The promising non-noble electrocatalyst with well-defined structure is significant for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for the renewable energy devices like zinc-air batteries (ZABs). Herein, the four phenyl-linked cobaltporphyrin-based covalent organic polymers (COPs-1-4) with the different edge substituents (1 = -tBu, 2 = -Me, 3 = -F, and 4 = -CF) are firstly designed and synthesized via a simple, efficient one-pot method. With the increase of electron donating capacity of the substituents, the highest occupied molecular orbital energy (E) gradually increases in the order of COP-4 < COP-3 < COP-2 < COP-1. Consequently, the optimal COP-1 with -tBu edge groups exhibits the highest half-wave potential (E) of 0.84 V (vs. RHE) among the four COPs, which is comparable with commercial Pt/C in alkaline media. The DFT calculations further reveal that with strong electron donating capacity, the Gibbs free energy decreases in the order of COP-4 > COP-3 > COP-2 > COP-1 by modulating the adsorption energy of OOH* at rate-determining step (RDS) to promote ORR activity. Furthermore, introducing Ni (II) and Co (II) into porphyrin centers afford the bimetallic CoNi-COP-1 with both Co-N, Ni-N active sites and edge substituted -tBu. The synergistic effect of Co, Ni bimetallic active sites and strong electron-donating -tBu substituents renders the CoNi-COP-1 the highest HOMO and smallest energy gap between the E and E among the as-prepared five COPs, which leads to more filling electrons of its LUMO level, and thus exhibits the excellent ORR and OER bifunctional catalytic activities with an E as high as 0.85 V and an overpotential (η) of 0.34 V at 10 mA cm in alkaline media, superior to monometallic Co-containing COPs-1-4. In particular, the assembled ZABs with bifunctional catalyst CoNi-COP-1 possesses high power density (94.10 mW cm), high specific capacity (841.71 mAh g) and long durability of over 160,000 s. This work exemplifies the rational design of pyrolysis-free non-noble metal COP-based electrocatalyst through optimizing the intrinsic metal center and its secondary coordination environment.

Step-scheme (S-scheme) heterojunction has attracted much attention in the design of heterostructures for photocatalysts. In this study, we successfully utilized the principle of electrostatic self-assembly to load ultrathin ZnInS nanosheets onto snowflake-like CuS using a simple grinding method, and synthesized CuS/ZnInS S-scheme heterojunctions according to the different work functions (Φ). At the optimal CuS loading ratio (5 wt%), the hydrogen yield of the CuS/ZnInS composites reaches 5.58 mmol·h·g, which is 5.12 times higher than that of pure ZnInS (1.09 mmol·h·g). The apparent quantum efficiency (AQE) of the CuS/ZnInS composites reaches 5.8 % (λ = 370 nm), which is an improvement compared to pure ZnInS (2.7 %). The AQE of pure ZnInS is 0.4 %, while the AQE of CuS/ZnInS composites is enhanced to 1.0 % at λ = 456 nm. The heterojunction interface of CuS and ZnInS builds a built-in electric field (IEF), which greatly reduces the recombination rate of photogenerated electrons and holes, retains highly reduced photoelectrons in the conduction band (CB) of ZnInS. The snowflake structure of CuS effectively increases the active sites and specific surface area, and improves the light absorption. This work opens a new avenue for designing photocatalysts, synergizing energy development and protecting the environment.

A new type of pH-sensitive hydrogel containing supramolecular structures was fabricated from maleimide-functionalized polyrotaxane, ɛ-polylysine and furan-functionalized hyaluronic acid by Diels-Alder reaction and amino-maleimide reaction. Firstly, pseudo polyrotaxane was obtained through self-assembly of polyethylene glycol and α-cyclodextrin, and then capped with 1-adamantanecarboxylic acid to convert it into polyrotaxane. Secondly, a maleimide-functionalized slidable crosslinker was obtained by modifying the polyrotaxane with 3-maleimide propionic acid, and furan-functionalized hyaluronic acid was prepared by modifying it with 2-furanmethylamine. Thirdly, the hydrogel cotaining supramolecular structures was fabricated from the prepared slidable crosslinker, ɛ-polylysine, and furan-functionalized hyaluronic acid in mixed solvent of water and N,N-dimethylformamide. Taking gel mass fraction and swelling ratio as two indicators, the formation parameters of hydrogel were optimized through single- factor experiments. The pH-sensitivity, rheological properties, self-healing performance, and degradation behavior of the hydrogel were investigated. Cytotoxicity assay, live/dead stains, and hemolysis assay were done to verify the biocompatibility of the hydrogel. Finally, the slow-release behavior of the hydrogel containing lidocaine hydrochloride was studied. The hydrogel possesses good biocompatibility, pH-sensitivity, self-healing behavior, degradation, and drug-controlled release, and can find broad application in biomaterials.

