Heteroatom-doped Carbon Research Articles

Heteroatom doping carbon film derived from hyphae as a self-supporting cathode for advanced lithium sulfur batteries

Much attention has been paid to lithium sulfur battery due to its high energy density. However, low S loading and poor cycling stability have hindered their commercialization. In this work, a porous carbon film with rich heteroatom doping was prepared from the Penicillium chrysogenum hyphae film by freezing drying and high-temperature carbonization. Then the carbon film loaded polysulfide solution was utilized as a self-supporting cathode for Li-S batteries. The self-supporting cathode exhibited good rate performance (513.1 mAh/g at 1C) and improved cycling stability (more than 400 cycles) under a high current density (0.5C). This is mainly attributed to the abundant heteroatoms that provided active sites with superior adsorption ability for lithium polysulfide, which not only enhanced the cycling stability but also facilitated the conversion kinetics. Besides, the fibrous network morphology with affluent porous structures inherited from hyphae provided a large specific surface area and sufficient space for accommodating active substances. This work shows the great potential of hyphae derived porous carbon electrodes for high-performance energy storage applications.

Heteroatoms-doped carbon dots as dual probes for heavy metal detection

The utilization of l-cysteine in hydrothermal synthesis allows for the manufacture of carbon dots (CDs) that are doped with heteroatoms including oxygen, nitrogen, and sulfur (N, S, O-doped CDs). CDs have a particle size ranging from 1 to 3 nm, with an average particle size of 2.5 nm. N, S, and O-doped CDs display a blue fluorescence emission at a wavelength of 425 nm. It shows a reliance on the specific excitation wavelength between 320 and 500 nm. It has a selective quenching effect specifically with copper (Cu2+) ions when exposed to interactions with heavy metal ions, as compared to other metal ions. The assay has a limit of detection (LOD) of 2 μM and exhibits a linear correlation within the concentration range of 10–33.3 μM. The fluorescence mechanism was elucidated by employing various analytical techniques, such as transmission electron microscopy (TEM), high-resolution TEM , UV–Vis spectroscopy, zeta potential analysis, and conductometry. An analysis of the data reveals that Cu2+ ions exhibit a strong attraction to the external surface of N, S, and O-doped CDs, leading to the formation of aggregates. N, S, and O-doped CDs can be also used as probes for electrochemical investigations utilizing cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) to produce Nyquist and Bode plots. The electrochemical results offer substantiation for the interaction between Cu2+ ions and N, S, and O-doped CDs. Zero-dimensional carbon nanomaterials, i.e. CDs, can improve the detection of heavy metals using optical and electrochemical methods.

Molybdenum carbide nanoclusters with ultrafast electron transfer ability promotes molecular oxygen selective electrocatalytic reduction to hydroxyl radicals for pollutant control

A treatment strategy of in situ generation and activation of hydrogen peroxide to degrade pollutants by the heterogeneous Fenton-like technology is promising for water pollution. However, the selective activation of oxygen to hydroxyl radicals (OH) by cathode materials is still challenging. Here, molybdenum carbide (MoC) supported on a heteroatoms-doped (N, P, S) carbon carrier catalyst was successfully prepared, which rapidly produced OH and degraded paracetamol (APAP) pollutants. A high APAP degradation efficiency with a specific energy consumption of 0.24 kWh g−1 TOC was achieved. After 10 sets of continuous operations, the APAP degradation rate remains unchanged. Combined with density functional theory calculations, molecular oxygen adsorption obtains one electron with proton hydrogen transfer to hydroperoxyl (OOH) on the MoC surface, and the adsorbed OOH directly activate into OH due to the ultrafast electron transfer ability of MoC. Differential charge density analysis also shows that Mo transfers electrons to O. This strategy provides a new idea for optimizing catalysts to improve the heterogeneous Fenton-like performance.

