Hollow Carbon Spheres Research Articles

Sulfur, fluorine, and nitrogen tri-doped carbon hollow spheres for enhanced electrochemical performance in sodium-ion batteries

Sulfur, fluorine, and nitrogen tri-doped carbon hollow spheres for enhanced electrochemical performance in sodium-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.

Radial channel boosting stress release in hollow carbon spheres for high-rate sodium ions storage

Carbon spheres are appealing anode materials for advanced sodium ions batteries. However, several major hurdles to address are the stress-accumulation associated with the drastic volume change, the sluggish sodium ions diffusion kinetics, and poor electrochemically active sites inside. Herein, the von Mises stress distribution uncovers the critical role of the radial channel on the strain relaxation behavior based on the finite element method. Based on the finite element simulation, the radial porous hollow carbon spheres are proposed and synthesized by a universal strategy with a hard-template approach and dynamic graphitization. RPHCSs dominate opened micro-mesoporous features through the shell. With fast sodium ion diffusivity kinetics and much more accessible electrochemical active sites in shell, RPHCSs electrodes deliver a high specific capacity of 103.0 mAh g−1 even at 4000 mA g−1 with a high capacity contribution ratio > 0.1 V (81.1 %), suggesting its great superiority in the application of high-rate sodium ions storage. Such architecture provides a promising structural platform for the fabrication of high-performance carbon spheres material for other electrochemical energy storage systems.

Hydrophobic-treated yolk-shell SnS2@CSs Z-scheme confinement reactor for solar-electro-driven hydrogen peroxide production in neutral media

The diffusion and adsorption properties of the O2/H2O corpuscles at active sites play a crucial role in the fast photo-electrocatalytic reaction of hydrogen peroxide (H2O2) production. Herein, SnS2 nanosheets with abundant interfacial boundaries and large specific areas are encapsulated into hollow mesoporous carbon spheres (CSs) with flexibility, producing a yolk-shell SnS2@CSs Z-scheme photocatalyst. The nanoconfined microenvironment of SnS2@CSs could enrich O2/H2O in catalyst cavities, which allows sufficient internal O2 transfer, improving the surface chemistry of catalytic O2 to O2− conversion and increasing reaction kinetics. By shaping the mixture of SnS2@CSs and polytetrafluoroethylene (PTFE) on carbon felt (CF) using the vacuum filtration method, the natural air-breathing gas diffusion photoelectrode (AGPE) was prepared, and it can achieve an accumulated concentration of H2O2 about 12 mM after a 10 h stability test from pure water at natural pH without using electrolyte and sacrificial agents. The H2O2 product is upgraded through one downstream route of conversion of H2O2 to sodium perborate. The improved H2O2 production performance could be ascribed to the combination of the confinement effect of SnS2@CSs and the rich triple phase interfaces with the continuous hydrophobic layer and hydrophilic layer to synergistically modulate the photoelectron catalytic microenvironment, which enhanced the transfer of O2 mass and offered a stronger affinity to oxygen bubbles. The strategy of combining the confined material with the air-breathing gas diffusion electrode equips a wide practical range of applications for the synthesis of high-yield hydrogen peroxide.

D-band center engineering of single Cu atom and atomic Ni clusters for enhancing electrochemical CO2 reduction to CO

The rational design of catalysts with atomic dispersion and a deep understanding of the catalytic mechanism is crucial for achieving high performance in CO2 reduction reaction (CO2RR). Herein, we present an atomically dispersed electrocatalyst with single Cu atom and atomic Ni clusters supported on N-doped mesoporous hollow carbon sphere (CuSANiAC/NMHCS) for highly efficient CO2RR. CuSANiAC/NMHCS demonstrates a remarkable CO Faradaic efficiency (FECO) exceeding 90% across a potential range of −0.6 to −1.2 V vs. reversible hydrogen electrode (RHE) and achieves its peak FECO of 98% at −0.9 V vs. RHE. Theoretical studies reveal that the electron redistribution and modulated electronic structure—notably the positive shift in d-band center of Ni 3d orbital—resulting from the combination of single Cu atom and atomic Ni clusters markedly enhance the CO2 adsorption, facilitate the formation of *COOH intermediate, and thus promote the CO production activity. This study offers fresh perspectives on fabricating atomically dispersed catalysts with superior CO2RR performance.

