Hollow Carbon Nanospheres Research Articles

Atomic modulation of FeN4 sites on hollow carbon nanospheres by neighboring Mn atoms for ultra-stable Zn-air batteries

The sluggish oxygen reduction/evolution reaction (ORR/OER) at the oxygen electrode has significantly hindered the development of Zn-air batteries. Modulating single-atom active sites with neighboring atoms is an effective strategy to enhance ORR/OER activity. Herein, an ordered assembly strategy is employed to anchor FeN4 sites onto hollow carbon nanospheres and then Mn atoms are introduced to modulate the FeN4 sites to construct a electrocatalyst (Fe,Mn-HCNS). Theoretical simulations reveal that neighboring Mn atoms induces a negative shift in the d-band center of Fe, thereby optimizing the adsorption–desorption of key oxygenated intermediates and accelerating ORR/OER kinetics. In addition, the introduction of Mn atoms optimizes the energy barrier for Fe dissolution, which inhibits the demetalation of the FeN4 site. The assembled aqueous Zn-air battery demonstrates ultrahigh open-circuit voltage (1.55 V) and outstanding durability (2000 h at 10 mA cm−2). This work provides an insightful prospect for neighboring Mn atoms in enhancing oxygen electrocatalytic activity at FeN4 sites, thereby advancing the development of superior electrocatalysts.

Controlled fabrication of hierarchical porous carbon nanospheres with high doped nitrogen content for high-performance adsorbent of biomacromolecule

Constructing nitrogen-doped porous carbons with high specific surface area, rapid mass transfer channels, and positive charge is a crucial requirement for high-performance adsorbents. Herein, by the kinetic self-assembly synthesis strategy, we prepared nitrogen-doped hierarchical porous carbon spheres (N-HPCS) with adjustable pore structure, high specific surface area, and high nitrogen doping content (8.88 %). By using ethylenediamine as an assisted polymerization and assembly agent, the hydrolysis and condensation rate of tetraethyl orthosilicate (TEOS) as the silica source and the condensation rate of 3-aminophenol and formaldehyde as the phenolic resin precursor were controlled by adjusting ammonia volume as the alkaline catalyst to tune kinetic self-assembly of silica and phenolic resin components, thus achieving their simultaneous or sequential nucleus and growth. After carbonization and selective silica etching, three types of carbon nanospheres with center-radial pores, hollow center-radial pores and hollow structure were obtained. High nitrogen doping content endowed the nanospheres with positive charge. Through adsorption experiments on the bovine serum albumin (BSA) and Hemoglobin (Hb) as typical biological macromolecules, hollow carbon nanospheres with center-radial pores exhibited excellent adsorption performance for BSA(622.34 mg g−1) and Hb(759.96 mg g−1). Our fabricated N-HPCS may become a potential candidate for high-performance adsorption materials.

Co nanoparticles confined in N-doped hollow carbon nanospheres as multifunctional oxidase mimic for colorimetric detection of L-Cysteine and Hg2+

In contrast to peroxidase-mimicking nanozymes, oxidase mimics directly employ molecular oxygen (O2) as oxidant to generate reactive oxygen species (ROS). Generally, transition metal-based nanozymes exhibit poor oxidase-like activity. We herein constructed a colorimetric sensor based on Co-based oxidase mimic, where the Co nanoparticles were encapsulated in hollow N-doped carbon nanospheres (Co-N/C). Co nanoparticles confined catalyst effectively anchored the active part, which greatly influenced the catalytic activity of the oxidase-mimic nanozymes. Due to the antioxidative property of L-Cysteine (L-Cys) and the specific complexation between L-Cys and Hg2+, the rationally designed Co-N/C could be utilized to detect L-Cys and Hg2+. The proposed sensing platform exhibited wide linear ranges of 1–30 μM for L-Cys and 0.6–30 μM for Hg2+, respectively. The excellent selectivity of the constructed sensor showed the reliability and practicality for the assay of L-Cys and Hg2+ in fetal bovine serum. The spatial confinement can prevent the aggregation of Co nanoparticles, boosting the stability and catalytic performance in colorimetric sensing.

