An Amino-functionalized Covalent Organic Framework Coating for Highly Efficient Solid Phase Microextraction of Trace Phenols in Water
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摘要:
酚类化合物是一类常见的环境污染物，由于浓度低、极性较强且样品基质复杂，对其分析检测前需采用样品前处理技术以进行有效地分离和富集。固相微萃取（SPME）是一种集采样、富集、进样于一体的无溶剂前处理技术，与气相色谱-质谱（GC-MS）等联用可实现复杂基质中痕量有机物的快速富集和检测。本文采用无溶剂合成策略，一步合成了氨基改性的共价有机骨架（COFs）材料（TpPa-NH2），合成方法简单绿色，无需溶剂。将其制备成SPME涂层，以5种酚类化合物作为目标分析物，基于顶空模式进行萃取，结合GC-MS作为检测手段，建立了SPME-GC-MS检测酚类化合物的新方法。与未氨基改性的TpPa-1涂层相比，TpPa-NH2萃取酚类化合物的性能是其3~5倍，表明氨基官能团可有效地提高萃取酚类化合物的性能。在最佳条件下，该方法线性范围为10~5.0×104ng/L，线性相关系数为0.996~0.999，检出限为1.30~5.35ng/L。涂层批内的相对标准偏差（RSD）在4.2%~8.9%之间，批间的RSD在2.6%~8.2%之间，且该涂层可以重复使用90次以上。基于TpPa-NH2涂层材料建立的SPME-GC-MS检测酚类化合物的分析方法，已成功应用于环境水样标准物质中酚类化合物的检测。
要点(1) 采用无溶剂合成策略，利用表面活性剂PF127高温裂解产生的还原性气体一步合成了氨基改性的共价有机骨架材料。
(2) 材料中的氨基官能团能提升对酚类化合物的萃取性能。
(3) 氨基功能化共价有机骨架SPME涂层与GC-MS联用能实现水体中酚类化合物的高灵敏检测。
HIGHLIGHTS(1) Amino modified covalent organic framework materials were synthesized by one step solvent-free synthetic strategy using the reducing gas produced by high temperature decomposition of surfactant PF127.
(2) Amino functional groups can improve the extraction performance of materials toward phenolic compounds, whereas the nitro functional group is not conducive to the extraction of phenolic compounds.
(3) The high-sensitivity determination of phenolic compounds in water was realized using amino functionalized covalent organic frameworks as solid phase microextraction coating combined with GC-MS.
Abstract:BACKGROUNDPhenolic compounds, as ubiquitous pollutants, should be effectively separated by sample pretreatment technology prior to analysis because of the low concentration, strong polarity and complex sample matrix. Solid phase microextraction (SPME) is a solvent-free pretreatment technology integrating sampling, enrichment and injection. Combined with gas chromatography-mass spectrometry (GC-MS), it can achieve the rapid enrichment and detection of trace organic compounds in a complex matrix.
OBJECTIVESTo develop a sensitive, simple, and environmentally friendly method for the determination of trace phenols.
METHODSAn amino functionalized covalent organic framework (TpPa-NH2) was synthesized by a solvent-free method in one step. SPME was used as the coating, four kinds of phenolic compounds were used as target analytes, and a new method for the detection of phenolic compounds was established by headspace extraction mode combined with GC-MS.
RESULTSThe extraction performance of TpPa-NH2 was 3-5 times that of TpPa-1. Under the optimum conditions, the established analysis method for four phenols had wide linear ranges (10-5.0×104ng/L), high linear correlation coefficients (0.996-0.999), and low detection limits (1.30-5.35ng/L). Both the intra-fiber repeatability (RSD from 2.2%-9.2%) and inter-fiber reproducibility (RSD from 4.2%-8.9%) were satisfactory, and the coating can be reused more than 90 times.
CONCLUSIONSThe introduction of an amino group can effectively improve the extraction performance of TpPa for phenolic compounds. The established method establishes the sensitive, convenient and green detection of phenolic compounds in actual samples, demonstrating a good application prospect.
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图 2 TpPa-NH2涂层的扫描电子显微镜图像
a—不锈钢丝；b—TpPa-NH2涂层表面；c—TpPa-NH2涂层横截面。
Figure 2. SEM diagrams of TpPa-NH2 coating (a—Stainless steel wire; b—Coating surface of TpPa-NH2; c—Coating cross section of TpPa-NH2)
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图 3 (a) TpPa-NH2的热重分析曲线；(b)三种材料的红外光谱图对比
Figure 3. (a)Thermal gravimetric analysis of TpPa-NH2; (b) FT-IR spectra diagrams of TpPa-NH2, TpPa-1 and TpPa-NO2
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图 4 TpPa-NH2涂层萃取和解吸条件的优化
a—萃取温度；b—萃取时间；c—解吸温度；d—解吸时间。
Figure 4. Performance optimization of TpPa-NH2 coating (a: Extraction temperature; b: Extraction time; c: Desorption temperature; d: Desorption time)
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图 5 (a) TpPa-1、TpPa-NH2、TpPa-NO2、TpPa-N涂层性能的对比；(b) TpPa-NH2涂层的可重复使用性
Figure 5. (a) Performance comparison of TpPa-1, TpPa-NH2, TpPa-NO2, TpPa-N coatings; (b) Reusability of coating of TpPa-NH2
表 1 TpPa-NH2涂层萃取5种酚类化合物的分析性能
Table 1 Analysis performance of 5 kinds of phenolic compounds by TpPa-NH2 coating
酚类化合物 线性范围
(ng/L)R2 检出限
(ng/L)RSD(%) 批内重复性(n=3) 批间重复性(n=3) 2-NP 20~5.0×104 0.998 4.64 7.1 2.6 2,4-DMP 10~5.0×104 0.996 1.81 4.2 8.2 2,6-DMP 10~5.0×104 0.997 1.30 7.1 8.1 2,4-DCP 20~5.0×104 0.996 5.35 5.7 5.4 2,4,6-TCP 20~5.0×104 0.999 4.59 8.9 3.4 
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表 2 与已报道的基于SPME-GC-MS检测酚类的材料对比
Table 2 Comparison with the reported materials for the detection of phenols based on SPME-GC-MS
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表 3 本文方法与国家标准方法检测酚类化合物结果对比
Table 3 Comparison of results with the study method and national standard methods for detection of the phenols
酚类化合物检测方法 进样量 检出限 《水质酚类化合物的测定液液萃取法/气相色谱法》 (HJ 676—2013) 500mL 0.5~3.4μg/L 《固体废物酚类化合物的测定气相色谱法》(HJ 711—2014) 100mL 2~6μg/L 本文方法 10.0μL 1.30~5.35ng/L
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表 4 标准物质分析结果
Table 4 Analytical results of the reference materials
标准品 酚类化合物 参考值
(μg/L)测定值
(μg/L)RSD(%)
(n=5)BWQ8341—2016 2-NP 5±0.15 5.10±0.00 0.04 2,4-DMP 5±0.15 4.95±0.05 0.92 2,4-DCP 5±0.15 5.37±0.04 0.83 2,4,6-TCP 5±0.15 5.04±0.15 2.90 BWQ8236—2016 2-NP 5±0.15 5.09±0.19 3.90 2,4-DMP 5±0.15 4.93±0.02 0.44 2,4-DCP 5±0.15 5.36±0.04 0.87 2,4,6-TCP 5±0.15 4.98±0.08 1.60
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