Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design princi...Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.展开更多
A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose...A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose(NC)-based propellants.Single-crystal X-ray diffraction,nuclear magnetic resonance,highresolution mass spectrometry,Fourier transform infrared(FT-IR)spectroscopy,and UV-Vis spectroscopy were used to characterize the structures of the synthesized fullerene anisole derivative stabilizers.Methyl violet,differential scanning calorimetry test,isothermal weight loss,vacuum stability test,and adiabatic accelerated test were used to study their compatibility with NC and their ability to stabilize NC.The results show that the designed and synthesized novel fullerene anisole derivative stabilizer has good compatibility with NC,and their overall stabilizing effects on NC are better than those of the traditional stabilizers,diphenylamine(DPA),and N,N’-dimethyl-N,N’-diphenylurea(C2).The stabilizing effects was ranked as:3b>2d>2a>2c>C2>2b>DPA>NC.In addition,FT-IR analysis and electron spin resonance spectroscopy were applied to explore the stability mechanism of fullerene-based stabilizers to NC.The results reveal that the new fullerene stabilizer can adsorb and effectively eliminate the nitrogen oxide free radicals generated by NC degradation;therefore,it can forbid the autocatalytic degradation of NC and stabilize NC.展开更多
Density functional theory （DFT） calculations on two isomers of C68 with the minimal number of fused pentagon pairs, its anions and Sc3N as well as Sc3N@C68 （6140） metallofullerene were carded out at the B3LYP/6-3...Density functional theory （DFT） calculations on two isomers of C68 with the minimal number of fused pentagon pairs, its anions and Sc3N as well as Sc3N@C68 （6140） metallofullerene were carded out at the B3LYP/6-31G^＊ level. The optimized configurations and electrostatic potential distributions have been obtained. The calculated results show that the electrostatic potentials of C68 （6140） inside the sphere have three minima in the middle of the double bonds at fusion of two hexagonal rings. In contrast, potential minimum Vmin（r） of C68 （6275） inside the sphere occurs at the center of the sphere. Concerning the two isomers of C68, the largest regions with the most negative MEP outside the sphere are both localized in the neighborhood of pentagon-pentagon vertex fusions. They constitute the most probable active sites in chemical reactions. Our results present a reasonable explanation for the bonding between scandium atoms and fullerene cage.展开更多
To achieve efficient polymer solar cells(PSCs)with full utilization of the whole spectrum,the multicomponent devices are of great importance to be deeply explored,especially for their capability of one-step fabricatio...To achieve efficient polymer solar cells(PSCs)with full utilization of the whole spectrum,the multicomponent devices are of great importance to be deeply explored,especially for their capability of one-step fabrication.However,the research about one same binary system simultaneously derivated various multi-component PSC is still very limited.Herein,we achieved the whole constructions from one binary host to different ternary systems and even the quaternary one.The ternary strategies with fullerene acceptor,PC_(71)BM,and non-fullerene acceptor,BT_(6)IC-BO-4Cl,as the third component,both boosted the device efficiencies of PBT4Cl-Bz:IT-4F binary system from about 9% to comparatively beyond 11%.Despite the comparable improvement of performance,there existed other similarities and differences in two ternary strategies.In detail,the isotropic carrier transport of PC_(71)BM which largely elevated the fill factor(FF)in the corresponding devices,while the strong absorption of BT_(6)IC-BO-4Cl enhanced the short current density(J_(SC))most.More interestingly,quaternary devices based on PBT4Cl-Bz:IT-4F:PC71 BM:BT_(6)IC-BO-4Cl could combine both advantages of fullerene and non-fullerene ternary strategies,further pumped the J_(SC) from 16.44 to the highest level of 19.66 mA cm^(-2) among all devices,eventually resulted in an optimized efficiency of 11.69%.It reveals that both fullerene and non-fullerene ternary strategies have their unique feature to elevate the device performance either by efficient isotropic carrier transport or better coverage of whole sunlight spectrum and easy tunable energy levels from organic materials.The key is how to integrate the two pathways in one system and provide a more competitive solution facing high-quality PSCs.展开更多
The solvent-free mechanochemical reaction and the liquid-phase reaction of C60 with ethyl 2-diazopropionate prepared in situ or preformed from alanine ethyl ester hydrochloride and sodium nitrite have been investigate...The solvent-free mechanochemical reaction and the liquid-phase reaction of C60 with ethyl 2-diazopropionate prepared in situ or preformed from alanine ethyl ester hydrochloride and sodium nitrite have been investigated. Methanofullerene 1 and fulleroids 2 and 3 from these reactions were obtained, meanwhile the pyrazoline intermediate was not observed. Fulleroids 2 and 3 can be converted to methanofullerene 1 in refluxing toluene.展开更多
