalysts for photocatalytic hydrogen production

The construction of heterojunctions is one of efficacious ways to improve the charge transfer and suppress the recombination of photoexcited electron-hole pairs for enhancing reactive activities of photocatalysts. Ternary NiS-ReS2/CdS composites are synthesized via a one-step hydrothermal method and the heterojunction nanostructures are achieved. The NiS-ReS2/CdS photocatalyst exhibits the superior photocatalytic activity with a hydrogen production rate up to 139 mmol g−1 h−1, which is much higher than binary composites and pure CdS. The contributions of the dual cocatalysts NiS and ReS2 are verified to narrower bandgaps, lower resistances and increase photocurrent density of NiS-ReS2/CdS, promoting the absorption of visible light and the migration of photoinduced electrons. The NiS-ReS2/CdS heterostructures provide a possible dual Z-scheme path for the rapid transfer of electrons. The tailoring of the dual cocatalysts is effective to improve the photocatalytic hydrogen production.

A Geometrically Flexible Three-Dimensional Nanocarbon.

The development of architecturally unique molecular nanocarbons by bottom-up organic synthesis is essential for accessing functional organic materials awaiting technological developments in fields such as energy, electronics, and biomedicine. Herein, we describe the design and synthesis of a triptycene-based three-dimensional (3D) nanocarbon, GFN-1, with geometrical flexibility on account of its three peripheral π-panels being capable of interconverting between two curved conformations. An effective through-space electronic communication among the three π-panels of GFN-1 has been observed in its monocationic radical form, which exhibits an extensively delocalized spin density over the entire 3D π-system as revealed by electron paramagnetic resonance and UV-vis-NIR spectroscopies. The flexible 3D molecular architecture of GFN-1, along with its densely packed superstructures in the presence of fullerenes, is revealed by microcrystal electron diffraction and single-crystal X-ray diffraction, which establish the coexistence of both propeller and tweezer conformations in the solid state. GFN-1 exhibits strong binding affinities for fullerenes, leading to host-guest complexes that display rapid photoinduced electron transfer within a picosecond. The outcomes of this research could pave the way for the utilization of shape and electronically complementary nanocarbons in the construction of functional coassemblies.

Additive manufacturing of copper parts using extrusion and sinter-based technology: evaluation of the influence of printing parameters and debinding method

PurposeThis work is focused on the realization of copper parts using the material extrusion additive manufacturing debinding and sintering (MEX+D&S) technology.Design/methodology/approachA highly filled filament with 90 Wt.% of copper is used to realize nine different combinations varying the printing speed and the flow rate. The following thermal debinding and sintering are performed at 483 °C and 1057 °C, respectively, burying the samples in specific refractory powder and carbon. The green and sintered density are measured and an inspection at optical microscope is implemented for a detailed internal analysis of the defects.FindingsThe samples, that reported the highest values of the green density, become the worst in the sintered condition due to evident swelling defect generated by the entrapped polymer during the thermal debinding. On the other hand, the parts with the lower values of green density allowed to achieve a satisfying density value without significant external defects.Originality/valueThe realization of copper parts through laser-based additive manufacturing technologies shows several troubles related to the rapid heat transfer and the high reflectivity of copper, which is a hinder of the absorption of the laser power. The MEX+D&S becomes an easier and economical alternative for the realization of copper parts. The internal inspection of the samples revealed the need for the improvement on the process chain, adopting a different debinding process to open channels during the thermal debinding to avoid the entrapment of the polymer.

Efficient and rapid digestion of proteins with a dual-enzyme microreactor featuring 3-D pores formed by dopamine/polyethyleneimine/acrylamide-coated KIT-6 molecular sieve

