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Heterojunctions photocatalysts play a crucial role in achieving high solar-hydrogen conversion efficiency. In this work, we mainly focus on the charge transfer dynamics and pathways for sulfides-based Schottky junctions in the photocatalytic water splitting process to clarify the mechanism of heterostructures photocatalysis. Sulfides-based Schottky junctions (CdS/CoP and CdS/1T-MoS2) were successfully constructed for photocatalytic water splitting. Because of the higher work function of CdS than that of CoP and 1T-MoS2, the direction of the built-in electric field is from CoP or 1T-MoS2 to semiconductor. Therefore, CoP and 1T-MoS2 can act as electrons acceptors to accelerate the transfer of photo-generated electron on the surface of CdS, thus improving the charge utilization efficiency. Meanwhile, CoP and 1T-MoS2 as active sites can also promote the water dissociation and lower the H+ reduction overpotential, thus contributing to the excellent photocatalytic hydrogen production activity (23.59 mmol·h-1·g-1 and 1195.8 mol·h-1·g-1 for CdS/CoP and CdS/1T-MoS2).
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Photocatalysis represents a sustainable strategy for addressing energy shortages and global warming. The main challenges in the photocatalytic process include limited light absorption, rapid recombination of photo-induced carriers, and poor surface catalytic activity for reactant molecules. Defect engineering in photocatalysts has been proven to be an efficient approach for improving solar-to-chemical energy conversion. Sulfur vacancies can adjust the electron structure, act as electron reservoirs, and provide abundant adsorption and activate sites, leading to enhanced photocatalytic activity. In this work, we aim to elucidate the role of sulfur vacancies in photocatalytic reactions and provide valuable insights for engineering high-efficiency photocatalysts with abundant sulfur vacancies in the future. First, we delve into the fundamental understanding of photocatalysis. Subsequently, various strategies for fabricating sulfur vacancies in photocatalysts are summarized, along with the corresponding characterization techniques. More importantly, the enhanced photocatalytic mechanism, focusing on three key factors, including electron structure, charge transfer, and the surface catalytic reaction, is discussed in detail. Finally, the future opportunities and challenges in sulfur vacancy engineering for photocatalysis are identified.
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Dispersion of single atoms (SAs) in the host is important for optimizing catalytic activity. Herein, we propose a novel strategy to tune oxygen vacancies in CeO2-X directionally anchoring the single atom platinum (PtSA), which is uniformly dispersed on the rGO. The catalyst's performance for the hydrogen evolution reaction (HER) can be enhanced by controlling different densities of CeO2-X in rGO. The PtSA performs best optimally densified and loaded on homogeneous and moderately densified CeO2-X/rGO (PtSA-M-CeO2-X/rGO). It exhibited higher activity in HER with an overpotential of 25â mV at 0.5â M H2SO4 and 33â mV at 1 KOH than that of almost reported electrocatalysts. Furthermore, it exhibited stability for 90â hours at -100â mA cm-2 in 1 KOH and -150â mA cm-2 in 0.5â M H2SO4 conditions, respectively. Through comprehensive experiments and theoretical calculations, the suitable dispersion density of PtSA on the defects of CeO2-X with more active sites gives the potential for practical applications. This research paves the way for developing single-atom catalysts with exceptional catalytic activity and stability, holding promise in advanced green energy conversion through defects engineering.
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Mechanoelectrical energy conversion is a potential solution for the power supply of miniaturized wearable and implantable systems; yet it remains challenging due to limited current output when exploiting low-frequency motions with soft devices. We report a design of a hydrogel generator with mechanoionic current generation amplified by orders of magnitudes with engineered structural and chemical asymmetry. Under compressive loading, relief structures in the hydrogel intensify net ion fluxes induced by deformation gradient, which synergize with asymmetric ion adsorption characteristics of the electrodes and distinct diffusivity of cations and anions in the hydrogel matrix. This engineered mechanoionic process can yield 4 mA (5.5 A m-2) of peak current under cyclic compression of 80 kPa applied at 0.1 Hz, with the transferred charge reaching up to 916 mC m-2 per cycle. The high current output of this miniaturized hydrogel generator is beneficial for the powering of wearable devices, as exemplified by a controlled drug-releasing system for wound healing. The demonstrated mechanisms for amplifying mechanoionic effect will enable further designs for a variety of self-powered biomedical systems.