Fullerenes (C 60 /C 70 ), clays and rocks near the Permian-Triassic (P/T) boundary in the Meishan section of South China are explored by means of comprehensive analytical techniques, including ultrasonic extraction wi...Fullerenes (C 60 /C 70 ), clays and rocks near the Permian-Triassic (P/T) boundary in the Meishan section of South China are explored by means of comprehensive analytical techniques, including ultrasonic extraction with column purification, high-performance liquid chromatography (HPLC) and matrix assisted laser desorption/ionization time-of- flight mass spectrometry (MALDI TOF MS). The study confirms the existence of fullerenes toward the P/T event boundary and their absence in clays and limestones beyond the boundary. In particular, the white clay, known as the event boundary, contains fullerenes of 0.33 ppb, while the red material, as the first lamina fill of goethite and gypsum on the base of the white clay, contains fullerenes of 1.23 ppb, and the last lamina of 2.50 ppb. Significantly, distinct enrichment of fullerenes is coincident with the disappearance of fossil records of marine species (94%) just at the base of the white clay, implying that geological fullerenes would be one of temporal remnants led by the P/T catastrophic event. This work strongly supports that fullerenes would be one of significant records of the P/T catastrophic event but their origin remains to be studied further.展开更多
Onion-like fullerenes synthesized by arc discharge in water were used as support of Pt nanoparticles as electrocatalytic materials for direct methanol fuel cell. Uniform platinum nanoparticles with the average diamete...Onion-like fullerenes synthesized by arc discharge in water were used as support of Pt nanoparticles as electrocatalytic materials for direct methanol fuel cell. Uniform platinum nanoparticles with the average diameter of about 4.3 nm were well dispersed on the surface of onion-like fullerenes by impregnation-reduction method. The morphologies and microstructures of the as-prepared composites were studied by means of XRD and TEM. Electrochemical analysis shows that this kind of nano material may be an excellent candidate to be used as the support of catalyst for methanol electrochemical oxidation.展开更多
基金This study is supported by the National Natural Science Foundation of China(21925104)the Natural Science Foun-dation of Hubei Province(2021CFA020)the start-up funding of Huazhong University of Science and Technology(3004110178).
文摘Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.
基金financial support received from the Natural Science Foundation of China(Grant No.51972278)Outstanding Youth Science and Technology Talents Program of Sichuan(Grant No.19JCQN0085)Open Project of State Key Laboratory of Environment-friendly Energy Materials(Southwest University of Science and Technology,Grant No.20fksy16)。
文摘A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose(NC)-based propellants.Single-crystal X-ray diffraction,nuclear magnetic resonance,highresolution mass spectrometry,Fourier transform infrared(FT-IR)spectroscopy,and UV-Vis spectroscopy were used to characterize the structures of the synthesized fullerene anisole derivative stabilizers.Methyl violet,differential scanning calorimetry test,isothermal weight loss,vacuum stability test,and adiabatic accelerated test were used to study their compatibility with NC and their ability to stabilize NC.The results show that the designed and synthesized novel fullerene anisole derivative stabilizer has good compatibility with NC,and their overall stabilizing effects on NC are better than those of the traditional stabilizers,diphenylamine(DPA),and N,N’-dimethyl-N,N’-diphenylurea(C2).The stabilizing effects was ranked as:3b>2d>2a>2c>C2>2b>DPA>NC.In addition,FT-IR analysis and electron spin resonance spectroscopy were applied to explore the stability mechanism of fullerene-based stabilizers to NC.The results reveal that the new fullerene stabilizer can adsorb and effectively eliminate the nitrogen oxide free radicals generated by NC degradation;therefore,it can forbid the autocatalytic degradation of NC and stabilize NC.
基金the Department of Education of Liaoning Province (No. 2024201057)
文摘Density functional theory （DFT） calculations on two isomers of C68 with the minimal number of fused pentagon pairs, its anions and Sc3N as well as Sc3N@C68 （6140） metallofullerene were carded out at the B3LYP/6-31G^＊ level. The optimized configurations and electrostatic potential distributions have been obtained. The calculated results show that the electrostatic potentials of C68 （6140） inside the sphere have three minima in the middle of the double bonds at fusion of two hexagonal rings. In contrast, potential minimum Vmin（r） of C68 （6275） inside the sphere occurs at the center of the sphere. Concerning the two isomers of C68, the largest regions with the most negative MEP outside the sphere are both localized in the neighborhood of pentagon-pentagon vertex fusions. They constitute the most probable active sites in chemical reactions. Our results present a reasonable explanation for the bonding between scandium atoms and fullerene cage.
