CN116478397B - Preparation of CN@PANI composite material and method for detecting trace ferric iron by using same - Google Patents
Preparation of CN@PANI composite material and method for detecting trace ferric iron by using same Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 58
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims 7
- 238000001514 detection method Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 230000001052 transient effect Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical compound [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 3
- 238000000227 grinding Methods 0.000 claims 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 2
- 238000005303 weighing Methods 0.000 claims 2
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明公开了一种光聚合合成聚苯胺复合材料CN@PANI，并将其作为传感器定量检测Fe(III)的方法。常温下采用非金属半导体材料g‑C3N4光诱导合成CN@PANI，所得CN@PANI的重均分子量可达222405Da，多分散性系数为1.6，表明其分子量分布均匀，纯度和聚合度高。对于Fe(III)的检测，CN@PANI复合材料具有反应时间短、特异性识别和检测限低的优点，检测限可达61.768ppt。
The present invention discloses a method for synthesizing a polyaniline composite material CN@PANI by photopolymerization and using it as a sensor for quantitative detection of Fe(III). CN@PANI is synthesized by light-induced synthesis of a non-metallic semiconductor material g‑C 3 N 4 at room temperature. The weight average molecular weight of the obtained CN@PANI can reach 222405Da, and the polydispersity coefficient is 1.6, indicating that its molecular weight distribution is uniform, and the purity and degree of polymerization are high. For the detection of Fe(III), the CN@PANI composite material has the advantages of short reaction time, specific recognition and low detection limit, and the detection limit can reach 61.768ppt.
Description
本发明属于环境与高分子合成领域，涉及到新型传感器CN@PANI的制备，制备高分子量聚苯胺的同时实现高灵敏度检测三价铁。The invention belongs to the field of environment and polymer synthesis, and relates to the preparation of a novel sensor CN@PANI, and realizes high-sensitivity detection of trivalent iron while preparing high molecular weight polyaniline.
背景技术Background technique
聚苯胺(PANI)因其优异的传感性能、导电性和耐腐蚀性而受到越来越多的关注。因此，其简单的合成路径成为了一个值得研究的课题。但是聚苯胺的合成条件极其苛刻，不仅需要氧化剂，而且需要低温环境，极度消耗能源，污染环境。近年来，能源短缺和环境污染日益严重。工业废水中的重金属、染料、石油泄漏、和排放的其它污染物已经对人类造成了不可挽回的损害。例如，过量的Fe(III)会导致水体呈现赤橙色且变浑浊，水体中的溶解氧迅速降低，导致水体生物死亡和严重的环境污染。而人体内过量或不足的Fe(III)都会导致细胞环境失衡并诱发疾病，例如贫血、癌症、智力下降和糖尿病等。寻找一种高灵敏高选择性的Fe(III)检测方法具有重要意义。Polyaniline (PANI) has attracted increasing attention due to its excellent sensing performance, conductivity and corrosion resistance. Therefore, its simple synthesis route has become a topic worthy of study. However, the synthesis conditions of polyaniline are extremely harsh. It not only requires an oxidant, but also requires a low temperature environment, which consumes energy extremely and pollutes the environment. In recent years, energy shortages and environmental pollution have become increasingly serious. Heavy metals, dyes, oil spills, and other pollutants discharged in industrial wastewater have caused irreparable damage to humans. For example, excessive Fe(III) will cause the water to appear reddish orange and become turbid, and the dissolved oxygen in the water will decrease rapidly, leading to the death of aquatic organisms and serious environmental pollution. Excessive or insufficient Fe(III) in the human body will cause cellular environmental imbalance and induce diseases such as anemia, cancer, intellectual decline and diabetes. It is of great significance to find a highly sensitive and selective Fe(III) detection method.
光催化技术因其生态友好、操作简单、低成本、低能耗、高效等优点而受到聚合领域的广泛关注。因此，它被认为是合成高聚物的一种很有前途的策略。现阶段常用的Fe(III)检测方法，分光光度法虽然方法简单，但灵敏度不高。采用邻菲罗啉分光光度法，建立了酸腐蚀液中铁离子含量测定方法，该方法相对偏差较小，但需要浓酸环境。为了改善这些缺点，考虑使用光电化学，解决灵敏度问题的同时，扩大了检测范围。其中，瞬态光电流有数值且稳定，因此是输出物理量信号的一种不错选择。Photocatalytic technology has attracted extensive attention in the field of polymerization due to its advantages such as eco-friendliness, simple operation, low cost, low energy consumption, and high efficiency. Therefore, it is considered to be a promising strategy for the synthesis of polymers. At present, the commonly used Fe(III) detection method, spectrophotometry, is simple in method but not very sensitive. A method for determining the iron ion content in acid corrosion solution was established using o-phenanthroline spectrophotometry. This method has a relatively small deviation, but requires a concentrated acid environment. In order to improve these shortcomings, the use of photoelectrochemistry is considered to solve the sensitivity problem while expanding the detection range. Among them, the transient photocurrent has a numerical value and is stable, so it is a good choice for outputting physical quantity signals.
