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2019 Volume 35 Issue 11
2019, 35(11): 1165-1167
doi: 10.3866/PKU.WHXB201906028
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2019, 35(11): 1168-1169
doi: 10.3866/PKU.WHXB201902026
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2019, 35(11): 1170-1170
doi: 10.3866/PKU.WHXB201902027
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2019, 35(11): 1171-1172
doi: 10.3866/PKU.WHXB201903040
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2019, 35(11): 1173-1174
doi: 10.3866/PKU.WHXB201904063
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2019, 35(11): 1175-1176
doi: 10.3866/PKU.WHXB201902012
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2019, 35(11): 1177-1178
doi: 10.3866/PKU.WHXB201904088
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2019, 35(11): 1179-1182
doi: 10.3866/PKU.WHXB201906068
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2019, 35(11): 1183-1185
doi: 10.3866/PKU.WHXB201906062
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2019, 35(11): 1186-1206
doi: 10.3866/PKU.WHXB201902002
Abstract:
The sol-gel method, developed for over 150 years, is a conventional route for designing and preparing various kinds of metal oxide materials. In the sol-gel method, different chemical agents are homogenously mixed together in aqueous or organic solutions. During the evaporation of the solvents, the solution transforms to sol and gel through polycondensation or polyesterification reaction, and the dried gel is obtained after the complete evaporation of the solvent. Then, the dried precursor is often heat-treated in air at high temperature to induce the formation of oxide materials, especially the multi-component oxide materials that are difficult to prepare using other methods. Recently, new developments have been achieved in the sol-gel method. The application of the sol-gel method has been extended to the preparation of metallic nanomaterials, especially the alloy nanocrystals. For instance, the sol-gel method can be used to prepare CoPt and FePt hard magnetic alloy nanocrystals; CoCrCuNiAl high-entropy alloy nanocrystals; Ni3Fe and Cu3Pt alloy nanocrystals with equilibrium-ordered crystalline phases; and Ni, Cu, Bi, Sb, Te, Ag, Pt, and Pd monometallic nanocrystals. This article reviews the recent progresses in the sol-gel method for designing and preparing metallic and alloy nanocrystals, as well as the detailed experimental procedures and the different metallic nanocrystals that can be obtained by the sol-gel method. The crystalline phase formed in the final calcined products can be determined from the thermodynamic calculations of the sol-gel method. The thermodynamic model involves the calculation of the Gibbs free energy change of the reaction between the metallic oxide and reducing gases, such as hydrogen. A negative change and a positive change in the Gibbs free energy of the reaction correspond to the formation of metallic and alloy crystalline phases, or oxide crystalline phase, respectively. Based on the thermodynamic calculations and the relationship between the Gibbs free energy and standard electrodynamic potential of the chemical reaction, a new parameter, metal oxide standard electrode potential, was proposed. This electrode potential is different from the conventional standard metal electrode potential. A metallic crystalline phase is obtained if the electrode potential of the corresponding metal oxide is positive, while a metal oxide crystalline phase is obtained if the electrode potential of the metal oxide is negative. We also discuss the possible applications, including the magnetic and electrocatalytic applications, of the metallic and alloy nanocrystals that have been obtained by the sol-gel method. Finally, the future prospects of the application of the sol-gel method in designing metallic and alloy nanocrystals are discussed. ![]()
The sol-gel method, developed for over 150 years, is a conventional route for designing and preparing various kinds of metal oxide materials. In the sol-gel method, different chemical agents are homogenously mixed together in aqueous or organic solutions. During the evaporation of the solvents, the solution transforms to sol and gel through polycondensation or polyesterification reaction, and the dried gel is obtained after the complete evaporation of the solvent. Then, the dried precursor is often heat-treated in air at high temperature to induce the formation of oxide materials, especially the multi-component oxide materials that are difficult to prepare using other methods. Recently, new developments have been achieved in the sol-gel method. The application of the sol-gel method has been extended to the preparation of metallic nanomaterials, especially the alloy nanocrystals. For instance, the sol-gel method can be used to prepare CoPt and FePt hard magnetic alloy nanocrystals; CoCrCuNiAl high-entropy alloy nanocrystals; Ni3Fe and Cu3Pt alloy nanocrystals with equilibrium-ordered crystalline phases; and Ni, Cu, Bi, Sb, Te, Ag, Pt, and Pd monometallic nanocrystals. This article reviews the recent progresses in the sol-gel method for designing and preparing metallic and alloy nanocrystals, as well as the detailed experimental procedures and the different metallic nanocrystals that can be obtained by the sol-gel method. The crystalline phase formed in the final calcined products can be determined from the thermodynamic calculations of the sol-gel method. The thermodynamic model involves the calculation of the Gibbs free energy change of the reaction between the metallic oxide and reducing gases, such as hydrogen. A negative change and a positive change in the Gibbs free energy of the reaction correspond to the formation of metallic and alloy crystalline phases, or oxide crystalline phase, respectively. Based on the thermodynamic calculations and the relationship between the Gibbs free energy and standard electrodynamic potential of the chemical reaction, a new parameter, metal oxide standard electrode potential, was proposed. This electrode potential is different from the conventional standard metal electrode potential. A metallic crystalline phase is obtained if the electrode potential of the corresponding metal oxide is positive, while a metal oxide crystalline phase is obtained if the electrode potential of the metal oxide is negative. We also discuss the possible applications, including the magnetic and electrocatalytic applications, of the metallic and alloy nanocrystals that have been obtained by the sol-gel method. Finally, the future prospects of the application of the sol-gel method in designing metallic and alloy nanocrystals are discussed.