Synthesis of N/P/S Co-doped porous carbons by carbonizing polyphosphazene microspheres for highly selective adsorption of Pb (II)

Heteroatom-doping has emerged as a promising approach for enhancing the properties of carbon materials, particularly in the treatment of heavy-metal wastewater. However, the simultaneous synthesis of multi-heteroatom co-doped carbon materials poses significant complexity and challenges. Consequently, there is an increasing demand for the development of non-toxic and straightforward methods to prepare such materials. In this study, we present a novel approach for the synthesis of N/P/S co-doped porous carbonaceous adsorbents using polyphosphazene as precursors. Our focus is specifically on their effectiveness in adsorbing Pb (II). The results reveal that the synthesized adsorbents, denoted as carbonized polyphosphazene or CZ-600 exhibited a high carbon content co-doped with N, P and S atoms, as well as an abundance of oxygen-containing functional groups and a porous structure. These characteristics collectively contribute to the exceptional adsorption capacity of CZ-600 for Pb (II), with a maximum adsorption capacity of 121.7 mg/g and an equilibrium time as short as 20 min. Further investigations of the adsorption process involve fitting adsorption isotherm, kinetic, and thermodynamic models, revealing chemical adsorption as the predominant mechanism, supported by contributions from micropore adsorption and electrostatic interactions. This work proposes a sustainable and efficient solution for the treatment heavy-metal wastewater, which not only advances the understanding of heteroatom-doped carbon materials but also provides valuable insights into their practical applications in environmental remediation.

Renewable lignin-derived heteroatom-doped porous carbon nanosheets as an efficient oxygen reduction catalyst for rechargeable zinc-air batteries

Lignin upgrading to various functional products is promising to realize high-value utilization of low-cost and renewable biomass waste, but is still in its infancy. Herein, using industry waste lignosulfonate as the biomass-based carbon source and urea as the dopant, we constructed a heteroatom-doped porous carbon nanosheet structure by a simple NaCl template-assisted pyrolytic strategy. Through the synergistic effect of the NaCl template and urea, the optimized lignin-derived porous carbon catalyst with high content of active nitrogen species and large specific surface area can be obtained. As a result, the fabricated catalysts exhibited excellent electrocatalytic oxygen reduction activity, as well as good methanol tolerance and stability, comparable to that of commercial Pt/C. Moreover, rechargeable Zn-air batteries assembled with this electrocatalyst have a peak power density of up to 150 mW cm-2 and prominent long-term cycling stability. This study offers an inexpensive and efficient way for the massive production of highly active metal-free catalysts from the plentiful, inexpensive and environmentally friendly lignin, offering a good direction for biomass waste recycling and utilization.

Advanced Carbon Electrocatalysts for Selective Oxygen Reduction into Hydrogen Peroxide: Understandings of Active Sites

Review Advanced Carbon Electrocatalysts for Selective Oxygen Reduction into Hydrogen Peroxide: Understandings of Active Sites Jiaxin Su 1,2, Bingbing Xiao 1,2, Jun Wang 1,2,* and Xiaofeng Zhu 1,2,* 1 State Key Laboratory of Environment-Friendly Energy Materials, School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, China 2 Tianfu Institute of Research and Innovation, Southwest University of Science and Technology, Chengdu 610299, China * Correspondence: junwang091@163.com (J.W.); xfzhu@swust.edu.cn (X.Z.) Received: 17 January 2024; Revised: 25 January 2024; Accepted: 19 February 2024; Published: 5 March 2024 Abstract: Electrochemical conversion of oxygen-to-hydrogen peroxide (H2O2) through oxygen reduction (ORR) is becoming a green and effective solution to replacing conventional anthraquinone industry. Advanced carbon is currently one of the most promising catalysts for H2O2 electrosynthesis by a selective two-electron ORR (2e-ORR), owing to its chemical and catalytic merits. To realize better performance of 2e-ORR over advanced carbons, extensive efforts is devoted to constructing highly efficient carbon-based active sites, which requests in-depth understanding of their underlying catalytic roles. Here, an informative and critical review of recent investigations on active sites on advanced carbons for 2e-ORR is provided. Together with our recent findings, the review first highlights the promoting progress on heteroatom-doped carbons, and their direct/indirect contributions for 2e-ORR has been emphasized. Simultaneously, defect engineering of carbon scaffold is briefly demonstrated as a practical strategy for achieving outstanding H2O2 production. Meanwhile, the review also offers analysis on striking influence of surface modification for carbon active site. Finally, challenges and perspectives of the advanced carbon catalysts for 2e-ORR are outlined. Such reviewed fundamentals of active sites in this emerging field would shed light to future impactful progress in ORR and broader research of energy and catalysis.

