The global greenhouse effect makes it urgent to deal with the increasing greenhouse gases. In this paper the performance of MgO-decorated carbon nanotubes for CO2 adsorption is investigated through first principles ca...The global greenhouse effect makes it urgent to deal with the increasing greenhouse gases. In this paper the performance of MgO-decorated carbon nanotubes for CO2 adsorption is investigated through first principles calculations. The results show that the MgO-decorated carbon nanotubes can adsorb CO2 well and are relatively insensitive to O2 and N2 at the same time. The binding energy arrives at 1.18 eV for the single-MgO-decorated carbon nanotube adsorbing one CO2 molecule, while the corresponding values for O2 and N2 are 0.55 eV and 0.06 eV, respectively. In addition, multi-molecule adsorption is also proved to be very satisfactory. These results indicate that MgO-decorated carbon nanotubes have great potential applications in industrial and environmental processes.展开更多
The effects of B and N dopings and H2O adsorption on the structural stability and the field emission properties of cone-capped carbon nanotubes （CCCNTs） were investigated by using the density-functional theoretical ...The effects of B and N dopings and H2O adsorption on the structural stability and the field emission properties of cone-capped carbon nanotubes （CCCNTs） were investigated by using the density-functional theoretical calculation. The adsorption of H2O can increase the structural stability and decrease the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital （HOMO-LUMO gap） of the CCCNTs. The strength of total electric field on the top of the H2O-adsorbed CCCNTs is larger than that of the B-doped and the N-doped CCCNTs, electrons will be emitted primarily from the H2O-adsorbed CCCNTs at the same applied voltage. Therefore, the H2O adsorption can lower the threshold voltage for the CCCNTs. While the B and the N dopings produce opposite effects. The HOMO-LUMO gap of the N-doped CCCNTs is the widest among all the gaps of the CCCNTs.展开更多
Recently, Hsieh and Horng [1] published the paper entitled as above. In section 3 results and discussion, the authors mentioned the first and the second order kinetic models without any quotations. In fact these two k...Recently, Hsieh and Horng [1] published the paper entitled as above. In section 3 results and discussion, the authors mentioned the first and the second order kinetic models without any quotations. In fact these two kinetic models have been published [2-5]. In order to distinguish a kinetics model based on the ad- sorption capacity of a solid from the one based on the concentration of a solution, Lagergren＇s first-order rate equation has been called pseudo-first-order [6-7]. The Lagergren＇s equation has been widely cited, but there are far more mistakes made in the quotation and in the reference section of papers, including the title, the author＇s name, journal title, year of publishing, volume, and page number [3]. In addition, the second order kinetic expression for the adsorption systems of divalent metal ions using sphagnum moss peat has been reported by Ho [8].展开更多
Recently, many attempts have been made to use carbon nanotubes in analytical chemistry, especially in adsorption of heavy metal ions from water. In this study, multiwalled carbon nanotubes (MWCNTs) were functionalized...Recently, many attempts have been made to use carbon nanotubes in analytical chemistry, especially in adsorption of heavy metal ions from water. In this study, multiwalled carbon nanotubes (MWCNTs) were functionalized with tris(2-aminoethyl) amine. The functionalized nanoparticles were characterized using Fourier transform infrared (FTIR), thermal gravimetric analyzer (TGA), elemental analysis, and Raman spectroscopy. The results revealed that the functionalization reaction was successfully accomplished. Lead adsorption from water was carried out using functionalized MWCNTs and measured by flame atomic absorption spectrometry (FAAS). The effects of pH, shaking time, initial metal ion concentration, and adsorbent dosage on the adsorption process were studied via batch method. The results obtained showed that removal of lead ions strongly depended on the pH. Desorption study revealed that lead ions adsorbed on the functionalized MWCNTs could be desorbed at pH 3 due to breakage of complexes formed on the sorbent surface. Maximum adsorption capacity of the sorbent under the optimal conditions was 43 mg/g. This favorable adsorption capacity suggests that functionalized carbon nanotubes can be applied for removal of lead from water solutions. The data obtained were fitted with the Langmuir and Freundlich isotherm adsorption models and Langmuir model showed better agreement with the experimental data.展开更多