2019, 35(11): 1207-1223
doi: 10.3866/PKU.WHXB201811011
Abstract:
Flexible electronic devices have attracted immense attention in recent years. Conventional electronics that are predominantly fabricated with rigid metallic materials demonstrate poor flexibility. Compared to traditional electronic devices, flexible electronic devices with better flexibility can adapt to different working environments. Consequently, they fit perfectly with different systems with minimal rejections. However, such flexible electronic devices need to achieve good extensibility and flexibility without compromising on their electronic properties. Therefore, new challenges and requirements arise while fabricating conductive materials. Manufacturing of flexible metal electrodes for flexible electronic devices include strategies such as reducing the thickness of the electrodes and designing electrodes with unique structures. However, these technologies are complex and expensive. Carbon nanotube (CNT) films exhibit good flexibility, excellent conductivity, good chemical and thermal stability, as well as good optical transparency, making them ideal candidates for flexible electronics. Therefore, the preparation and application of CNT films for the development of next generation flexible electronics have been extensively studied. In this review, we summarize the recent advances in the preparation of CNT films and their application in flexible electronic devices. Initially, the two main kinds of preparation methods for CNT films—dry and wet methods—are introduced. The dry methods for CNT film preparation include the membrane extraction method based on a vertical array of CNTs and the floating catalytic chemical vapor deposition method. Moreover, the wet methods predominantly discussed include vacuum filtration method, impregnation method, electrodeposition method, self-assembly method, and spraying method. Subsequently, the latest research advancements in assembly techniques, their performance and applications in various flexible electronics are discussed. This review primarily introduces the application of CNT films in the fields of flexible sensors, flexible energy devices, flexible transistors, and flexible display screens. The fundamentals of typical flexible sensors, such as strain sensors, pressure sensors, gas sensors, temperature sensors, and humidity sensors are presented. Besides, flexible lithium-ion batteries, flexible nanogenerators, and flexible thermoelectric devices based on CNT films are also investigated. Moreover, other flexible electronic devices, such as flexible transparent conductive film, flexible transistor, and flexible photodetector, based on CNT films are briefly described. Finally, advanced flexible electronics based on CNT films are summarized. The challenges and future prospects of these films are also discussed. ![]()
Flexible electronic devices have attracted immense attention in recent years. Conventional electronics that are predominantly fabricated with rigid metallic materials demonstrate poor flexibility. Compared to traditional electronic devices, flexible electronic devices with better flexibility can adapt to different working environments. Consequently, they fit perfectly with different systems with minimal rejections. However, such flexible electronic devices need to achieve good extensibility and flexibility without compromising on their electronic properties. Therefore, new challenges and requirements arise while fabricating conductive materials. Manufacturing of flexible metal electrodes for flexible electronic devices include strategies such as reducing the thickness of the electrodes and designing electrodes with unique structures. However, these technologies are complex and expensive. Carbon nanotube (CNT) films exhibit good flexibility, excellent conductivity, good chemical and thermal stability, as well as good optical transparency, making them ideal candidates for flexible electronics. Therefore, the preparation and application of CNT films for the development of next generation flexible electronics have been extensively studied. In this review, we summarize the recent advances in the preparation of CNT films and their application in flexible electronic devices. Initially, the two main kinds of preparation methods for CNT films—dry and wet methods—are introduced. The dry methods for CNT film preparation include the membrane extraction method based on a vertical array of CNTs and the floating catalytic chemical vapor deposition method. Moreover, the wet methods predominantly discussed include vacuum filtration method, impregnation method, electrodeposition method, self-assembly method, and spraying method. Subsequently, the latest research advancements in assembly techniques, their performance and applications in various flexible electronics are discussed. This review primarily introduces the application of CNT films in the fields of flexible sensors, flexible energy devices, flexible transistors, and flexible display screens. The fundamentals of typical flexible sensors, such as strain sensors, pressure sensors, gas sensors, temperature sensors, and humidity sensors are presented. Besides, flexible lithium-ion batteries, flexible nanogenerators, and flexible thermoelectric devices based on CNT films are also investigated. Moreover, other flexible electronic devices, such as flexible transparent conductive film, flexible transistor, and flexible photodetector, based on CNT films are briefly described. Finally, advanced flexible electronics based on CNT films are summarized. The challenges and future prospects of these films are also discussed.
2019, 35(11): 1224-1231
doi: 10.3866/PKU.WHXB201901072
Abstract:
Functionalized ionic liquids containing ether groups can be obtained through reasonable design. The unique properties of ether-based functionalized ionic liquids are attractive for a variety of practical applications. To further develop these ether-based functionalized ionic liquids, it is important to accurately describe the thermophysical properties of ether-based functionalized ionic liquids and to predict, simulate, and optimize theoretical models of thermophysical properties. Herein, the ether-functionalized ionic liquids [MOEMIm]Cl and [EOEMIm]Cl were characterized by nuclear magnetic resonance spectroscopy, elemental analysis, and thermogravimetric analysis. The density (ρ), surface tension (γ), and refractive index (nD) of [MOEMIm]Cl and [EOEMIm]Cl were measured at 5 K intervals between 288.15 and 328.15 K. Based on the obtained experimental data, the molar volume (V), molecular volume (Vm), standard entropy (S(298)0), and lattice energy (UPOT) of [MOEMIm]Cl and [EOEMIm]Cl were calculated and the data obtained at 298.15 K were compared. The comparison results agreed well with the literature values within the experimental error range and indicated that both [MOEMIm]Cl and [EOEMIm]Cl exhibit small lattice energies and are in the molten state at room temperature (T = 298.15 K). Based on these experimental data, the molar surface Gibbs free energy (gs), molar surface entropy (s), molar surface enthalpy (h), molar polarization (Rm), and molar polarizability (αp) of [MOEMIm]Cl and [EOEMIm]Cl were also calculated. The calculation results show that the molar surface enthalpy (h) is approximately constant, that is, the molar surface constant pressure heat capacity is close to zero, indicating that the process of heat capacity change from the inside to the surface of the ionic liquid is an equivalent coulomb process. Simultaneously, the calculation results showed that the molar polarization (Rm) and molar polarizability (αp) of the ionic liquids were independent of temperature, indicating that Rm and αp reflect the induced dipole effect of the ionic liquid. The molar surface Gibbs free energy definition equation was combined with the Lorentz-Lorenz equation to obtain a novel modified Lorentz-Lorenz equation and was used to predict the surface tension of the [MOEMIm]Cl and [EOEMIm]Cl liquids. The values predicted using this combined equation were highly correlated with the experimental values. ![]()
Functionalized ionic liquids containing ether groups can be obtained through reasonable design. The unique properties of ether-based functionalized ionic liquids are attractive for a variety of practical applications. To further develop these ether-based functionalized ionic liquids, it is important to accurately describe the thermophysical properties of ether-based functionalized ionic liquids and to predict, simulate, and optimize theoretical models of thermophysical properties. Herein, the ether-functionalized ionic liquids [MOEMIm]Cl and [EOEMIm]Cl were characterized by nuclear magnetic resonance spectroscopy, elemental analysis, and thermogravimetric analysis. The density (ρ), surface tension (γ), and refractive index (nD) of [MOEMIm]Cl and [EOEMIm]Cl were measured at 5 K intervals between 288.15 and 328.15 K. Based on the obtained experimental data, the molar volume (V), molecular volume (Vm), standard entropy (S(298)0), and lattice energy (UPOT) of [MOEMIm]Cl and [EOEMIm]Cl were calculated and the data obtained at 298.15 K were compared. The comparison results agreed well with the literature values within the experimental error range and indicated that both [MOEMIm]Cl and [EOEMIm]Cl exhibit small lattice energies and are in the molten state at room temperature (T = 298.15 K). Based on these experimental data, the molar surface Gibbs free energy (gs), molar surface entropy (s), molar surface enthalpy (h), molar polarization (Rm), and molar polarizability (αp) of [MOEMIm]Cl and [EOEMIm]Cl were also calculated. The calculation results show that the molar surface enthalpy (h) is approximately constant, that is, the molar surface constant pressure heat capacity is close to zero, indicating that the process of heat capacity change from the inside to the surface of the ionic liquid is an equivalent coulomb process. Simultaneously, the calculation results showed that the molar polarization (Rm) and molar polarizability (αp) of the ionic liquids were independent of temperature, indicating that Rm and αp reflect the induced dipole effect of the ionic liquid. The molar surface Gibbs free energy definition equation was combined with the Lorentz-Lorenz equation to obtain a novel modified Lorentz-Lorenz equation and was used to predict the surface tension of the [MOEMIm]Cl and [EOEMIm]Cl liquids. The values predicted using this combined equation were highly correlated with the experimental values.
