N-doped Carbon Nanotubes Research Articles

Novel N-doped carbon nanotubes impregnated Mn spheres with polydopamine coating as an efficient polysulfide immobilizer for Li-S batteries

Lithium-sulfur (Li-S) batteries are one of the most promising energy storage and conversion devices due to the high theoretical capacity and cost-effectiveness of sulfur. However, they still suffer from sluggish redox kinetics and the shuttle effect caused by complex polysulfides. In this work, graphitic carbon nitride (g-C3N4) is utilized as a template and further hydrothermally treated with an Mn source and glucose. The pyrolysis of g-C3N4 gives rise to N-doped carbon nanotubes, producing abundant sites for physical confinement and chemical adsorption of polysulfides, while glucose carbonization brings forth amorphous carbon and Mn source produces metal spheres. Afterward, polydopamine (PDA) induces N-doped carbon coating and promotes interface connection as well as electron immigration. This synergistic design possesses a high surface area of micropores and mesopores to aggregate sulfur and accelerate redox kinetics. As a result, the N-doped carbon nanotube with Mn spheres and PDA coating@sulfur (CN/Mn-PDA@S) exhibits a high reversible capacity of 813.5 mAh g−1 at 1 C with a decay rate of 0.064% per cycle and remarkable capacity retention at 2 C with rate performance up to 4 C. Therefore, the novel design of N-doped carbon nanotubes with Mn spheres and PDA coating serves as an efficient polysulfide immobilizer for Li-S batteries.

In-situ grown NiFeLDH nanosheets over nitrogen rich amorphous carbon nanotubes: An electrochemical sensing platform for the detection of depression biomarker

In this work, intrinsic conductivity mismatch of NiFe layered double hydroxide (NFL) catalysts and agglomeration of nanosheets were addressed by introducing N doped carbon nanotubes (NCNTs) which improves catalytic activity. Using a one-step wet chemical process, CNT-supported NiFeLDH nanosheets (NFL/NCNTx, x=20, 50 and 100) were effectively created. This work delves into the lower level sensitive electrochemical detection of serotonin (5-HT) by utilising synergy of CNT and LDH. The modified NFL/NCNT exhibits better electrochemical activity, appreciable sensitivity and spanned a concentration range of 0.01 - 400 μM with detection limit stood at 1.2 nM due to the plethora of electrochemical active surface area, remarkable conductivity and appreciable stability. Impressively, 96.0 - 96.8 % and 96.7 - 97.2 % recovery rates achieved in human urine and serum samples were well close to HPLC data, signifying its feasibility for real-time monitoring. The operational stability of the proposed sensor retained up to 89.13 % for 6 weeks. The present study highlights that tailoring NFL-NCNT heterojunction is an important strategy for the development of active and stable sensing platform.

A Bamboo-structured N-Doped Carbon Nanotubes Encapsulated PdCo Nanoparticles: Synthesis and Catalytic Performance for Furfural Hydrogenation to Furfural Alcohol

A Bamboo-structured N-Doped Carbon Nanotubes Encapsulated PdCo Nanoparticles: Synthesis and Catalytic Performance for Furfural Hydrogenation to Furfural Alcohol

Melamine derived N-doped Carbon nanotubes: A durable catalyst support for Pt nanoparticles in proton exchange membrane fuel cell

Melamine derived N-doped Carbon nanotubes: A durable catalyst support for Pt nanoparticles in proton exchange membrane fuel cell

Manganese nanoparticles catalyzed the formation of mesoporous helical nitrogen-doped carbon nanotubes enabled aldosterone biosensing