First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the ca...First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.展开更多
Recently,Li-CO_(2) battery has gradually become a research hotspot due to its high discharge capacity,energy density and environmental benefits.However,it has been an important problem for researchers because of its s...Recently,Li-CO_(2) battery has gradually become a research hotspot due to its high discharge capacity,energy density and environmental benefits.However,it has been an important problem for researchers because of its slow decomposition kinetics and difficult to generalize to practical application.Herein,we prepared copper polyphthalocyanine-carbon nanotubes composites(CuPPc-CNTs)by solvothermal in-situ polymerization of copper phthalocyanine on the surface of carbon nanotubes as cathode for reversible Li-CO_(2) batteries,which exhibits a high discharge capacity of 18,652.7 mAh·g^(-1) at current density of 100 mA·g^(-1),1.64 V polarization at 1,000 mA·g^(-1),and a stable cycles number of 160 is close to 1,630 h of charge-discharge process at 200 mA·g^(-1).Copper polyphthalocyanine has highly efficient copper single-atom catalytic sites with excellent CO_(2) adsorption and activation,while carbon nanotubes provide a conductive network.The synergistic effect of the two compounds enables it to have excellent catalytic activity.The density functional theory(DFT)calculation proved that the addition of copper polyphthalocyanine significantly improved the CO_(2) adsorption and activation process.This study provides an opportunity for the research of covalent organic polymers(COPs)single-atom catalyst in Li-CO_(2) battery field.展开更多
Oxygen and nitrogen adsorption in single walled carbon nanotube (SWCNT) is studied by density function and discrete variational (DFT-DVM) method.The models of O 2 and N 2 adsorption in the SWCNT are optimized based...Oxygen and nitrogen adsorption in single walled carbon nanotube (SWCNT) is studied by density function and discrete variational (DFT-DVM) method.The models of O 2 and N 2 adsorption in the SWCNT are optimized based on the energy minimization.The calculated results of density of state,populations and energy gaps of the molecular orbitals show that oxygen adsorption in SWCNT increases the carbon nanotube`s electrical conductivity more notably than nitrogen adsorption,which is consistent with the experiment.展开更多
The first principles study was performed on the stability of Ag adsorbed on the internal walls of single-walled carbon nanotube （SWCNT） and loaded on acid modified SWCNT. The calculation results show that Ag can be ...The first principles study was performed on the stability of Ag adsorbed on the internal walls of single-walled carbon nanotube （SWCNT） and loaded on acid modified SWCNT. The calculation results show that Ag can be adsorbed stably on the internal walls of SWCNT. With the increase of SWCNT diameter, the adsorption energy increases in a certain range. Ag can also be loaded on the modified SWCNT surface in the form of COOAg and OAg groups, and COOAg group is more stable than OAg group. For either the adsorption on the inner SWCNT or the load on the modified SWCNT surface, only a small proportion of the Ag ions can be stably bonded to the walls of SWCNT.展开更多
Using first-principles calculations,the contact between the scandium(Sc) and semiconducting carbon nanotube(CNT) is investigated.This is one of the best quality of n-type contacts.Two junction models with(8,0) CNT on ...Using first-principles calculations,the contact between the scandium(Sc) and semiconducting carbon nanotube(CNT) is investigated.This is one of the best quality of n-type contacts.Two junction models with(8,0) CNT on low-index Sc surfaces are constructed to elucidate the structural and electronic properties of Sc/CNT junctions.Analyses based on density of states and charge difference reveal that strong chemical bonds are formed between Sc and C atoms due to hybrid states of Sc 3d state and C 2π state.With respect to Ti(0001)/CNT junction,we find the dipole layer formed at the interface of Sc(0001)/CNT is comparable with that of Ti(0001)/CNT but gives a negative barrier at the interface.This indicates that the excellent contact properties of Sc metal electrode are caused by its low work function and excellent binding with CNT.展开更多