The microreactor with two types of immobilized enzymes, exhibiting excellent orthogonal performance, represents an effective approach to counteract the reduced digestion efficiency resulting from the absence of a single enzyme cleavage site, thereby impacting protein identification. In this study, we developed a hydrophilic dual-enzyme microreactor characterized by rapid mass transfer and superior enzymatic activity. Initially, we selected KIT-6 molecular sieve as the carrier for the dual-IMER due to its three-dimensional network pore structure. Modification involved co-deposition of polyethyleneimine (PEI) and acrylamide (AM) as amine donors, along with dopamine to enhance material hydrophilicity. Remaining amino and double bond functional groups facilitated stepwise immobilization of trypsin and Glu-C. Digestion times for bovine serum albumin (BSA) and bovine hemoglobin (BHb) on the dual-IMER were significantly reduced compared to solution-based digestion (1 min vs. 36 h), resulting in improved sequence coverage (91.30% vs. 82.7% for BSA; 90.24% vs. 89.20% for BHb). Additionally, the dual-IMER demonstrated excellent durability, retaining 96.08% relative activity after 29 reuse cycles. Enhanced protein digestion efficiency can be attributed to several factors: (1) KIT-6’s large specific surface area, enabling higher enzyme loading capacity; (2) Its three-dimensional network pore structure, facilitating faster mass transfer and substance diffusion; (3) Orthogonality of trypsin and Glu-C enzyme cleavage sites; (4) The spatial effect introduced by the chain structure of PEI and glutaraldehyde’s spacing arm, reducing spatial hindrance and enhancing enzyme–substrate interactions; (5) Mild and stable enzyme immobilization. The KIT-6-based dual-IMER offers a promising technical tool for protein digestion, while the PDA/PEI/AM-KIT-6 platform holds potential for immobilizing other proteins or active substances.

Construction of a Composite Sn‐DLC Artificial Protective Layer with Hierarchical Interfacial Coupling Based on Gradient Coating Technology Toward Robust Anodes for Zn Metal Batteries

AbstractDeveloping a robust zinc (Zn) anode, free from Zn dendrites and unwanted side reactions, relies on designing a durable and efficient interfacial protection layer. In this study, gradient coating technology is employed to construct a hierarchically structured composite of Sn with diamond‐like carbon (DLC/Sn‐DLC) as an artificial protective layer. The DLC framework endows DLC/Sn‐DLC layer with high stability and adaptability, achieving long‐term stability of the anode–electrolyte interface. The gradual‐composite Sn, with its Sn─O─C interface chemical bonds, facilitates rapid charge transfer and offers ample zincophilic sites at the base, promoting uniform Zn2+ reduction reaction and deposition. Additionally, the DLC/Sn‐DLC composite exhibits a “lotus effect” and favorable hydrophobic properties, preventing water‐reduced side reactions. Leveraging this structural design and the synergistic cooperation of DLC and Sn, the DLC/Sn‐DLC@Zn electrode demonstrates remarkable Zn plating/stripping reversibility, eliminating Zn dendrites and side reactions. Notably, under a high current density of 10 mA cm−2, the DLC/Sn‐DLC@Zn anode‐based symmetrical cell exhibits stable operation for over 1550 h, with a low nucleation overpotential of 101 mV. The DLC/Sn‐DLC@Zn||Mn3O4‐CNTs full battery delivers a high capacity of 109.8 mAh cm−2 after 5800 cycles at 2 A g−1, and the pouch cell shows potential for energy storage applications.

Ultra-trace leakage detection of 1, 2-dimethoxyethane in Lithium-Ion battery electrolyte via lacunary polyoxometalates-driven synthesis of NiO/Si-NiWO4/WO3 heterostructure nanofibers

Early detection of electrolyte leakage is crucial to prevent thermal runaway in lithium-ion batteries (LIBs). Gas sensors offer a potential solution, however, designing sensing materials that can sensitively identify organic molecules from electrolyte leakage remains a great challenge. Herein, the heterostructured NiO/Si-NiWO4/WO3 nanofibers (NFs) were achieved as a sensing material for highly sensitive detection of 1, 2-dimethoxyethane (DME), a typical electrolyte organic molecule. This was accomplished using the highly negatively charged lacunary polyoxometalates (POMs) TBA4H6[SiW9O34]·2 H2O (α-SiW9) and Ni2+ as precursors, resulting in a series of uniform Si-NiWO4/WO3 decorated NiO NFs synthesized through a two-step process involving electrospinning followed by thermal oxidation. By utilizing the synergistic effect of abundant active interfaces, rapid carrier transfer, and a large specific surface area inherent to NFs, the sensor shows high sensitivity (1.87–300 ppb DME), reliable reproducibility and stability, and superior selectivity. Moreover, the sensor is highly responsive to electrolyte leakage simulations, making it a strong candidate for safety systems of LIBs. The study outlines a cost-effective method for preparing NiO/Si-NiWO4/WO3 NFs, setting a foundation for developing various heterostructured nanomaterials with POMs as precursors.

Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations.

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH2-MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonancespectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min-1. Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to themetal-organic frameworksurface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. The constructed photo-enzyme coupled system successfully combines enzyme catalysis' selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

Rationally Designed L12-Pt2RhFe Intermetallic Catalyst with High CO-Tolerance for Alkaline Methanol Electrooxidation.