Strong metal-support interaction induced by oxygen vacancies to enhance the activity and durability of Pt/TiO2/ hollow carbon nanospheres ORR catalyst

For the commercial Pt-loaded carbon ORR catalysts used in proton exchange membrane fuel cells (PEMFC), carbon support corrosion, along with the migration and aggregation of Pt nanoparticles (NPs) due to the weak interaction between Pt NPs and carbon, leads to a drastic reduction in both electrocatalytic activity and stability. Hence, exploring active and steady supports is crucial to restrain the activity loss and stabilize Pt catalysts. In this work, a composite support consisting of hollow carbon nanospheres (HC) and TiO2 NPs with abundant oxygen vacancies (OV) loaded with Pt NPs (PTHC-H) was designed and synthesized. Experiment results show that PTHC-H exhibits superior activity and stability compared to PTHC-N (TiO2 with lower OV content) and commercial Pt/C catalyst. Specifically, PTHC-H delivers a half-wave potential of 0.883V versus reversible hydrogen electrode. And its mass activity and half-wave potential decrease by only 15.96% and 7mV, respectively, after 10,000 cycles of accelerated durability testing. The excellent activity and stability are ascribed to the enhanced metal-support interaction induced by OV, which can optimize the Pt d-band center and suppresses the migration and aggregation of Pt NPs. This work may be favorable for designing efficient and durable anti-corrosion nano catalysts.

Tribological properties of oil impregnated carbon nanocapsules modified with polydopamine-polyethyleneimine

Self-lubricating microcapsules can reduce the coefficient of friction/wear and improve the tribological properties of polymer composites. Impregnation of prefabricated shell with core substances is a versatile and applicable route to obtain the microcapsules. In this work, double shell nanocapsules (PA@C HSM) with particle size of 448nm, shell thickness of 65nm are obtained by incorporating paraffin wax (PA) into the pre-synthesized hollow carbon nanospheres (PHCs)and then packaged by co-depositing with polydopamine (PDA) and polyethylenimine (PEI). The PDA/PEI transition shell increase the surface roughness of the nanocapsule and enhance the compatibility with the polymer matrix which will contribute to the improved oil storage ability and thermal stability of the nanocapsules as well. The distinguished mechanical interlocking and chemical interface bonding between PDA/PEI layer and EP matrix effectively facilitates mitigating the unfavorable impact of PA@C HSM on the mechanical properties of the composite with the modulus of the 7.5wt.% PA@C HSM/EP composites increased by 17.44%. As for the tribological performance of PA@C HSM/EP composite, the tribological properties are boosted remarkably and the friction coefficient and wear rate of 7.5%PA@C HSM/EP composite are reduced by 77.69% and 98.79% compared with pure EP material.

Engineered nanozyme-cascade catalyzed reaction for rapid acid phosphatase detection

The utilization of artificial multienzyme-catalyzed cascade reactions have greatly benefited biosensors. This study presents a novel nanoreactor consisting of manganese ions-doped hollow carbon nanospheres (Mn@HCNs), which can rapidly transform molecular information into an easily comprehensible colorimetric signal. The Mn@HCNs nanoreactor was utilized to detect acid phosphatase (ACP) within a range of 0.5–10 mU/mL, achieving a limit of detection (LOD) as low as 0.0851 mU/mL. The superiority of our nanoreactor over traditional ACP detection methods stems from its exceptional substrate affinity and the multi-enzymatic behaviors of Mn@HCNs. Especially, the specific POD-like activity (SA) value of Mn@HCNs was superior to most reported Fe3O4 and other single-atom enzymes. Furthermore, this nanoreactor exhibited exceptional selectivity against protein and ion interference, and was furthered to detect ACP in clinical serum samples. The work may extend the development of artificial multienzyme-catalyzed cascade reactions for molecular biosensors and clinical application.

