Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unl...Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.展开更多
Two series of stable and soluble fulleropyrrolidines have been prepared from the reactions of C60, glycine or its N-arylated derivatives and aliphatic aldehydes or ketones in refluxing toluene or chlorobenzene. The ne...Two series of stable and soluble fulleropyrrolidines have been prepared from the reactions of C60, glycine or its N-arylated derivatives and aliphatic aldehydes or ketones in refluxing toluene or chlorobenzene. The new C60 derivatives represent new useful building blocks for further preparation of more funcionalized C60 derivatives.展开更多
The selection of photoactive layer materials for organic solar cells(OSCs) is essential for the photoelectric conversion process.It is well known that chlorophyll is an abundant pigment in nature and is extremely valu...The selection of photoactive layer materials for organic solar cells(OSCs) is essential for the photoelectric conversion process.It is well known that chlorophyll is an abundant pigment in nature and is extremely valuable for photosynthesis.However,there is little research on how to improve the efficiency of chlorophyll-based OSCs by matching chlorophyll derivatives with excellent non-fullerene acceptors to form heterojunctions.Therefore in this study we utilize a chlorophyll derivative,Ce_(6)Me_(3),as a donor material and investigate the performance of its heterojunction with acceptor materials.Through density functional theory,the photoelectric performances of acceptors,i ncluding the fullerene derivative PC_(71)BM and the terminal halogenated non-fullerene DTBCIC series,are compared in detail.It is found that DTBCIC-C1 has better planarity,light absorption,electron affinity,charge reorganization energy and charge mobility than others.Ce_(6)Me_(3) has good energy level matching and absorption spectral complementarity with the investigated acceptor molecules and also shows good electron donor properties.Furthermore,the designed Ce_(6)Me_(3)/DTBCIC interfaces have improved charge separation and reorganization rates(K_(CS)/K_(CR)) compared with the Ce_(6)Me_(3)/PC_(71)BM interface.This research provides a theoretical basis for the design of photoactive layer materials for chlorophyll-based OSCs.展开更多
Using bowl shaped carbon intermediates to construct dihedral fullerenes is an advisable method. Assu- ming that cap shaped C21 extends the size through building pentagons and hexagons at the U and V clefts of the brim...Using bowl shaped carbon intermediates to construct dihedral fullerenes is an advisable method. Assu- ming that cap shaped C21 extends the size through building pentagons and hexagons at the U and V clefts of the brims, a series of homologous carbon intermediates was generated, in which most of the members have been unknown up to now. The joins between these homologous intermediates gave the C3 dihedral series under the restriction of C3 sym- metrical axis. The investigations point out that the stabilities of these fullerenes not only relate to the shapes of cages and the co-planarities of polygons, but also associate with the equalizations of bond lengths and the pentagonal dis- tributions. The stabilities reveal that the pentagonal distribution in cages is not negligible to the Jr delocalization, be- sides the co-planarities of hexagons and pentagons. Analyzing the possible Stone-Wales（SW） rearrangements in those fullerenes with dehydrogenated pyracyclene units（DPUs） can help us to find out the highly stable isomers. Based on the geometrical optimizations, the calculations provided the theoretical chemical shifts of unknown fullerenes and the data reconfirmed the existence of members C78 and C84. The symmetry adaptation analyses for the frontier orbitals support the formative mechanism of consecutive pentagonal and hexagonal fusions, but the simulated routes are more complicated than the pentagon road（PR） mechanism, which include not only C2 but also C3 additive reactions.展开更多
The electronic structure and reactivities of Fe（CO）n （n = 3~5） addition to different fullerenes have been investigated through the first-principles calculations, and the results indicate that Fe（CO）3 and Fe（CO...The electronic structure and reactivities of Fe（CO）n （n = 3~5） addition to different fullerenes have been investigated through the first-principles calculations, and the results indicate that Fe（CO）3 and Fe（CO）4 can be adsorbed to the outside network of fullerene via hollow and bridge sites, respectively. Both of them have larger binding energy, but when Fe（CO）5 is adsorbed via the top site, the binding energy is relatively smaller. According to the directional curvature theory, the reactivities of Fe（CO）3 addition to the fullerenes are determined by KM of the ring center, and those of Fe（CO）4 addition by KD of the C–C bond curvature; while for Fe（CO）5, it presents weak reactivities in the addition reaction because of the larger volume effect. No matter whether the addition reaction takes place on the hollow or bridge site, the binding energies show a linear relationship with KD. This work further enriched the directional curvature theory and applied the isolobel analogy theory in the fullerene addition reactions.展开更多