基金the financial support by the National Natural Science Foundation of China(21733005,21975115,51773087)Shenzhen Fundamental Research Program(KQJSCX20180319114442157,JCYJ20170817111214740,JCYJ20180302180238419)+4 种基金Shenzhen Nobel Prize Scientists Laboratory Project(C17213101)Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)Guangdong Innovative and Entrepreneurial Research Team Program(2016ZT06G587)Shenzhen Sci-Tech Fund(KYTDPT20181011104007)the supported by Center for Computational Science and Engineering at SUSTech。
文摘To achieve efficient polymer solar cells(PSCs)with full utilization of the whole spectrum,the multicomponent devices are of great importance to be deeply explored,especially for their capability of one-step fabrication.However,the research about one same binary system simultaneously derivated various multi-component PSC is still very limited.Herein,we achieved the whole constructions from one binary host to different ternary systems and even the quaternary one.The ternary strategies with fullerene acceptor,PC_(71)BM,and non-fullerene acceptor,BT_(6)IC-BO-4Cl,as the third component,both boosted the device efficiencies of PBT4Cl-Bz:IT-4F binary system from about 9% to comparatively beyond 11%.Despite the comparable improvement of performance,there existed other similarities and differences in two ternary strategies.In detail,the isotropic carrier transport of PC_(71)BM which largely elevated the fill factor(FF)in the corresponding devices,while the strong absorption of BT_(6)IC-BO-4Cl enhanced the short current density(J_(SC))most.More interestingly,quaternary devices based on PBT4Cl-Bz:IT-4F:PC71 BM:BT_(6)IC-BO-4Cl could combine both advantages of fullerene and non-fullerene ternary strategies,further pumped the J_(SC) from 16.44 to the highest level of 19.66 mA cm^(-2) among all devices,eventually resulted in an optimized efficiency of 11.69%.It reveals that both fullerene and non-fullerene ternary strategies have their unique feature to elevate the device performance either by efficient isotropic carrier transport or better coverage of whole sunlight spectrum and easy tunable energy levels from organic materials.The key is how to integrate the two pathways in one system and provide a more competitive solution facing high-quality PSCs.
文摘The solvent-free mechanochemical reaction and the liquid-phase reaction of C60 with ethyl 2-diazopropionate prepared in situ or preformed from alanine ethyl ester hydrochloride and sodium nitrite have been investigated. Methanofullerene 1 and fulleroids 2 and 3 from these reactions were obtained, meanwhile the pyrazoline intermediate was not observed. Fulleroids 2 and 3 can be converted to methanofullerene 1 in refluxing toluene.
基金the National Natural Science Foundation of China(No.40072055,40232025) the Research Fund for the Doctoral Program of Higher Education(No.20040290005).
文摘Fullerenes (C 60 /C 70 ), clays and rocks near the Permian-Triassic (P/T) boundary in the Meishan section of South China are explored by means of comprehensive analytical techniques, including ultrasonic extraction with column purification, high-performance liquid chromatography (HPLC) and matrix assisted laser desorption/ionization time-of- flight mass spectrometry (MALDI TOF MS). The study confirms the existence of fullerenes toward the P/T event boundary and their absence in clays and limestones beyond the boundary. In particular, the white clay, known as the event boundary, contains fullerenes of 0.33 ppb, while the red material, as the first lamina fill of goethite and gypsum on the base of the white clay, contains fullerenes of 1.23 ppb, and the last lamina of 2.50 ppb. Significantly, distinct enrichment of fullerenes is coincident with the disappearance of fossil records of marine species (94%) just at the base of the white clay, implying that geological fullerenes would be one of temporal remnants led by the P/T catastrophic event. This work strongly supports that fullerenes would be one of significant records of the P/T catastrophic event but their origin remains to be studied further.
基金This work was financially supported by National Basic Research Program of China (No.2004CB217808), National Natural Science Foundation of China (No.20471041) Key Project of National Natural Science Foundation of China (No.90306014), Natural Science Foundation of Shanxi Province (No.20051018) and Shanxi Research Fund for Returned Scholars (No.200428,200523).
文摘Onion-like fullerenes synthesized by arc discharge in water were used as support of Pt nanoparticles as electrocatalytic materials for direct methanol fuel cell. Uniform platinum nanoparticles with the average diameter of about 4.3 nm were well dispersed on the surface of onion-like fullerenes by impregnation-reduction method. The morphologies and microstructures of the as-prepared composites were studied by means of XRD and TEM. Electrochemical analysis shows that this kind of nano material may be an excellent candidate to be used as the support of catalyst for methanol electrochemical oxidation.