2019, 35(11): 1232-1240
doi: 10.3866/PKU.WHXB201901025
Abstract:
TiO2 is a semiconductor material with excellent photoelectrochemical properties that can provide photocathodic protection for metals. However, TiO2 can only absorb ultraviolet (UV) light at wavelengths of < 380 nm because of its wide band gap. In addition, photo-induced electron-hole pairs in the TiO2 semiconductor easily recombine, which leads to a low photoelectric conversion efficiency. Another shortcoming is that pure TiO2 semiconductors cannot sustain photocathodic protection in the dark, which may limit their practical applications to provide photocathodic protection. To address these shortcomings, various modification methods have been established by preparing TiO2 composite materials to improve their photoelectrochemical properties. In this study, a ZnSe- and MoO3-modified TiO2 nanotube composite film with charge storage ability was prepared to enhance its photocathodic protection effect on stainless steel. A TiO2 nanotube array film was prepared on a Ti foil via anodic oxidation and then MoO3 and ZnSe particles were deposited onto the film by cyclic voltammetry and pulse electrodeposition, respectively, to afford a ZnSe/MoO3/TiO2 nanotube composite film having a cascade band structure. Scanning electron microscopy observations showed that the TiO2 film consisted of ordered nanotubes with an average inner diameter of approximately 100 nm and wall thickness of approximately 15 nm. This nanotube structure remained intact after MoO3 and ZnSe particle deposition on the film. Energy dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses indicated that the prepared nanotube composite film was composed of ZnSe, MoO3, and TiO2. The UV-Vis absorption and photoluminescence spectra showed that the photoresponse of the composite film was extended to the visible light region and the photo-induced electron-hole pair recombination was reduced. Photoelectrochemical and electrochemical measurements indicated that the photocurrent intensity of the composite film in a 0.5 mol·L−1 KOH solution was two-fold higher than that of the pure TiO2 film. Under white light illumination, the ZnSe/MoO3/TiO2 composite film decreased the potential of the coupled 403 stainless steel (403SS) in a 0.5 mol·L−1 NaCl solution by 470 mV (relative to the corrosion potential), demonstrating an effective photocathodic protection effect. It should be noted that the composite film exhibited a charge storage capability and could continuously provide cathodic protection for 22.5 h after illumination was stopped. In addition, electrochemical impedance spectroscopy results indicated that the composite film significantly decreased the charge transfer resistance of the coupled 403SS, highlighting the photocathodic protection effect on 430SS. ![]()
TiO2 is a semiconductor material with excellent photoelectrochemical properties that can provide photocathodic protection for metals. However, TiO2 can only absorb ultraviolet (UV) light at wavelengths of < 380 nm because of its wide band gap. In addition, photo-induced electron-hole pairs in the TiO2 semiconductor easily recombine, which leads to a low photoelectric conversion efficiency. Another shortcoming is that pure TiO2 semiconductors cannot sustain photocathodic protection in the dark, which may limit their practical applications to provide photocathodic protection. To address these shortcomings, various modification methods have been established by preparing TiO2 composite materials to improve their photoelectrochemical properties. In this study, a ZnSe- and MoO3-modified TiO2 nanotube composite film with charge storage ability was prepared to enhance its photocathodic protection effect on stainless steel. A TiO2 nanotube array film was prepared on a Ti foil via anodic oxidation and then MoO3 and ZnSe particles were deposited onto the film by cyclic voltammetry and pulse electrodeposition, respectively, to afford a ZnSe/MoO3/TiO2 nanotube composite film having a cascade band structure. Scanning electron microscopy observations showed that the TiO2 film consisted of ordered nanotubes with an average inner diameter of approximately 100 nm and wall thickness of approximately 15 nm. This nanotube structure remained intact after MoO3 and ZnSe particle deposition on the film. Energy dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses indicated that the prepared nanotube composite film was composed of ZnSe, MoO3, and TiO2. The UV-Vis absorption and photoluminescence spectra showed that the photoresponse of the composite film was extended to the visible light region and the photo-induced electron-hole pair recombination was reduced. Photoelectrochemical and electrochemical measurements indicated that the photocurrent intensity of the composite film in a 0.5 mol·L−1 KOH solution was two-fold higher than that of the pure TiO2 film. Under white light illumination, the ZnSe/MoO3/TiO2 composite film decreased the potential of the coupled 403 stainless steel (403SS) in a 0.5 mol·L−1 NaCl solution by 470 mV (relative to the corrosion potential), demonstrating an effective photocathodic protection effect. It should be noted that the composite film exhibited a charge storage capability and could continuously provide cathodic protection for 22.5 h after illumination was stopped. In addition, electrochemical impedance spectroscopy results indicated that the composite film significantly decreased the charge transfer resistance of the coupled 403SS, highlighting the photocathodic protection effect on 430SS.