Primary aldosteronism (PA) is the foremost form of secondary hypertension that affects 5–20 % of healthy humans via the excessive secretion of aldosterone (ALD), which increases the level of potassium excretion and thus produces various critical combined diseases. Thus, determining trace-level ALD content in human blood or urine samples is a crucial factor in diagnosing a life-threatening disease called PA. Herein, nanosized manganese particles encapsulated within the tunable helical-shaped N-doped mesoporous carbon nanotubes (Mnx@H-NCNTs) are synthesized by a simple and facile ball-milling method at different reaction times (1, 6, 12, and 18 h). The influence of ball-milling process time on the final morphology of the as-synthesized Mnx@H-NCNTs nanostructures is systematically investigated. In order to fabricate an ALD biosensor electrode, the immobilization of Anti-ALD antibodies (Anti-ALD) on the surface of the Mn@H-NCNTs-12H electrode (Anti-ALD/Mn@H-NCNTs-12H) is achieved via the interactions of combined interactions of hydrogen bonds, Van der Waals’ force, negatively charged carboxylic acid functionalities of antibodies and positively charged metal centers, and π-π stacking interaction between nucleosides of Anti-ALD and mesoporous H-NCNTs. In addition, BSA was used as a blocking additive for covering non-specific adsorption sites of Anti-ALD/Mnx@H-NCNTs (BSA/Anti-ALD/Mn@H-NCNTs-12H) nanostructured electrodes. The BSA/Anti-ALD/Mn@H-NCNTs-12H can be used as an effective signal amplifying probe for ALD detection through a noticeable reduction in the amperometric i-t current response over a linear range from 1 to 2500 pM, with a LOD of 0.72 pM (S/N = 3). The practical applicability of BSA/Anti-ALD/Mn@H-NCNTs-12H is further demonstrated by the detection of ALD from 1 to 20 nM in human blood or urine samples with a recovery ranging from 90.5 to 97.0 %, indicating its potential use in clinical analysis.

Boosting HER performance by using plasma prepared N-doped CNTs to support Pt nanoparticles

Developing highly-efficient and stable Pt-based catalysts towards alkaline hydrogen evolution reaction (HER) offers a promising strategy for future renewable energy. In this work, radio-frequency (RF) cold plasma-prepared N-doped MWCNTs were adopted to support Pt nanoparticles (NPs) (Pt/NCNTs) via pretreating MWCNTs with RF nitrogen plasma and combining with traditional thermal reduction method. The as-synthesized Pt/NCNT featured an ultra-small size of Pt NPs (1.5 nm) and plentiful doped nitrogen, exhibiting ultra-low overpotential of 28 mV@10 mA cm−2 and ultra-high mass activity of 3.2 A mg Pt−1@100 mA in 1 M KOH solution, which are superior to those of commercial 20 wt% Pt/C catalyst. This is because RF plasma can realize fast, high-efficient and specific N-doping structure of MWCNTs. The lone electron pairs of N species (mainly pyri-N and pyrr-N) on MWCNTs surface transfer to the empty orbitals of Pt NPs, forming a strong coordination effect between Pt and nitrogen, thereby boosting the alkaline HER catalytic performance.

Bamboo-like nitrogen-doped carbon nanotubes directly grown from commercial carbon black for encapsulating FeCo nanoparticles as efficient oxygen reduction electrocatalysts

Efficient methods for preparing carbon nanotube (CNT)-confined metal catalysts are of great significance for electrocatalysis. Hence, in this study, Fe and Co promoters were added to the precursors of commercial carbon black and melamine to form N-doped CNTs confined bimetallic catalysts (FeCo@N-CNTs) via in situ pyrolysis. The FeCo@N-CNT catalysts exhibited a bamboo-like morphology with FeCo alloy nanoparticles encapsulated in the CNTs and high activity toward the oxygen reduction reaction, with a half-wave potential of 0.864 mV, higher than that of commercial Pt/C (0.827 mV) in alkaline solutions. The catalytic performance is attributable to the synergistic effects between the FeCo alloy and N-doped CNT structure. Moreover, the confinement of the FeCo nanoparticles inside the CNTs imparted the prepared catalysts with resistance to methanol poisoning and long-term stability. This versatile method of synthesizing CNTs directly from carbon black provides a new strategy for preparing high-performance non-precious-metal-based N-doped CNT catalysts for practical fuel cell applications.

Nanoarchitectured Fe3C@N-Doped C/FeVO4 as High-Performance Anode for Sodium-Ion Batteries.

Ferric vanadate exhibits potential as an attractive anode material for sodium-ion batteries (SIBs) due to the multiple oxidation states of vanadium and natural abundances of iron. However, the design and fabrication of high-performance ferric vanadate-based SIB anode materials with unique composite nanostructures are still challenging. Herein, a facile self-template method is reported to synthesize 1D nanostructured Fe3C@N-doped C/FeVO4 (Fe3C@NC/FeVO4) anode materials by the combination of morphology regulation with hybrid composite construction, for the first time. To this end, a 1D Fe, N-doped carbon nanotube (FeNC) is used as a template, followed by etching and re-growth to obtain the 1D Fe3C@N-doped C/FeVO4 nanostructure. The introduction of Fe3C can improve its electronic conductivity and enhance capacitive behavior. Additionally, the 1D nanostructure can effectively shorten the ions transport path and alleviate volume expansion during the charge-discharge processes. With these advantages, the SIBs using such anodes show a remarkable rate performance with a capacity of 325.4mAhg-1 at 0.1Ag-1, 150.6mAhg-1 at 5Ag-1, and excellent cycling stability with a reversible capacity of 139.6mAhg-1 at 1Ag-1 after 1500 cycles. This work offers a new strategy for the future development of SIBs with ferric vanadate-based anode.