Fullerene-based electron-transporting layers(ETLs)significantly influence the defect passivation and device performance of inverted perovskite solar cells(PSCs).However,theπ-cage structures of fullerenes lead to a st...Fullerene-based electron-transporting layers(ETLs)significantly influence the defect passivation and device performance of inverted perovskite solar cells(PSCs).However,theπ-cage structures of fullerenes lead to a strong tendency to self-aggregate,which affects the long-term stability of the corresponding PSCs.Experimental results revealed that[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)-based ETLs exhibit a certain degree of self-aggregation that affects the stability of the device,particularly under continuous irradiation stress.To modulate the aggregation behavior,we replaced a methyl hydrogen of PCBM with a phenyl group to yield[6,6]-phenyl-C61-butyric acid benzyl ester(PCBB).As verified through X-ray crystallography,this minor structural modification results in more non-covalent intermolecular interactions,which effectively enhanced the electron-transporting ability of the PCBB-based ETL and led to an efficiency approaching 20%.Notably,the enhanced intermolecular forces of PCBB suppressed its self-aggregation,and the corresponding device showed significantly improved stability,retaining approximately 90%of its initial efficiency after 600 h under one-sun irradiation with maximum power point tracking.These findings provide a viable approach for the design of new fullerene derivatives to tune their intermolecular interactions to suppress self-aggregation within the ETL for highperformance PSCs.展开更多
This article only deals with the topic of intense interest to us and to a considerable extent of our own experimental results on the synthesis, characterization and application of C60-containing functional polymers su...This article only deals with the topic of intense interest to us and to a considerable extent of our own experimental results on the synthesis, characterization and application of C60-containing functional polymers such as poly(N-vinylcarbazole), polystyrene and polyacrylonitrile-based fullerene polymers. The results demonstrate that [60]fullerene and be directly incorporated into a variety of functional polymers by copolymerization or grafting, but also can be used to modify or improve the electronic, optical and physicochemical properties of polymers. Both the stereo-electroniceffect and me steric hindrance of C60 have an important influence on the structure and physicochemical properties of the parent polymer.展开更多
Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobi...Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensation with polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride in acetone respectively under argon atmosphere. It was found that the four noble metal complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The regioselectivity of platinum complexes for styrene increases remarkably by introducing C-60 moiety. Factors influencing catalytic activity and the mechanism have been investigated.展开更多
In this study, the evolution of C60F18 molecules on a Cu（001） surface was studied by means of scanning tunneling microscopy and density functional theory calculations. The results showed that fluorinated fuUerenes ...In this study, the evolution of C60F18 molecules on a Cu（001） surface was studied by means of scanning tunneling microscopy and density functional theory calculations. The results showed that fluorinated fuUerenes （tortoise-shaped polar C60F18） decay on Cu（001） surfaces by a step-by-step detachment of F atoms from the C60 cage. The most favorable adsorption configuration was realized when the F atoms of C60F18 pointed towards the Cu surface and six F atoms were detached from it. The results also showed that a further decay of C60F12 molecules strongly depended on the initial C60F18 coverage. The detached F atoms initially formed a two-dimensional （2D） gas phase which then slowly transformed into F-induced surface structures. The degree of contact between the C60F12 molecules and the Cu（001） surface depended on the density of the 2D gas phase. Hence, the life-time of fluorinated fullerenes was determined by the density of the 2D gas phase, which was affected by the formation of new F-induced structures and the decay of C60F12 molecules.展开更多
The topological characters of all fullerene isomers from C30 to C70 with respect to their number of shared pentagon bonds have been investigated. Systematic calculations were also carried out at the B3LYP/6-31G^＊ lev...The topological characters of all fullerene isomers from C30 to C70 with respect to their number of shared pentagon bonds have been investigated. Systematic calculations were also carried out at the B3LYP/6-31G^＊ level. It is found that the most stable structure has the smallest number of shared pentagon bonds, and the relative energies of a given size show an increasing tendency to rise with Nss number which denotes the number of C-C bonds shared by pentagon. The topological criterion that has extremely low computational cost can be used as filtering principle to prescreen the thermodynamically viable fullerenes and predict the relative stability of isomers.展开更多