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Designing and fabricating highly efficient oxygen evolution reaction (OER) electrocatalytic materials for water splitting is a promising and practical approach to green and sustainable low-carbon energy systems. Herein, a facile in situ growth self-template strategy by using ZIF-67 as a consumable layered double hydroxides (LDHs) template and silver nanowires (AgNWs) as 1D conductive cascaded substrate to controllably synthesize the target AgNWs@CoFe-LDH composites with unique hollow shell sugar gourd-like structure and enhanced directional electron transport effect is reported. The AgNWs exhibit the key functions of the close connection of CoFe-LDH nanocages and the support of the directional electron transport effect in the composite catalyst inducing electrons directionally moving from CoFe-LDH to AgNWs. Meanwhile, the CoFe-LDH nanocages with ultrathin nanosheets and hollow structural properties show abundant active sites for electrocatalytic oxygen generation. The versatile AgNWs@CoFe-LDH catalyst with optimized components, enhanced directional electron transport, and synergistic effect achieves high OER performance with the overpotential of 207 mV and long-term 50 h stability at 10 mA cm-2 in an alkaline medium. Moreover, in-depth insights into the microstructure, structure-activity relationships, identification of key intermediate species, and a proton-coupled four-electron OER mechanism based on experimental discovery and theoretical calculation are also demonstrated.
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Constructing catalytic electrodes with green economy, stability, and high efficiency is crucial for achieving overall economic water splitting. Herein, a matrix-type bismuth-modulated nickel-boron electrodes loaded on sulfurized copper foils (Bi-NiBx@CFS) is synthesized via in situ mild electroless plating. This electrode features a 2-dimensional (2D) matrix-type nanosheet structure with uniform, large pores, providing more active sites and ensuring a high gas transmission rate. Notably, the crystalline-amorphous structure constituted by the photothermal materials Bi and NiBx is loaded onto sulfide-based heterostructures. This enhances the catalytic activity through the "local photothermal effect" strategy. A performance enhancement of approximately 10 % is achieved for the Bi-NiBx@CFS at a current density of 10 mA cm-2 using this strategy at 298 K. This enhancement is equivalent to increasing the temperature of conventional electrolyte solutions by 321 K. In addition, the overpotential required to catalytically drive seawater splitting at the same current density is only 1.486 V. The Bi-NiBx@CFS electrode operates stably for 200 h without any performance degradation at industrial-grade current densities. The Bi-NiBx@CFS electrode under the "localized photothermal effect" strategy is expected to be a new type of electrocatalyst for overall seawater splitting.
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The strategic progression toward highly efficient transition metal electrocatalytic electrodes is crucial to achieving efficiency and long-term stability in hydrogen production from authentic seawater sources. This work reports the development of a self-supporting, heterogeneous and corrosion-resistant iron sulfur-based catalytic electrode via a streamlined, one-step process involving sulfide etching and electroless plating on an iron foam substrate (IF). This new electrode, named NiS-FeS@IF, involves a nanostructured NiS-FeS catalytic material that combines in situ, resulting in a thin, ultrathin nanospherical layer on the IF. This construction has low overpotentials of merely 322 mV for the hydrogen evolution reaction (HER) and 563 mV for the oxygen evolution reaction (OER) with a current density of 500 mA cm-2 in alkaline simulated seawater electrolytes. Importantly, the NiS-FeS@IF electrode enduring more than 500 h at an industrial grade high current density of 1 A cm-2 without noteworthy performance deterioration. The unique and uniformly dispersed morphology of NiS-FeS facilitates intensified interfacial electron transfer, optimizes active site exposure and provides efficient channels for the rapid release and mass transfer of gas bubbles. This work introduces a novel approach for the facile preparation of efficient electrode materials.