Boosting Li–S Battery Performance by Regulating Microstructures of Porous Hollow Carbon Nanospheres from Lignites

Boosting Li–S Battery Performance by Regulating Microstructures of Porous Hollow Carbon Nanospheres from Lignites

Peroxydisulfate activation by copper nanoparticles doped highly graphitized hollow carbon spheres for thiocyanate degradation

Thiocyanate (SCN-) is a toxic and refractory inorganic pollutant commonly found in industrial wastewater. This paper proposes an innovative solution to enhance the activation of peroxydisulfate (PDS) by designing a highly graphitized hollow carbon nanosphere structure catalyst doped with copper nanoparticles, thereby achieving efficient and complete degradation of SCN-. Specifically, the active sites and electron transfer ability of the catalyst were improved by controlling the pyrolysis temperature and acid etching time during the catalyst preparation process, thereby optimizing the PDS activation rate and SCN- degradation rate. In the optimized Cu-NPs@C/PDS system, a low dose of Cu-NPs@C-650–6 catalyst (0.2 g/L) and PDS ([PDS]0: [SCN-]0 = 3: 1) was sufficient to achieve 100 % degradation of 100 mg/L SCN- within 20 min. The non-radical oxidation pathway combined with singlet oxygen (1O2) and direct electron transfer process was identified as the main degradation mechanism of SCN-. The unique oxidation mechanism provided a higher SCN- degradation reaction rate constant (k1 = 0.39 min−1) and stronger environmental ion resistance. Density functional theory (DFT) calculations show that the CO bond is the primary PDS active site for the formation of inside-out electron delocalization, and the S atom in SCN- is a vulnerable site. This work offers technological support for the treatment of water bodies holding emerging electron-rich pollutants in addition to fresh insights into the creation of efficient catalysts for metal-carbon composites.

Synthesis of ultra-high nitrogen doped hollow mesoporous carbon nanospheres via a universal solid–liquid interface self-assembly strategy

Functional mesoporous polymers, particularly their derived hollow mesoporous carbon spheres (HMCS), have introduced new opportunities in the field of energy storage. Traditional synthesis methods for HMCS typically rely on chemical etching, which often results in uniform chemical properties and structural control, thereby limiting their application in large-scale production and diverse fields. Therefore, in this study, we report a novel strategy for obtaining HMCS through the direct pyrolysis of a core matrix, melamine–formaldehyde resin (MF), to achieve hollow structures and ultra-high nitrogen doping (approximately 14.8 wt%). This new solid–liquid interfacial self-assembly approach enables the production of HMCS with remarkable electrochemical performance and practical application prospects in sodium-ion half-cells and full cells, thanks to the high nitrogen doping and unique structure. Notably, this strategy has been validated for its general applicability across 1D, 2D, and 3D solid matrices. Additionally, by adjusting the calcination temperature, this method allows for precise control over both the core size and nitrogen content of the egg yolk-shell structure mesoporous carbon spheres. In summary, the mesoporous materials developed in this study demonstrate flexibility, simplicity, versatility, and structural diversity, offering significant insights for future applications in energy storage and other fields.

Rigid-flexible coupling multistage carbon composite materials based on hybrid crosslinking as anodes for ultra long-cycling lithium-ion batteries

Graphene have garnered considerable attention owing to their disordered structure, wide layer spacing, and cost-effectiveness. The hierarchical porous structure of porous reduced graphene oxide (rGO) nanosheets with hollow carbon nanospheres offers advantages such as an intact conductive network and a robust structure. However, since the hollow carbon nanospheres are physically in contact with rGO, they are randomly dispersed on the graphene surface, severely impeding fast electron transport and resulting in poor electrochemical performance. In this study, we introduced a third layer of a polypyrrole (PPy) -derived carbon film on the basis of porous rGO sheets and hollow carbon nanospheres. The HCGP-200 anode was successfully prepared to effectively encapsulate hollow carbon nanospheres on rGO sheets through the synergistic effect of rGO and the PPy-derived carbon film. The HCGP-200 anode exhibits robust cycling performance (780 mAh g−1 after 2200 cycles at 5 A g−1) and excellent rate capacity. Additionally, it demonstrates outstanding cycling stability and remarkable capacity retention (450 mAh g−1 after 3000 cycles) even at ultra-high current densities of 20 A g−1. The ingenious design and preparation of HCGP-200 is of great significance in guiding the application of high-power appliances.

Precisely Designed Ultra-Small CoP Nanoparticles-Decorated Hollow Carbon Nanospheres as Highly Efficient Host in Lithium-Sulfur Batteries.