Fast and efficient reduction of nitroaromatic compounds with copper oxides supported nitrogen-sulfur Co-doped porous carbon material derived metal-organic framework

The expansion of heteroatom-doped carbons with metal-organic frameworks (MOFs) as precursors under heat treatment has attracted extensive attention for the betterment of the catalytic attributes of carbon-based catalysts. After simply pyrolyzing metal-organic framework (MOF) mixed with thiourea (CH4N2S) particles, N and S-doped porous carbon substrates with favorable structural and compositional properties are obtained. The as-synthesized material, which is named CuxO@CNS-400 acts as a heterogeneous catalyst in the reduction reaction of nitro-aromatic compounds, which has superior performance with high activity. The morphology, structure, and physicochemical properties of CuxO@NSC-400 were successfully synthesized and characterized using XRD, TEM, TGA, FE-SEM, EDX, FT-IR, and Raman. In particular, CuxO@CNS-400, obtained by pyrolysis at 400 °C, demonstrates excellent catalytic efficiency of 98 % and high catalytic cycling stability for rapid and highly efficient nitro aromatics reduction.

Fluorescent carbon dots in situ polymerized biodegradable semi-interpenetrating tough hydrogel films with antioxidant and antibacterial activity for applications in food industry

A flexible, antioxidant, biodegradable, and UV-resistant polymeric nanocomposite hydrogel with heteroatom-doped carbon dots (CDs) has been fabricated using a simple one-step in situ free radical gelation process. The hydrogel formation and their physico-mehcanical characteristics have been assessed by rheology, uniaxial tensile and compression testing. The water uptake behaviour of the hydrogels is controlled by the CDs by manipulating their internal morphology and porosity. The porous nature of the hydrogels has been found from their scanning electron microscopic images which are also supported by their anomalous diffusion-based transport mechanism. The rheological signatures of the hydrogels show delayed network rupturing due to the secondary physical crosslinking alleviated by CDs. Moreover, CDs are directly influencing the permeabilites (oxygen and moisture) by lowering the values compared to their neat hydrogel films which are essential for a packing material. The biodegradability of the hydrogel films showed gradual weight loss (<75 %) within 3 weeks. The hydrogel films also have been qualified to be acted as antibacterial and antioxidant material. The shelf-life and non-leaching of CDs from gel matrices are also performed which shows its excellent capability to be used as a potential antibacterial, biodegradable, antioxidant alternative packaging material in food sectors.

Ni-doped sites in yeast-derived catalysts for efficient electrochemical synthesis of hydrogen peroxide

The electrochemical synthesis of hydrogen peroxide (H2O2) via the 2-electron pathway of oxygen reduction reaction offers a green and on-site product. However, there remains an urgent need to develop cost-efficient electrocatalysts with H2O2 productivity that meets practical industrial-scale requirements. In this study, yeast-derived carbon material loaded with multiple Ni active sites achieved electrochemical synthesis of H2O2 at industrial current density. The precursor of heteroatom-doped carbon material was obtained through high-dispersed Ni(II) adsorption on yeast cells. By adjusting the pyrolysis temperature and Ni loading dosage, the carbon framework, pore structure, and Ni active sites within the obtained Ni/yeast were successfully regulated. Ni/yeast featured with highly active Ni single-atom sites, metallic Ni nanoparticles and Ni2P nanoparticles, enabling stable running for 10 h at 200 mA cm−2 in a flow cell. Ni/yeast exhibits remarkable H2O2 Faradaic efficiency of 94.6 % and a yield of 35.3 mol gcat−1h−1. The abundant pore structure and multiple Ni active sites within Ni/yeast provide promising avenues for manipulating heteroatom-doped carbon materials in H2O2 electrosynthesis.

Revolutionizing Zn-Air batteries with chainmail catalysts: Ultrathin carbon-encapsulated FeNi alloys on N-doped graphene for enhanced oxygen electrocatalysis

The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) pose significant challenges for the viability of rechargeable Zn-air batteries. Developing efficient, cost-effective, stable, and dual-purpose oxygen electrocatalysts remains a formidable hurdle. In this study, we successfully synthesized a highly promising chainmail catalyst named FeNi@NC, comprising ultrathin carbon shells encapsulating FeNi alloy nanoparticles on N-doped graphene-like nanosheets. The strong synergistic effects between FeNi alloys and N-doped carbon shells result in outstanding bifunctional catalytic activity, particularly in alkaline media. Consequently, Zn-air batteries incorporating FeNi@NC as the catalyst demonstrate exceptional performance, operating reliably at high power density with extended lifespan. Furthermore, computational analyses provided further confirmation of the catalytic activity and revealed that the electron transfer from FeNi alloy nanoparticles to the carbon shells activates the carbon surface, leading to enhanced catalytic performance. This research not only sheds light on the rational design and synthesis of heteroatom-doped carbon materials supporting the growth-constrained transition metal alloys but also offers a practical solution for advancing the application of Zn-air batteries.