因此本发明采用非金属半导体材料g-C3N4常温下光诱导聚合CN@PANI复合材料，不仅无需传统的氧化剂，更无需低温环境。旨在提高Fe(III)检测的灵敏度，扩大检测范围，通过电化学工作站输出瞬态光电流，并根据光电流的大小确定Fe(III)浓度。然而，目前我们尚未查到这类CN@PANI的制备，以及在Fe(III)检测领域应用的技术和专利。Therefore, the present invention uses a non-metallic semiconductor material gC 3 N 4 to induce photopolymerization of CN@PANI composite material at room temperature, which not only does not require traditional oxidants, but also does not require a low-temperature environment. It aims to improve the sensitivity of Fe(III) detection, expand the detection range, output transient photocurrent through an electrochemical workstation, and determine the Fe(III) concentration based on the size of the photocurrent. However, we have not yet found the preparation of this type of CN@PANI, as well as the technology and patents for its application in the field of Fe(III) detection.
发明内容Summary of the invention
为实现本发明目的，本发明的技术方案是以g-C3N4作为光引发剂，光聚合合成聚苯胺复合材料CN@PANI，并将其作为传感器定量检测Fe(III)的方法。常温下采用非金属半导体材料g-C3N4光诱导合成CN@PANI，所得CN@PANI的重均分子量可达222405Da，多分散性系数为1.6，表明其分子量分布均匀，纯度和聚合度高。对于Fe(III)的检测，CN@PANI复合材料具有反应时间短、特异性识别和检测限低的优点，检测限可达61.768ppt。该发明所采用的技术方案按照以下步骤进行：To achieve the purpose of the present invention, the technical solution of the present invention is to use g-C 3 N 4 as a photoinitiator, photopolymerize and synthesize a polyaniline composite material CN@PANI, and use it as a sensor to quantitatively detect Fe(III). CN@PANI is synthesized by light-induced synthesis of non-metallic semiconductor material g-C 3 N 4 at room temperature. The weight average molecular weight of the obtained CN@PANI can reach 222405Da, and the polydispersity coefficient is 1.6, indicating that its molecular weight distribution is uniform, and the purity and degree of polymerization are high. For the detection of Fe(III), the CN@PANI composite material has the advantages of short reaction time, specific recognition and low detection limit, and the detection limit can reach 61.768ppt. The technical solution adopted by the invention is carried out according to the following steps:
在具体实施方案中，本发明提供了一种CN@PANI复合材料的制备及其检测痕量三价铁的方法。其特征在于，包括下列步骤：In a specific embodiment, the present invention provides a method for preparing a CN@PANI composite material and detecting trace trivalent iron therefrom, characterized in that the method comprises the following steps:
(a)称取尿素和三聚氰胺控制其质量比在1∶1-1∶4之间，放入研钵，充分研磨后放入陶瓷坩埚中，并用锡纸包裹住坩埚。将坩埚放入马弗炉中，从室温以2-6℃ min-1的升温速率，加热至500-600℃，保温2-5h，自然降至室温后取出，得到块状g-C3N4；(a) Weigh urea and melamine to control the mass ratio between 1:1-1:4, put them into a mortar, grind them thoroughly, put them into a ceramic crucible, and wrap the crucible with tin foil. Put the crucible into a muffle furnace, heat it from room temperature to 500-600°C at a heating rate of 2-6°C min -1 , keep it warm for 2-5h, cool it to room temperature naturally, and then take it out to obtain blocky gC 3 N 4 ;
(b)将块状g-C3N4充分研磨后配制成10-30g L-1g-C3N4悬浊液，搅拌3-30min后，超声5-30min。离心机中以1000-4000r min-1的转速离心1-5min。所得上清液即g-C3N4纳米片溶液，命名为CN；(b) Grind the blocky gC 3 N 4 thoroughly to prepare a 10-30 g L -1 gC 3 N 4 suspension, stir for 3-30 min, and then ultrasonicate for 5-30 min. Centrifuge at a speed of 1000-4000 r min -1 for 1-5 min. The resulting supernatant is the gC 3 N 4 nanosheet solution, named CN;