The small size of the nanoparticles used to obtain high surface area photocatalysts makes their removal from solution difficult. Producing photocatalysts on substrates would alleviate this limitation. Adding heterojunctions to photocatalysts, for example, TiO/Ag, could improve photocatalytic performance due to Schottky junction formation and introduce antibacterial properties.

High performance film capacitor has attracted widespread attention due to their increasing applications in electronic devices. However, the insufficient dielectric properties of dielectrics in capacitors severely restrict their practical application. In this work, the dielectric performances of polyarylene ether nitrile (PEN) are effectively enhanced by the synthesizing and employing of carboxylated PEN (CPEN) modified one-dimensional (1D) strontium barium titanate nanorod (BSTNR) (CPEN@BSTNR), as well as applying of hot stretching technique. CPEN@BSTNR is prepared via the synthesizing of BSTNR, modifying with γ-Aminopropyl triethoxysilane (KH550), and grafting by CPEN. Deriving from the 1D structure of BSTNR and the peripheral modification by CPEN, compatibility of CPEN@BSTNR in PEN has been significantly improved. Moreover, CPEN@BSTNR orients in the polymer matrix attributing to the hot stretching. Consequently, the hot stretched 16 wt% CPEN@BSTNR/PEN film exhibits an increased dielectric constant of 17.30 and maintained a breakdown strength of 204.1 kV/mm. As a result, this stretched composite film demonstrates an energy density up to 3.19 J/cm, with a 300 % improvement over pure PEN. This enhanced dielectric properties of PEN presents a promising avenue for the fabrication of high performance film capacitors.

Photocatalytic colloids enable light-triggered nonequilibrium interactions and are emerging as key components for the self-assembly of colloidal molecules (CMs) out of equilibrium. However, the material choices have largely been limited to inorganic substances and the potential for reconfiguring structures through dynamic light control remains underexplored, despite light being a convenient handle for tuning nonequilibrium interactions. Here, we introduce photoresponsive N,O-containing covalent organic polymer (NOCOP) colloids, which display multi-wavelength triggered fluorescence and switchable diffusiophoretic interactions with the addition of triethanolamine. Our system can form various flexible structures, including AB-type molecules and linear chains. By varying the relative sizes of active to passive colloids, we significantly increase the structural diversity of AB-type molecules. Most importantly, we demonstrate in-situ transitions between different isomeric configurations and the reversible assembly of various structures, enabled by on-demand light ON and OFF control of diffusiophoretic interactions. Our work introduces a new photoresponsive colloidal system and a novel strategy for constructing and reconfiguring colloidal assemblies, with promising applications in microrobotics, optical devices, and smart materials.

Reducing the size of catalysts and tuning their electronic structure and interfacial properties are key to enhancing catalytic performance. Herein, a series of quantum-sized Co-based nanodot composites, including CoO/C, CoS/C, CoN/C, and CoP/C, were synthesized using chemical vapor deposition (CVD) methods. By means of experimental measurement and theoretical calculation, CoP/C exhibited more robust electrochemical response than other Co-based compounds in electrochemical oxidation of NH (HzOR) and hydrogen evolution reaction (HER). The catalytic activities of CoP/C can be further enhanced by introducing Co vacancies on the surface of CoP/C (labeled as CoP/C). The results demonstrated that CoP/C not only exhibited notable electrochemical responses at an ultra-low NH concentration of 0.67 μM, showcasing its potential for ultra-sensitive NH detection but also realized HzOR instead of the oxygen evolution reaction (OER) half-reaction, thereby lowering the overpotential to 2.0 mV at 10.0 mA cm. Finally, a Zn-hydrazine (Zn-Hz) battery was fabricated as a promising energy conversion device, showing the exceptional practical value of CoP/C.