Hollow ultra-microporous carbon spheres as high-rate anode nanomaterials for sodium-ion batteries

Hollow porous carbon spheres are considered as promising anode nanomaterials for sodium-ion batteries (SIBs), but suffer from the problems of poor rate and cycling performances. Typical improvement strategies by creating micropores or mesopores are used to boost cycling and rata performances. Herein, hollow porous carbon spheres (HPCS) with ultra-micropores are prepared as anode nanomaterials for SIBs. The optimized HPCS-2 delivers a decent capacity of 272.3 mAh g−1 at 0.1 A g−1, a capacity retention rate of 96.62% over 500 cycles at 2 A g–1, and, in particular, a remarkable rate performance of 233.64 mAh g–1 at 10 A g–1. The great enhancement is elucidated predominantly by the abundant ultra-micropores that provide rapid ion-transport pathways and accelerated sodium-ion diffusion coefficient. The results promise rational design and preparation of high-rate carbon anode nanomaterials for sodium storage.

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.

Hierarchical heterostructures of MXene and mesoporous hollow carbon sphere for improved ion accessibility and rate performance

The development of electrode materials with a hierarchically porous structure and good electrical connection is key to improving the charging-discharging rate and energy density of supercapacitors. However, the restacking issue of two-dimensional nanomaterials, such as MXene, seriously hinders the diffusion of electrolyte ions. Different from the extensively used sacrificing template method, a hierarchical heterostructure of electrically conducting mesoporous hollow carbon spheres (MHCS) and MXene composite electrode is designed and achieved through simple vacuum filtration without further template removing procedures. This direct preparation strategy not only effectively improves the specific surface area of the electrode but also enhances the abundant surface pores and good conductivity of MHCS, improving the penetration of the electrolyte solution and shortening the ion transport path, leading to a pronounced improvement in specific capacitance and rate performance of the electrodes. Additionally, the influence of sheath thickness of MHCSs on ion transfer rate is deeply discussed. The introduction of carbon nanotubes (CNTs) further improves conductivity and stability while maintaining good flexibility. Consequently, the MXene/MHCS/CNT film delivers a high specific capacitance (395F g−1 at 2 mV s−1), outstanding rate performance (70.9 % at 1000 mV s−1), and excellent cycling stability (98.3 % capacity retention after 10,000 cycles). Furthermore, the assembled symmetric supercapacitor provides a maximum energy density of 14.48 Wh kg−1. This work provides a quick and effective approach for constructing high performance 3D MXene architectures for fast ion transfer electrodes.

Nitrogen-doped hollow carbon sphere composite Mn3O4 as an advanced host for lithium-sulfur battery

As the most promising advanced energy storage system, lithium-sulfur batteries (LSBs) are highly favored by the researchers because of their advantages of high energy density (2500 W h kg−1), low cost and non-pollution. However, the low conductivity, volume expansion of sulfur, and shuttle effect are still the great hindrance to the practical application of LSBs. Herein, the above problems can be addressed through the following strategies: (1) Hollow carbon microspheres with high specific surface area were constructed as sulfur hosts to increase sulfur loading while also being able to enhance the physical adsorption of polysulfides; (2) the loading of Mn3O4 particles on the basis of hollow carbon microspheres facilitates the capture and adsorption of polysulfides; (3) the hollow carbon sphere structure as a conductive network can provide more pathways for rapid electrical/ionic transport and also accelerate electrolyte wetting. Moreover, the thinner shell of hollow carbon microsphere is conducive to ion diffusion and speed up the reaction rate. Thus, the NHCS/Mn3O4/S composites exhibit a high discharge specific capacity of 1010.3 mAh g−1 at first and still maintained a reversible capacity of 269.2 mAh g−1 after 500 cycles. This work presents a facile sustainable and efficient synergistic strategy for the development of advanced LSBs.