(c)分别量取10-30mL CN，1-5mL苯胺ANI，5-10mL 3-8M的HNO3和1-5mL去离子水加入到石英试管中，用1M的HCl调节初始pH至1-3，并充分搅拌，得到聚苯胺的前体溶液；(c) respectively measuring 10-30 mL CN, 1-5 mL aniline ANI, 5-10 mL 3-8 M HNO 3 and 1-5 mL deionized water into a quartz test tube, adjusting the initial pH to 1-3 with 1 M HCl, and stirring well to obtain a polyaniline precursor solution;
(d)将步骤(c)中装有聚苯胺前体溶液的试管放入南京胥江机电厂的XPA-7光化学反应仪中进行5-10h的光聚合。该反应仪具体参数如下：300-500W光强可调的高压汞灯固定在具有循环水冷凝***的密闭石英冷阱中，光源与石英试管表面的距离为12cm，石英试管外表面的光强为2-3mW cm-2。实验过程中，通过冷却水的不断循环，光催化反应过程中反应器内部环境温度保持20-30℃；(d) The test tube containing the polyaniline precursor solution in step (c) is placed in the XPA-7 photochemical reactor of Nanjing Xujiang Electromechanical Plant for 5-10 hours of photopolymerization. The specific parameters of the reactor are as follows: a 300-500W high-pressure mercury lamp with adjustable light intensity is fixed in a closed quartz cold trap with a circulating water condensation system, the distance between the light source and the surface of the quartz test tube is 12cm, and the light intensity on the outer surface of the quartz test tube is 2-3mW cm -2 . During the experiment, the internal ambient temperature of the reactor is maintained at 20-30°C during the photocatalytic reaction by continuous circulation of cooling water;
(e)光聚合反应结束后，将溶液离心，将沉淀物冷冻干燥后得到聚苯胺复合材料CN@PANI；(e) After the photopolymerization reaction is completed, the solution is centrifuged and the precipitate is freeze-dried to obtain the polyaniline composite material CN@PANI;
(f)将壳聚糖溶于冰醋酸中，配成1-3g L-1的混合液，搅拌30-90min；(f) dissolving chitosan in glacial acetic acid to prepare a mixed solution of 1-3 g L -1 , and stirring for 30-90 min;
(g)在离心管中加入0.5-3mL步骤(f)的混合液和0.5-5mg CN@PANI，配成0.5-3gL-1的混合液，超声处理1-5min；(g) adding 0.5-3 mL of the mixed solution of step (f) and 0.5-5 mg of CN@PANI to a centrifuge tube to prepare a mixed solution of 0.5-3 g L -1 , and ultrasonically treating for 1-5 min;
(h)量取10-30μL步骤(f)的混合液滴在导电玻璃的导电侧，由其自动扩散，并密封过夜；(h) measuring 10-30 μL of the mixed solution of step (f) and dropping it on the conductive side of the conductive glass to allow it to spread automatically, and sealing it overnight;
(i)分别以步骤(h)获得的负载CN@PANI的导电玻璃、Ag/AgCl电极和Pt片为工作电极、参比电极和对电极。使用强度为500mW cm-2的可见光作为光源，无外加电压下，在醋酸-醋酸铵缓冲溶液中测量瞬态光电流；(i) Using the CN@PANI-loaded conductive glass, Ag/AgCl electrode and Pt sheet obtained in step (h) as the working electrode, reference electrode and counter electrode, respectively. Using visible light with an intensity of 500 mW cm -2 as the light source, and measuring the transient photocurrent in an acetic acid-ammonium acetate buffer solution without an applied voltage;
(j)当醋酸-醋酸铵缓冲液中含相同浓度的不同阳离子时，可以测CN@PANI对Fe(III)的特异性识别；当醋酸-醋酸铵缓冲液中含不同浓度的Fe(III)时，可以得到Fe(III)浓度与瞬态光电流之间的关系。(j) When the acetic acid-ammonium acetate buffer contains different cations at the same concentration, the specific recognition of CN@PANI for Fe(III) can be measured; when the acetic acid-ammonium acetate buffer contains different concentrations of Fe(III), the relationship between the Fe(III) concentration and the transient photocurrent can be obtained.