In this study,we report the synthesis of novel palladium nanoflowers(Pd NFs)on amino-functionalized fullerene(C60-NH2)by hydrothermal self-assembly growth using ethylenediamine(EA)as a functional reagent.The successfu...In this study,we report the synthesis of novel palladium nanoflowers(Pd NFs)on amino-functionalized fullerene(C60-NH2)by hydrothermal self-assembly growth using ethylenediamine(EA)as a functional reagent.The successful formation of Pd nanoflowers supported amino-functionalized fullerene(C60-NH2/Pd NFs)is evidenced by UV-vis and powder X-ray diffraction(XRD).The morphology of Pd NFs over the C60-NH2 surface has been investigated by high-resolution transmission electron microscopy(TEM)and Fourier-transform infrared(FT-IR)techniques.The supported Pd nanoflowers(Pd NFs/C60-NH2)exhibit remarkably superior catalytic activity toward the reduction of 4-nitrophenol(4-NP).It exhibits remarkable UV-vis spectra response from 4-nitrophenol to 4-aminophenol(4-AP)(99%in 2.0 min)with a turnover frequency of 12.35 min^-1.Its excellent catalytic stability and durability offer the promising application in catalysis.展开更多
We have performed a comparative theoretical study on the adsorption of nitric oxide （NO） on Zn12012 and Mgt2012 nanocages in terms of their energetic, geometric, and electronic properties. It has been found that NO ...We have performed a comparative theoretical study on the adsorption of nitric oxide （NO） on Zn12012 and Mgt2012 nanocages in terms of their energetic, geometric, and electronic properties. It has been found that NO adsorption on the MgO nanocage is energetically more favorable than that on the ZnO one. In contrast to the ZnO nanocage, HOMO-LUMO energy gap （Eg） of MgO one is dramatically decreased in the presence of NO molecule so that it is transformed from an intrinsic semiconductor （Eg≈5.00 eV） to a p-type one （Eg≈1.93 eV）. We have predicted that electronic and conductance properties of the Mg12012 nanocage are sensitive toward NO molecule, thus it may be potential candidate in detection of NO molecules.展开更多
Structural stability and Si-substitution pattern in fullerene cage of C_(60−n)Sin are thoroughly investigated by integrating density functional calculations with a colorbond graph(CBG)model.We find that the parameteri...Structural stability and Si-substitution pattern in fullerene cage of C_(60−n)Sin are thoroughly investigated by integrating density functional calculations with a colorbond graph(CBG)model.We find that the parameterized CBG model with genetic algorithms can efficiently scan the large configuration space of alloy and therefore identify the low-energy region within the first-principles accuracy.Low-energy(stable)structures of C_(60−n)Sin in carbon-rich region(1≤n≤30)were identified and the silicon atoms are found to tend to aggregate in the fullerene cage.The mixing energy of these low-energy structures is ~35 meV/atom and insensitive to the Si concentration.We expect that these alloy fullerene cages can be synthesized experimentally at elevated temperatures.展开更多
While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are ca...While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).展开更多
基金financially supported by the National Natural Science Foundation of China (No.50773038,and No.20974093)National Basic Research Program of China (973 Program) (No.2007CB936000)+3 种基金the Fundamental Research Funds for the Central Universities (2009QNA4040)Qianjiang Talent Foundation of Zhejiang Province (2010R10021)the Foundation for the Author of National Excellent Doctoral Disser-tation of China (No.200527)China Postdoctoral Science Foundation (No.20100471707)
文摘Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.
文摘Two series of stable and soluble fulleropyrrolidines have been prepared from the reactions of C60, glycine or its N-arylated derivatives and aliphatic aldehydes or ketones in refluxing toluene or chlorobenzene. The new C60 derivatives represent new useful building blocks for further preparation of more funcionalized C60 derivatives.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 12074059, 11974152, and 11404055)Heilongjiang Postdoctoral Fund (Grant No. LBH-Q21061)。
文摘The selection of photoactive layer materials for organic solar cells(OSCs) is essential for the photoelectric conversion process.It is well known that chlorophyll is an abundant pigment in nature and is extremely valuable for photosynthesis.However,there is little research on how to improve the efficiency of chlorophyll-based OSCs by matching chlorophyll derivatives with excellent non-fullerene acceptors to form heterojunctions.Therefore in this study we utilize a chlorophyll derivative,Ce_(6)Me_(3),as a donor material and investigate the performance of its heterojunction with acceptor materials.Through density functional theory,the photoelectric performances of acceptors,i ncluding the fullerene derivative PC_(71)BM and the terminal halogenated non-fullerene DTBCIC series,are compared in detail.It is found that DTBCIC-C1 has better planarity,light absorption,electron affinity,charge reorganization energy and charge mobility than others.Ce_(6)Me_(3) has good energy level matching and absorption spectral complementarity with the investigated acceptor molecules and also shows good electron donor properties.Furthermore,the designed Ce_(6)Me_(3)/DTBCIC interfaces have improved charge separation and reorganization rates(K_(CS)/K_(CR)) compared with the Ce_(6)Me_(3)/PC_(71)BM interface.This research provides a theoretical basis for the design of photoactive layer materials for chlorophyll-based OSCs.