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As a typical spinel oxide, nickel cobaltite (NiCo2O4) is considered to be a promising and reliable oxygen evolution reaction (OER) catalyst due to its abundant oxidation states and the synergistic effect of multiple metal species. However, the electrocatalytic OER performance of NiCo2O4 has always been limited by the low specific surface area and poor intrinsic conductivity of spinels. Herein, the hedgehog-like molybdenum-doped NiCo2O4 (Mo-NiCo2O4) catalyst was prepared as an efficient OER electrocatalyst via a facile hydrothermal method followed with high-temperature annealing. The Mo-NiCo2O4-0.075 with Mo doping concentration of â¼ 1.95 wt% exhibits excellent OER performance with a low overpotential of 265 mV at a current density of 10 mA·cm-2and a Tafel slope of 126.63 mV·dec-1, as well as excellent cyclingstability.The results demonstrated that the hedgehog-like structure provides Mo-NiCo2O4 with the high surface area and mesopores that enhance electrolyte diffusion and optimal active site exposure. The in-situ Raman spectra and density functional theory calculations show that the Mo cations doping improve the intrinsic conductivity of the NiCo2O4 while modulating the chemisorption of intermediates. Meanwhile, the energy barriers of *OH and O* formation decrease significantly after Mo doping, effectively facilitating water dissociation and optimizing the reaction kinetics.
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Developing high-efficiency photothermal seawater desalination devices is of significant importance in addressing the shortage of freshwater. Despite much effort made into photothermal materials, there is an urgent need to design a rapidly synthesized photothermal evaporator for the comprehensive purification of complex seawater. Therefore, we report on all-in-one FeOx-rGO photothermal sponges synthesized via solid-phase microwave thermal shock. The narrow band gap of the semiconductor material Fe3O4 greatly reduces the recombination of electron-hole pairs, enhancing non-radiative relaxation light absorption. The abundant π orbitals in rGO promote electron excitation and thermal vibration between the lattices. Control of the surface hydrophilicity and hydrophobicity promotes salt resistance while simultaneously achieving the purification of various complex polluted waters. The optimized GFM-3 sponge exhibitedan enhanced photothermal conversion rate of 97.3% and a water evaporation rate of 2.04 kg/(m2·hr), showing promising synergistic water purification properties. These findings provide a highly efficient photothermal sponge for practical applicationsof seawater desalination and purification,as well as develop a super-rapid processing methodology for evaporation devices.
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Purificação da Água , Água , Micro-Ondas , Água do Mar , Água Doce , ElétronsRESUMO
Construction of ultra-stable, flexible, efficient and economical catalytic electrodes is of great significance for the seawater electrolysis for hydrogen production. This work is grounded in a one-step mild electroless plating method to construct industrial-grade super-stable overall water splitting (OWS) catalytic electrodes (Fe1-Ni1P@GF) by growing loose and porous spore-like Fe1-Ni1P conductive catalysts in situ on flexible glass fibre (GF) insulating substrates with precise elemental regulation. Cost-effective Fe regulation boosts the electronic conductivity and charge transfer ability to achieve the construction of high intrinsic activity and strong electron density electrodes. Fe1-Ni1P@GF exhibits remarkable catalytic performance in hydrogen and oxygen evolution reaction (HER and OER), providing current densities of 10 mA cm-2 for HER and 100 mA cm-2 for OER at overpotentials of 51 and 216 mV, respectively. Moreover, it achieves 10 mA cm-2 at 1.42 V for OWS, and exhibits stable operation for over 1440 h at 1000 mA cm-2 in quasi-industrial environment of 6.0 M KOH + 0.5 M NaCl, without any performance degradation. This strategy enables the preparation of universally applicable P-based electrodes (ternary, quaternary, etc.) and large-area flexible electrodes (paper or cotton), significantly expands the practicality of the electrodes and demonstrating promising potential for industrial applications.