2019, 35(11): 1241-1247
doi: 10.3866/PKU.WHXB201812031
Abstract:
In order to meet high-performance propulsion system requirements for aerospace technology and severe future restrictions on hydrazine use, research on non-toxic, high-performance, and low-cost propulsion technology is urgently needed. The N2O-C2 hydrocarbon monopropellant NOFBX (Nitrous Oxide Fuel Blend) provides significant benefits for meeting these criteria and has become a focus of increased research in recent years. In this study, a chemical kinetic model for NOFBX combustion that integrates the reduced C2 sub-mechanism, the N2O sub-mechanism in the literature, and the N2O/CH species reaction mechanism has been developed. The present mechanism consists of 52 species and 325 elementary reactions. For better predictions of ignition and combustion characteristics, the kinetic parameters of the sensitive reactions with comparatively high rate constant uncertainties have been revised. The present model has been validated against published experimental data, including flow reactor results on N2O/H2O/N2 mixture decomposition, shock tube ignition delay times on N2O/C2 hydrocarbons diluted with N2 or Ar mixtures, heat flux of flat flame laminar flame speeds on N2O/C2H2 diluted with N2 mixtures, and Bunsen flame laminar flame speeds on N2O/C2H4 diluted with N2 mixtures. Additionally, this study compares the new model to other published small hydrocarbon fuel kinetic models with a NOx sub-mechanism. The experimental validations show that the present model accurately captures the nitrous oxide decomposition process and precisely predicts N2O, O2, NO, and NO2 vital species concentration distributions. For all N2O-C2 hydrocarbon fuel systems (ethane-, ethylene-, and acetylene-nitrous oxide), the ignition delay times predicted by the present model are in good agreement with the experimental data. Furthermore, at a wider range of initial temperatures (1100-1700 K), initial pressures (0.1-1.6 MPa), and equivalence ratios (0.5-2.0) for the ignition delay times of ethylene-nitrous oxide, the present model exhibits improved predictions of experimental data. For the laminar flame speeds of N2O-C2H2 and N2O-C2H4 mixtures, the present model generally exhibits satisfactory predictions of the experimental data over the whole range of equivalence ratios (0.6-2.0). However, at initial pressure 0.1 MPa and equivalence ratios of 1.0-1.6 for N2O-C2H4 laminar flame speeds, the present model slightly underestimates experimental data. Considering the much higher uncertainty of the measured laminar flame speeds by the Bunsen flame method, this discrepancy is acceptable. Due to the small scale, full experimental validations and good applicability, the present model can be used to further research on multi-dimensional combustion simulation in NOFBX engine combustors. ![]()
In order to meet high-performance propulsion system requirements for aerospace technology and severe future restrictions on hydrazine use, research on non-toxic, high-performance, and low-cost propulsion technology is urgently needed. The N2O-C2 hydrocarbon monopropellant NOFBX (Nitrous Oxide Fuel Blend) provides significant benefits for meeting these criteria and has become a focus of increased research in recent years. In this study, a chemical kinetic model for NOFBX combustion that integrates the reduced C2 sub-mechanism, the N2O sub-mechanism in the literature, and the N2O/CH species reaction mechanism has been developed. The present mechanism consists of 52 species and 325 elementary reactions. For better predictions of ignition and combustion characteristics, the kinetic parameters of the sensitive reactions with comparatively high rate constant uncertainties have been revised. The present model has been validated against published experimental data, including flow reactor results on N2O/H2O/N2 mixture decomposition, shock tube ignition delay times on N2O/C2 hydrocarbons diluted with N2 or Ar mixtures, heat flux of flat flame laminar flame speeds on N2O/C2H2 diluted with N2 mixtures, and Bunsen flame laminar flame speeds on N2O/C2H4 diluted with N2 mixtures. Additionally, this study compares the new model to other published small hydrocarbon fuel kinetic models with a NOx sub-mechanism. The experimental validations show that the present model accurately captures the nitrous oxide decomposition process and precisely predicts N2O, O2, NO, and NO2 vital species concentration distributions. For all N2O-C2 hydrocarbon fuel systems (ethane-, ethylene-, and acetylene-nitrous oxide), the ignition delay times predicted by the present model are in good agreement with the experimental data. Furthermore, at a wider range of initial temperatures (1100-1700 K), initial pressures (0.1-1.6 MPa), and equivalence ratios (0.5-2.0) for the ignition delay times of ethylene-nitrous oxide, the present model exhibits improved predictions of experimental data. For the laminar flame speeds of N2O-C2H2 and N2O-C2H4 mixtures, the present model generally exhibits satisfactory predictions of the experimental data over the whole range of equivalence ratios (0.6-2.0). However, at initial pressure 0.1 MPa and equivalence ratios of 1.0-1.6 for N2O-C2H4 laminar flame speeds, the present model slightly underestimates experimental data. Considering the much higher uncertainty of the measured laminar flame speeds by the Bunsen flame method, this discrepancy is acceptable. Due to the small scale, full experimental validations and good applicability, the present model can be used to further research on multi-dimensional combustion simulation in NOFBX engine combustors.
2019, 35(11): 1248-1258
doi: 10.3866/PKU.WHXB201901062
Abstract:
Propylene is widely used as a raw material for producing polypropylene, acrylonitrile, propylene oxide, etc. Typical manufacturing processes for propylene (steam cracking and FCC process) are over-reliant on petroleum resources and cannot meet the rapidly growing global demands. New routes for producing propylene from non-oil resources, particularly methanol-to-propylene (MTP) technology, have attracted increasingly more attention, where a fixed-bed reactor is used and ZSM-5 zeolite is the best alternative catalyst. However, structural optimization of ZSM-5 to enhance the lifetime and propylene selectivity and a deep understanding of the mechanism of the MTP reaction are still considerable challenges. For the conventional ZSM-5 zeolite, carbon deposition preferentially occurs near the outer surface of the zeolite particles because of the high acid density on the external surface, which accelerates the deactivation by blocking the outer pore openings, especially in a long-term MTP reaction. Large amounts of external strong acids also promote secondary reactions, such as hydrogen transfer reactions, resulting in a decrease in propylene selectivity. To study the effects of strong and weak acid distributions of ZSM-5 zeolite on the MTP reaction, two series of boron-modified ZSM-5 zeolites were designed: B-Al-ZSM-5 zeolites by one-step synthesis and Al-ZSM-5@B-ZSM-5 core-shell zeolites by two-step synthesis. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) mapping, N2 physical adsorption-desorption, temperature-programmed desorption of ammonia (NH3-TPD) and 1, 3, 5-triisopropylbenzene (TIPB) cracking, and B1-Al-ZSM-5 and Al@B1-ZSM-5, B2-Al-ZSM-5 and Al@B2-ZSM-5, and B3-Al-ZSM-5 and Al@B3-ZSM-5 samples in the two series were found to have similar texture properties, acid amounts and acid strengths, but different B and Al elemental distributions and acid distributions. We used these two sets of samples to compare the effect of different strong and weak acid distributions—a uniform distribution and a gradient distribution of strong and weak acids on the performance of the MTP reaction. The results showed that samples with a uniform distribution of strong and weak acids have higher propylene selectivity due to lower strong and weak acid densities, whereas samples with a gradient acid distribution have a longer catalytic lifetime in the MTP reaction due to the absence of strong acid density and higher weak acid density on the outer surface. The different acid distributions lead to two different carbon deposition modes. Carbon deposition of the sample with the uniform acid distribution preferentially formed on the outer surface, resulting in rapid deactivation by blocking external micropores and leaving the internal active centers not fully utilized. However, for the sample with the gradient acid distribution, the carbon-blocking rate of the external surface considerably decreased, which increased the time that the reactant molecules had to enter the internal micropores. Thus, the utilization rate of the active centers and the catalytic lifetime of the Al-ZSM-5@B-ZSM-5 core-shell sample considerably increased. ![]()