Advance Heteroatom Dopants Nitrogen, Boron, Sulphur and Phosphorus on Carbon Dots Towards Histamine Detection in Fish Sample

This study introduces heteroatom-doped carbon dots (CDs), namely boron-sulphur (BS-CDs) and nitrogen-phosphorus (NP-CDs), highlighting their potential as optical materials for sensitive histamine detection in sensor applications. Synthesized through facile pyrolysis of citric acid cores with non-metal dopants, resulting in confirmed graphene-like structures and uniform spheres with crystal diameters below 3 nm of BS-CDs and NP-CDs. The optical properties exhibited blue fluorescence, with emission wavelengths of 280 nm (QY 0.08%) and 420 nm (QY 1.72%) for BS-CDs and NP-CDs, respectively. Despite declined fluorescence intensities due to interfering components, both CDs demonstrated low selectivity for histamine, which increased the intensity in its presence. Notably, BS-CDs exhibited superior detectability of histamine at a low concentration of 26.3 ppm compared to 42.8 ppm for NP-CDs. Cytotoxicity studies indicated low toxicity for both CDs, positioning them as promising candidates for further development as histamine detectors

A gasification strategy to anchor Fe, Ni dual-sites on biomass-derived N, P co-doped porous carbon as an efficient bifunctional catalyst for Zn-air batteries

The fabrication of distinct sites on the carbonized substrate as bifunctional oxygen catalysts is pivotal for enhancing the practicality of Zn-air batteries, but remains a formidable challenge. Herein, a gas doping strategy is reported for anchoring Ni nanoparticles and further increasing FeNx sites on biomass-derived Fe, N, and P co-doped porous carbonized materials as highly efficient bifunctional electrocatalysts. The inherent porous structure and heteroatom of rattan tea provide a superior carrier for Fe and Ni-based active species. Notably, the as-prepared Ni@FeNPC/Fef shows unprecedented capability for oxygen reduction reaction and excellent catalytic activity for oxygen evolution reaction. In situ Raman spectroscopy studies shed light on the role of FeNx and heteroatom-doped carbon during the oxygen reduction reaction. Density functional theory calculations verify the catalytic mechanism on various active sites of Ni@FeNPC/Fef. Moreover, the Ni@FeNPC/Fef-based Zn-air battery maintains cyclic stability for over 400 h with negligible voltage degradation. This strategy endows a novel route for converting biomass into practical electrocatalysts for diverse energy-related systems.

Encapsulating Sulfur into a Gel-Derived Nitrogen-Doped Mesoporous and Microporous Carbon Sponge for High-Performance Lithium-Sulfur Batteries.

The practical application of Li-S batteries (LSBs) has long been impeded by the inefficient utilization of sulfur and slow kinetics. Utilizing conductive carbonaceous frameworks as a host scaffold presents an efficient and cost-effective approach to enhance sulfur utilization for redox reactions in LSBs. However, the interaction of pure carbon materials with lithium polysulfide intermediates (LiPSs) is limited to weak van der Waals forces. Hence, the development of an economical method for synthesizing heteroatom-doped carbon materials for sulfur fixation is of paramount importance. In this study, we introduce a hierarchical porous nitrogen-doped carbon sponge (NPCS) with an exceptionally high BET surface area of 3182.2 m2 g-1, achieved through a facile template-assisted polymerization method. The incorporation of inorganic salts, free radical polymerization, and deuteric freeze-drying techniques facilitates the formation of hierarchical pores within the NPCS. After sulfur fixation, the resulting S/NPCS electrode demonstrates remarkable electrochemical performance in LSBs. Specifically, it achieves an 80% sulfur utilization rate, maintains a high reversible specific capacity of 400 mA h g-1 even after 600 cycles at a demanding current density of 5.0 A g-1, and exhibits superior rate capability. It is believed that this work will inspire the rational design of cost-effective carbon-based electrodes for high-performance LSBs.

Pulsed Laser Manufactured Heteroatom Doped Carbon Dots via Heterocyclic Aromatic Hydrocarbons for Improved Tribology Performance.