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The electrocatalytic nitrogen reduction reaction (eNRR) is a sustainable and green alternative to the traditional Haber-Bosch process. However, the chemical inertness of nitrogen gas and the competitive hydrogen evolution reaction significantly limit the catalytic performance of eNRR. Although tungsten oxide-based eNRR catalysts could donate unpaired electrons to the antibonding orbitals of N2 and accept lone electron pairs from N2 to dissociate NîN triple bonds, the low electrical conductivity and the influence of the variable valence of W still affect the catalytic activity. Herein, a high-performance eNRR catalyst WOx nanoparticle/nitrogen-doped porous carbon (WOx/NPC) was prepared by a one-step thermal pyrolysis method. The results reveal that WOx gradually changes from the dominant WO2 phase to the WO3 phase. WOx/NPC-700 °C with WO2 NPs anchored on the surfaces of NPC via W-N bonding could deliver a high NH3 yield of 46.8 µg h-1 mg-1 and a high faradaic efficiency (FE) of 10.2%. The edge W atomic site on WOx/NPC is demonstrated to be the active center which could activate a stable NîN triple bond with an electron-donating ability. Benefiting from the covalent interaction between the WOx nanoparticles and NPC, WOx/NPC also shows high electrocatalytic stability.
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Developing electrocatalysts with high energy conversion efficiency is urgently needed. In this work, P-Fe3O4/Fe@C electrodes with rich under-coordinated Fe atom interfaces are constructed for efficient pH-universal water splitting. The introduction of under-coordinated Fe atoms into the P-Fe3O4/Fe@C interface can increase the local charge density and polarize the 3d orbital lone electrons, which promotes water adsorption and activation to release more H*, thus elevating electrocatalytic activity. As a donor-like catalyst, P-Fe3O4/Fe@C displays excellent electrocatalytic performance with overpotentials of 160 mV and 214 mV in acidic and alkaline electrolytes at 10 mA cm-2, in addition to pH-universal long-term stability.
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Efficient dispersion of nanoparticles (NPs) is a crucial challenge in the preparation and application of composites that contain NPs, particularly in coatings, inks, and related materials. Physical adsorption and chemical modification are the two common methods used to disperse NPs. However, the former suffers from desorption, and the latter is more specific and has limited versatility. To address these issues, we developed a novel photo-cross-linked polymeric dispersant, comb-shaped benzophenone-containing poly(ether amine) (bPEA), using a one-pot nucleophilic/cyclic-opening addition reaction. The results demonstrated that the bPEA dispersant forms a dense and stable shell on the surface of pigment NPs through physical adsorption and subsequent chemical photo-cross-linking, which effectively overcome the drawbacks of the desorption occurred in physical adsorption and the specificity of the chemical modification. By means of the dispersing effect of bPEA, the obtained pigment dispersions show high solvent, thermal, and pH stability without flocculation during storage. Moreover, the NPs dispersants show good compatibility with screen printing, coating, and 3D printing, endowing the ornamental products with high uniformity, color fastness, and less color shading. These properties make bPEA dispersants ideal candidates in fabrication dispersions of other NPs.
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Designing nonprecious metal-based electrocatalysts to yield sustainable hydrogen energy by large-scale seawater electrolysis is challenging to global emissions of carbon neutrality and carbon peaking. Herein, a series of highly efficient, economical, and robust Ni-P-based nanoballs grown on the flexible and anti-corrosive hydrophobic asbestos (NiPx @HA) is synthesized by electroless plating at 25 °C toward alkaline simulated seawater splitting. On the basis of the strong chemical attachment between 2D layered substrate and nickel-rich components, robust hexagonal Ni5 P4 crystalline modification, and fast electron transfer capability, the overpotentials during hydrogen/oxygen evolution reaction (HER/OER) are 208 and 392 mV at 200 mA cm-2 , and the chronopotentiometric measurement at 500 mA cm-2 lasts for over 40 days. Additionally, the versatile strategy is broadly profitable for industrial applications and enables multi-elemental doping (iron/cobalt/molybdenum/boron/tungsten), flexible substrate employment (nickel foam/filter paper/hydrophilic cloth), and scalable synthesis (22 cm × 22 cm). Density functional theory (DFT) also reveals that the optimized performance is due to the fundamental effect of incorporating O-source into Ni5 P4 . Therefore, this work exhibits a complementary strategy in the construction of NiPx -based electrodes and offers bright opportunities to produce scalable hydrogen effectively and stably in alkaline corrosive electrolytes.