2.根据权利要求1所述的一种CN@PANI复合材料的制备及其检测痕量三价铁的方法，其特征在于：2. The method for preparing a CN@PANI composite material and detecting trace trivalent iron therefrom according to claim 1, characterized in that:
(1)所述CN@PANI复合材料的制备条件为：CN，ANI，5M HNO3和去离子水的体积比为5∶0.75∶2∶1；(1) The preparation conditions of the CN@PANI composite material are as follows: the volume ratio of CN, ANI, 5M HNO 3 and deionized water is 5:0.75:2:1;
(2)与本征态聚苯胺相比，所述CN@PANI复合材料的电导率提升了4个数量级；(2) Compared with intrinsic polyaniline, the electrical conductivity of the CN@PANI composite material is increased by 4 orders of magnitude;
(3)CN@PANI复合材料的重均分子量为222405Da，特性粘度为12.21dL g-1，多分散性系数为1.62；(3) The weight average molecular weight of the CN@PANI composite material is 222405Da, the intrinsic viscosity is 12.21dL g -1 , and the polydispersity coefficient is 1.62;
(4)所述CN@PANI复合材料检测Fe(III)具有反应时间短、特异性识别和检测限低的优点，检测限可达61.768ng L-1。(4) The CN@PANI composite material has the advantages of short reaction time, specific recognition and low detection limit for detecting Fe(III), and the detection limit can reach 61.768 ng L -1 .
本发明的目的在于提供一种可高灵敏度检测环境中三价铁且高分子量的CN@PANI复合材料的制备方法，同时有效提高聚苯胺的分子量，电导率以及对Fe(III)检测的灵敏度。本发明开发的光聚合材料为含Fe(III)废水的检测提供了数据基础和理论支撑，具有较大的应用前景。The purpose of the present invention is to provide a method for preparing a high molecular weight CN@PANI composite material that can detect trivalent iron in the environment with high sensitivity, and effectively improve the molecular weight, conductivity and sensitivity of polyaniline to Fe(III) detection. The photopolymer material developed by the present invention provides a data basis and theoretical support for the detection of Fe(III)-containing wastewater, and has great application prospects.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
附图一是CN@PANI的固态13C核磁共振图谱；Figure 1 is the solid-state 13 C NMR spectrum of CN@PANI;
附图二是ICN@PANI的分子量分布图和特性粘度；Figure 2 is the molecular weight distribution and intrinsic viscosity of ICN@PANI;
附图三是CN@PANI对不同离子的瞬态光电流强度比较图；Figure 3 is a comparison of the transient photocurrent intensity of CN@PANI for different ions;
附图四是(a)CN@PANI对不同浓度Fe(III)的瞬态光电流响应.(b)瞬态光电流强度与log C的线性关系图。Figure 4 is (a) the transient photocurrent response of CN@PANI to different concentrations of Fe(III). (b) the linear relationship between transient photocurrent intensity and log C.
最佳实施方式Best Mode for Carrying Out the Invention
下面以具体实施例详细介绍本发明的实施方法和步骤。The implementation methods and steps of the present invention are described in detail below with reference to specific embodiments.
实施例1：Embodiment 1:
(1)分别称取4g尿素和8g三聚氰胺，放入研钵，充分研磨后放入陶瓷坩埚中，盖盖子并用锡纸包裹住坩埚。将坩埚放入马弗炉中，马弗炉程序设定如下：3℃ min的升温速率，加热至550℃，保温4h，自然降温，第二天取出。得到块状g-C3N4；(1) Weigh 4 g urea and 8 g melamine respectively, put them into a mortar, grind them thoroughly, and put them into a ceramic crucible. Cover the crucible with a lid and wrap it with tin foil. Put the crucible into a muffle furnace. The muffle furnace program is set as follows: heating rate of 3 °C min, heating to 550 °C, keeping the temperature for 4 h, cooling naturally, and taking it out the next day. Obtain blocky gC 3 N 4 ;
(2)取1g g-C3N4充分研磨后分散到50mL去离子水中，搅拌5min后，超声30min。离心机中以2000r min-1的转速离心3min。所得上清液即g-C3N4纳米片溶液，命名为CN；(2) Take 1 g of gC 3 N 4 and grind it thoroughly and disperse it in 50 mL of deionized water. After stirring for 5 min, ultrasonicate it for 30 min. Centrifuge it at 2000 r min -1 for 3 min. The resulting supernatant is the gC 3 N 4 nanosheet solution, named CN;
(3)分别量取20mL CN，3mL ANI，8mL 5M HNO3和4mL去离子水加入到石英试管中，用1M的HCl调节初始pH至1.5，并充分搅拌，得到聚苯胺的前体溶液；(3) 20 mL CN, 3 mL ANI, 8 mL 5 M HNO 3 and 4 mL deionized water were respectively added to a quartz test tube, the initial pH was adjusted to 1.5 with 1 M HCl, and the mixture was stirred thoroughly to obtain a polyaniline precursor solution;
