氮掺杂石墨烯的p型场效应及其精细调控

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.     

Adsorption phenomena at high pressures and temperatures 4. Isotherms of excess and absolute adsorption of Kr on NaA zeolite

The problem of conversion of an isotherm of excess adsorption measured experimentally into values of the total amount of the adsorbate (absolute adsorption) has been formulated. Five isotherms of excess adsorption of krypton on NaA zeolite were measured (at 334–500 K) at equilibrium pressures of -160 MPa. The corresponding isotherms of the total amount were calculated and the temperature dependences of the parameters of an equation describing the isotherms of excess adsorption were identified. It was shown that at high temperatures and pressures, krypton atoms diffuse into the -cavities of the NaA zeolite.For Part 3, seeRuss. Chem. Bull., 1996, 45, 534 (Engl. Transl.).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1138–1142, May, 1996.     

Use of Quantitative Structure Activity Relationship Methods in Predicting Activated Carbon Adsorption Isotherms for Hazardous Air Pollutants

Abstract

A quantitative structure activity relationship (QSAR) approach is presented to predict gas phase activated carbon adsorption capacities and isotherms for several organic chemicals and their binary mixtures. F,x peri menial adsorption data reported in the literature for various binary mixtures on two di ercnt carbons were used to validate this predictive approach. The QSAR-predicted and experimental adsorption capacities for di erent chemical mixtures of small apolar hydrocarbons at di erent temperatures on two di erent carbons under a range of total pressures and gas phase compositions agreed well with r₂ = 0.85 for a total of 338 data points.     

Synthesis and Characterization of Gold Nanoparticle‐Functionalized Ordered Mesoporous Materials

We report the synthesis and characterization of three different ordered mesoporous materials, labeled MCM‐48, SBA‐155, and SBA‐16 type materials, which were functionalized with gold nanoparticles using three different strategies. The functionalization strategies can be categorized as (i) in situ growth of gold nanoparticles, (ii) template loading, and (iii) diffusion loading of prefabricated gold nanoparticles. Two different particle sizes were employed in the latter two strategies, 5 nm and 10 nm. For all mesoporous structures, functionalization strategies, and particle sizes attempted, the materials retained their long‐range order upon incorporation of nanoparticles. From the adsorption isotherms, incorporation of gold nanoparticles altered the pore structure of the mesoporous support of some of the SBA‐15 and SBA‐16 type materials, with the effect on incorporation on the pore structure being particle size dependent in most cases. The majority of gold nanoparticles were found to reside on the external surface of the materials regardless of substrate and functionalization strategy; however, for the in situ synthesis and the template loading strategies, a significant fraction of the particles was determined to reside within the pore system of the material. In situ growth resulted in the highest content of gold nanoparticles in the solid phase. The relative effectiveness in retaining gold nanoparticles in the solid phase for each functionalization strategy was determined to be, in descending order, in situ synthesis, template loading, and diffusion loading.     

Removal of Cobalt Ions from Aqueous Solution by Adsorption onto Cross-Linked Calcium Alginate Beads

The removal of cobalt ions from dilute aqueous solutions using cross linked calcium alginate beads as the adsorbent is reported in this article. The influence of various experimental parameters such as pH, initial metal ion concentration, contact time and solid to liquid ratio were studied. The adsorption data were applied to Langmuir and Freundlich isotherm equations and various static parameters were calculated. It was observed that the uptake of cobalt ions was found to increase with time and that maximum adsorption was obtained within the first 60 minutes of the process. These results indicate that the cross linked calcium alginate beads have potential for removing cobalt ions from industrial waste water.     

Synthesis of new derivatized pyrazole based ligands and their catecholase activity studies

A synthesis of three new tripodal ligands: 3-[bis-(3,5-dimethyl-pyrazol-1-ylmethyl)-amino]-propan-1-ol L1, 3-[bis-(5-methyl-3-carbomethoxy-pyrazol-1-ylmethyl)-amino]-propan-1-ol, L2 and 3-[bis-(5-methyl-3-carboethoxy-pyrazol-1-ylmethyl)-amino]-propan-1-ol L3 is reported. The in situ-generated copper(II) complexes of three new compounds (L1–L3) were examined for their catalytic activities and were found to catalyse the oxidation reaction of catechol to o-quinone with the atmospheric dioxygen. These activities depend on the nature of the ligand and the copper salts.     

