石墨相氮化碳材料在样品前处理中的研究进展

作为一种新型非金属材料,石墨相氮化碳以其独特的优点,如简单的制备方法、优良的化学及热稳定性、良好的生物兼容性和无毒性等,受到越来越多的关注。石墨相氮化碳及其复合材料目前已被广泛应用于电催化、光催化、生物成像等领域。由于具有大的比表面积,同时又是富电子的疏水材料,石墨相氮化碳相关材料被认为是一种理想的样品前处理吸附剂。该文探讨了近年来石墨相氮化碳及其复合材料作为固相萃取、分散固相萃取、磁性固相萃取、固相微萃取吸附剂在样品前处理中的应用,并对未来的发展趋势和应用前景进行了展望,以期为相关领域的研究提供帮助。     

Introduction of a biowaste/graphene oxide nanocomposite as a coating for a metal alloy based SPME fiber: Application to screening of polycyclic aromatic hydrocarbons

The present study introduces a high efficiency metal alloy-based solid-phase microextraction (SPME) fiber coated with a green biowaste nanocomposite of chicken feet yellow membrane mixed with graphene oxide (CFYM/GO). An Al/Cr commercial heating element (aluchrom, AC) has been selected as the fiber substrate and designed as coiled form (CAC-SPME) to enhance its extraction and pre-concentration capacity. The fabricated fiber, CAC-SPME/CFYM/GO, has been employed for the extraction and pre-concentration of some commonly seen PAHs in different standard/real samples prior to their high performance liquid chromatography- ultraviolet (HPLC-UV) analyzing. The synthesized materials and the fibers surface were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy analysis and Brunauer-Emmett-Teller surface area analysis. Under the optimized experimental conditions, low detection limits (LOD, 0.039–0.30 µg L^–1), wide linear ranges (LR, 0.13–643 µg L^–1) and good relative recoveries (RR, 76.20–105.60%) were achieved for all the target analytes. The materials applied to prepare this fiber were low-priced and accessible and also eliminated the need for expensive coating substances. In addition, using of the AC alloy substrate was increased the fiber physicochemical resistance and solved the breakage drawback of the conventional SPME fibers. Moreover, simple fabrication, high rigidity, long service life and high extraction capacity were some of the other advantages of the suggested fiber. Therefore, the proposed method can be utilized successfully for the routine analysis of PAHs in different matrixes.     

An in situ temperature‐programmed XPS study of the surface chemical reactions of thiophene with Ag/titania

The Ag/titania sorbent for the ultradeep desulfurization of liquid fuels was characterized by electron spin resonance and was found to contain nearly the stoichiometric titania, without significant concentration of Ti³⁺ or the reactive oxygen species. The surface chemical reactions of thiophene adsorbed on the Ag/titania were studied by temperature‐programmed XPS from 25 to 525 °C upon in situ thermal annealing in high vacuum and in situ oxidation by oxygen gas. The titania support is not chemically reactive under those conditions. Silver oxide in the Ag/titania sorbent is converted to Ag₂ S without formation of the transient surface sulfates or sulfites and is further oxidized by molecular oxygen. Copyright © 2010 John Wiley & Sons, Ltd.     

Removal of uranium (VI) from nuclear effluents onto aluminophosphate and silicoaluminophosphate molecular sieves

Aluminophosphate and silicoaluminophosphate molecular sieves with both five (AFI) and eleven (AEL) type structures are synthesized by hydrothermal crystallization at 473 K, using tripropylamine and dipropylamine as a structure-directing template. The as-prepared AFI and AEL sieves are characterized and then assessed as sorbents for uranium (VI) from radioactive effluents. The sorption process is used to reduce the volumes of effluents and convert them into a stable solid waste. The batch experimental studies are carried out to evaluate the AEL and AFI structure effect on the removal of uranium. The AlPO₄-5, SAPO-5, AlPO₄-11 and SAPO-11 are applied to radioactive effluents with different activities obtained from Nuclear Research Center of Draria, Algeria. Important decontamination factor values are obtained for AFI sorbents. Thermodynamic parameters, namely, the enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) for each sorption process are calculated. The collected results indicated that sorbents are effective materials for the removal of uranium (VI) ions, the sorbent with AFI structure being a highly effective material for the removal of uranium (VI) ions from nuclear effluents.     

