Recent advances in producing hollow carbon spheres for use in sodium−sulfur and potassium−sulfur batteries

Sodium-sulfur(Na-S)and potassium-sulfur(K-S)batteries for use at room temperature have received widespread attention because of the abundance and low cost of their raw materials and their high energy density.However,their development is restricted by the shuttling of polysulfides,large volume expansion and poor conductivity.To overcome these obstacles,an effective approach is to use carbon-based materials with abundant space for the sulfur that has sulfiphilic sites to immobilize it,and a high electrical conductivity.Hollow carbon spheres(HCSs)with a controllable structure and composition are promising for this purpose.We consider recent progress in optimizing the electrochemical performance of Na-/K-S batteries by using these materials.First,the advantages of HCSs,their synthesis methods,and strategies for preparing HCSs/sulfur composite materials are reviewed.Second,the use of HCSs in Na-/K-S batteries,along with mechanisms underlying the resulting performance improvement,are discussed.Finally,prospects for the further development of HCSs for metal−S batteries are presented.

Core-shell mesoporous carbon hollow spheres as Se hosts for advanced Al-Se batteries

Incorporating a selenium(Se)positive electrode into aluminum(Al)-ion batteries is an effective strategy for improving the overall battery performance.However,the cycling stability of Se positive electrodes has challenges due to the dissolution of intermediate reaction products.In this work,we aim to harness the advantages of Se while reducing its limitations by preparing a core-shell mesoporous carbon hollow sphere with a titanium nitride(C@TiN)host to load 63.9wt%Se as the positive electrode material for Al-Se batteries.Using the physical and chemical confinement offered by the hollow mesoporous carbon and TiN,the obtained core-shell mesoporous carbon hollow spheres coated with Se(Se@C@TiN)display superior utilization of the active material and remarkable cycling stability.As a result,Al-Se batteries equipped with the as-prepared Se@C@TiN composite positive electrodes show an initial discharge specific capacity of 377 mAh·g^(-1)at a current density of 1000 mA·g^(-1)while maintaining a discharge specific capacity of 86.0 mAh·g^(-1)over 200 cycles.This improved cycling performance is ascribed to the high electrical conductivity of the core-shell mesoporous carbon hollow spheres and the unique three-dimensional hierarchical architecture of Se@C@TiN.

Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO_(2) electroreduction

Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.

Electrochemical hydrogen evolution efficiently boosted by interfacial charge redistribution in Ru/MoSe_(2) embedded mesoporous hollow carbon spheres

The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.

Hierarchical porous nitrogen,oxygen,and phosphorus ternary doped hollow biomass carbon spheres for high-speed and long-life potassium storage

Limited lithium resources have promoted the exploration of new battery technologies.Among them,potassium-ion batteries are considered as promising alternatives.At present,commercial graphite and other carbon-based materials have shown good prospects as anodes for potassium-ion batteries.However,the volume expansion and structural collapse caused by periodic K+insertion/extraction have severely restricted further development and application of potassium-ion batteries.A hollow biomass carbon ball(NOP-PB)ternarily doped with N,O,and P was synthesized and used as the negative electrode of a potassium-ion battery.X-ray photoelectron spectroscopy,Fourier‐transform infrared spectroscopy,and transmission electron microscopy confirmed that the hollow biomass carbon spheres were successfully doped with N,O,and P.Further analysis proved that N,O,and P ternary doping expands the interlayer distance of the graphite surface and introduces more defect sites.DFT calculations simultaneously proved that the K adsorption energy of the doped structure is greatly improved.The solid hollow hierarchical porous structure buffers the volume expansion of the potassium insertion process,maintains the original structure after a long cycle and promotes the transfer of potassium ions and electrons.Therefore,the NOP‐PB negative electrode shows extremely enhanced electrochemical performance,including high specific capacity,excellent long‐term stability,and good rate stability.