Structural design of hierarchical porous biomass carbon with a built-in electric field for efficient peroxymonosulfate activation

Biomass-derived carbon materials have excellent adsorption capacity and cost-effectiveness, and the electron interactions between multiphase composite materials improve the efficiency of water pollutant removal by advanced oxidation processes (AOPs). Herein, a multistage biochar catalyst in which metallic cobalt-embedded carbon tubes are prepared uniformly on the surface of kapok tubes is designed and fabricated. The closely connected structure grown in situ accelerates electron migration and forms a directional transfer electric field. The N-doped carbon nanotube encapsulated Co nanoparticles growth on the kapok biochar/PMS (Co-N-KBC/PMS) system removes tetracycline hydrochloride (TCH) at a rate 11.8 times higher than that of KBC/PMS. Free radicals (SO4•−, •OH, and •O2–) and non-free radicals (1O2) are generated in conjunction with electron transfer during PMS activation. The cobalt sites and C=O groups are possible active sites. Density-functional theory (DFT) calculations verify the built-in electric field from N-KBC to the Co surface, which accelerates electron transfer and improves TCH removal. The results reveal an effective strategy to activate PMS and address environmental remediation by utilizing carbon materials derived from biomass.

Study on the synthesis of CoFe/CoFe2O4@NCNTs derived from ZnFeCo-ZIF with abundant heterostructures and oxygen vacancies as bifunctional catalyst for ORR/OER in zinc-air batteries

The rational design of bifunctional catalysts for oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) in alkaline electrolyte is of great significance for zinc-air batteries (ZABs). In this study, different types of Fe/Co compounds and nitrogen-doped carbon-based composite catalysts from trimetallic zeolitic-imidazole-framework-derived (ZnFeCo-ZIF) were synthesized by adjusting the ratio of Zn/Fe/Co. Among them, the synthesized CoFe/CoFe2O4-N-doped carbon nanotubes (CoFe/CoFe2O4@NCNTs) have abundant Fe-Nx and Co-Nx activity sites, heterostructures and oxygen vacancies. The experimental results reveal that the electrons of CoFe are transferred to CoFe2O4 at the interface of CoFe/CoFe2O4, which not only enhances the electron transfer ability, but also induces oxygen vacancies to improve the adsorption/desorption capacity of O2 and intermediates. Meanwhile, metal atoms are uniformly dispersed in the N-doped carbon nanotubes to form metal–N sites with high catalytic activity. Therefore, the CoFe/CoFe2O4@NCNTs exhibit excellent electrocatalytic performance, possessing a half-wave potential (E1/2) of 0.878 V and a prominent limiting-current densities (JL) of 6.281 mA cm−2 for ORR, and a low overpotential of 344 mV at 10 mA cm−2 for OER. In particular, the CoFe/CoFe2O4@NCNTs-equiped ZAB possesses a higher open-circuit voltage (1.50 V), a greater maximum power density (193.42 mW cm−2) and a longer cycling performance (160 h). The density functional theory (DFT) calculations show that the CoFe/CoFe2O4 heterostructure can induce the rapid transfer of electrons at the CoFe/CoFe2O4 interface, which promotes the change of the surface electronic structure of the catalyst, and thus helps to enhance the ability of the catalyst to transfer electrons.

The application of Co3S4@NCNT/NCHS with excellent bifunctional catalytic activity in aqueous and flexible Zn-air batteries