Traditional laser-assisted method (top-down synthesis strategy) is applied in the preparation of carbon dots (CDs) by cutting larger carbon materials, which requires harsh conditions, and the size distribution of the CDs is seldom monodisperse. In this work, heteroatom-doped CDs, represented by N,S co-doped CDs (N,S-CDs), can be prepared successfully by pulsed laser irradiation of heterocyclic aromatic hydrocarbons-based small molecule compound solution. The friction coefficient (COF) of base oil PAO decreases from 0.650 to 0.093, and the wear volume reduces by 92.0% accompanied by 1 wt.% N,S-CDs addition, while the load-bearing capacity is improved from 100 to 950 N. The excellent lubrication performance is mainly attributed to the formation of a robust tribofilm via a tribochemical reaction between N,S-CDs and friction pairs, and the N,S-CDs can play a mending effect and polishing effect for worn surfaces. Furthermore, the lubricant containing heteroatom doped CDs are capable of being prepared in situ via pulsed laser irradiation of heterocyclic aromatic hydrocarbons in base oil, which can avoid the redispersed problem of nano-additive in base oil to maintain long-term dispersion, with COF of 0.103 and low wear volume ≈1.99 × 105 µm3 (76.9% reduction) even after standing for 9 months.

Research Experiences via Integrating Simulations and Experiments (REVISE): A Model Collaborative Research Project for Undergraduate Students in CO2 Sorbent Design.

Undergraduate research experiences are an instrumental component of student development, increasing conceptual understanding, promoting inquiry-based learning, and guiding potential career aspirations. Moving one step further, as research continues to become more interdisciplinary, there exists potential to accelerate student growth by granting additional perspectives through collaborative research. This study demonstrates the utilization of a model collaborative research project, specifically investigating the development of sorbent technologies for efficient CO2 capture, which is an important research area for improving environmental sustainability. A model CO2 sorbent system of heteroatom-doped porous carbon is utilized to enable students to gain knowledge of adsorption processes, through combined experimental and computational investigations and learnings. A particular emphasis is placed on creating interdisciplinary learning experiences, exemplified by using density functional theory (DFT) to understand molecular interactions between doped carbon surfaces and CO2 molecules as well as explain underlying physical mechanisms that govern experimental results. The experimental observations about CO2 sorption performance of doped ordered mesoporous carbons (OMCs) can be correlated with simulation results, which can explain how the presence of heteroatom functional groups impact the ability of porous carbon to selectively adsorb CO2 molecules. Through an inquiry-focused approach, students were observed to couple interdisciplinary results to construct holistic explanations, while developing skills in independent research and scientific communications. This collaborative research project allows students to obtain a deeper understanding of sustainability challenges, cultivate confidence in independent research, prepare for future career paths, and most importantly, be exposed to strategies employing interdisciplinary research approaches to address scientific challenges.

Heteroatom-doped porous carbon materials for high performance supercapacitors

Heteroatom-doped carbon materials have considerable potential for applications in energy storage devices (ESDs). In this study, an interconnected B/N/O/P co-doped porous carbon materials (B5-CPPCN-700) was synthesised using a simple one-step method with zinc nitrate hexahydrate and 4′-(4-phosphonylphenyl)−3,2′:6′,3″-terpyridine as raw materials through KOH activation. The as-prepared B5-CPPCN-700 had a large specific surface area, rough surface for ion adsorption, and suitable pore size distribution for electron transport. Moreover, the co-doped B/N/O/P species—particularly the B species—in B5-CPPCN-700 provided active sites and additional pseudocapacitance. These structural and morphological features ensured a high specific capacitance of 503.3 F/g at 0.5 A/g. Furthermore, the assembled symmetric supercapacitor delivered a satisfactory specific energy, specific power (14.98 Wh/kg at 300 W/kg and 6.97 Wh/kg at 22,800 W/kg), and specific capacitance (149.8 F/g at 0.5 A/g and 77.2 F/g at 40 A/g). This study paves the way for the preparation of high-capacitance porous carbon materials for ESDs.

Aerobically Autoxidized Self-Charge Concept Derived from Synergistic Pyrrolic Nitrogen and Catechol Configurations in N, O Co-Doped Carbon Cathode Material.