Designing porous carbon materials with metal phosphides as host materials holds promise for enhancing the cyclability and durability of lithium-sulfur (Li-S) batteries by mitigating sulfur poisoning and exhibiting high electrocatalytic activity. Nevertheless, it is urgent to precisely control the size of metal phosphides to further optimize the polysulfide conversion reaction kinetics of Li-S batteries. Herein, a subtlety regulation strategy was proposed to obtain ultra-small CoP nanoparticles-decorated hollow carbon nanospheres (CoP@C) by using spherical polyelectrolyte brush (SPB) as the template with stabilizing assistance from polydopamine coating, which also works as carbon source. Leveraging the electrostatic interaction between SPB and Co2+, ultra-small Co particles with sizes measuring 5.5±2.6 nm were endowed after calcination. Subsequently, through a gas-solid phosphating process, these Co particles were converted into CoP nanoparticles with significantly finer sizes (7.1±3.1 nm) compared to state-of-the-art approaches. By uniformly distributing the electrocatalyst nanoparticles on hollow carbon nanospheres, CoP@C facilitated the acceleration of Li-ion diffusion and enhanced the conversion reaction kinetics of polysulfides through adsorption-diffusion synergy. As a result, Li-S batteries utilizing the CoP@C/S cathode demonstrated an initial specific discharge capacity of 850.0 mAh g-1 at 1.0 C, with a low-capacity decay rate of 0.03 % per cycle.

The synthesis of hollow carbon nanospheres from potato starch and the application in supercapacitor

The synthesis of high-valued carbon nanomaterials from biomass has always been a hot topic. The work reports the preparation of hollow carbon nanospheres (HCNs) from potato starch with one-step carbonization, in which self-made MgO powder is utilized as the template. In this study, an attempt was made to change carbonization temperature to control HCNs in diameter, wall thickness and pore distribution. Results show that the sample obtained at 800 °C (HCN-800) has a thinner wall thickness (about 12.1 nm), smaller and more uniform diameter (average diameter of 46.2 nm), as well as possesses a high specific surface area (619.53 m2 g−1) and the largest pore volume (2.8994 cm3 g−1). An application in supercapacitor has been verified for the HCNs in the work. In the three-electrode system, the HCN-800 exhibits excellent electrochemical performance, such as superior specific capacitance (324.8 F g−1 at 0.5 A g−1), high rate performance (215.7 F g−1 at 50 A g−1) and outstanding cycling stability (92.83 % capacitance retention after 10,000 cycles). Moreover, an assembled symmetric supercapacitor shows an energy density of 11.1 Wh kg−1 at a power density of 427 W kg−1, far exceeding that of previously reported carbon electrode materials. In short, the work provides a novel way to synthesize high-value-added HCNs from cheap biomass precursors, which have potential applications in the field of supercapacitors and other energy storage devices.

Three-dimensional carbon microclusters organized by hollow carbon nanospheres for stable Li metal anodes: enabling high packing density and low tortuosity via self-assembly

Three-dimensional carbon microclusters organized by hollow carbon nanospheres for stable Li metal anodes: enabling high packing density and low tortuosity via self-assembly

Salt-separated strategy for construction of hollow carbon nanospheres with tunable size based on α-cyclodextrin

Hollow carbon nanospheres (HCNs) have attracted much attention in the field of science and technology for their excellent properties; however, developing a versatile synthesis strategy for the preparation of HCNs remains a great challenge. The successful manipulation of size and shell thickness of HCNs is essential to meet their structural varieties and practical applications. Herein, HCNs were prepared directly from the renewable α-Cyclodextrin (α-CD) by a novel and simple salt-separated strategy with direct carbonization method is reported. The synthesis differs from the traditional template method in that it is characterized by the introduction of salt for separation and protection, the carbonization does not require the passage of protective gas, and the salt can be recycled. Thus, this method is very cost-effective and environmentally benign. In addition, the HCNs size in this system can be adjusted on demand by simply adjusting the concentration of α-CD, thus realizing that the HCNs size is adjustable in the range of 90–700 nm and adjustable shell thickness in the range of 20–250 nm. This work provides a new insight into the preparation of high-performance carbon materials in an environmentally friendly manner.

Tailored Hollow Mesoporous Carbon Nanospheres from Soft Emulsions Enhance Kinetics in Sodium Batteries.