To replace precious metals and reduce production costs for large-scale hydrogen production, developing stable, high-performance transition metal electrocatalysts that can be used in a wide range of environments is desirable yet challenging. Herein, a self-supported hybrid catalyst (NiFeCrS/NF) with high electrocatalytic activity was designed and constructed using conductive nickel foam as a substrate via manipulation of the cation doping ratio of transition metal compounds. Due to the strong coupling synergy between the metal sulfides NiS, FeS, and CrS, as well as their interaction with the conductive nickel foam (NF), the energy barrier for catalytic reactions is reduced, and the charge transfer rate is enhanced. This significantly improves the hydrogen evolution reaction (HER) performance of NiFeCrS/NF, achieving a current density of 10 mA cm with an overpotential of just 66 mV. Furthermore, doping with chromium generates different valence states of Cr during the catalytic process, which can synergize with the high-valent Fe and Ni, promoting the formation of oxygen vacancies and enriching the active sites for the oxygen evolution reaction (OER). Consequently, at a current density of 10 mA cm in 1.0 M KOH, the overpotential for OER is only 223 mV for NiFeCrS/NF. Additionally, the in situ grown of self-supporting nanoflower structure on NiFe-LDH not only provides a large catalytic surface area but also facilitates electrolyte penetration during the catalytic process, endowing NiFeCrS/NF with high long-term stability. When used as a bifunctional catalyst for overall water splitting, the NiFeCrS/NF||NiFeCrS/NF electrolyzer requires only 1.29 V to deliver a current density of 10 mA cm. Simultaneously, Cr doping protects the Fe sites by maintaining stable valence states, ensuring high performance and stability of NiFeCrS/NF, even when it is utilized for seawater splitting. This strategy offers novel concepts for creating catalysts based on non-precious metals that can be utilized in various application scenarios.

Photothermocatalytic CO reduction has been considered as a green and sustainable strategy for solar-to-fuel conversion, since it can utilize the solar energy to simultaneously provide heat input and produce photogenerated charge carriers. To this end, exploring photothermal catalysts with broad-band absorption, high photo-heat conversion and charge separation efficiency is highly desirable. In this work, an innovative CsBiBr/MoS (CBB/MoS) composite has been elaborately constructed to investigate the photothermocatalytic performance towards CO reduction. In this composite, MoS plays dual roles: with photoinduced self-heating effect, it can act as an extra heater to accelerate the catalytic reaction, and meanwhile serves as a cocatalyst to promote charge separation by forming S-scheme heterojunction with CBB. As expected, the developed CBB/MoS composite delivered outstanding photothermocatalytic activity for CO reduction without any extra heat input, with the CO production rate reaching 172.79 μmol gh. As confirmed by experimental tests and theoretical calculations, the superior photothermocatalytic CO reduction performance of CBB/MoS was attributed to the synergetic effect of high photo-thermo transformation efficiency and highly improved charge separation. The present work offers a potential strategy for developing highly-efficient photothermal catalysts used in artificial photosynthesis.

Dynamic fluorescent switches with multiple light outputs offer promising opportunities for advanced security encryption. However, the achievement of dynamic emission, particularly when based on the timing of external stimuli, continues to present a significant challenge. Herein, a unique dynamic fluorescent switch was developed by integrating spiropyran molecules (SP) into a core-shell structure (SiO@Tb-MOF). The core-shell structure, derived from lanthanide complexes and silica microspheres, was synthesized under solvothermal conditions. This structure not only preserves the green fluorescence emission of Tb-MOF, but also results in a substantial specific surface area and mesoporous pore size from SiO, which is advantageous for incorporating SP molecules to create a dynamic fluorescent switch, SP ⊂ SiO@Tb-MOF. Upon exposure to ultraviolet light, SP gradually transitions into the merocyanine form (MC), displaying a pronounced absorption band at approximately 550 nm. Concurrently, a fluorescence resonance energy transfer (FRET) process is initiated between Tb and the merocyanine isomers. With prolonged exposure to UV light, the fluorescence color shifts progressively from green to red, facilitated by the ongoing FRET process. Moreover, SP ⊂ SiO@Tb-MOF is doped with polydimethylsiloxane to fabricate a film. Utilizing time-dependent fluorescence, dynamic encryption patterns and advanced information encryption were investigated. This work provides a design basis for how to better construct core-shell structures and combine them with SP molecules to prepare dynamic fluorescent materials, and paves a way for constructing advanced encryption materials with higher safety requirements.