Aerobically autoxidized self-charging concept has drawn significant attraction due to its promising chemical charge features without external power supply. Particularly, heteroatom-doped carbon materials with abundant oxidizable sites and good conductivity are expected to be ideal cathode materials. However, there is no well-defined aerobically autoxidized self-charging concept based on heteroatom-doped carbon materials, significantly hindering the design of related carbon cathodes. An aerobically autoxidized self-chargeable concept derived from synergistic effect of pyrrolic nitrogen and catechol configuration in carbon cathode using model single pyrrolic nitrogen and oxygen (N-5, O) co-doped carbon and O-enriched carbon is proposed. First, self-charging of N-5, O co-doped carbon cathode can be achieved by aerobic oxidation of pyrrolic nitrogen and catechol to oxidized pyrrolic nitrogen and ortho-quinone configurations, respectively. Second, introducing a single pyrrolic nitrogen configuration enhanced acidic wettability of N-5, O co-doped carbon facilitating air self-charge/galvanic discharge involving proton removal/introduction. Third, synergistic effect of pyrrolic nitrogen and hydroxyl species with the strong electron-donating ability to conjugated carbon-based backbone endows N-5, O co-doped carbon with a higher highest occupied molecular orbital (HOMO) energy level more susceptible to oxidation charging. The assembled Cu/Carbon batteries can drive a timer after every air-charging run. This promising aerobically autoxidized self-charging concept can inspire exploring high-efficiency self-charging devices.

Discarded Perseaamericana leaf-derived natural O, Mg, and Ca self-doped activated carbon and its applications as electrode materials for high-performance symmetric supercapacitors

Recently, there has been growing research interest in the fabrication of heteroatom-doped porous carbon from biomass. Herein, natural O, Mg, and Ca self-doped activated carbon was fabricated from discarded Persea americanaleaves via a one-step route strategy. By varying the carbonization temperature (500, 600, 700, and 800 °C), the as-fabricated DPAL-AC exhibits a high surface area (875.775 m2/g) and rich natural O, Mg, and Ca heteroatoms composition. The symmetric device product (DPAL-AC700) exhibits a high gravimetric capacitance of 209 F/gat 1 A/g. In addition, the device delivered an energy density of 28.4 Wh/kg at a power density of 135.5 W/kg. This work presents a novel approach to producing self-doped activated carbon with natural heteroatoms, which can enhance the performance of symmetric supercapacitors.

Boosted hydrogen evolution kinetics of heteroatom-doped carbons with isolated Zn as an accelerant

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present a practical strategy to rationally design a model catalyst with a single zinc (Zn) atom coordinated with nitrogen and sulfur atoms in a multilevel carbon matrix. The Zn site exhibits an atomic interface configuration of ZnN4S1, where Zn's electron injection effect enables thermal-neutral hydrogen adsorption on neighboring atoms, pushing the activity boundaries of carbon electrocatalysts toward electrochemical hydrogen evolution to an unprecedented level. Experimental and theoretical analyses confirm the low-barrier Volmer-Tafel mechanism of proton reduction, while the multishell hollow structures facilitate the hydrogen evolution even at high current intensities. This work provides insights for understanding the actual active species during hydrogen evolution reaction and paves the way for designing high-performance electrocatalysts.

Organic polymer coating induced multiple heteroatom-doped carbon framework confined Co1-xS@NPSC core-shell hexapod for advanced sodium/potassium ion batteries

Synthesis of advanced structure and multiple heteroatom-doped carbon based heterostructure materials are the key to the preparation of high-performance energy storage electrode materials. Herein, the hexapod-shaped Co1-xS@NPSC has been triumphantly prepared using hexapod ZIF-67 as the sacrificial template to prepare Co1-xS inner core and N, P, and S tri-doped carbon (NPSC) as the shell through the carbonization of the organic polymer precursor. When applied as anode for Na+ batteries (SIBs) and K+ batteries (PIBs), Co1-xS@NPSC presents the high reversible specific capability of 747.4 mAh/g at 1.0 A/g after 235 cycles and 387.8 mAh/g at 5.0 A/g after 760 cycles for SIBs, as well as 326.7 mAh/g at 1.0 A/g after 180 cycles for PIBs. The excellent storage capacity and rate capability of Co1-xS@NPSC is ascribed to hexapod structure of ZIF-67 unlike the common dodecahedron, which is constructed with interior porous and exterior framework repository, donating supplemental active sites, and doping of multiple heteroatoms forming organic polymer coating inhibiting the volume expansion and restrains the agglomeration of Co1-xS nanoparticles. This approach has paved a bright avenue to exploit promising anode materials with novel structure and hetero-atom doping for high-performance energy storage devices.