In this work, we prepared a hybrid structure Co3S4@NCNT/NCHS using SiO2 nanospheres as a template. The structure is supported by hollow carbon spheres (NCHS), which are coated by Co3S4 nanoparticles and cross-linked N-doped carbon nanotubes. The combination of Co3S4 with N-doped carbon material significantly improves the electrocatalytic activity. In addition, the presence of N-doped carbon nanotubes induces more defects, which can regulate the electronic configuration of the material and improve its electrical conductivity. Therefore, Co3S4@NCNT/NCHS has good catalytic performance. At 10 mA cm−2, the OER overpotential of Co3S4@NCNT/NCHS is only 230 mV, which is lower than that of the commercial catalyst RuO2, and the ORR half-wave potential can reach 0.80 V. In the battery discharge test, Co3S4@NCNT/NCHS based ZABs can discharge continuously for 71.5 h, the specific capacity of 790.12 mA h g−1, power density of 113.09 m W cm−2, better than Pt/C+RuO2 battery. When the current density is 3 mA cm−2, ZABs assembled with Co3S4@NCNT/NCHS as catalyst can maintain a voltage gap of 0.62 V to 0.63 V within 300 h without significant change. When the current density is increased to 5 mA cm−2, ZABs based on Co3S4@NCNT/NCHS can be stably cycled for 300 h at a voltage gap between 0.80 V and 0.82 V.

Lithium ion battery-assisted solar-driven water splitting

Electrocatalytic water splitting is an efficient strategy to substitute traditional fossil fuels with renewable energy H2. However, its scalable implementation, especially outdoors, has been hindered due to the lack of highly efficient and stable electrocatalysts and high-cost external electricity from the power grid. Here, we develop a hybrid nanostructure comprising N-doped carbon nanotube (NCNT) covalent-linked cobalt disulfide nanoparticles (CoS2-NPs) confined in hollow carbon nanocages (h-CoS@NC). As a bifunctional electrocatalyst for overall water splitting, the multi-heterostructure exhibits superior catalytic activities towards both hydrogen and oxygen-containing intermediates. Inspiringly, a two-electrode electrolyzer combined with the multi-heterostructure realizes a current density of 10 mA cm−2 at a low cell voltage of 1.58 V. When employing an anode of lithium ion battery (LIB), the h-CoS@NC delivers a high specific capacity of 1040 mAh g−1 at 0.1 A g−1 and maintains a considerable capacity of 648 mAh g−1, especially at rate of 5 A g−1. Furthermore, a large capacity of 582 mAh g−1 is achieved at 0.1 A g−1 for sodium ion battery. Moreover, theoretical calculations interpret that the enhanced electrochemical activities of h-CoS@NC should be attributed to the interaction between the CoS2 and carbon matrix, which effectively regulates the local electronic structures and weakens water adsorption/dissociation energies. As a proof-of-concept, a self-powered water splitting system integrating solar-charged lithium-ion battery with a water splitting electrolyzer achieves a steady H2 evolution rate at 0.4 A.

Effect of nitrogen-doped type on fracture toughness improvement and crack growth resistance of carbon nanotube/epoxy nanocomposites: Combined multiscale analysis approach

Recently, nitrogen-doped carbon nanotubes (N-doped CNTs) have received great attention in nanocomposite design. It has become highly necessary to develop predictive models to elucidate their toughning behavior. In this study, the effects of CNTs with three different types of N-doped functional groups (quaternary, pyrrolic, and pyridinic) on the fracture toughness (FT) and crack growth of polymer nanocomposites are predicted using a multiscale analysis approach. To scale up from the nanoscale to the macroscale, a multiscale analysis approach integrating molecular dynamics, micromechanics theory, linear fracture mechanics theory, and a phase-field fracture model (PFFM) is adopted. The toughness enhancement trends of the three different types of N-doped functional groups were quantified by considering four toughening mechanisms (CNT debonding, plastic nanovoid growth, CNT pull-out, and CNT rupture), and compared with experimental result. The results show that the excellent interphase and interfacial properties of quaternary and pyridinic functional groups significantly improve the FT and crack growth resistance of N-doped CNT/epoxy nanocomposites. Our study provides high-performance solutions for experimental studies pertaining to the FT and crack growth of N-doped CNT/epoxy nanocomposites.

Boosting oxygen reduction performance by copper-iron co-doped on ZIF-derived N-doped carbon nanotubes

Developing high-efficiency non-noble metal catalysts for the oxygen reduction reaction (ORR) is paramount for sustainable energy conversion. In this study, we proposed a Cu, Fe co-doped zeolite imidazole framework (ZIF)-derived nitrogen-doped carbon nanotubes catalyst (Cu–Fe@CNTs/NC) obtained by hydrothermal method and pyrolysis. The electrochemical results showed that Cu–Fe@CNTs/NC exhibited favorable oxygen reduction performance and good stability under alkaline electrolyte. The incorporation of Cu and Fe bimetallic dopants promoted the carbon nanotubes growth on ZIF nanosheets, and the collaborative action of Cu and Fe enhanced its ORR catalytic activity. These findings provide an innovative way to prepare high active non-platinum ORR catalysts.