It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L12-Pt2RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt2RhFe/C achieves a superior mass activity of 6.43 A mgPt -1, which is 2.23-fold and 3.53-fold higher than those of PtRu/C and Pt/C. Impressively, the Pt2RhFe/C exhibits a significant enhancement in durability owing to its high CO-tolerance and stability. Density functional theory calculations reveal that high performance of Pt2RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt-CO···OH-Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.

Enhancing Sustainable Analytical Chemistry in Liquid Chromatography: Guideline for Transferring Classical High-Performance Liquid Chromatography and Ultra-High-Pressure Liquid Chromatography Methods into Greener, Bluer, and Whiter Methods.

This review is dedicated to sustainable practices in liquid chromatography. HPLC and UHPLC methods contribute significantly to routine analytical techniques. Therefore, the transfer of classical liquid chromatographic methods into sustainable ones is of utmost importance in moving toward sustainable development goals. Among other principles to render a liquid chromatographic method green, the substitution of the organic solvent component in the mobile phase with a greener one received great attention. This review concentrates on choosing the best alternative green organic solvent to replace the classical solvent in the mobile phase for easy, rapid transfer to a more sustainable normal phase or reversed-phase liquid chromatography. The main focus of this review will be on describing the transfer of non-green to green and white chromatographic methods in an effort to elevate sustainability best practices in analytical chemistry. The greenness properties and greenness ranking, in addition to the chromatographic suitability of seventeen organic solvents for liquid chromatography, are mentioned to have a clear insight into the issue of rapidly choosing the appropriate solvent to transfer a classical HPLC or UHPLC method into a more sustainable one. A simple guide is proposed for making the liquid chromatographic method more sustainable.

Steering sulfur reduction kinetics of lithium-sulfur batteries by interfacial microenvironment modulation

Catalytic conversion of lithium polysulfides (LiPSs) is considered as an effective avenue to suppress the shuttle effect of lithium-sulfur (Li-S) batteries, for which the interfacial microenvironment constructed by the interaction between electrocatalysts and LiPSs plays a pivotal role in modulating the sulfur reduction kinetics. However, most of previous reports mainly focused on modulating the band structure of electrocatalysts or LiPSs alone to enhance the catalytic activity rather than considering the interfacial microenvironment as a whole. Herein, we propose a binary descriptor composed of the energy difference between d-band of electrocatalysts and p-band of LiPSs (ΔεM-S) and the antibonding filling degree (εABF), which capture the energy band contributions from both electrocatalysts and LiPSs, to reveal the influence of interfacial microenvironment on sulfur reduction kinetics. Among different designed electrocatalysts, NiO presents a moderate LiPSs anchoring capacity and rapid electron transfer kinetics owing to the optimal ΔεM-S and decreased εABF after interacting with LiPSs, which lead to a robust interfacial microenvironment and thus guarantee a continuous catalytic conversion of LiPSs in the long-term cycling. Such a fundamental understanding of catalytic activity toward LiPSs from the viewpoint of interfacial microenvironment provides an alternative avenue for designing highly efficient electrocatalysts for Li-S batteries.

Sulfur-vacancy-modified ZnIn2S4/TpPa-1 S-scheme heterojunction with enhanced internal electric field for boosted photocatalytic hydrogen production

The construction of S-scheme heterojunction is an effective approach to accelerate photocarrier transfer and improve charge utilization, thus promoting photocatalytic hydrogen evolution. Herein, we report, for the first time, the construction of a S-scheme heterojunction based on sulfur-vacancy-modified ZnIn2S4 (Sv-ZIS) and covalent organic frameworks (COFs), by in-situ growth of Sv-ZIS on COF TpPa-1 (composed of 1,3,5-triformylphloroglucinol and p-phenylenediamine). Under visible-light irradiation, in the absence of cocatalyst, the optimal Sv-ZIS/TpPa-1 (5:1) (with a Sv-ZIS: TpPa-1 mass ratio of 5:1) achieved an enhanced hydrogen production rate of 2745 μmol g−1 h−1 than parent ZIS/TpPa-1 (5:1), with an AQE of 4.67 % at 420 nm. Theoretical calculations confirmed that sulfur-vacancy enlarged the internal electric field (IEF) in Sv-ZIS/TpPa-1, leading to greater interfacial charge transfer from Sv-ZIS to TpPa-1 than that of ZIS to TpPa-1. The enhanced IEF and rapid separation and transfer of photocarriers following S-scheme charge transfer mechanism synergistically guaranteed the improved performance.