Synthesis and characterization of mixed ligand complexes of cobalt(II) with some nitrogen and sulfur donors

Mixed ligand complexes of Co(II) with nitrogen and sulfur donors, Co(OPD)(S–S) · 2H₂O and Co(OPD)(S–S)L₂ [OPD = o-phenylenediamine; S–S = 1,1-dicyanoethylene-2,2-dithiolate (i-MNT^2?) or 1-cyano-1-carboethoxyethylene-2,2-dithiolate (CED^2?); L = pyridine (py), α-picoline (α-pic), β-picoline (β-pic), or γ-picoline (γ-pic)], have been isolated and characterized by analytical data, molar conductance, magnetic susceptibility, electronic, and infrared spectral studies. The molar conductance data reveal non-electrolytes in DMF. Magnetic moment values suggest low-spin and high-spin complexes. The electronic spectral studies suggest distorted octahedral stereochemistry around Co(II) in these complexes. Infrared spectral studies suggest bidentate chelating behavior of i-MNT^2?, CED^2?, or OPD while other ligands are unidentate in their complexes.     

Fluorine as a Regiocontrol Element in the Ring Opening of Bicyclic Aziridiniums

The origin of the variation in the regioselectivity of the nucleophilic ring opening of a series of bicyclic aziridinium ions derived from N‐alkylprolinols was investigated by quantum‐chemical computations (M06‐2X/6‐31+G(d,p)‐SMD). These aziridiniums differ only in the degree and the configurations of F‐substitution at C(4). With the azide ion as nucleophile, the ratio of the piperidine to the pyrrolidine product was computed. An electrostatic gauche effect influences the conformation of the adjoining five‐membered ring in the fluorinated bicyclic aziridinium. This controls the regioselectivity of the aziridinium ring opening.     

氮气氛中合成杂氮球烯,碳纳米管及纳米晶体的研究

氮气氛中合成杂氮球烯、碳纳米管及纳米晶体的研究詹梦熊，余荣清，王育煌，杨士姚，程大典，刘朝阳，郑兰荪（厦门大学化学系，厦门，３６１００５）关键词杂氮球烯，碳纳米管，纳米晶体，氮气氛自球烯及碳纳米管常规制备方法问世以来［１，２］，制备方法的改进一直成为...     

Optimum isotherm equation and thermodynamic interpretation for aqueous 1,1,2-trichloroethene adsorption isotherms on three adsorbents

Aqueous 1,1,2-trichloroethene (TCE) adsorption isotherms were obtained on Ambersorb^1® 563 and 572 adsorbents and Filtrasorb^2® 400 granular activated carbon (GAC). The data for Ambersorb 563 adsorbent covers TCE concentrations from 0.0009 to 600 mg/L. The data for each adsorbent was fit to 15 isotherm equations to determine an optimum equation.The best equation for the TCE adsorption isotherms is the Dubinin-Astakov (DA) isotherm. The DA isotherm coefficients were used to estimate the TCE micropore volume and the adsorption potential distribution. For each adsorbent, the TCE micropore volume is equivalent to the N₂ porosimetry micropore volume. The mean adsorption potential is 18.8, 13.0, and 8.9 kJ/mol, with coefficients of variation of 0.37, 0.53, and 0.67, for Ambersorb 563 and 572 adsorbents and Filtrasorb 400 GAC, respectively. Thus, Ambersorb 563 adsorbent has the most energetic and most homogeneous adsorption volume, while Filtrasorb 400 GAC has the least energetic and most heterogeneous adsorption volume. For these reasons, Ambersorb 563 adsorbent has the highest TCE capacity at low concentrations, whereas Filtrasorb 400 GAC has the highest TCE capacity at high concentrations. The performance of Ambersorb 572 adsorbent is generally intermediate to the other two adsorbents.