The phosphorus-doped single wall carbon nanotube(PSWCNT) is studied by using First-Principle methods based on Density Function Theory(DFT).The formation energy,total energy,band structure,geometry structure and densit...The phosphorus-doped single wall carbon nanotube(PSWCNT) is studied by using First-Principle methods based on Density Function Theory(DFT).The formation energy,total energy,band structure,geometry structure and density of states are calculated.It is found that the formation energy of the P-doped single carbon nanotubes increases with diameters;the total energy of carbon nanotubes with the same diameter decreases as the doping rate increases.The effects of impurity position on the impurity level are discussed.It illustrates that the position of the impurity level may depend on the C-P-C bond angle.According to the above results,it is feasible to substitute a carbon atom with a phosphorus atom in SWCNT.It is also found that P-doped carbon nanotubes are N type semiconductor.展开更多
Electrocatalytic CO_(2) reduction to CH_(4) remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped car...Electrocatalytic CO_(2) reduction to CH_(4) remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped carbon nanotubes(NixCuy-NCNT)for electrocatalytic CO_(2) reduction reaction(CO_(2)RR)via hydrothermal method followed by pyrolysis.The optimized Ni_(1)Cu_(1)-NCNT demonstrated a superior CO_(2)RR performance,achieving 99.7%FECH_(4)(FE=Faradaic efficiency)and 11.54 mA·cm^(−2) current density at−1.2 V vs.reversible hydrogen electrode(RHE),which outperformed single metal counterparts.Its outstanding performance was due to the electrons transferred from Cu to Ni and Ni-Cu alloy shifted the d-band center toward the Fermi level,which was more conducive to the intermediate formation.In situ electrochemical attenuated total reflection(EC-ATR)and density functional theory(DFT)calculations revealed the appearance of *CHO intermediate and the pathway during the CO_(2)RR process.The design of the bimetallic electrocatalyst in this study provides a new perspective for the highly selective reduction of CO_(2).展开更多
First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surfa...First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surface. Calculations indicate that the C-O bond is weakened upon adsorption compared with that over perfect surface. In addition, with the density increase of the defective sites, the adsorption energies of the defect-CO configuration increase whereas the C-O bond nearly remains constant.展开更多
基金Project supported by the National Natural Science foundation of China (Grant No.60925016)
文摘The global greenhouse effect makes it urgent to deal with the increasing greenhouse gases. In this paper the performance of MgO-decorated carbon nanotubes for CO2 adsorption is investigated through first principles calculations. The results show that the MgO-decorated carbon nanotubes can adsorb CO2 well and are relatively insensitive to O2 and N2 at the same time. The binding energy arrives at 1.18 eV for the single-MgO-decorated carbon nanotube adsorbing one CO2 molecule, while the corresponding values for O2 and N2 are 0.55 eV and 0.06 eV, respectively. In addition, multi-molecule adsorption is also proved to be very satisfactory. These results indicate that MgO-decorated carbon nanotubes have great potential applications in industrial and environmental processes.
基金supported by the National Natural Science Foundation of China(Grant Nos.50771082,60776822,and 11075135)the Natural Science Foundation of Shaanxi Education Department,China(Grant No.09JK807)
文摘The effects of B and N dopings and H2O adsorption on the structural stability and the field emission properties of cone-capped carbon nanotubes （CCCNTs） were investigated by using the density-functional theoretical calculation. The adsorption of H2O can increase the structural stability and decrease the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital （HOMO-LUMO gap） of the CCCNTs. The strength of total electric field on the top of the H2O-adsorbed CCCNTs is larger than that of the B-doped and the N-doped CCCNTs, electrons will be emitted primarily from the H2O-adsorbed CCCNTs at the same applied voltage. Therefore, the H2O adsorption can lower the threshold voltage for the CCCNTs. While the B and the N dopings produce opposite effects. The HOMO-LUMO gap of the N-doped CCCNTs is the widest among all the gaps of the CCCNTs.
文摘Recently, Hsieh and Horng [1] published the paper entitled as above. In section 3 results and discussion, the authors mentioned the first and the second order kinetic models without any quotations. In fact these two kinetic models have been published [2-5]. In order to distinguish a kinetics model based on the ad- sorption capacity of a solid from the one based on the concentration of a solution, Lagergren＇s first-order rate equation has been called pseudo-first-order [6-7]. The Lagergren＇s equation has been widely cited, but there are far more mistakes made in the quotation and in the reference section of papers, including the title, the author＇s name, journal title, year of publishing, volume, and page number [3]. In addition, the second order kinetic expression for the adsorption systems of divalent metal ions using sphagnum moss peat has been reported by Ho [8].