基金Supported by the National Natural Science Foundation of China（No.21373140）.
文摘Using bowl shaped carbon intermediates to construct dihedral fullerenes is an advisable method. Assu- ming that cap shaped C21 extends the size through building pentagons and hexagons at the U and V clefts of the brims, a series of homologous carbon intermediates was generated, in which most of the members have been unknown up to now. The joins between these homologous intermediates gave the C3 dihedral series under the restriction of C3 sym- metrical axis. The investigations point out that the stabilities of these fullerenes not only relate to the shapes of cages and the co-planarities of polygons, but also associate with the equalizations of bond lengths and the pentagonal dis- tributions. The stabilities reveal that the pentagonal distribution in cages is not negligible to the Jr delocalization, be- sides the co-planarities of hexagons and pentagons. Analyzing the possible Stone-Wales（SW） rearrangements in those fullerenes with dehydrogenated pyracyclene units（DPUs） can help us to find out the highly stable isomers. Based on the geometrical optimizations, the calculations provided the theoretical chemical shifts of unknown fullerenes and the data reconfirmed the existence of members C78 and C84. The symmetry adaptation analyses for the frontier orbitals support the formative mechanism of consecutive pentagonal and hexagonal fusions, but the simulated routes are more complicated than the pentagon road（PR） mechanism, which include not only C2 but also C3 additive reactions.
基金Supported by the National Natural Science Foundation of China (No. 21073034)the State Key Laboratory of Structural Chemistry (No. 20090060)
文摘The electronic structure and reactivities of Fe（CO）n （n = 3~5） addition to different fullerenes have been investigated through the first-principles calculations, and the results indicate that Fe（CO）3 and Fe（CO）4 can be adsorbed to the outside network of fullerene via hollow and bridge sites, respectively. Both of them have larger binding energy, but when Fe（CO）5 is adsorbed via the top site, the binding energy is relatively smaller. According to the directional curvature theory, the reactivities of Fe（CO）3 addition to the fullerenes are determined by KM of the ring center, and those of Fe（CO）4 addition by KD of the C–C bond curvature; while for Fe（CO）5, it presents weak reactivities in the addition reaction because of the larger volume effect. No matter whether the addition reaction takes place on the hollow or bridge site, the binding energies show a linear relationship with KD. This work further enriched the directional curvature theory and applied the isolobel analogy theory in the fullerene addition reactions.
基金financial supports from the National Natural Science Foundation of China(51902110,51802102 and 21805101)the Scientific Research Funds of Huaqiao University(19BS105,16BS201 and 17BS409)+1 种基金Fundamental Research Funds for the Central Universities(ZQN-806,ZQN-PY607)the US National Science Foundation for generous support of this work under CHE1801317。
文摘Fullerene-based electron-transporting layers(ETLs)significantly influence the defect passivation and device performance of inverted perovskite solar cells(PSCs).However,theπ-cage structures of fullerenes lead to a strong tendency to self-aggregate,which affects the long-term stability of the corresponding PSCs.Experimental results revealed that[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)-based ETLs exhibit a certain degree of self-aggregation that affects the stability of the device,particularly under continuous irradiation stress.To modulate the aggregation behavior,we replaced a methyl hydrogen of PCBM with a phenyl group to yield[6,6]-phenyl-C61-butyric acid benzyl ester(PCBB).As verified through X-ray crystallography,this minor structural modification results in more non-covalent intermolecular interactions,which effectively enhanced the electron-transporting ability of the PCBB-based ETL and led to an efficiency approaching 20%.Notably,the enhanced intermolecular forces of PCBB suppressed its self-aggregation,and the corresponding device showed significantly improved stability,retaining approximately 90%of its initial efficiency after 600 h under one-sun irradiation with maximum power point tracking.These findings provide a viable approach for the design of new fullerene derivatives to tune their intermolecular interactions to suppress self-aggregation within the ETL for highperformance PSCs.
基金Project supported by the National Natural Science Foundation of China (No. 29671007, 29890216)
文摘This article only deals with the topic of intense interest to us and to a considerable extent of our own experimental results on the synthesis, characterization and application of C60-containing functional polymers such as poly(N-vinylcarbazole), polystyrene and polyacrylonitrile-based fullerene polymers. The results demonstrate that [60]fullerene and be directly incorporated into a variety of functional polymers by copolymerization or grafting, but also can be used to modify or improve the electronic, optical and physicochemical properties of polymers. Both the stereo-electroniceffect and me steric hindrance of C60 have an important influence on the structure and physicochemical properties of the parent polymer.