Experimental validation of an effective carbon number-based approach for the gas chromatography–mass spectrometry quantification of ‘compounds lacking authentic standards or surrogates’

For the quantitative analysis of ‘compounds lacking authentic standards or surrogates’ (CLASS) in environmental media, we previously introduced an effective carbon number (ECN) approach to develop an empirical equation for the prediction of their response factor (RF). In this research, a series of laboratory experiments were carried out to benchmark the reliability of an ECN approach for sorbent tube/thermal desorption/gas chromatography (GC)/mass spectrometry (MS) applications. First, the ECN values were determined using external calibration data from 25 reference volatile organic compounds (VOCs) using two MS dectectors (quadrupole (Q) and time-of-flight (TOF)). Then, a certified standard mixture of 54 VOCs was analyzed by each system as a simulated unknown sample. The analytical bias, assessed in terms of percentage difference (PD) between the certified and ECN-predicted mass values, averaged 19.2 ± 16.1% (TOF-MS) and 28.2 ± 27.6% (Q-MS). The bias using a more simplified carbon number (CN)-based prediction increased considerably, yielding 53.4 ± 53.3% (TOF-MS) and 61.7 ± 81.3% (Q-MS). However, the bias obtained using the ECN-based prediction decreased significantly to yield average PD values of 9.84 ± 7.28% (TOF-MS) and 16.8 ± 8.35% (Q-MS), if the comparison was limited to 26 (out of 54) VOCs with CN ≥ 4 (i.e., 25 aromatics and hexachlorobutadiene).     

Spherical silica particles decorated with graphene oxide nanosheets as a new sorbent in inorganic trace analysis

Graphene oxide (GO) is a novel material with excellent adsorptive properties. However, the very small particles of GO can cause serious problems is solid-phase extraction (SPE) such as the high pressure in SPE system and the adsorbent loss through pores of frit. These problems can be overcome by covalently binding GO nanosheets to a support. In this paper, GO was covalently bonded to spherical silica by coupling the amino groups of spherical aminosilica and the carboxyl groups of GO (GO@SiO₂). The successful immobilization of GO nanosheets on the aminosilica was confirmed by scanning electron microscopy and X-ray photoelectron spectroscopy. The spherical particle covered by GO with crumpled silk wave-like carbon sheets are an ideal sorbent for SPE of metal ions. The wrinkled structure of the coating results in large surface area and a high extractive capacity. The adsorption bath experiment shows that Cu(II) and Pb(II) can be quantitatively adsorbed at pH 5.5 with maximum adsorption capacity of 6.0 and 13.6 mg g⁻¹, respectively. Such features of GO nanosheets as softness and flexibility allow achieving excellent contact with analyzed solution in flow-rate conditions. In consequence, the metal ions can be quantitatively preconcentrated from high volume of aqueous samples with excellent flow-rate. SPE column is very stable and several adsorption–elution cycles can be performed without any loss of adsorptive properties. The GO@SiO₂ was used for analysis of various water samples by flame atomic absorption spectrometry with excellent enrichment factors (200–250) and detection limits (0.084 and 0.27 ng mL⁻¹ for Cu(II) and Pb(II), respectively).     

New method for determination of (E)-resveratrol in wine based on microextraction using packed sorbent and ultra-performance liquid chromatography

An ultra-fast and improved analytical methodology based on microextraction by packed sorbent (MEPS) combined with ultra-performance LC (UPLC) was developed and validated for determination of (E)-resveratrol in wines. Important factors affecting the performance of MEPS such as the type of sorbent material (C2, C8, C18, SIL, and M1), number of extraction cycles, and sample volume were studied. The optimal conditions of MEPS extraction were obtained using C8 sorbent and small sample volumes (50-250 μL) in one extraction cycle (extract-discard) and in a short time period (about 3 min for the entire sample preparation step). (E)-Resveratrol was eluted by 1×250 μL of the mixture containing 95% methanol and 5% water, and the separation was carried out on a high-strength silica HSS T3 analytical column (100 mm × 2.1 mm, 1.8 μm particle size) using a binary mobile phase composed of aqueous 0.1% formic acid (eluent A) and methanol (eluent B) in the gradient elution mode (10 min of total analysis). The method was fully validated in terms of linearity, detection (LOD) and quantification (LOQ) limits, extraction yield, accuracy, and inter/intra-day precision, using a Madeira wine sample (ET) spiked with (E)-resveratrol at concentration levels ranging from 5 to 60 μg/mL. Validation experiments revealed very good recovery rate of 95±5.8% RSD, good linearity with r(2) values >0.999 within the established concentration range, excellent repeatability (0.52%), and reproducibility (1.67%) values (expressed as RSD), thus demonstrating the robustness and accuracy of the MEPS(C8) /UPLC-photodiode array (PDA) method. The LOD of the method was 0.21 μg/mL, whereas the LOQ was 0.68 μg/mL. The validated methodology was applied to 30 commercial wines (24 red wines and six white wines) from different grape varieties, vintages, and regions. On the basis of the analytical validation, the MEPS(C8)/UPLC-PDA methodology shows to be an improved, sensitive, and ultra-fast approach for determination of (E)-resveratrol in wines with high resolving power within 6 min.