Repairable body-centered cubic Fe0 anchoring on porous hollow nitrogen-doped carbon spheres with adjusting electron distribution for efficient electrocatalytic ammonia synthesis

Electrocatalytic nitrogen reduction reaction (ENRR) is a promising and efficient method for ammonia production. However, ENRR is restricted by the adsorption and activation of N2. Herein, an efficient nitrogen reduction reaction (NRR) electrocatalyst loaded with zero valent iron (ZVI) particles onto porous nitrogen-doped carbon (NC) hollow spheres is reported. The optimal Fe@10N3C-950 exhibits excellent performance with high ammonia (NH3) yield (152.28 µg h−1 mgcat−1) and Faradaic efficiency (FE, 54.55 %) at − 0.3 V (versus reversible hydrogen electrode, vs. RHE). Bader charge shows that the adsorbed N2 acquires more electrons from Fe sites with body-centered cubic (BCC) structure to better activate N2. Moreover, i-t experiments are performed before electrocatalytic NH3 production to effectively eliminate the effect of oxidation on ZVI and thus, maintain high ENRR activity for Fe@10N3C-950. Theoretical calculations indicate that nitrogen doping not only reduces the Gibbs free energy of rate determining step (RDS), but the BCC-structured Fe can also decrease the energy barriers of N2 activation and RDS.

Controllable fiberization engineering of cobalt anchored mesoporous hollow carbon spheres for positive feedback to electromagnetic wave absorption

In order to overcome the limitations of single attenuation mechanism materials in effectively absorbing electromagnetic waves (EMW), meticulous microstructural design of composites and an elevated degree of integration of wave absorbing mechanisms are crucial. Utilizing mesoporous hollow carbon spheres as precursors, PCHM@ComXn (X = Se, S, O) nano-microspheres were synthesized by anchoring cobalt nanoparticles on the surface, controllable encapsulating in continuous fiber structure by electrostatic spinning technique subsequently. The carbon shell-cavity core configuration interspersed with nanoparticles has the advantage of light weight, low density and extensive defects. Abundant heterogeneous interface in carbon fiber offers excellent electrical conductivity and high specific surface area, while a three-dimension conductive network optimizes the transmission loss to incident EMW. The efficient synergy of multiple mechanisms enables PCHM@CoSe2/CNFs to achieve a strong reflection loss of −50.55 dB at a matched thickness of 2.0 mm, while the EABmax value can be extended to a remarkable 6.80 GHz at 2.3 mm, which is considerably superior to fiber samples encapsulating other cobalt-based nanoparticles of the same family. This work provides an innovative direction for the development of high-performance EMW absorbers.

Conductive layer coupled mesoporous hard carbon enabling high rate and initial Coulombic efficiency for potassium ion battery

Hard carbon with rich mesopores is considered as one of the most promising anodes for potassium-ion batteries, resulting from its shortened ions diffusion distance, good electrolyte penetration ability, and highly released stress. However, the well-developed pore channels tend to separate graphite-domains and enlarge direct contact area between electrode/electrolyte, which easily cause discontinuous electrons transfer paths and extra electrolyte depletion, thus leading to poor rate performance and initial Coulombic efficiency (ICE). Hence, we propose polyaniline conductive layer coated hollow mesoporous carbon spheres (HMCS@PAN) tailored based on local protonation reaction strategy, which can enhance conductivity and simultaneously maintain considerable pore structure, accounting for an ultrahigh-rate performance (233.9 mAh/g at 5 A/g) and long cycling life (216.8 mAh/g at 5 A/g over 2000 cycles). Besides, PAN coating can inhibit the direct contact between inner pore channels and electrolyte and reduce the excessive depletion of active ions in the filling of pores with larger pore size, which is conducive to building an even, stable, and inorganic-rich solid electrolyte interphase (SEI) layer, resulting in an excellent ICE (70.7%). This work provides a guidance for the structure design of mesopore hard carbon to improve its rate and ICE.