文摘Recently, many attempts have been made to use carbon nanotubes in analytical chemistry, especially in adsorption of heavy metal ions from water. In this study, multiwalled carbon nanotubes (MWCNTs) were functionalized with tris(2-aminoethyl) amine. The functionalized nanoparticles were characterized using Fourier transform infrared (FTIR), thermal gravimetric analyzer (TGA), elemental analysis, and Raman spectroscopy. The results revealed that the functionalization reaction was successfully accomplished. Lead adsorption from water was carried out using functionalized MWCNTs and measured by flame atomic absorption spectrometry (FAAS). The effects of pH, shaking time, initial metal ion concentration, and adsorbent dosage on the adsorption process were studied via batch method. The results obtained showed that removal of lead ions strongly depended on the pH. Desorption study revealed that lead ions adsorbed on the functionalized MWCNTs could be desorbed at pH 3 due to breakage of complexes formed on the sorbent surface. Maximum adsorption capacity of the sorbent under the optimal conditions was 43 mg/g. This favorable adsorption capacity suggests that functionalized carbon nanotubes can be applied for removal of lead from water solutions. The data obtained were fitted with the Langmuir and Freundlich isotherm adsorption models and Langmuir model showed better agreement with the experimental data.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51002014,51202017,and 51372095)the Research Fund for the Doctoral Program of Higher Education of China(Grant No.20120061120039)+2 种基金the Funds from the Science and Technology Department of Jilin Province,China(Grant Nos.20120745 and 20130101029JC)the Funds from the Department of Education of Jilin Province,China(Grant No.2013279)the Youth Science Research Foundation of Liaoning University,China(Grant No.2013LDQN20)
文摘First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.
基金The authors acknowledge the financial support for this work from the Natural Science Foundation of Jiangsu Province(Nos.BK20190413 and BK20210616)the National Defense Technology Innovation Special Zone Spark Project(No.2016300TS00911901)+3 种基金the China Postdoctoral Science Foundation(No.2019M661825)the Jiangsu Key Laboratory of Electrochemical Energy-Storage Technologies(EEST2021-2)the Funding of Research and Practice Innovation Program in NUAA for Graduate Education(No.xcxjh20210605)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Recently,Li-CO_(2) battery has gradually become a research hotspot due to its high discharge capacity,energy density and environmental benefits.However,it has been an important problem for researchers because of its slow decomposition kinetics and difficult to generalize to practical application.Herein,we prepared copper polyphthalocyanine-carbon nanotubes composites(CuPPc-CNTs)by solvothermal in-situ polymerization of copper phthalocyanine on the surface of carbon nanotubes as cathode for reversible Li-CO_(2) batteries,which exhibits a high discharge capacity of 18,652.7 mAh·g^(-1) at current density of 100 mA·g^(-1),1.64 V polarization at 1,000 mA·g^(-1),and a stable cycles number of 160 is close to 1,630 h of charge-discharge process at 200 mA·g^(-1).Copper polyphthalocyanine has highly efficient copper single-atom catalytic sites with excellent CO_(2) adsorption and activation,while carbon nanotubes provide a conductive network.The synergistic effect of the two compounds enables it to have excellent catalytic activity.The density functional theory(DFT)calculation proved that the addition of copper polyphthalocyanine significantly improved the CO_(2) adsorption and activation process.This study provides an opportunity for the research of covalent organic polymers(COPs)single-atom catalyst in Li-CO_(2) battery field.
文摘Oxygen and nitrogen adsorption in single walled carbon nanotube (SWCNT) is studied by density function and discrete variational (DFT-DVM) method.The models of O 2 and N 2 adsorption in the SWCNT are optimized based on the energy minimization.The calculated results of density of state,populations and energy gaps of the molecular orbitals show that oxygen adsorption in SWCNT increases the carbon nanotube`s electrical conductivity more notably than nitrogen adsorption,which is consistent with the experiment.