Designing and fabricating nanozymes with photoactivity for CO reduction poses a significant challenge. Here, a hierarchically structured ZFs-tpyNi heterojunction nanozyme, comprising a terpyridine-based Ni complex supported on ZrO nanoframes, has been created through an interfacial engineering strategy for efficient CO reduction under visible light. Due to its unique structural and compositional advantages, ZFs-tpyNi demonstrates superior photocatalytic CO-to-CO conversion compared to its counterpart of ZFs and tpyNi, achieving a CO yield of 18.2 µmol and a selectivity of 92.4 % with a high apparent quantum efficiency of 0.96 % in 3 h. These innovative catalysts also show excellent durability for at least eight cycles without a loss in performance, maintaining a remarkable structural stability with no obvious collapse of its framework and morphology. Systematic investigations reveal that ZFs-tpyNi heterostructures exhibit a high specific surface area advantageous for the effective loading of tpyNi and exposure of active sites. The robust ZFs framework, characterized by extensive porosity, prevents nanoparticle agglomeration and accelerates mass transfer during catalysis. Additionally, the spatially heterogeneous interface enables precise modulation of band alignment and bandgap dynamics in nanozymes, enhancing light absorption and promoting the generation and separation of photogenerated charge carriers. Consequently, the nanozyme demonstrates enhanced CO adsorption and activation capabilities, leading to improved selectivity of catalytic products. This work aims at highlight the role of nanozyme catalysts in sustainable energy production.

The electrocatalytic CO reduction reaction (CORR) is one of the most important electrocatalytic reactions. Starting from a well-defined *CO intermediate, the CORR can bifurcate into two pathways, either forming a hydrogenation product by *CO bond hydrogenation or leading to CO desorption by *C bond cleavage. However, it is perplexing why many dual-atom catalysts (DACs) exhibit high CO selectivity in experiments, despite previous theoretical studies arguing that the *CO bond hydrogenation is thermodynamically more favorable than the *C bond breaking. Furthermore, the selectivity is contingent upon the potential and is perturbed by the hydrogen evolution reaction (HER), which is far from clear. Using ab initio molecular dynamics and a "slow-growth" sampling method to evaluate the potential-dependent kinetics, we uncover the selectivity origin of CORR to CO on a typical NC-based DAC (CuFe-N-C). Importantly, the results show that at higher CO* coverage, CO* desorption kinetics are accelerated, while the competing *CO bond hydrogenation reaction is inhibited at varying potentials. Furthermore, the selectivity of the HER is observed to increase as the potential decreases. However, at higher CO* coverage, the energy barrier for the *C bond cleavage is lower than that for HER, suggesting that HER is suppressed on CuFe-N-C. Our work unlocks a long-standing puzzle about the selectivity of important DAC catalysts for CORR and provides insights for more effective catalyst design.

Superhydrophobic coatings have important application potential and value in the field of metal corrosion protection. However, the practical application of the superhydrophobic coating is significantly hindered by their poor durability. In this study, a durable superhydrophobic coating with repairable micro/nanostructures is prepared by femtosecond laser directly writing micropillar structures on the surface of thermal-responsive shape-memory materials. The resultant superhydrophobic coating has excellent structural recovery function against mechanical pressing or scratches due to the unique shape-memory ability of the coating. Apart from the healing property, the superhydrophobic coating also has remarkable durability against 400 cycles of tape peeling, 3 kg water flow impact, 250 cm sandpaper abrasion, and immersion in solutions with different pH values for 48 h. This durable superhydrophobicity-memory coating can effectively protect metals from corrosion damage. Take the example of Mg alloy, the low-frequency impedance moduli of the coated sample can be increased by 10 orders of magnitude compared to bare Mg alloy. The coating is able to maintain superhydrophobicity even after being immersed in corrosive solution for 107 days. Moreover, the anti-corrosion property of the coating after mechanical damage can also be recovered by heating treatment. It is anticipated that this durable superhydrophobicity-memory coating prepared in this study can provide important theoretical value and reference basis for promoting the application of superhydrophobic coatings in the field of corrosion protection.

In this work, four types of protic ionic liquids were prepared for use as pure water additives to investigate the effect of anionic alkyl chains on the tribological and drilling performance of a titanium alloy. Copper block immersion tests and electrochemical tests were conducted to compare their corrosion resistance. The results indicate that the ionic liquid containing OH and CC in the anionic alkyl chain led to stronger adsorption onto the metal substrate, providing excellent tribological performance and the highest corrosion inhibition rate (η = 98.45 %). According to density functional theory, wear scar surface analysis, and molecular dynamics simulation, the low energy gap of the anion (ΔE = 0.033 Ha) indicated that it exhibited higher reactivity. Thus, it was more susceptible to frictional chemical reactions with the metal substrate under the action of frictional heat during shearing, ultimately forming a friction film with a thickness of 20-97 nm. The ionic liquid demonstrated good wetting properties in a drilling test, enabling its effective penetration into the gaps between the drill bit and the workpiece to achieve lubrication and cooling effects. Thus, the axial force and drilling temperature were significantly reduced. Additionally, biotoxicity tests indicated that the ionic liquid is an environmentally friendly substance.