基金The project was financially supported by the National Natural Science Foundation of China (Grant 29573115).
文摘Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensation with polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride in acetone respectively under argon atmosphere. It was found that the four noble metal complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The regioselectivity of platinum complexes for styrene increases remarkably by introducing C-60 moiety. Factors influencing catalytic activity and the mechanism have been investigated.
文摘In this study, the evolution of C60F18 molecules on a Cu（001） surface was studied by means of scanning tunneling microscopy and density functional theory calculations. The results showed that fluorinated fuUerenes （tortoise-shaped polar C60F18） decay on Cu（001） surfaces by a step-by-step detachment of F atoms from the C60 cage. The most favorable adsorption configuration was realized when the F atoms of C60F18 pointed towards the Cu surface and six F atoms were detached from it. The results also showed that a further decay of C60F12 molecules strongly depended on the initial C60F18 coverage. The detached F atoms initially formed a two-dimensional （2D） gas phase which then slowly transformed into F-induced surface structures. The degree of contact between the C60F12 molecules and the Cu（001） surface depended on the density of the 2D gas phase. Hence, the life-time of fluorinated fullerenes was determined by the density of the 2D gas phase, which was affected by the formation of new F-induced structures and the decay of C60F12 molecules.
基金This work was supported by NNSFC (20471034) and Youth Foundation of Shanxi Province (20051011)
文摘The topological characters of all fullerene isomers from C30 to C70 with respect to their number of shared pentagon bonds have been investigated. Systematic calculations were also carried out at the B3LYP/6-31G^＊ level. It is found that the most stable structure has the smallest number of shared pentagon bonds, and the relative energies of a given size show an increasing tendency to rise with Nss number which denotes the number of C-C bonds shared by pentagon. The topological criterion that has extremely low computational cost can be used as filtering principle to prescreen the thermodynamically viable fullerenes and predict the relative stability of isomers.
基金financially supported by the Natural Science Foundation of Shanxi Province,China(No.201801D121042)。
文摘In this study,we report the synthesis of novel palladium nanoflowers(Pd NFs)on amino-functionalized fullerene(C60-NH2)by hydrothermal self-assembly growth using ethylenediamine(EA)as a functional reagent.The successful formation of Pd nanoflowers supported amino-functionalized fullerene(C60-NH2/Pd NFs)is evidenced by UV-vis and powder X-ray diffraction(XRD).The morphology of Pd NFs over the C60-NH2 surface has been investigated by high-resolution transmission electron microscopy(TEM)and Fourier-transform infrared(FT-IR)techniques.The supported Pd nanoflowers(Pd NFs/C60-NH2)exhibit remarkably superior catalytic activity toward the reduction of 4-nitrophenol(4-NP).It exhibits remarkable UV-vis spectra response from 4-nitrophenol to 4-aminophenol(4-AP)(99%in 2.0 min)with a turnover frequency of 12.35 min^-1.Its excellent catalytic stability and durability offer the promising application in catalysis.
文摘We have performed a comparative theoretical study on the adsorption of nitric oxide （NO） on Zn12012 and Mgt2012 nanocages in terms of their energetic, geometric, and electronic properties. It has been found that NO adsorption on the MgO nanocage is energetically more favorable than that on the ZnO one. In contrast to the ZnO nanocage, HOMO-LUMO energy gap （Eg） of MgO one is dramatically decreased in the presence of NO molecule so that it is transformed from an intrinsic semiconductor （Eg≈5.00 eV） to a p-type one （Eg≈1.93 eV）. We have predicted that electronic and conductance properties of the Mg12012 nanocage are sensitive toward NO molecule, thus it may be potential candidate in detection of NO molecules.
基金supported from Academia Sinica and Nanyang Technological University.
文摘Structural stability and Si-substitution pattern in fullerene cage of C_(60−n)Sin are thoroughly investigated by integrating density functional calculations with a colorbond graph(CBG)model.We find that the parameterized CBG model with genetic algorithms can efficiently scan the large configuration space of alloy and therefore identify the low-energy region within the first-principles accuracy.Low-energy(stable)structures of C_(60−n)Sin in carbon-rich region(1≤n≤30)were identified and the silicon atoms are found to tend to aggregate in the fullerene cage.The mixing energy of these low-energy structures is ~35 meV/atom and insensitive to the Si concentration.We expect that these alloy fullerene cages can be synthesized experimentally at elevated temperatures.
基金This work was in part supported by the Hong Kong Research Grants Council(HKUST6062/98P and DAG96/97 SC11).
文摘While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).