基金This work was supported by the Program for Changjiang Scholars and Innovative Research Team in University （No. IRT0972）, the National Natural Science Foundation of China （Nos. 50874079, 51002102）, the Natural Science Foundation of Shanxi Province （No. 2009021026） and the Top Young Academic Leaders of Higher Learning Institutions of Shanxi, 2011.
文摘The first principles study was performed on the stability of Ag adsorbed on the internal walls of single-walled carbon nanotube （SWCNT） and loaded on acid modified SWCNT. The calculation results show that Ag can be adsorbed stably on the internal walls of SWCNT. With the increase of SWCNT diameter, the adsorption energy increases in a certain range. Ag can also be loaded on the modified SWCNT surface in the form of COOAg and OAg groups, and COOAg group is more stable than OAg group. For either the adsorption on the inner SWCNT or the load on the modified SWCNT surface, only a small proportion of the Ag ions can be stably bonded to the walls of SWCNT.
基金Project(No.10151064201000006)supported by the Natural Science Foundation of Guangdong Provincethe President Fund of South China Agricultural University(No.4900-K08226),China
文摘Using first-principles calculations,the contact between the scandium(Sc) and semiconducting carbon nanotube(CNT) is investigated.This is one of the best quality of n-type contacts.Two junction models with(8,0) CNT on low-index Sc surfaces are constructed to elucidate the structural and electronic properties of Sc/CNT junctions.Analyses based on density of states and charge difference reveal that strong chemical bonds are formed between Sc and C atoms due to hybrid states of Sc 3d state and C 2π state.With respect to Ti(0001)/CNT junction,we find the dipole layer formed at the interface of Sc(0001)/CNT is comparable with that of Ti(0001)/CNT but gives a negative barrier at the interface.This indicates that the excellent contact properties of Sc metal electrode are caused by its low work function and excellent binding with CNT.
基金Supported by the Natural Science Foundation of Fujian Province of China (Grant No. A0220001)
文摘The phosphorus-doped single wall carbon nanotube(PSWCNT) is studied by using First-Principle methods based on Density Function Theory(DFT).The formation energy,total energy,band structure,geometry structure and density of states are calculated.It is found that the formation energy of the P-doped single carbon nanotubes increases with diameters;the total energy of carbon nanotubes with the same diameter decreases as the doping rate increases.The effects of impurity position on the impurity level are discussed.It illustrates that the position of the impurity level may depend on the C-P-C bond angle.According to the above results,it is feasible to substitute a carbon atom with a phosphorus atom in SWCNT.It is also found that P-doped carbon nanotubes are N type semiconductor.
基金supported by the National Natural Science Foundation of China(No.52170065).
文摘Electrocatalytic CO_(2) reduction to CH_(4) remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped carbon nanotubes(NixCuy-NCNT)for electrocatalytic CO_(2) reduction reaction(CO_(2)RR)via hydrothermal method followed by pyrolysis.The optimized Ni_(1)Cu_(1)-NCNT demonstrated a superior CO_(2)RR performance,achieving 99.7%FECH_(4)(FE=Faradaic efficiency)and 11.54 mA·cm^(−2) current density at−1.2 V vs.reversible hydrogen electrode(RHE),which outperformed single metal counterparts.Its outstanding performance was due to the electrons transferred from Cu to Ni and Ni-Cu alloy shifted the d-band center toward the Fermi level,which was more conducive to the intermediate formation.In situ electrochemical attenuated total reflection(EC-ATR)and density functional theory(DFT)calculations revealed the appearance of *CHO intermediate and the pathway during the CO_(2)RR process.The design of the bimetallic electrocatalyst in this study provides a new perspective for the highly selective reduction of CO_(2).
基金Supported by the National Natural Science Foundation of China (No. 10676007) and NCETFJ
文摘First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surface. Calculations indicate that the C-O bond is weakened upon adsorption compared with that over perfect surface. In addition, with the density increase of the defective sites, the adsorption energies of the defect-CO configuration increase whereas the C-O bond nearly remains constant.