Shadow sphere lithography (SSL) offers unparalleled advantages in fabricating complex nanostructures, yet optimizing these structures remains challenging due to vast parameter spaces. This study presents a general optimization framework for SSL-fabricated nanostructures, demonstrated through chiral metamaterials. The approach combines a custom SSL program, a novel mathematical model for eliminating redundant structures, and machine learning (ML) analysis of finite-difference time-domain (FDTD) simulations. Applied to rotated nanohole arrays (RHAs), this framework efficiently navigates a 7200-structure parameter space, identifying optimal configurations with circular dichroism (CD) and g-factor up to 3.23˚ and 0.28, respectively. Experimental validation of optimized RHAs shows good agreement with predictions, exhibiting twice the chiral response of random configurations. Notably, the framework reduces the dataset by 86%, significantly decreasing computational costs. This optimization framework enables faster, more systematic, and more efficient optimization of structures manufactured using SSL, potentially accelerating discoveries in nanophotonics, plasmonics, and chiral sensing applications.

Strong molecule-electrode coupling originating from orbit hybridization between gold and the delocalized molecular wires in single-molecule junctions facilitates facile transport towards smart molecular devices. In this paper, we report ultra-highly conductive single-molecule circuits based on highly delocalized nickel bis(dithiolene) (NiS) molecular junctions using scanning tunneling microscope break junction technique. Single-molecule charge transport measurement of both NiS reveals they exhibits high conductance of 10G and 10G, respectively. Moreover, under intervention of high bias voltage the molecular conductance could be further improved to approximately 10G, the highest value reported to date with similar molecular lengths. Theoretical calculations suggest that the strong hybridization of the π-channels and the gold electrodes in both junctions exists and it further extends from molecule-electrode interfaces to metal electrodes as visualized by the isosurface plots of the transmitting eigenstate, which lead to not only a distinct energy shift of the dominated LUMO peaks toward Fermi level, but also broad peaks in the LUMO resonance in the transmission functions. In addition, the both molecular junctions show remarkable photoconductance of approximately 10G under resonant light excitation, due to possible exciton binding in these junctions. Interestingly, the conductance switching of both molecular junctions under optoelectronic modulation is highly reversible, forming a multi-stimulus responsive molecular switch. This work not only provides a building block for fabricating highly conducting molecular wires with strong molecule-electrode coupling, but also lays a foundation for designing optoelectronic modulated functional molecule-scale devices.

Titanium dioxide (TiO) is a kind of generally used photocatalyst with the assistance of UV light. To utilize the visible light and save the energy, herein, a titanium (Ti)-based nanocomposite, i.e. PPDs/C-hTiO, was designed and prepared based on carbon (C)-doping and photosensitive polymer dots (PPDs) nano-hybridization. This design synergistically narrowed the band gap energy (E) and strengthened absorption of the visible light. As a result, PPDs/C-hTiO exerted remarkably high catalytic ability under visible light, surpassing that of commercial TiO (i.e. P25) under UV light. PPDs/C-hTiO succeeded in assisting the degradation of sulindac with a degradation efficiency of 96.7%±1.25% within 10 min under visible light. The degradation process was driven by the generation of hydroxyl radical, superoxide radical and holes, and the total biotoxicity of degradation products was decreased compared to the parent compound. This study creatively combined the C-doping and PPDs nano-hybridization to construct a visible light Ti-based photocatalyst, proposing a potential technique for addressing current aquatic environmental issues.

Recently, photocatalytic technology has been widely used as a sustainable method to address environmental pollution issues. Herein, BiOCl/Bi-MOF (BOC/Bi-MOF) based semiconductor photocatalysts with S-scheme heterojunction were fabricated by an in situ growth method, and the photocatalytic activity of the materials was explored for CO reduction and pollutant degradation. As confirmed by density functional theory calculations and physiochemical characterizations, the established S-scheme heterojunction confers enhanced carrier separation efficiency and retention of redox capability to the BOC/Bi-MOF. Through an improved combination of charge separation and surface reactions, the prepared BOC/Bi-MOF efficiently reduces CO solely to CO. The heterojunction as catalyst is more durable and effective than any of its single component. The CO evolution rate of the optimized composite catalyst was 7.66 and 33.10 times of those of BiOCl and Bi-MOF, respectively. In addition, BOC/Bi-MOF exhibits a high efficiency in the photocatalytic degradation of the pollutant rhodamine B (RhB) in aqueous environments, and the pollutant was completely removed within 20 min. Due to the generation of interfacial potential differences, the internal electric field (IEF) generation at heterogeneous interfaces facilitates the separation and transfer of photogenic charges. This work demonstrated a practical and effective route for in situ growth of S-scheme heterojunctions with high efficiencies in CO reduction and RhB degradation.