Synergistically promoting the catalytic conversion of polysulfides via in-situ construction of Ni-MnO2 heterostructure on N-doped hollow carbon spheres towards high-performance sodium-sulfur batteries

The room-temperature sodium-sulfur (RT Na-S) battery is considered to be a highly promising electrochemical energy storage device, attributed to its high energy density, rich sulfur reserve, and nontoxicity. However, it is constrained by the polysulfide shuttling and the low intrinsic conductivity of active sulfur. A sacrificial template method has been used to develop hetero-structured Ni-MnO2 embedded in micro/mesoporous hollow carbon spheres (HCS@Ni-MnO2) to overcome these challenges. As evidenced by electrochemical properties and computational results, the construction of hetero-structured Ni-MnO2 provides a strong affinity to polysulfides. Meanwhile, the highly conductive in-situ constructing Ni-MnO2 structure has strong adsorption to soluble sodium polysulfides and effectively improves the catalytic conversion. The micro- and mesoporous hollow carbon sphere improves the reactivity of the sulfur cathodes and physically suppresses polysulfides shuttling. Befitting from the physical and chemical confinement and the fast redox reaction of polysulfides, the as-prepared S/HCS@Ni-MnO2 cathode exhibits a high capacity of 1031.7 mAh g−1 at 0.2 A g−1 after 100 cycles, surpassing the capacities of S/HCS@Ni (820.3 mAh g−1), S/HCS@MnO2 (942.4 mAh g−1) and S/HCS (866.7 mAh g−1). Moreover, the battery with S/HCS@Ni-MnO2 cathode also exhibits excellent cycle life (586.8 mAh g−1 at 5 A g−1 after 1000 cycles) and a high rate performance (553.8 mAh g−1 at 10 A g−1). This study provides an efficient strategy for synthesizing multiple compound hetero-structured materials to facilitate the development of energy storage applications.

Enhancing the Lewis acidity of single atom Tb via introduction of boron to achieve efficient photothermal synergistic CO2 cycloaddition

Nowadays, it is becoming increasingly urgent to lower the escalating carbon dioxide (CO2) to reduce greenhouse effect. Fortunately, it is an ideal strategy by using the inexhaustible solar energy as the driving force to manipulate the cycloaddition reaction, the atomic efficiency of which is 100 %. This work represents the first attempt on utilization of rare-earth metal Tb with atomic dispersion, and the structure of Tb coordinated with 4 N-atoms and 2B-atoms was constructed on interconnected carbon hollow spheres. The introduction of electron-deficient B reduces the electron density of Tb, thereby boosting Lewis acidity and promoting the occurrence of ring-opening reaction. The mechanism exploration enunciates that TbN4B2/C is a photothermal synergistic catalyst, the combined action of photogenerated electrons and strong Lewis acidic site of Tb reduces the free energy of the rate-determining step, and then improving the yield of cyclic carbonate up to 739 mmol g-1h−1.

Amino-Induced CO2 Spillover to Boost the Electrochemical Reduction Activity of CdS for CO Production.

A considerable challenge in CO2 reduction reaction (CO2RR) to produce high-value-added chemicals comes from the adsorption and activation of CO2 to form intermediates. Herein, an amino-induced spillover strategy aimed at significantly enhancing the CO2 adsorption and activation capabilities of CdS supported on N-doped mesoporous hollow carbon sphere (NH2-CdS/NMHCS) for highly efficient CO2RR is presented. The prepared NH2-CdS/NMHCS exhibits a high CO Faradaic efficiency (FECO) exceeding 90% from -0.8 to -1.1V versus reversible hydrogen electrode (RHE) with the highest FECO of 95% at -0.9V versus RHE in H cell. Additional experimental and theoretical investigations demonstrate that the alkaline -NH2 group functions as a potent trapping site, effectively adsorbing the acidic CO2, and subsequently triggering CO2 spillover to CdS. The amino modification-induced CO2 spillover, combined with electron redistribution between CdS and NMHCS, not only readily achieves the spontaneous activation of CO2 to *COOH but also greatly reduces the energy required for the conversion of *COOH to *CO intermediate, thus endowing NH2-CdS/NMHCS with significantly improved reaction kinetics and reduced overpotential for CO2-to-CO conversion. It is believed that this research can provide valuable insights into the development of electrocatalysts with superior CO2 adsorption and activation capabilities for CO2RR application.

Cu Single Atoms Embedded in N-Doped Hollow Carbon Spheres for Simultaneous Electrochemical Detection of Hydroquinone and Catechol

Cu Single Atoms Embedded in N-Doped Hollow Carbon Spheres for Simultaneous Electrochemical Detection of Hydroquinone and Catechol

Single atoms/metal nanoparticles-decorated hollow carbon spheres as oxygen reduction catalyst for zinc-air batteries

Non-platinum electrocatalyst development for improving the oxygen reduction reaction (ORR) is critical in electrochemical energy conversion applications such as zinc-air batteries (ZABs). Herein, we developed dual Fe-Co single atoms and Co nanoparticles embedded N-doped hollow carbon (Fe-Co/N-HCS-x) catalysts via the carbonization of polypyrrole (PPy)@zeolitic imidazolate framework (ZIF) core–shell particles, with various PPy concentrations. PPy serves as a secondary nitrogen source that enhances nitrogen amount and promotes metal dispersion to increase active sites density. The Fe-Co/N-HCS-x catalysts with optimized PPy concentration control demonstrated improved ORR performance in alkaline media, with a half-wave potential (E1/2) of 0.921 V and an onset potential (Eonset) of 1.019 V. Fe-Co/N-HCS-x also exhibited high ZABs performance, with a power density of 244.6 mW cm−2 and an operating time of more than 100 h. Our research contributes to the development of optimized active sites for ORR, which can be applied to new electrochemical storage and conversion systems.

Electrode and Electrolyte Co-Energy-Storage Electrochemistry Enables High-Energy Zn-S Decoupled Batteries.

In the search for next-generation green energy storage solutions, Cu-S electrochemistry has recently gained attraction from the battery community owing to its affordability and exceptionally high specific capacity of 3350mAhgs -1. However, the inferior conductivity and substantial volume expansion of the S cathode hinder its cycling stability, while the low output voltage limits its energy density. Herein, a hollow carbon sphere (HCS) is synthesized as a 3D conductive host to achieve a stable S@HCS cathode, which enables an outstanding cycling performance of 2500 cycles (over 9 months). To address the latter, a Zn//S@HCS alkaline-acid decoupled cell is configured to increase the output voltage from 0.18 to 1.6V. Moreover, an electrode and electrolyte co-energy storage mechanism is proposed to offset the reduction in energy density resulting from the extra electrolyte required in Zn//S decoupled cells. When combined, the Zn//S@HCS alkaline-acid decoupled cell delivers a record energy density of 334Whkg-1 based on the mass of the S cathode and CuSO4 electrolyte. This work tackles the key challenges of Cu-S electrochemistry and brings new insights into the rational design of decoupled batteries.

Pd Nanocatalysts supported on hollow carbon spheres for heck reaction: Void-confinement effect with varying space size in liquid-phase processes

Pd Nanocatalysts supported on hollow carbon spheres for heck reaction: Void-confinement effect with varying space size in liquid-phase processes