Fullerenes and derivatives as electrocatalysts: Promises and challenges

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.

Fullerenes的光化学与光物理性质

本文对Fullerenes自发现以来在光化学和光物理领域的研究进展,以及它的分离方法进行了综述。

Determination of Fullerenes (C60/C70) from the Permian-Triassic Boundary in the Meishan Section of South China

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.

Pt/onion-like fullerenes as catalyst for direct methanol fuel cell

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.

Mechanical properties of aluminum-based nanocomposite reinforced with fullerenes

The strengthening effect of fullerenes in aluminum matrix composites was investigated. The composites are produced using a two-step ball-milling technique combined with a hot rolling process. First, fullerene aggregates, where fullerene molecules initially come together to form giant particles(~200 μm in diameter) via van der Waals bonding, are shattered into smaller particles(~1 μm in diameter) by planetary milling. Second, primarily ball-milled fullerenes are dispersed in aluminum powder via attrition milling. Finally, aluminum/fullerene composite powder is consolidated by hot-rolling at 480 °C. For the composite sheet, grain refinement strengthening and dispersion hardening by fullerenes are accomplished at the same time, thereby exhibiting HV ~222 of Vickers hardness(e.g., ~740 MPa of yield strength) with only 2%(volume fraction) of fullerenes.

New Solution Method of Pi-Orbital Axis Vector and Its Applications in Fullerenes and Carbon Nanotubes

A new solution method to perform the pi-orbital axis vector analysis was developed in this paper. The model of circular cone was built and the solution equations of the pyramidalization angle were obtained based on the model and the space analytic geometry. Our method merely requires the atomic coordinates of the conjugated central atom and the three attached atoms. Moreover, systematic calculations on the pyramidalization angles of fullerenes and carbon nanotubes were performed using the method we developed. The relationship of pyramidalization angle and the stability for the carbon cages and tubes was also discussed.

High stability of the goldalloy fullerenes:A density functional theory investigation of M_(12)@Au_(20)(M=Na,Al,Ag,Sc,Y,La,Lu,and Au) clusters

Discovering highly stable metal fullerenes such as the celebrated C 60 is interesting in cluster science as they have potential applications as building blocks in new nanostructures.We here investigated the structural and electronic properties of the fullerenes M 12 @Au 20（M=Na,Al,Ag,Sc,Y,La,Lu,and Au）,using a first-principles investigation with the density functional theory.It is found that these compound clusters possess a similar cage structure to the icosahedral Au 32 fullerene.La 12 @Au 20 is found to be particularly stable among these clusters.The binding energy of La 12 @Au 20 is 3.43 eV per atom,1.05 eV larger than that in Au 32.The highest occupied molecular orbital-lowest unoccupied molecular orbital（HOMO-LUMO） gap of La 12 @Au 20 is only 0.31 eV,suggesting that it should be relatively chemically reactive.

Evaluation of Transient Absorption Spectra of N, N, N, N- Tetra - ( p -methylphenyl ) - 4, 4- diamino - 1, 1- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C_(60) / C_(70) ) by Laser Flash Photolysis

Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N, N tetra - ( p-methylphenyl ) - 4, 4 diamino - 1, 1- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. Quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C60 / C70 ) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes ( C60 / C70 ) and radical cations of TPDAE appear.

Fullerenes中文定名的建议

一）Ｆｕｌｅｒｅｎｅｓ一词仍无令人满意的中文译名，我们曾经建议采用“球碳”或“”的译名，下面先简述提出“球碳”为译名的理由。（１）Ｆｕｌｅｒｅｎｅｓ只含碳元素，是石墨和金刚石的同素异形体，不是化合物，因此称其为“某某碳”是合情合理的。“某某碳”按汉...

BET Surface Area and Porous Structure of Fullerenes and Fullerene Soots

ＩｎｔｒｏｄｕｃｔｉｏｎＡｆａｓｃｉｎａｔｉｎｇｓｏｌｉｄｂｌａｃｋｃｏｎｄｅｎｓａｔｅ（ｈｅｒｅｃａｌｅｄｆｕｌｅｒｅｎｅｓｏｏｔ）ｉｓｇｅｎｅｒａｔｅｄｉｎｔｈｅｇａｓｐｈａｓｅａｎｄｄｅｐｏｓｉｔｅｄｄｕｒｉｎｇｔｈｅｄｉｓｃｈａｒｇｅｉｎａＫ...

Plasma-Chemical Synthesis of Nanosized Powders-Nitrides,Carbides,Oxides,Carbon Nanotubes and Fullerenes

In this article the plasma-chemical synthesis of nanosized powders （nitrides, car- bides, oxides, carbon nanotubes and fullerenes） is reviewed. Nanosized powders - nitrides, carbides, oxides, carbon nanotubes and fullerenes have been successfully produced using different techniques, technological apparatuses and conditions for their plasma-chemical synthesis.

Properties of Boron-Substituted Heterofullerenes

On the basis of a succinct description of geometrical configurations for giant fullerenes,the electronic properties and structural distortions of heterofullerenes C_(N-1)B(N=60,180,240,420,540,720,780)are analyzed by the extended Su-Schrieffer-Heeger model.In comparison with their pristine fullerenes CN,local distortions and mid-gap states are found to occur in boron-doped giant fullerenes.