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Lightweight polymer-based nanostructured aerogels are crucial for electromagnetic interference (EMI) shielding to protect electronic devices and humans from electromagnetic radiation. The construction of three-dimensional (3D) conductive networks is crucial to realize the excellent electromagnetic shielding performance of polymer-based aerogels. However, it is difficult to realize the interconnection of different conductive fillers in the polymer matrix, which limits the further improvement of their performance. Herein, 3D ordered hierarchical porous Fe3O4-decorated carbon nanotube (Fe3O4@CNT)/MXene/cross-linked aramid nanofiber (c-ANF)/polyimide (PI) aerogels were prepared via a unidirectional freezing strategy. Benefiting from the magnetic loss effect of Fe3O4 magnetic nanoparticles, the conductive and dielectric loss effects of CNTs, and the multiple reflections induced by the 3D ordered hierarchical porous structure, the Fe3O4@CNTs/MXene/c-ANFs/PI (FMCP) aerogels with the same contents of 8 wt % of Fe3O4@CNTs and MXene exhibit a high absolute EMI shielding effectiveness (SE) of up to 67.42 dB and a microwave reflection (SER) of 0.60 dB. More importantly, the phase transition of a small amount of MXene to TiO2 optimizes the impedance matching and transmission and then improves the microwave absorption. The FMCP aerogel has an outstanding normalized surface specific SE (SSE/t) which is up to 62,654 dB cm2·g-1. Meantime, the FMCP aerogels also show super-elasticity and could maintain 91.72% of the maximum stress after 1000 cycles of compression release under a fixed deformation of 60%.
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Electrochemical oxygen evolution reaction (OER) always plays an important role in many electrochemical energy storage and conversion systems. Owing to the slow kinetics mainly brought from multiple proton-coupled electron transfer steps, the design and exploit low-cost, highly active, durable OER electrocatalysts are of significant importance. Although the black phosphorus (BP) shows good electrocatalytic OER performance, it still faces the problems of poor intrinsic activity and low stability due to its instability under ambient conditions. The NiFe-LDH was assembled onto the surfaces of exfoliated BP (EBP) nanoflakes to realize the interfacial coupling between them, achieving an effective improvement in electrocatalytic activity and stability. Benefitting from the interfacial P-O bonding, the NiFe-LDH@EBP hybrid shows high OER activity with a low overpotential of â¼240 mV@10 mA cm-2 toward OER under alkaline conditions, as well as the good stability. Density functional theory (DFT) calculations proved that the interface-coupling of NiFe-LDH on BP promotes charge transfer kinetics and balances the adsorption/desorption of reaction intermediates, ultimately imparting excellent OER electrocatalytic activity.
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Patients with diabetic foot ulcers usually suffer from inefficient epithelisation and angiogenesis accompanied by chronic wound healing. Diabetic foot ulcers remain a major challenge in clinical medicine; however, traditional treatments are incapable of transdermal drug delivery, resulting in a low drug delivery rate. We report the development of Ti2C3 MXenes-integrated poly-γ-glutamic acid (γ-PGA) hydrogel microneedles to release asiaticoside (MN-MXenes-AS). Asiaticoside was loaded into PGA-MXenes hydrogel to facilitate cell proliferation while regulating angiogenesis. The characterisation and mechanical strength of the microneedles were investigated in vitro, and the wound-healing efficacy of the microneedles was confirmed in diabetic mice. MXenes significantly improved the mechanical strength of microneedles, while γ-PGA hydrogels provided a moist microenvironment for wound healing. Mice treated with MN-MXenes-AS demonstrated obvious improvements in wound healing process. We successfully fabricated an MXenes-integrated microneedle that possesses sufficient rigidity to penetrate the cuticle for subcutaneous drug delivery, thereby accelerating diabetic wound healing. We demonstrated that MN-MXenes-AS is effective in promoting growth both in vivo and in vitro. Collectively, our data show that MN-MXenes-AS accelerated the healing of diabetic foot ulcers, supporting the use of these microneedles in the treatment of chronic wounds.