Propylene is widely used as a raw material for producing polypropylene, acrylonitrile, propylene oxide, etc. Typical manufacturing processes for propylene (steam cracking and FCC process) are over-reliant on petroleum resources and cannot meet the rapidly growing global demands. New routes for producing propylene from non-oil resources, particularly methanol-to-propylene (MTP) technology, have attracted increasingly more attention, where a fixed-bed reactor is used and ZSM-5 zeolite is the best alternative catalyst. However, structural optimization of ZSM-5 to enhance the lifetime and propylene selectivity and a deep understanding of the mechanism of the MTP reaction are still considerable challenges. For the conventional ZSM-5 zeolite, carbon deposition preferentially occurs near the outer surface of the zeolite particles because of the high acid density on the external surface, which accelerates the deactivation by blocking the outer pore openings, especially in a long-term MTP reaction. Large amounts of external strong acids also promote secondary reactions, such as hydrogen transfer reactions, resulting in a decrease in propylene selectivity. To study the effects of strong and weak acid distributions of ZSM-5 zeolite on the MTP reaction, two series of boron-modified ZSM-5 zeolites were designed: B-Al-ZSM-5 zeolites by one-step synthesis and Al-ZSM-5@B-ZSM-5 core-shell zeolites by two-step synthesis. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) mapping, N2 physical adsorption-desorption, temperature-programmed desorption of ammonia (NH3-TPD) and 1, 3, 5-triisopropylbenzene (TIPB) cracking, and B1-Al-ZSM-5 and Al@B1-ZSM-5, B2-Al-ZSM-5 and Al@B2-ZSM-5, and B3-Al-ZSM-5 and Al@B3-ZSM-5 samples in the two series were found to have similar texture properties, acid amounts and acid strengths, but different B and Al elemental distributions and acid distributions. We used these two sets of samples to compare the effect of different strong and weak acid distributions—a uniform distribution and a gradient distribution of strong and weak acids on the performance of the MTP reaction. The results showed that samples with a uniform distribution of strong and weak acids have higher propylene selectivity due to lower strong and weak acid densities, whereas samples with a gradient acid distribution have a longer catalytic lifetime in the MTP reaction due to the absence of strong acid density and higher weak acid density on the outer surface. The different acid distributions lead to two different carbon deposition modes. Carbon deposition of the sample with the uniform acid distribution preferentially formed on the outer surface, resulting in rapid deactivation by blocking external micropores and leaving the internal active centers not fully utilized. However, for the sample with the gradient acid distribution, the carbon-blocking rate of the external surface considerably decreased, which increased the time that the reactant molecules had to enter the internal micropores. Thus, the utilization rate of the active centers and the catalytic lifetime of the Al-ZSM-5@B-ZSM-5 core-shell sample considerably increased.
2019, 35(11): 1259-1266
doi: 10.3866/PKU.WHXB201901056
Abstract:
Organic field effect transistors (OFETs) have great potential in flexible sensor and display driver applications. However, there are immense challenges in the development of large-area and high-quality thin-film fabrications. In this article, we introduce a method to fabricate patterned organic semiconductor films by oxygen plasma treatment and the synergy of Marangoni and coffee-ring effects. The procedure is as follows: First, we spin-coated the cyclic transparent amorphous fluoropolymers (CYTOP) on the substrate in the form of a hydrophobic layer. Then, parts of the substrate surface were treated with plasma and modified to make them hydrophilic. By comparing the water contact angle on the plasma treated surface with that on the untreated surface, we optimized the treating time to get a relatively uniform water contact angle on a different region of the substrate surface. The plasma treated substrate was dipped into 2, 7-dioctyl[1]benzothieno[3, 2-b][1]benzothiophene (C8-BTBT) solution with methylbenzene and carbon tetrachloride as a mixed solvent, and then lifted from it. So the mixed solution flowed down rapidly on the hydrophobic portion of the surface, leaving droplet on the hydrophilic portion. Subsequently, the droplet started evaporating under the synergy of Marangoni and coffee-ring effects. Based on the difference between the hydrophilic and hydrophobic portions on the substrate surface, we successfully obtained the patterned C8-BTBT thin films on the substrate. Furthermore, the solvent ratio was optimized while growing the C8-BTBT film to adjust the boiling point of the solution, which was due to a fully covered surface was obtained. From the grazing-incidence X-ray diffraction (GIXRD) measurement of the films with three different concentrations, we observed that increasing in the concentration of the solution yielded different molecular orientations. Based on the three films, OFETs with bottom gate and top contact structure were fabricated. Moreover, the mobility and the on/off current ratio became more uniform with the progressive increase in the concentration of the solution. This may be attributed to the increase in the number of different molecular orientations and charge transfer channels. Although the increase in the number of different molecular orientations might lead to the decrease in mobility, it could improve the alignment of the electric field and also increase π–π stacking direction of the molecules, which promote highly uniform device performance distribution. Since uniform distribution of device performance is significant for practical applications, we believe the transistors that are fabricated at the highest concentration are better than those generated at lower concentrations. Thus, on the 5 cm × 5 cm substrate, it is observed that the average mobility of the transistors is 7.9 cm2·V-1·s-1, and all the devices have threshold voltages less than -2 V with the on/off current ratio of 104. This work is significant for the fabrication of large-area and high-performance thin films and transistors. ![]()
Organic field effect transistors (OFETs) have great potential in flexible sensor and display driver applications. However, there are immense challenges in the development of large-area and high-quality thin-film fabrications. In this article, we introduce a method to fabricate patterned organic semiconductor films by oxygen plasma treatment and the synergy of Marangoni and coffee-ring effects. The procedure is as follows: First, we spin-coated the cyclic transparent amorphous fluoropolymers (CYTOP) on the substrate in the form of a hydrophobic layer. Then, parts of the substrate surface were treated with plasma and modified to make them hydrophilic. By comparing the water contact angle on the plasma treated surface with that on the untreated surface, we optimized the treating time to get a relatively uniform water contact angle on a different region of the substrate surface. The plasma treated substrate was dipped into 2, 7-dioctyl[1]benzothieno[3, 2-b][1]benzothiophene (C8-BTBT) solution with methylbenzene and carbon tetrachloride as a mixed solvent, and then lifted from it. So the mixed solution flowed down rapidly on the hydrophobic portion of the surface, leaving droplet on the hydrophilic portion. Subsequently, the droplet started evaporating under the synergy of Marangoni and coffee-ring effects. Based on the difference between the hydrophilic and hydrophobic portions on the substrate surface, we successfully obtained the patterned C8-BTBT thin films on the substrate. Furthermore, the solvent ratio was optimized while growing the C8-BTBT film to adjust the boiling point of the solution, which was due to a fully covered surface was obtained. From the grazing-incidence X-ray diffraction (GIXRD) measurement of the films with three different concentrations, we observed that increasing in the concentration of the solution yielded different molecular orientations. Based on the three films, OFETs with bottom gate and top contact structure were fabricated. Moreover, the mobility and the on/off current ratio became more uniform with the progressive increase in the concentration of the solution. This may be attributed to the increase in the number of different molecular orientations and charge transfer channels. Although the increase in the number of different molecular orientations might lead to the decrease in mobility, it could improve the alignment of the electric field and also increase π–π stacking direction of the molecules, which promote highly uniform device performance distribution. Since uniform distribution of device performance is significant for practical applications, we believe the transistors that are fabricated at the highest concentration are better than those generated at lower concentrations. Thus, on the 5 cm × 5 cm substrate, it is observed that the average mobility of the transistors is 7.9 cm2·V-1·s-1, and all the devices have threshold voltages less than -2 V with the on/off current ratio of 104. This work is significant for the fabrication of large-area and high-performance thin films and transistors.