Mesoporous materials endowed with a hollow structure offer ample opportunities due to their integrated functionalities; however, current approaches mainly rely on the recruitment of solid rigid templates, and feasible strategies with better simplicity and tunability remain infertile. Here, we report a novel emulsion-driven coassembly method for constructing a highly tailored hollow architecture in mesoporous carbon, which can be completely processed on oil-water liquid interfaces instead of a solid rigid template. Such a facile and flexible methodology relies on the subtle employment of a 1,3,5-trimethylbenzene (TMB) additive, which acts as both an emulsion template and a swelling agent, leading to a compatible integration of oil droplets and composite micelles. The solution-based assembly process also shows high controllability, endowing the hollow carbon mesostructure with a uniform morphology of hundreds of nanometers and tunable cavities from 0 to 130 nm in diameter and porosities (mesopore sizes 2.5-7.7 nm; surface area 179-355 m2 g-1). Because of the unique features in permeability, diffusion, and surface access, the hollow mesoporous carbon nanospheres exhibit excellent high rate and cycling performances for sodium-ion storage. Our study reveals a cooperative assembly on the liquid interface, which could provide an alternative toolbox for constructing delicate mesostructures and complex hierarchies toward advanced technologies.

Silver-Assisted Chemical Etching for the Fabrication of Porous Silicon N-Doped Nanohollow Carbon Spheres Composite Anodes to Enhance Electrochemical Performance.

Silicon (Si) shows great potential as an anode material for lithium-ion batteries. However, it experiences significant expansion in volume as it undergoes the charging and discharging cycles, presenting challenges for practical implementation. Nanostructured Si has emerged as a viable solution to address these challenges. However, it requires a complex preparation process and high costs. In order to explore the above problems, this study devised an innovative approach to create Si/C composite anodes: micron-porous silicon (p-Si) was synthesized at low cost at a lower silver ion concentration, and then porous silicon-coated carbon (p-Si@C) composites were prepared by compositing nanohollow carbon spheres with porous silicon, which had good electrochemical properties. The initial coulombic efficiency of the composite was 76.51%. After undergoing 250 cycles at a current density of 0.2 A·g-1, the composites exhibited a capacity of 1008.84 mAh·g-1. Even when subjected to a current density of 1 A·g-1, the composites sustained a discharge capacity of 485.93 mAh·g-1 even after completing 1000 cycles. The employment of micron-structured p-Si improves cycling stability, which is primarily due to the porous space it provides. This porous structure helps alleviate the mechanical stress caused by volume expansion and prevents Si particles from detaching from the electrodes. The increased surface area facilitates a longer pathway for lithium-ion transport, thereby encouraging a more even distribution of lithium ions and mitigating the localized expansion of Si particles during cycling. Additionally, when Si particles expand, the hollow carbon nanospheres are capable of absorbing the resulting stress, thus preventing the electrode from cracking. The as-prepared p-Si utilizing metal-assisted chemical etching holds promising prospects as an anode material for lithium-ion batteries.

KOH-activated hollow carbon spheres with surface functionalization for high-capacity and long-cycle-life lithium-selenium batteries

Lithium-selenium (Li-Se) batteries are considered promising alternatives to lithium-ion batteries due to their higher volumetric capacity and energy density. However, they still face limitations in efficiently utilizing the active selenium. Here, we develop surface-functionalized mesoporous hollow carbon nanospheres as the selenium host. By using KOH activation, the surface of the carbon nanospheres is functionalized with hydroxyl groups, which greatly improve the utilization of selenium and facilitate the conversion of lithium selenides, leading to much higher capacities compared to ZnCl2 activation and untreated carbon nanospheres. Theory and experimental evidence suggest that surface hydroxyl groups can enhance the reduction conversion of polyselenides to selenides and facilitate the oxidation reaction of selenides to elemental selenium. In-situ and ex-situ characterization techniques provided additional confirmation of the hydroxyl groups electrochemical durability in catalyzing selenium conversion. The meticulously engineered Se cathode demonstrates a high specific capacity of 594 mA h g−1 at 0.5C, excellent rate capability of 464 mA h g−1 at 2C, and a stable cycling performance of 500 cycles at 2C with a capacity retention of 84.8 %, corresponding to an ultra-low-capacity decay rate of 0.0144 % per cycle, surpassing many reported lithium-selenium battery technologies.