On the ECI and CEI of Boron-Nitrogen Fullerenes

The eccentric connectivity index and connective eccentricity index are important topological indices for chemistry. In this paper, we investigate the eccentric connectivity index and connective eccentricity index of boron-nitrogen fullerenes, respectively. And we give computing formulas of eccentric connectivity index and connective eccentricity index of all boron-nitrogen fullerenes with regular structure.

HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC SEPARATION OF FULLERENES

High-performance liquid chromatographic systems for the separation of buckminsterfullerene(C_(60)) and related fullerene C_(70) were investigated with methanol/benzene or methanol/toluene (35/65-60/40 in Ⅴ/Ⅴ) as eluant in C18 reversed phase column. The system is suitable for fast analysis of fullerenes at lower percentage of methanol, and repeatly large scale perparation at higher percentage of methanol.

APPLICATION OF FULLERENES TO THE STUDY ON ITIES Ⅰ:INHIBITION TO THE TRANSFER OF TMA^+

For the first time,fullerenes are applied to the study on the interface between two immisible electrolyte solutions.Experiments show they are a new kind of inhibitors. Obvious inhibitive behavior to the TMA^+ transfer across the water/nitrobenzene interface is observed.

Different Charging-Induced Modulations of Highest Occupied Molecular Orbital Energies in Fullerenes in Comparison with Carbon Nanotubes and Graphene Sheets

The highest occupied molecular orbital（HOMO） energies of fullerenes are found by quantitative first-principles calculations to be raised by negative charging, and the rising rate rank of the fullerenes is C60 >C70 >C80 >C90>C100 >C180. Then we compare fullerenes with carbon nanotubes（CNTs） and graphene sheets（GSs） and find that the increase of the HOMO energy of a fullerene is much faster than that of CNTs and graphene sheets with the same number of C atoms. The rising rate rank is fullerene>CNT>GS, which holds no matter what the number of C atoms is or which structure the fullerene isomer is. This work paves a new path for developing all-carbon devices with low-dimensional carbon nanomaterials as different functional elements.

Single Covalent Bonding Structure in Fullerenes, Carbon Nanotubes and Closed Nanotubes

The present paper deals with carbon in highly organized solids like graphene and its three-dimensional derivatives: fullerenes, carbon nanotubes and capped carbon nanotubes. It proposes an alternative to the typical bonding pattern exposed in literature. This novel bonding pattern involves alternating positively and negatively charged carbon atoms around hexagonal rings, then a few uncharged and partially bonded atoms close to the pentagon rings. The article focuses on fullerenes inscribed into a regular icosahedron, then addressing the most common fullerenes like C60. Carbon atoms are found to have predominantly three single bonds and less often two separated single bonds. The same pattern explains equally well carbon nanotubes and closed-tip nanotubes, of which C70 is a special case.

Heat Transport in Double-Bond Linear Chains of Fullerenes

Heat transport in one kind of double-bond linear chains of fullerenes （C60＇s） is investigated by the classical nonequilibrium molecular dynamics method. It is found that the negative differential thermal resistance （NDTR） is more likely to occur at larger temperature difference and shorter length. In addition, with the increase of the length, the thermal conductivity of the chains increases, and NDTR region shrinks and vanishes in the end. The temperature profiles reveal that a large temperature jump exists at a high-temperature boundary of the chains when NDTR occurs. These results may be helpful for designing thermal devices where low-dimensional C60 polymers can be used.

Quantum Chemical Studies of Endofullerenes (M@C_(60)) Where M = H_(2)O, Li^(+), Na^(+), K^(+), Be^(2+), Mg^(2+), and Ca^(2+)

Quantum chemical calculations were performed to investigate the structural and electronic properties of seven endofullerenes. The interaction energies indicated that all of the chemical species are stable inside the fullerene for each complex. The ionization potential and electron affinity values suggest that the endofullerenes consisting of alkaline earth ions are the most reactive and that the dipole moment decreased according to the following order: Be2+@C60 (4.75) > Mg2+@C60 (3.14) > Ca2+@C60 (2.24) > Li+@C60 (1.26) > Na+@C60 (0.76) > H2O@C60 (0.24) > K+@C60 (0.00 Debye). These results imply that the solubility of endofullerenes in a polar solvent may increase from H2O@C60 to Be2+@C60. The energetic gaps indicate that Be2+@C60 and Mg2+@C60 possess a higher electrical conductivity, and the UV spectra show a shift in the bands to the visible light region. The results of this work may be useful for the development of new endofullerenes.

Fullerenes for rechargeable battery applications:Recent developments and future perspectives

The development of high-performance batteries is inseparable from the exploration of new materials.Among them,fullerene C60 as an allotrope of carbon has many unique properties that are beneficial for battery applications,including precise structure,controllable derivatization,good solubility,and rich redox chemistry.In this review,we summarize the recent progress of fullerene-based materials in the field of rechargeable batteries and the key issues that need to be solved in the future application of fullerene.We hope this review can provide guidance and stimulate research about the applications of fullerenes in the field of energy storage.