2019, 35(11): 1267-1275
doi: 10.3866/PKU.WHXB201812053
Abstract:
As a new fluorescent nanomaterial, carbon dots (CDs) have many advantages, such as uniform particle size distribution, good light stability, adjustable excitation-emission wavelength, and surface modification. Moreover, one of the fascinating characters of CDs is that they are considered to be low-toxic and eco-friendly alternatives in chemical and biological analyses. They have exhibited broad application prospects in the fields of analysis, detection, and bioimaging. Silkworm excrement is dried and easily available. A large number of hydroxyl and carboxyl compounds in silkworm excrement can be used as ideal starting materials for the preparation of CDs. Also, compounds containing nitrogen and sulfur in silkworm excrement can be used as nitrogen and sulfur sources; thus, when used in the preparation of CDs, silkworm excrement can impart many more unique properties to CDs. Nitrogen-containing CDs prepared by microwave synthesis have an average hydration diameter of 4.86 nm. Elemental analysis data show that the prepared CDs contained 59.84% carbon, 5.46% nitrogen, and 2.32% sulfur. XPS spectra reveals sulfur (2p), carbon (1s), nitrogen (1s), and oxygen (1s) in CDs. FTIR data demonstrate that the prepared CDs may contain hydroxyl, amino, carbonyl, sulfonic, ester, and ether functional groups as well as carbon-nitrogen structures. The XRD pattern of the CDs has a broader peak of the amorphous carbon phase at approximately 2θ = 24.6°, and only D bands (at ~1400 cm-1) can be obviously detected in the Raman spectra of CDs. The intensity of fluorescence emission peak of CDs increases first and then decreases with the increase in excitation wavelength. The maximum intensity of fluorescence emission shifts gradually with the red shift of the excitation wavelength, and the relationship between excitation and emission wavelengths is exponential. In the pH ranging from 2.18 to 10.24, the fluorescence emission intensity of CDs decreases gradually with the increase in pH, and the maximum fluorescence emission intensity shifts gradually with the increase in pH. There is a linear relationship between pH and maximum emission wavelength. The fluorescence emission intensity of CDs decreases gradually with the increase in metal ion concentration. Under neutral conditions, CDs can selectively detect Cu2+. Under acidic conditions, CDs can detect Cu2+, Fe3+, Al3+, Ni2+, and Fe2+ separately without interference from other ions. There is a Stern-Volmer linear relationship between metal ion concentration and fluorescence intensity. The intensity of the fluorescence emission peak of CDs decreases with the increase in temperature, which may be due to the non-radiative transition process caused by molecular thermal motion. There is a linear relationship between temperature and fluorescence intensity. The maximum fluorescence emission intensity of CDs gradually shifts with the increase in polarity of the dispersed solvents. There is a linear relationship between fluorescence intensity and empirical constant ET of solvent polarity. Compared with the reported CDs prepared from natural products, silkworm-excrement-based CDs have abundant surface groups although they do not have an obvious crystal structure, which makes them have excellent response to various environmental factors (pH, temperature, ion concentration, temperature, solvent polarity, etc.) in a wide range. Above all, the fluorescence property changes with multiple environmental parameters will facilitate a broad application of silkworm-excrement-based CDs in biodetection and imaging. ![]()
As a new fluorescent nanomaterial, carbon dots (CDs) have many advantages, such as uniform particle size distribution, good light stability, adjustable excitation-emission wavelength, and surface modification. Moreover, one of the fascinating characters of CDs is that they are considered to be low-toxic and eco-friendly alternatives in chemical and biological analyses. They have exhibited broad application prospects in the fields of analysis, detection, and bioimaging. Silkworm excrement is dried and easily available. A large number of hydroxyl and carboxyl compounds in silkworm excrement can be used as ideal starting materials for the preparation of CDs. Also, compounds containing nitrogen and sulfur in silkworm excrement can be used as nitrogen and sulfur sources; thus, when used in the preparation of CDs, silkworm excrement can impart many more unique properties to CDs. Nitrogen-containing CDs prepared by microwave synthesis have an average hydration diameter of 4.86 nm. Elemental analysis data show that the prepared CDs contained 59.84% carbon, 5.46% nitrogen, and 2.32% sulfur. XPS spectra reveals sulfur (2p), carbon (1s), nitrogen (1s), and oxygen (1s) in CDs. FTIR data demonstrate that the prepared CDs may contain hydroxyl, amino, carbonyl, sulfonic, ester, and ether functional groups as well as carbon-nitrogen structures. The XRD pattern of the CDs has a broader peak of the amorphous carbon phase at approximately 2θ = 24.6°, and only D bands (at ~1400 cm-1) can be obviously detected in the Raman spectra of CDs. The intensity of fluorescence emission peak of CDs increases first and then decreases with the increase in excitation wavelength. The maximum intensity of fluorescence emission shifts gradually with the red shift of the excitation wavelength, and the relationship between excitation and emission wavelengths is exponential. In the pH ranging from 2.18 to 10.24, the fluorescence emission intensity of CDs decreases gradually with the increase in pH, and the maximum fluorescence emission intensity shifts gradually with the increase in pH. There is a linear relationship between pH and maximum emission wavelength. The fluorescence emission intensity of CDs decreases gradually with the increase in metal ion concentration. Under neutral conditions, CDs can selectively detect Cu2+. Under acidic conditions, CDs can detect Cu2+, Fe3+, Al3+, Ni2+, and Fe2+ separately without interference from other ions. There is a Stern-Volmer linear relationship between metal ion concentration and fluorescence intensity. The intensity of the fluorescence emission peak of CDs decreases with the increase in temperature, which may be due to the non-radiative transition process caused by molecular thermal motion. There is a linear relationship between temperature and fluorescence intensity. The maximum fluorescence emission intensity of CDs gradually shifts with the increase in polarity of the dispersed solvents. There is a linear relationship between fluorescence intensity and empirical constant ET of solvent polarity. Compared with the reported CDs prepared from natural products, silkworm-excrement-based CDs have abundant surface groups although they do not have an obvious crystal structure, which makes them have excellent response to various environmental factors (pH, temperature, ion concentration, temperature, solvent polarity, etc.) in a wide range. Above all, the fluorescence property changes with multiple environmental parameters will facilitate a broad application of silkworm-excrement-based CDs in biodetection and imaging.