(4)将步骤(c)中装有聚苯胺前体溶液的试管放入XPA-7光化学反应仪中进行8h的光聚合。该反应仪具体参数如下：光强为500W，主激发波长为365nm的高压汞灯固定在具有循环水冷凝***的密闭石英冷阱中，光源与石英试管表面的距离为12cm，石英试管外表面的光强为2.50mW cm-2。实验过程中，通过冷却水的不断循环，光催化反应过程中反应器内部保持25±1℃；(4) Place the test tube containing the polyaniline precursor solution in step (c) into an XPA-7 photochemical reactor for 8 hours of photopolymerization. The specific parameters of the reactor are as follows: the light intensity is 500W, the high-pressure mercury lamp with a main excitation wavelength of 365nm is fixed in a closed quartz cold trap with a circulating water condensation system, the distance between the light source and the surface of the quartz test tube is 12cm, and the light intensity on the outer surface of the quartz test tube is 2.50mW cm -2 . During the experiment, the temperature inside the reactor was maintained at 25±1℃ during the photocatalytic reaction by continuous circulation of cooling water;
(5)光聚合反应结束后，将溶液离心，将沉淀物冷冻干燥后得到CN@PANI；(5) After the photopolymerization reaction is completed, the solution is centrifuged and the precipitate is freeze-dried to obtain CN@PANI;
(6)将20mg壳聚糖溶于10mL冰醋酸中，配成2g L-1的混合液，搅拌1h。(6) Dissolve 20 mg of chitosan in 10 mL of glacial acetic acid to make a 2 g L -1 mixed solution and stir for 1 h.
(7)在离心管中加入1mL步骤(f)的混合液和0.5mg CN@PANI，配成0.5g L-1的混合液，超声处理3min。(7) Add 1 mL of the mixed solution from step (f) and 0.5 mg of CN@PANI to a centrifuge tube to make a 0.5 g L -1 mixed solution, and treat with ultrasound for 3 min.
(8)量取20μL步骤(f)的混合液滴滴在导电玻璃的导电侧，由其自动扩散，并密封过夜；(8) Measure 20 μL of the mixed solution in step (f) and drop it on the conductive side of the conductive glass to allow it to spread automatically, and then seal it overnight;
(9)分别以步骤(h)获得的负载CN@PANI的导电玻璃、Ag/AgCl电极和片状Pt为工作电极、参比电极和对电极。使用强度为565mW cm-2的可见光作为光源，无外加电压下，在醋酸-醋酸铵缓冲溶液(pH＝4.5)中测量瞬态光电流。(9) The CN@PANI-loaded conductive glass, Ag/AgCl electrode and Pt sheet obtained in step (h) were used as working electrode, reference electrode and counter electrode, respectively. The transient photocurrent was measured in acetic acid-ammonium acetate buffer solution (pH = 4.5) without an applied voltage using visible light with an intensity of 565 mW cm -2 as the light source.
(10)当醋酸-醋酸铵缓冲溶液含同浓度的不同阳离子时，可以测CN@PANI对Fe(III)的特异性识别，当醋酸-醋酸铵缓冲溶液含不同浓度的Fe(III)，可以得到Fe(III)浓度与瞬态光电流之间的关系Ip(nA)＝4817.75623+397.78043logC(M)。(10) When the acetic acid-ammonium acetate buffer solution contains different cations at the same concentration, the specific recognition of CN@PANI for Fe(III) can be measured. When the acetic acid-ammonium acetate buffer solution contains different concentrations of Fe(III), the relationship between the Fe(III) concentration and the transient photocurrent can be obtained: I p (nA) = 4817.75623 + 397.78043logC(M).
用本发明制备的CN@PANI的CN@PANI的重均分子量可达222405Da，多分散性系数为1.6，表明其分子量分布均匀，纯度和聚合度高。对于Fe(III)的检测，CN@PANI复合材料具有反应时间短、特异性识别和检测限低的优点，检测限可达61.768ppt。The weight average molecular weight of CN@PANI prepared by the present invention can reach 222405Da, and the polydispersity coefficient is 1.6, indicating that its molecular weight distribution is uniform, and its purity and degree of polymerization are high. For the detection of Fe(III), the CN@PANI composite material has the advantages of short reaction time, specific recognition and low detection limit, and the detection limit can reach 61.768ppt.
以上所述为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above descriptions are embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent process changes made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.
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