Traditional mono-functional anti-corrosion coatings are unable to meet the long-term corrosion resistance requirements of metal materials, therefore developing multifunctional anti-corrosion coatings have broad application prospects. In this work, long-lasting anti-corrosion coatings with superhydrophobic and self-healing properties were successfully prepared by in-situ growth of dual-ligand cerium-based metal-organic framework (Ce-MOF) on the surface of graphene oxide (GO), followed by chemical modification with polydopamine (PDA), resulting in 5B level of adhesion and excellent mechanical robustness. The superhydrophobic surface, as the external armor of the coating, can effectively block the penetrating path of corrosive media. Meanwhile, the MOF structure formed by the coordination of 2-mercaptobenzimidazole (2-M) with cerium ions endows the coating with smart self-healing properties and long-lasting corrosion resistance. Electrochemical tests showed that the low-frequency impedance modulus value of the superhydrophobic coating still reached 3.82 × 10 Ω cm after 30 days salt immersion. Due to the formation of protective films and insoluble precipitates at the defect site by 2-M and cerium ions, the scratches on the coating were significantly reduced after 40 days salt spray experiment, demonstrating the self-healing ability of the coating. This multifunctional anti-corrosion coating provides a new approach for preparing coatings with long-term effective corrosion resistance.

The integration of flexible structure batteries (FSBs) into electronic equipment is an effective method to significantly improve energy efficiency, whereas traditional battery separators, with poor mechanical properties, low liquid electrolyte capture ability, and weak thermal stability, cannot meet the practical requirements of various applications. To address these challenges, in this study, a multifunctional composite quasi-solid-state electrolyte (CQE) was synthesized by electrospinning poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) fibers on both sides of an aramid nanofibers (ANFs) fibrous film for application in high-performance FSBs. Here, the ANF film serves as a structural framework, thus enhancing the mechanical properties and thermal stability of the CQE, while the "thermal closed-hole effect" and liquid electrolyte capture capability of the PVDF-HFP film in the CQE improve the overall safety of the FSBs. The design strategy of combining 3D-printed electrodes and functional CQE is essential to achieving the integration of structural support and energy storage. Due to the unique characteristics of the CQE, the assembled full-battery (LiFePO//LiTiO) demonstrates superior cycling stability (500 cycles). The assembled rectangular bag battery was also shown to be capable of powering an LED lamp under bending conditions and external force, thus providing valuable insights into FSBs design in the field of energy storage.

Lithium-sulfur (Li-S) batteries have received significant attention due to their high theoretical energy density. However, the inherent poor conductivity of S and lithium sulfide (LiS), coupled with the detrimental shuttle effect induced by lithium polysulfides (LiPSs), impedes their commercialization. In this study, we develop NiCo alloy-decorated nitrogen-doped carbon double-shelled hollow polyhedrons (NC/NiCo DSHPs) as highly efficient catalysts for Li-S batteries. The distribution of NiCo alloy on both the inner and outer shells provides abundant catalytic active sites, effectively adsorbing LiPSs, mitigating the shuttle effect, and promoting the conversion between LiPSs and LiS, even at high sulfur loadings. This results in enhanced redox kinetics within the Li-S system. Moreover, the highly conductive carbon material framework, enriched with carbon nanotubes and graphitic carbon layers, can greatly promote the efficient electron transportation. Additionally, the improved ion diffusion rates benefiting from the hollow structure can also be realized. By harnessing these synergistic effects, Li-S batteries incorporating the double-shelled NC/NiCo DSHP catalysts achieved a high specific capacity of 1310 mAh/g at 0.2C and a superior rate performance of 621 mAh/g at 4C. Furthermore, excellent cycling performance with ultralow capacity fading rate of only 0.045 % per cycle after 800 cycles at 1C was achieved. When sulfur loading reaches 6 mg cm, a high capacity of 4.6 mAh cm at 0.1C after 100 cycles further validates the practical potential of this design. This study presents an innovative approach to alloy catalyst design, offering valuable insights for future research of Li-S batteries.