2019, 35(11): 1276-1281
doi: 10.3866/PKU.WHXB201902014
Abstract:
The excited states of transition metal complexes with a wide range of photochemical and photophysical properties have attracted considerable attention recently. However, the luminescence property is affected by concentration quenching in practical applications. Aggregation-induced emission (AIE) is an effective strategy to solve this problem. In this work, a new imidazole-based N^C^N Pt(Ⅱ) metal complex, PtP2IM, with the AIE property was synthesized and characterized according to its single crystal structure. Under visible light, we found that the metal complex undergoes a photo-oxidation reaction with the generation of a new red-emitting, imidazole/benzoylimino-based N^C^N' Pt(Ⅱ) metal complex, PtPIMO, which was also confirmed by the crystal structure. Additional studies on the reaction process and conditions of this photo-oxidation reaction were conducted using different methods, such as NMR, UV-Vis spectroscopy, and so on. The experimental results showed that the change from PtP2IM to PtPIMO gradually occurred, and the new photochemical reaction was finally concluded as the C＝C double bond in either one of the two imidazole rings of the PtP2IM complex was attacked by oxygen to generate a new complex, PtPIMO, under photoirradiation in air. Electron paramagnetic resonance (EPR) measurements demonstrated the production of singlet oxygen, which is an excited state of oxygen with a high energy. Through the density functional theory (DFT) calculations, the electronic transition was determined to be a metal to ligand charge transfer (MLCT) in which more energy could transfer from the triplet excited state of PtP2IM to the ground-state oxygen to generate singlet oxygen (1O2) with a high intersystem crossing (ISC) efficiency due to the spin-orbit coupling of Pt heavy atoms. When large amounts of the singlet capture agent, triethylenediamine (TEDA) were added, the previously observed UV-Vis spectra change that corresponded to the photo oxidation reaction was not detected, which means that the photo-oxidation reaction observed in the case of PtP2IM was because of the oxidation by singlet oxygen. When oxygen was removed, excellent photostability and an obvious aggregation-induced emission (AIE) were observed for PtP2IM with the luminescent quantum efficiency of PtP2IM in solution and as a film at ~3% and ~20%, respectively. Based on the packing structure in the crystal, we observed that there were no strong intermolecular interactions, such as π-π or Pt-Pt interactions. Additionally, many intermolecular CH―π bonds between the two adjacent PtP2IM molecules were observed, which could effectively limit the rotation of the peripheral phenyl group linked to the imidazole ring. Thus, the AIE property of PtP2IM was attributed to the restricted intramolecular rotation (RIR) effect of the peripheral flexible phenyl group that was linked to the imidazole ring in the solid state in which the vibration of multiple peripheral benzene rings was effectively suppressed. This decreased the non-radiative transition rate and induced the high luminescent quantum efficiency. In the aggregation state, PtP2IM still demonstrated the photo-oxidation reaction by singlet oxygen. Thus, we report a new Pt(Ⅱ) metal complex, PtP2IM, with the AIE property that can undergo an uncommon photo-oxidation reaction in the photo-excitation state. This work aimed to elucidate the basic photochemical and photophysics of transition metal complexes with the AIE property. ![]()
The excited states of transition metal complexes with a wide range of photochemical and photophysical properties have attracted considerable attention recently. However, the luminescence property is affected by concentration quenching in practical applications. Aggregation-induced emission (AIE) is an effective strategy to solve this problem. In this work, a new imidazole-based N^C^N Pt(Ⅱ) metal complex, PtP2IM, with the AIE property was synthesized and characterized according to its single crystal structure. Under visible light, we found that the metal complex undergoes a photo-oxidation reaction with the generation of a new red-emitting, imidazole/benzoylimino-based N^C^N' Pt(Ⅱ) metal complex, PtPIMO, which was also confirmed by the crystal structure. Additional studies on the reaction process and conditions of this photo-oxidation reaction were conducted using different methods, such as NMR, UV-Vis spectroscopy, and so on. The experimental results showed that the change from PtP2IM to PtPIMO gradually occurred, and the new photochemical reaction was finally concluded as the C＝C double bond in either one of the two imidazole rings of the PtP2IM complex was attacked by oxygen to generate a new complex, PtPIMO, under photoirradiation in air. Electron paramagnetic resonance (EPR) measurements demonstrated the production of singlet oxygen, which is an excited state of oxygen with a high energy. Through the density functional theory (DFT) calculations, the electronic transition was determined to be a metal to ligand charge transfer (MLCT) in which more energy could transfer from the triplet excited state of PtP2IM to the ground-state oxygen to generate singlet oxygen (1O2) with a high intersystem crossing (ISC) efficiency due to the spin-orbit coupling of Pt heavy atoms. When large amounts of the singlet capture agent, triethylenediamine (TEDA) were added, the previously observed UV-Vis spectra change that corresponded to the photo oxidation reaction was not detected, which means that the photo-oxidation reaction observed in the case of PtP2IM was because of the oxidation by singlet oxygen. When oxygen was removed, excellent photostability and an obvious aggregation-induced emission (AIE) were observed for PtP2IM with the luminescent quantum efficiency of PtP2IM in solution and as a film at ~3% and ~20%, respectively. Based on the packing structure in the crystal, we observed that there were no strong intermolecular interactions, such as π-π or Pt-Pt interactions. Additionally, many intermolecular CH―π bonds between the two adjacent PtP2IM molecules were observed, which could effectively limit the rotation of the peripheral phenyl group linked to the imidazole ring. Thus, the AIE property of PtP2IM was attributed to the restricted intramolecular rotation (RIR) effect of the peripheral flexible phenyl group that was linked to the imidazole ring in the solid state in which the vibration of multiple peripheral benzene rings was effectively suppressed. This decreased the non-radiative transition rate and induced the high luminescent quantum efficiency. In the aggregation state, PtP2IM still demonstrated the photo-oxidation reaction by singlet oxygen. Thus, we report a new Pt(Ⅱ) metal complex, PtP2IM, with the AIE property that can undergo an uncommon photo-oxidation reaction in the photo-excitation state. This work aimed to elucidate the basic photochemical and photophysics of transition metal complexes with the AIE property.