Liquid Gallium-Assisted Pyrolysis of MOF Affording CNT Non-Hollow Frameworks in High Yields for High-Performance Sodium-Ion Battery Anode.

Carbon materials have great potential for applications in energy, biology, and environment due to their excellent chemical and physical properties. Their preparation by carbonization methods encounters limitations and the carbon loss during pyrolysis in the form of gaseous molecules results in low yield of carbon materials. Herein a low-energy (600°C) and high-yield (82wt.%) carbonization strategy is developed using liquid gallium-assisted pyrolysis of metal-organic frameworks (MOFs) affording the N-doped carbon nanotube (CNT) non-hollow frameworks encapsulating Co nanoparticles. The liquid gallium layer offers protection against air, promotes heat transfer, and limits the escape of small carbonaceous gaseous molecules, which greatly improve the yields of the pyrolysis reaction. Experimental and theoretical results reveal that the synergistic interaction between CNTs and N/O-containing groups gives a non-hollow framework composed of N/O-enriched and open CNTs (NOCNTF-15, 15 denotes the 15mm thickness of the liquid gallium layer during the pyrolysis) with high specific capacity (185mAhg-1 at 10Ag-1) and ultra-stable cyclability (stable operation at 10Ag-1 and 50°C for 20000 cycles). This study provides a unique approach to carbonization that facilitates the practical application of low-cost CNTs and other MOFs-derived carbon materials in high-performance sodium-ion batteries (SIBs).

Preparation of MoSe2 nanosheets/nitrogen-doped carbon nanotubes and their electrochemical energy storage properties

Lithium-sulfur batteries can be used as excellent energy storage devices, but they still face some challenges in the practical application, such as the poor electrical conductivity of sulfur, the volume expansion of sulfur during the discharge process, and the dissolution of polysulfides. In this study, polypyrrole-coated molybdenum trioxide nanorods were used as templates for the simultaneous in-situ growth of MoSe2 nanosheets on the outer/inner sides of nitrogen-doped carbon nanotubes. When the MoSe2/N-carbon nanotubes (MoSe2/NC NTs) were used as sulfur carriers for lithium-sulfur battery, the large specific surface area of the N-carbon nanotubes facilitated the homogeneous loading of MoSe2 nanosheets and exposed more catalytically active sites of the MoSe2 nanosheets, increasing the contact area of electrolyte. In addition, the N-doped carbon nanotubes have excellent electrical conductivity, which greatly promotes the electrical conductivity of the cathode. The density functional theory calculations, adsorption experiments, and XPS results all confirm that the MoSe2/NC NTs are able to anchor lithium polysulfides through strong adsorption, thus effectively mitigating the shuttle effect of polysulfides. This study supplies a novel route for the preparation of sulfur host for advanced lithium-sulfur batteries.

Controllable Synthesis and Growth Mechanism of Cracked Cowpea-Like NCNT Encapsulated with Fe3N Nanoparticles for High-Performance Anode Material in Lithium-Ion Batteries

Fe3N nanocrystals embedded in cracked N-doped carbon nanotubes (Fe3N@NCNT) with a cowpea-like shape are innovatively prepared by metal-catalyzed graphitization and nitridization processes based on melamine and FeC2O4 precursor. The new in-situ synthesis strategy is proved to be effective to open the NCNT using a migratory metal carbide nanocatalyst via expansion effect and fabricate a metal nitride embedded NCNT with fully active ingredients. The detailed tip-growth mechanism of cracked NCNT with latitudinal-longitudinal graphene layers is studied by in-situ XRD analysis of the phase evolution of melamine and FeC2O4, and ex-situ SEM/TEM investigation of the topography correlation of NCNT and Fe3C floating catalyst. The Fe3N@NCNT microclews based anodes have a moderate carbon content of 35.45 wt%, electroactive NCNT conductive network, abundant microcracks and an open short-cavity system, showing a stable discharge capacity of 667 mAh g−1 at 0.1C, outstanding rate capability of 448 mAh g−1 at 5C and remarkable long-term cycling stability of 546 mAh g−1 after 600 cycles at 1C. The combined good electronic/ionic conductivity of cracked NCNT and robust mechanical stability of geometrically confined Fe3N nanoparticles contribute to the excellent redox activities, stabilized solid-electrolyte-interphase film and cycling durability of Fe3N@NCNT.