Fabrication of functional hollow carbon spheres with large hollow interior as active colloidal catalysts

In this study, we have established a facile method to synthesize functional hollow carbon spheres with large hollow interior, which can act as active colloidal catalysts. The method includes the following steps： first, hollow polymer spheres with large hollow interior were prepared using sodium oleate as the hollow core generator, and 2,4-dihydroxybenzoic acid and hexamethylene tetramine （HMT） as the polymer precursors under hydrothermal conditions; Fe3＋ or Ag＋ cations were then introduced into the as-prepared hollow polymer spheres through the carboxyl groups; finally, the hollow polymer spheres can be pseudomorphically converted to hollow carbon spheres during pyrolysis process, meanwhile iron or silver nanoparticles can also be formed in the carbon shell simultaneously. The structures of the obtained functional hollow carbon spheres were characterized by TEM, XRD, and TG. As an example, Ag-doped hollow carbon spheres were used as colloid catalysts which showed high catalytic activity in 4-nitrophenol reduction reaction.

Constructing a hollow core-shell structure of RuO_(2) wrapped by hierarchical porous carbon shell with Ru NPs loading for supercapacitor

Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large specific surface area, small density, large charge carrying capacity and so on. However, their synthesis processes were mostly complicated, and few researches reported one-step encapsulation of different valence states of precious metals in carbon-based materials. Hence, a novel hollow core-shell nanostructure electrode material, RuO_(2)@Ru/HCs, with a lower mass of ruthenium to reduce costs was constructed by one-step hydrothermal method with hard template and co-assembled strategy, consisting of RuO_(2) core and ruthenium nanoparticles(Ru NPs) in carbon shell. The Ru NPs were uniformly assembled in the carbon layer, which not only improved the electronic conductivity but also provided more active centers to enhance the pseudocapacitance. The RuO_(2) core further enhanced the material’s energy storage capacity. Excellent capacitance storage(318.5 F·g^(-1)at 0.5 A·g^(-1)), rate performance(64.4%) from 0.5 A·g^(-1)to 20 A·g^(-1), and cycling stability(92.3% retention after 5000 cycles) were obtained by adjusting Ru loading to 0.92%(mass). It could be attributed to the wider pore size distribution in the micropores which increased the transfer of electrons and protons. The symmetrical supercapacitor device based on RuO_(2)@Ru/HCs could successfully light up the LED lamp. Therefore, our work verified that interfacial modification of RuO_(2) and carbon could bring attractive insights into energy density for nextgeneration supercapacitors.

A Bi-layer Composite Film Based on TiO_2 Hollow Spheres, P25,and Multi-walled Carbon Nanotubes for Efficient Photoanode of Dye-sensitized Solar Cell

A bi-layer photoanode for dye-sensitized solar cell(DSSC) was fabricated, in which TiO_2 hollow spheres(THSs) were designed as a scattering layer and P25/multi-walled carbon nanotubes(MWNTs) as an under-layer. The THSs were synthesized by a sacrifice template method and showed good light scattering ability as an over-layer of the photoanode. MWNTs were mixed with P25 to form an under-layer of the photoanode to improve the electron transmission ability of the photoanode. The power conversion efficiency of this kind of DSSC with bi-layer was enhanced to 5.13 %,which is 14.25 % higher than that of pure P25 DSSC.Graphical Abstract A bi-layer composite photoanode based on P25/MWNTs-THSs with improved light scattering and electron transmission, which will provide a new insight into fabrication and structure design of highly efficient dyesensitized solar cells.

Consecutive hybrid mechanism boosting Na+storage performance of dual-confined SnSe2 in N,Se-doping double-walled hollow carbon spheres

Rationally designed hierarchical structures and heteroatomic doping of carbon are effective strategies to enhance the stability and electrical conductivity of materials.Herein,SnSe_(2)flakes were generated in the double-walled hollow carbon spheres(DWHCSs),in which N and Se atoms were doped in the carbon walls,to construct SnSe_(2)@N,Se-DWHCSs by confined growth and in-situ derivatization.The N and Sedoped DWHCSs can effectively limit the size increase of SnSe_(2),promote ion diffusion kinetics,and buffer volume expansion,which can be proved by electron microscope observation and density functional theory calculation.Consequently,the SnSe_(2)@N,Se-DWHCSs as an anode material for sodium ion batteries(SIBs)demonstrated a distinguished reversible capacity of 322.8 mAh g^(-1)at 5 A g^(-1)after 1000 cycles and a superior rate ability of 235.3 m Ah g^(-1)at an ultrahigh rate of 15 A g^(-1).Furthermore,the structure evolution and electrochemical reaction processes of SnSe2@N,Se-DWHCSs in SIBs were analyzed by exsitu methods,which confirmed the consecutive hybrid mechanism and the phase transition process.

Catalytic oxidation of pentanethiol on basic nitrogen doped carbon hollow spheres derived from waste tires

A series of basic nitrogen doped carbon hollow spheres(p-N-C) catalysts derived from waste tires were prepared by a green, facile and environmental “leavening” strategy for the catalytic oxidation of pentanethiol. Compared to pristine carbon, the p-N-C has a higher surface curvature conducive to the enrichment of substrates, leading to an excellent catalytic performance. This increased surface curvature of p-N-C was fabricated on the synergistic effect of two foaming agents((NH4)2 C2 O4 and NaHCO3), and the released gas also endows the spherical shell of p-N-C with a hierarchical porous structure, promoting the accessibility of active sites with pentanethiol. Pyridine-like and pyrrolic-like nitrogen atoms were investigated as reactive sites on the p-N-C to accelerate the electron transfer from sulfur to active surface oxygen and enhance the adsorption/oxidation process. As a result, the optimal p-N-C catalyst exhibits superior adsorption and oxidation performance(99.9%) of pentanethiol, outperforming the “unleavened”catalyst(20.8%). This work offers a new avenue for the fabrication of highly efficient materials for the desulfurization of fuel.

Enhanced photocatalytic H_(2) production performance of CdS hollow spheres using C and Pt as bi-cocatalysts

Photocatalytic H2 production from water splitting is an effective method to solve energy crisis and environmental pollution simultaneously.Herein,carbon@CdS composite hollow spheres(C@CdS-HS)are fabricated via a facile hydrothermal method using porous carbon hollow spheres(C-HS)as the template.The C@CdS-HS shows an excellent photocatalytic H2-generation rate of 20.9 mmol h^(−1) g^(−1)(apparent quantum efficiency of 15.3%at 420 nm),with 1.0 wt%Pt as a cocatalyst under simulated sunlight irradiation;this rate is 69.7,13.9,and 3.9 times higher than that obtained with pure CdS hollow spheres(CdS-HS),C@CdS-HS,and CdS-HS/Pt,respectively.The enhanced photocatalytic H_(2)-evolution activity of C@CdS-HS/Pt is due to the synergistic effect of C and Pt as the bi-cocatalyst.The C-HS serves not only as an active site provider but also as an electron transporter and reservoir.Moreover,C-HS has a strong photothermal effect that is induced by near infrared light,which kinetically accelerates the H_(2)-production reaction.Additionally,the underlying charge transfer pathway and process from CdS to C−HS is revealed.This work highlights the potential application of C-HS-based nanocomposites in solar-to-chemical energy conversion.

Amorphous Fe Nanoclusters Embedded inside Balloon-Like N-Doped Hollow Carbon for Efficient Electrocatalytic Oxygen Reduction

Rational designs of electrocatalytic active sites and architectures are of great importance to develop cost-efficient non-noble metal electrocatalysts towards efficient oxygen reduction reaction(ORR)for high-performance energy conversion and storage devices.In this work,active amorphous Fe-based nanoclusters(Fe NC)are elaborately embedded at the inner surface of balloonlike N-doped hollow carbon(Fe NC/Csphere)as an efficient ORR electrocatalyst with an ultrathin wall of about 10 nm.When evaluated for electrochemical performance,Fe NC/Csphere exhibits decent ORR activity with a diffusionlimited current density of~5.0 mA/cm^(2)and a half-wave potential of~0.81 V in alkaline solution,which is comparable with commercial Pt/C and superior to Fe nanoparticles supported on carbon sheet(Fe NP/C sheet)counterpart.The electrochemical analyses combined with electronic structure characterizations reveal that robust Fe-N interactions in amorphous Fe nanoclusters are helpful for the adsorption of surface oxygen-relative species,and the strong support effect of N-doped hollow carbon is benefitial for accelerating the interfacial electron transfer,which jointly contributes to improve ORR kinetics for Fe NC/Csphere.

自然光条件下光自芬顿/PMS协同体系处理新污染物的实验设计

为强化学生对新污染物处理理论和实验技能的掌握,设计了光自芬顿/过氧单硫酸盐(PMS)协同体系在自然光条件下对新污染物的强化降解实验。利用水热法和浸渍法制备改性氮化碳空心球MoS_(2)/TCN_(Cl-S)(P),以四环素(TC)作为新污染物代表,构建了光自芬顿/PMS协同体系,基于其耦合效应,提高在自然光条件下污染物的降解效率。结果表明,光自芬顿/PMS体系对TC在120min内的降解率可以达到80%,较不引入PMS的光自芬顿体系提高了30%。其原因在于光自芬顿反应中产生的H_(2)O_(2)与PMS发生协同作用,产生了更多的·O_(2)^(-)、SO_(4)^(-)·和^(1)O_(2)等活性自由基,从而提高了TC的降解效率。该实验设计体系有助于促进学生对高级氧化技术的掌握,为学生科研创新能力培养体系的构建提供参考。

相互连接的介孔空心碳球的制备及其在电容去离子(CDI)技术中的应用研究

以空心碳球的孔隙结构为研究对象,采用改良Stöber法成功合成了一种相互连接的介孔空心碳球(MHCSs),并将其作为电极材料系统地研究其介孔结构对电化学性能和电容去离子性能的影响。研究结果表明,相比于以微孔结构为主的相互连接空心碳球(HCSs),MHCSs具有更大的比表面积和更多的活性位点,从而提高了电极材料的比电容。大孔径提升了空心碳球的离子传输速率,而石墨化程度的提高则增加了电极材料的电导率,显著提升了材料的电容去离子性能。在100 mg·L^(-1)浓度的NaCl溶液中,HCSs和MHCSs的电吸附容量分别达到10.01和17.81 mg·g^(-1),MHCSs表现出优异的电容去离子性能。此外,在经历了30次吸附-解吸循环后,MHCSs在100 mg·L^(-1)NaCl溶液中仍能保持97.42%的初始脱盐能力,表现出良好的循环稳定性。此研究成果为介孔空心碳球材料在海水淡化、水处理领域的应用提供了有益的参考。

N、B共掺杂空心碳球结构设计及其锂硫电池性能研究

采用二氧化硅包覆限域碳化的方法,制备N、B共掺杂空心纳米碳球。碳球直径为245 nm,空腔内径为165 nm,比表面积为666 m^(2)/g。与非限域碳化空心碳球对比,限域碳化可以有效扩大碳球空腔直径。以空心碳球为载体制备碳硫复合正极材料,碳球的大空腔结构可以提高锂硫电池硫正极中单质硫的利用率和循环稳定性,复合材料0.1 C放电比容量809 mAh/g;1.0 C初始放电比容量716 mAh/g,循环300次后比容量551 mAh/g,每次容量损失率0.077%。同时,碳球的多孔壁层结构可以提高锂离子的传输动力学,材料表现出良好的倍率性能,5 C放电比容量为423 mAh/g。

BTA@HMCs/PANI微胶囊的制备及环氧涂层防腐性能

以硬模板法合成的中空介孔碳球(HMCs)为微容器,通过真空浸渍及原位聚合法成功制得负载缓蚀剂苯并三氮唑(BTA)的BTA@HMCs/PANI微胶囊。制备的微胶囊呈规则球形,平均粒径约为270nm,壁厚(50±10)nm,微胶囊芯材质量分数为31.0%。添加质量分数5%BTA@HMCs/PANI微胶囊的自修复环氧涂层具有最佳的防腐性能,盐水浸泡实验表明环氧复合涂层浸泡30d后无明显腐蚀现象,电化学阻抗实验表明,环氧复合涂层低频区的阻抗模量值较纯环氧涂层高2~3个数量级。文中同时揭示了微胶囊芯材腐蚀抑制剂BTA和微胶囊壁材聚苯胺(PANI)协同防腐机理。

PtPb/HCSs催化剂制备及电催化氧化甲醇研究

以二氧化硅微球作模板,葡萄糖为碳源,通过水热法成功合成粒径均一、尺寸较小的碳空心球(HCSs),并以此为载体合成碳空心球载铂铅纳米微粒复合催化剂(PtPb/HCSs),在1 mol.L-1CH3OH+0.5mol.L-1H2SO4混合溶液中考察了PtPb/HCSs催化剂对甲醇的电催化氧化性能。样品的成份、结构和形貌分别用SEM、TEM、XRD和EDS进行表征。循环伏安(CV)及计时电流法实验表明碳空心球载铂铅催化剂对于甲醇氧化具有良好的电催化活性及稳定性。PtPb/HCSs电极优异的催化性能归因于碳空心球的高比表面积以及Pb的协同作用,是一种优良的直接甲醇燃料电池(DMFC)阳极材料。

超轻型微球介电吸波材料性能及应用研究

为了实现吸波材料轻量化,本文通过设计材料微观结构及合成方法,将碳材料的介电特性与空心结构的低密度特性相结合,开发出一种超轻型材料,制备的碳空心球(C@air)材料具有优良的吸波性能。基于该材料分别制备吸波板材及可用于隐身飞机机翼前缘的吸波蜂窝芯,并对其进行电磁仿真及雷达反射截面积(RCS)测试,吸波蜂窝芯在同向水平极化下达到-32.3 dB,同向垂直极化下达到-27.2 dB。验证了该材料具有优秀的吸波性能及应用效果,为吸波材料的设计与应用提供思路。

Ru complex and N,P-containing polymers confined within mesoporous hollow carbon spheres for hydrogenation of CO_(2)to formate

The development of reliable catalysts with both excellent activity and recyclability for carbon dioxide(CO_(2))hydrogenation is challenging.Herein,a ternary hybrid heterogeneous catalyst,involving mononuclear Ru complex,N,P-containing porous organic polymers(POPs),and mesoporous hollow carbon spheres(Ru^(3+)-POPs@MHCS)is reported for CO_(2)hydrogenation to formate.Based on comprehensive structural analyses,we demonstrated that Ru^(3+)-POPs were successfully immobilized within MHCS.The optimized Ru^(3+)-0.5POPs@MHCS catalyst,which was obtained with about 5 wt.%Ru^(3+)and 0.5 mmol POPs polymers confined into 0.3 g MHCS,exhibited high catalytic activity for CO_(2)hydrogenation to formate(turnover number(TON)>1,200 for 24 h under mild reaction conditions(4.0 MPa,120℃))and improved durability,compared to Ru^(3+)catalysts without POPs polymers(Ru^(3+)-MHCS)and unencapsulated MHCS(Ru^(3+)-0.5POPs)catalysts.The improved catalytic performance is attributed to the high surface area and large pore volume of MHCS which favors dispersion and stabilization of Ru^(3+)-POPs.Furthermore,the MHCS and POPs showed high CO_(2)adsorption ability.Ru^(3+)-POPs encapsulated into MHCS reduces the activation energy barrier for CO_(2)hydrogenation to formate.