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Diabetes Mellitus Experimental , Pé Diabético , Animais , Diabetes Mellitus Experimental/tratamento farmacológico , Pé Diabético/tratamento farmacológico , Humanos , Hidrogéis , Camundongos , Triterpenos , CicatrizaçãoRESUMO
Achieving uniform Li deposition is vital for the construction of a safe but also efficient Li-metal anode for Li-metal batteries (LMBs). Herein, a facile coating strategy is used for forming an ultra-thin aramid nanofiber (ANF) membrane, with a network structure, on a Li anode (ANF-Li) as an artificial layer inhibiting Li dendrite's growth. The results show that under an ultra-high current density of 50 mA cm-2 , the ANF-Li|ANF-Li symmetric cells can be kept stably cycled for a period exceeding 300 h. The ANF-Li|LiFePO4 full cells exhibit a high-capacity retention of 80.1% after 1200 cycles at 1 C, showing a promising potential for LMBs application. Combined experimental results with theoretical calculations, the excellent performance of the ANF-Li anode is explored. Lithiophilic polar functional groups (CO, NH) appear in the surface and structure of ANF membrane, which offer high-concentration functional sites for the Li ions to realize an effective adhesion at the molecular level. This work also finds fiber-shaped lithium deposition for the first time. Furthermore, the nanoscale porosity of the ANF membrane not only provides fast pathways and channels for the diffusion of the electrolyte and Li transportation, but also eliminates the "weak links" of micron-scale Li dendrites penetrating the membrane.
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The development of non-noble metal electrocatalysts toward the oxygen evolution reaction (OER) is a key challenge in advancing electrocatalytic water splitting, which is essential for the commercialization of clean and renewable energy. A covalent organic framework (COF) has a precise and controllable structure, high π-π conjugation, large surface area, and porosity and shows great potential as an OER electrocatalyst. However, the relative conductivity and inherent instability greatly limit the further improvement of its performance. Herein, imine-based COF-supported Co/CoO nanoparticles (Co/CoO@COF) were developed for the high-performance electrocatalytic OER. For the Co/CoO@COF catalyst, Co/CoO could form a conjugation effect with the COF, which can increase the electron cloud density of the delocalized large π bond, then improve the conductivity. The combination of Co/CoO and COF effectively enhances the structural stability of the catalyst and enriches the catalytic active sites. Under alkaline conditions, the Co/CoO@COF shows a very low overpotential of 278 mV at a current density of 10 mA cm-2, and a Tafel slope of 80.11 mV dec-1 which is better than that of commercial RuO2.
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High-capacity and highly stable anode materials are some of the keys to the realization of the application of potassium-ion batteries (PIBs). Cobalt diselenide (CoSe2) has been regarded as a high-potential anode material for PIBs. However, solving the problems of sluggish kinetics and large volumetric expansion during intercalation/deintercalation of K+ ions is always very challenging in terms of cobalt diselenide-based anode materials. Herein, reduced graphene oxide-encapsulated polyphosphazene-derived S, P, and N codoped carbon (SPNC)-coated CoSe2 nanorods (CoSe2âSPNCârGO) were designed as PIB anode materials. CoSe2âSPNCârGO delivers an excellent reversible capacity of 287.2 mAh g-1 at 100 mA g-1. Benefiting from the coating of heteroatom-doped carbon and encapsulation of rGO, the CoSe2âSPNCârGO anodes exhibit a remarkable rate capability (100-1500 mA g-1 current density) and high stability (208.8 mAh g-1 after 500 cycles at 500 mA g-1). The results demonstrate that S, P, and N codoping in carbon layers provides active sites for K+ ion storage and increases the electrical conductivity. More importantly, the dual confinement of CoSe2 nanorods with carbon layers and rGO significantly reduced the volume expansion and kept the electrode structural integrity with repeating intercalation/deintercalation of K+ ions.