Preparation of inorganic oil-containing carbon nanocapsules and tribological properties of PA6 composites

Oil-containing polymer composites have garnered significant attention in the field of tribology due to their remarkable environmental stability and outstanding self-lubricating performance. It is important to develop an oil-containing polymer composite with excellent self-lubricating properties and mechanical properties. In this study, we successfully synthesized hollow mesoporous carbon nanospheres (HMCNs) with a particle size of about 200 nm and explored the key factors affecting their preparation. Subsequently, an impregnation technique was employed to create oil-containing nanocapsules (Oil@C) by using PAO40 lubricant as core material and HMCNs as wall material. Self-lubricating PAO40@HMCNs nanocapsules have an oil content of approximately 51.6 wt%. The unique mesoporous structure of HMCNs facilitates the controlled release of lubricants. During friction, the Oil@C in the polymer composites continuously provided lubricant to the worn surface, resulting in a remarkable 72.8 % reduction in the coefficient of friction and an 83.2 % decrease in wear rate. Analysis of the friction pair revealed that the PAO40 lubricant released from the nanocapsules played a crucial role in improving the tribological properties of the composites. The prepared PA6 composites exhibit outstanding tribological and self-lubricating properties, making them promising candidates for applications in mechanical parts, such as self-lubricating slide bearings.

NiCo2S4 nanotubes in situ anchored double-layered hollow carbon nanospheres towards enhanced overall water splitting

An efficient approach is developed to fabricate hybrid nanomaterials by anchoring in situ NiCo2S4 components on hollow double-layered carbon nanospheres (DCs). NiCo(CO3)(OH)2 is deposited on DCs and then reacted with S ions to create NiCo2S4 phase. Because of the homogeneous distribution of nanoparticles and well-developed interface, samples reveal excellent electrochemical activity. The compositions of NiCo2S4/hollow DCs (denoted as DCs-x-y, x and y are the molar ratios of Ni and Co in precursors) are adjusted to test the growth kinetics and morphology evolution. Under optimized conditions, the capabilities of composite sample DCs-0.20–0.30 outperform DCs and NiCo2S4 alone, which is ascribed to the high specific surface area and the existence of monodispersed hollow carbon spheres improving the distribution of NiCo2S4 and the overall conductivity to increase active sites. Especially, the optimized sample DCs-0.20–0.30 exhibits high performances and stability for enhanced hydrogen evolution reaction (HER) in both acidic and alkaline conditions and oxidation evolution reaction (OER) in alkaline electrolyte. Furthermore, using DCs-0.20–0.30 sample as both the cathode and anode in the alkaline electrolyzer, the current density of 10 and 100 mA cm−2 at 1.736 and 2.171 V are obtained. The sample also displays excellent durability for 20 h at 10 mA cm−2.

Mesoporous carbon hollow spheres with controllable pore structure for efficient lithium and aluminum ion storage

Mesoporous carbon hollow nanospheres (MCHS), synthesized via a block copolymer-mediated supramolecular self-assembly process, serve as both anode materials for lithium-ion batteries (LIBs) and cathode materials for aluminum-ion batteries (AIBs). By adjusting the carbonization temperature and the dosage of the pore extender, 1,3,5-trimethylbenzene (TMB), insights into the relationships among pore structure, crystal structure, and electrochemical properties of MCHS in Li/Al-ion batteries are gained. Their exceptional properties, including hierarchically porous structure, large surface area, tailored inner voids, mesoporous shells, and high electronic conductivity, contribute to high specific capacity, improved rate performances, and remarkable electrochemical stability. Crystallographic insights reveal that highly porous MCHS facilitate the intercalation of ionic lithium and aluminum species into the carbon crystal lattices while maintaining structural integrity. The appropriate mesopore size significantly impacts the storage of lithium or aluminum ions, with relatively larger mesopore sizes being more beneficial for aluminum ion storage compared to lithium ions. The optimal MCHS exhibit a stable discharge specific capacity of 330.8 mAh·g−1 after 800 cycles at a current density of 372 mA·g−1 (1C) in LIBs and 41.6 mAh·g−1 after 500 cycles at 74.4 mA·g−1 in AIBs.