P-NiFe2O4/N-Doped Carbon Nanotubes/NiFe Multi-Phase Heterojunctions for Overall Water Splitting and Urea Electrolysis.

The design and construction of highly efficient electrocatalysts for overall water splitting and urea electrolysis are significantly important for promoting energy conversion and realizing green hydrogen production. In this work, we constructed a multi-phase heterojunction through a simple hydrothermal and phosphorization process. The P-doped NiFe2O4 (P-NiFe2O4) nanoparticles were uniformly anchored on the bamboo-like N-doped carbon nanotubes (NCNTs) grown via a NiFe-alloy autocatalysis. The electronic structure and coordination environment of active species were optimized by the synergistic action of P doping, well-dispersed ultrafine NiFe2O4, and NCNTs matrix with good conductivity, enhancing their quantity and activity for electrocatalysis. Consequently, the P-NiFe2O4/NCNTs/NiFe exhibits excellent HER and OER activities with an overpotential of 111 and 266 mV at 10 mA cm-2 in 1 M KOH, respectively. The symmetrical overall water-splitting cell using P-NiFe2O4/NCNTs/NiFe as both anode and cathode delivers 10 mA cm-2 at a voltage of 1.604 V in 1 M KOH. Notably, the two-electrode cell requires a low voltage of 1.467 V to achieve a current density of 10 mA cm-2 in 1 M KOH solution with 0.6 M urea. This designed catalysts display outstanding reaction kinetics and catalytic stability. This work provides useful guidance for applying transition metal-based catalysts for hydrogen production.

One-step synthesis of magnetic N-doped carbon nanotubes derived from waste plastics for effective Cr(Ⅵ) removal

The magnetic nitrogen-doped carbon nanotube is prepared by one-pot using waste plastics as feedstock in the existence of the urea and Fe(NO3)3 for Cr(Ⅵ) removal form wastewater. The characterization analysis indicates that the nitrogen is successfully doped on the magnetic nitrogen-doped carbon nanotube with specific surface area of the 158.71 m2/g and saturation magnetization of the 36.47 emu g−1. The existence of the nitrogen group and Fe3C contributes to Cr(Ⅵ) removal by complexation and reduction with adsorption capacity of the 27.47 mg g−1. The adsorption data is fitting well with the Pseudo-second order model, demonstrating chemisorption of Cr(Ⅵ). The Cr(Ⅵ) removal mechanism analysis indicates that Fe0, Fe2+, H*, oxygen-containing group and nitrogen-containing group are crucial to Cr(Ⅵ) removal. The key mechanism of the enhanced Cr (VI) removal is the reductive capacity by dissolved Fe2+, which accounts for 23.6 % of the overall Cr(VI) removal. The magnetic nitrogen-doped carbon nanotube is prepared from waste plastic for Cr (VI) removal from wastewater.

Alleviated volume changes of germanium anode via facile chemical confinement strategy

Germanium (Ge) anode shows great promise in overcoming unsatisfied capacity and dendrite formation concerns facing conventional graphite anodes in next generation lithium ion batteries. However, volume changes during repeated alloying and de-alloying cycles seriously impair structural stability and cycle lifespan. In this work, a facile chemical confinement strategy has been firstly proposed to alleviate volume changes of Ge anode. Benefited from strong binding interaction between Ge and ZnS, discrete Ge nanoparticle can be successfully encapsulated within thin protective ZnS shell and N-doped carbon layer (Ge-ZnS@N-C) after two-step carbonization and sulfurization of polydopamine-coating Zn2GeO4 nanorod precursors. In contrast, bulk Ge aggregates and hollow N-doped carbon nanotubes can be formed without chemical confinement of ZnS. The as-prepared Ge-ZnS@N-C sample displays multifold structural merits, including nanosized Ge particles with highly electrochemical activity, sufficient pores and functional groups that facilitate ion diffusion. Besides, protective ZnS shell and N-doped carbon layer can suppress volume changes of Ge nanoparticles and guarantee high electrode reversibility, demonstrated by a series of in-situ and ex-situ experiments. The as-synthesized Ge-ZnS@N-C anodes exhibit stable long-cycle performance (1389.7 mAh/g after 450 cycles at a current density of 0.5 A/g) and excellent rate performance (548.5 and 397.8 mAh/g at 5.0 and 8.0 A/g, respectively).