2019, 35(11): 1282-1290
doi: 10.3866/PKU.WHXB201903002
Abstract:
Functionalized graphene has attracted significant interest over the past decade due to its unique physical properties and potential applications. Graphene oxide (GO), a readily scaled-up product, is a basic material for further functionalization. Using reductive processes, highly conductive reduced graphene oxide (RGO) can be obtained, which exhibits electrical and optical properties analogous to those of graphene. Moreover, due to the presence of oxygen-containing functional groups, its chemical reactivity and electronic properties can be easily tailored by chemical doping with nitrogen. However, developing strategies for doping graphene is challenging and the fundamental roles of the doping atom configuration and its environment on the resulting properties of graphene remain poorly understood. These properties are important for electrical and catalytic applications of graphene. Thus, synthesizing specific configurations of nitrogen-doped graphene and consequently investigating the electrical and catalytic properties of the product is imperative. Herein, we demonstrate an approach that allows for successful production of nitrogen-functionalized RGO using Schiff base condensation between the amino groups in an o-aryl diamine compound and the carbonyl groups in GO. Three typical nitrogen-containing species including o-phenylenediamine (OPD), 2, 3-diaminopyridine (23DAP), and bis(trifluoromethyl)-1, 2-diaminobenzene (BTFMDAB) were used for functionalizing the GO samples, and the corresponding RGO derivatives (OPD-RGO, 23DAP-RGO, and BTF-RGO) were obtained by thermal annealing. Pyrazine nitrogen was successfully introduced into graphitic framework, as confirmed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, thermal gravimetric analysis (TGA), Raman, and X-ray photoelectron spectroscopy (XPS). Field-effect transistors (FETs) based on the BTF-RGO exhibited hole-dominated ambipolar field-effect behavior with a Dirac point at a 9 V gate voltage and hole mobilities up to 2.5 times that of RGO. The weak p-type doping effect originated from the strongly electron-withdrawing trifluoromethyl groups. By studying the OPD-RGO and 23DAP-RGO-based FETs, containing pyrazine nitrogen and mixed pyrazine/pyridine nitrogen, respectively, we found that pyrazine nitrogen provided weak n-type doping effects, while pyridine nitrogen exhibited weak p-type doping effects due to its electron-withdrawing ability. Enhanced p-type doping effect was accompanied by the introduction of groups with stronger electron-withdrawing ability into the graphitic framework. Impressively, pyridine nitrogen in the pyrazine nitrogen-doped RGO yielded a weak p-type doped graphene due to the electron-withdrawing effect of the pyridine nitrogen. Nitrogen-doped graphene can be finely tuned from weak n-type to weak p-type doping by adjusting the electron-withdrawing ability of o-aryl diamine compounds. This study demonstrates the effect of nitrogen configuration and its surrounding environment on the electrical properties of RGOs, providing additional possible applications. ![]()
Functionalized graphene has attracted significant interest over the past decade due to its unique physical properties and potential applications. Graphene oxide (GO), a readily scaled-up product, is a basic material for further functionalization. Using reductive processes, highly conductive reduced graphene oxide (RGO) can be obtained, which exhibits electrical and optical properties analogous to those of graphene. Moreover, due to the presence of oxygen-containing functional groups, its chemical reactivity and electronic properties can be easily tailored by chemical doping with nitrogen. However, developing strategies for doping graphene is challenging and the fundamental roles of the doping atom configuration and its environment on the resulting properties of graphene remain poorly understood. These properties are important for electrical and catalytic applications of graphene. Thus, synthesizing specific configurations of nitrogen-doped graphene and consequently investigating the electrical and catalytic properties of the product is imperative. Herein, we demonstrate an approach that allows for successful production of nitrogen-functionalized RGO using Schiff base condensation between the amino groups in an o-aryl diamine compound and the carbonyl groups in GO. Three typical nitrogen-containing species including o-phenylenediamine (OPD), 2, 3-diaminopyridine (23DAP), and bis(trifluoromethyl)-1, 2-diaminobenzene (BTFMDAB) were used for functionalizing the GO samples, and the corresponding RGO derivatives (OPD-RGO, 23DAP-RGO, and BTF-RGO) were obtained by thermal annealing. Pyrazine nitrogen was successfully introduced into graphitic framework, as confirmed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, thermal gravimetric analysis (TGA), Raman, and X-ray photoelectron spectroscopy (XPS). Field-effect transistors (FETs) based on the BTF-RGO exhibited hole-dominated ambipolar field-effect behavior with a Dirac point at a 9 V gate voltage and hole mobilities up to 2.5 times that of RGO. The weak p-type doping effect originated from the strongly electron-withdrawing trifluoromethyl groups. By studying the OPD-RGO and 23DAP-RGO-based FETs, containing pyrazine nitrogen and mixed pyrazine/pyridine nitrogen, respectively, we found that pyrazine nitrogen provided weak n-type doping effects, while pyridine nitrogen exhibited weak p-type doping effects due to its electron-withdrawing ability. Enhanced p-type doping effect was accompanied by the introduction of groups with stronger electron-withdrawing ability into the graphitic framework. Impressively, pyridine nitrogen in the pyrazine nitrogen-doped RGO yielded a weak p-type doped graphene due to the electron-withdrawing effect of the pyridine nitrogen. Nitrogen-doped graphene can be finely tuned from weak n-type to weak p-type doping by adjusting the electron-withdrawing ability of o-aryl diamine compounds. This study demonstrates the effect of nitrogen configuration and its surrounding environment on the electrical properties of RGOs, providing additional possible applications.
2019, 35(11): 1291-1292
doi: 10.3866/PKU.WHXB201906079
Abstract:
