CN104568940B - Method for detecting hydrogen sulfide gas based on nanocrystalline celluloses - Google Patents
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 55
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 55
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- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 132
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Abstract
本发明涉及一种基于纳米晶纤维素检测硫化氢气体的方法。所述方法包括以下步骤：配制纳米晶纤维素溶液，加入铅离子溶液，通入待测气体，观察溶液颜色变化，用紫外‑可见分光光度计在300nm波长下检测。本发明的检测方法具有很好的选择性，所述检测方法可以特异性地检测硫化氢；所述检测方法检测快速，溶液的颜色在数秒钟内就能由无色转变为淡黄色或褐色，而且在一定时间内保持稳定；所述的检测方法灵敏度高，能检测到的硫化氢气体的最低浓度为1mg/m3；所述的检测方法所需试剂少，操作简单，便于推广应用。
The invention relates to a method for detecting hydrogen sulfide gas based on nanocrystalline cellulose. The method comprises the following steps: preparing a nanocrystalline cellulose solution, adding a lead ion solution, introducing a gas to be tested, observing the color change of the solution, and detecting at a wavelength of 300 nm with an ultraviolet-visible spectrophotometer. The detection method of the present invention has good selectivity, and the detection method can specifically detect hydrogen sulfide; the detection method is fast, and the color of the solution can be changed from colorless to light yellow or brown within a few seconds, Moreover, it remains stable within a certain period of time; the detection method has high sensitivity, and the minimum concentration of hydrogen sulfide gas that can be detected is 1 mg/m 3 ; the detection method requires few reagents, is simple to operate, and is convenient for popularization and application.
Description
技术领域technical field
本发明涉及有毒气体检测领域，尤其涉及一种基于纳米晶纤维素检测硫化氢气体的方法。The invention relates to the field of toxic gas detection, in particular to a method for detecting hydrogen sulfide gas based on nanocrystalline cellulose.
背景技术Background technique
硫化氢是一种无色有臭鸡蛋气味的气体，具有刺激性和窒息性。人主要通过呼吸系统接触硫化氢，当硫化氢浓度较低时，对呼吸道及眼的局部有刺激作用；当浓度较高时，会对全身的中枢神经系统造成影响，甚至导致窒息；当浓度极高时，会引起嗅觉疲劳而不觉其味。有机磷农药、皮革、硫化染料、颜料和动物胶等工业中都有硫化氢的产生，沼泽地、阴沟、化粪池和污物沉淀池等处作业时均可有大量硫化氢溢出，作业工人中毒并不罕见。Hydrogen sulfide is a colorless gas with the smell of rotten eggs, which is irritating and asphyxiating. People are mainly exposed to hydrogen sulfide through the respiratory system. When the concentration of hydrogen sulfide is low, it can stimulate the respiratory tract and the eyes; when the concentration is high, it will affect the central nervous system of the whole body, and even cause suffocation; When it is high, it will cause olfactory fatigue without feeling the taste. Hydrogen sulfide is produced in industries such as organophosphorus pesticides, leather, sulfur dyes, pigments, and animal glue. A large amount of hydrogen sulfide may overflow when operating in swamps, sewers, septic tanks, and sewage sedimentation tanks. Poisoning is not uncommon.
随着我国工业化进程的不断加快，空气中硫化氢的背景浓度也不断提高，因此，对空气中硫化氢的检测就显得意义重大，能检测出低浓度硫化氢对于人体健康就显得尤为重要。现行的硫化氢气体的检测方法主要有：1)碘量法；2)亚甲蓝法；3)乙酸铅反应速率法；4)着色长度检测管法；5)激光吸收光谱法；6)荧光分析法；7)金属氧化物传感器；8)电化学传感器；9)气相色谱法。其中，碘量法对于低含量气体取样时间较长，且人工操作繁琐，不利于数据化采集与传输；亚甲蓝法只适用于测定硫化氢浓度较稳定的净化天然气；着色长度检测管法准确度不高；荧光分子检测铅离子需要使用价格昂贵的发光设备，电化学传感器设计复杂，操作繁琐；气相色谱法虽然灵敏度高，但气相色谱仪对采气装置的预处理、气相色谱仪进样系统的配置和惰性化处理，以及对标准气体的配制水平都要求极高，往往测试结果重现性差，测试结果不准确。上述方法技术均存在一定的局限。因此有必要建立一种可以准确测定室内外空气环境中硫化氢的方法。With the continuous acceleration of my country's industrialization process, the background concentration of hydrogen sulfide in the air is also increasing. Therefore, the detection of hydrogen sulfide in the air is of great significance, and the ability to detect low-concentration hydrogen sulfide is particularly important for human health. The current detection methods of hydrogen sulfide gas mainly include: 1) iodometric method; 2) methylene blue method; 3) lead acetate reaction rate method; 4) coloring length detection tube method; 5) laser absorption spectroscopy; 6) fluorescence analytical method; 7) metal oxide sensor; 8) electrochemical sensor; 9) gas chromatography. Among them, the iodometric method takes a long time to sample low-content gas, and the manual operation is cumbersome, which is not conducive to data collection and transmission; the methylene blue method is only suitable for the determination of purified natural gas with a relatively stable hydrogen sulfide concentration; the coloring length detection tube method is accurate The sensitivity is not high; the detection of lead ions by fluorescent molecules requires the use of expensive luminescent equipment, the design of electrochemical sensors is complex, and the operation is cumbersome; although gas chromatography has high sensitivity, the pretreatment of gas extraction devices by gas chromatography and the sampling of gas chromatography The configuration and inertization of the system, as well as the level of standard gas preparation are extremely demanding, and the reproducibility of the test results is often poor and the test results are not accurate. There are certain limitations in the above methods and techniques. Therefore, it is necessary to establish a method that can accurately measure hydrogen sulfide in indoor and outdoor air environments.
发明内容Contents of the invention
本发明的目的在于建立一种硫化氢的检测方法，能够使得检测更加简单、低廉、高效。The purpose of the present invention is to establish a hydrogen sulfide detection method, which can make the detection simpler, cheaper and more efficient.
为达此目的，本发明采用以下技术方案：For reaching this purpose, the present invention adopts following technical scheme:
一方面，本发明提供了一种基于纳米晶纤维素(NCC)检测硫化氢气体的方法，所述方法包括如下步骤：首先配制纳米晶纤维素(NCC)溶液，然后向该溶液中加入铅离子溶液，通入待测硫化氢气体，观察溶液颜色变化并用紫外-可见分光光度计检测。In one aspect, the present invention provides a method for detecting hydrogen sulfide gas based on nanocrystalline cellulose (NCC), said method comprising the steps of first preparing a nanocrystalline cellulose (NCC) solution, and then adding lead ions to the solution solution, pass through the hydrogen sulfide gas to be tested, observe the color change of the solution and detect it with an ultraviolet-visible spectrophotometer.
本发明利用硫离子与铅离子生成硫化铅的反应检测硫化氢，纳米晶纤维素(NCC)起到分散硫化铅的作用。首先配制NCC溶液，当加入醋酸铅后，铅离子通过静电作用分散在NCC表面，此时溶液为无色，当通入硫化氢气体后，溶液中生成微米级的硫化铅与NCC的复合颗粒，NCC分散在颗粒当中，溶液颜色呈现为淡黄色或褐色。NCC可以起到稳定硫化铅的作用，使得溶液颜色稳定。The invention detects hydrogen sulfide by utilizing the reaction of sulfur ions and lead ions to generate lead sulfide, and the nanocrystalline cellulose (NCC) plays the role of dispersing the lead sulfide. First prepare the NCC solution. When lead acetate is added, the lead ions are electrostatically dispersed on the surface of the NCC. At this time, the solution is colorless. When the hydrogen sulfide gas is introduced, the composite particles of lead sulfide and NCC in the micron size are generated in the solution, NCC Dispersed among the particles, the solution color appears light yellow or brown. NCC can play the role of stabilizing lead sulfide, making the solution color stable.
作为优选技术方案，本发明中所述纳米晶纤维素溶液的终浓度为0.2-5mg/mL，例如可以是0.2mg/mL、0.4mg/mL、0.5mg/mL、0.8mg/mL、1.0mg/mL、1.2mg/mL、1.5mg/mL、1.8mg/mL、2.0mg/mL、2.5mg/mL、3mg/mL，优选为1mg/mL。As a preferred technical solution, the final concentration of the nanocrystalline cellulose solution in the present invention is 0.2-5mg/mL, such as 0.2mg/mL, 0.4mg/mL, 0.5mg/mL, 0.8mg/mL, 1.0mg /mL, 1.2mg/mL, 1.5mg/mL, 1.8mg/mL, 2.0mg/mL, 2.5mg/mL, 3mg/mL, preferably 1mg/mL.
优选地，所述铅离子溶液的终浓度为0.2-5mM，例如可以是0.2mM、0.4mM、0.5mM、0.8mM、1.0mM、1.2mM、1.5mM、1.8mM、2.0mM、2.5mM、3.0mM，优选为1mg/mL。Preferably, the final concentration of the lead ion solution is 0.2-5mM, such as 0.2mM, 0.4mM, 0.5mM, 0.8mM, 1.0mM, 1.2mM, 1.5mM, 1.8mM, 2.0mM, 2.5mM, 3.0 mM, preferably 1 mg/mL.
优选地，所述铅离子溶液为醋酸铅或硝酸铅溶液。Preferably, the lead ion solution is lead acetate or lead nitrate solution.
本发明中所述紫外-可见分光光度计的检测波长为300-500nm，例如检测波长可以是300nm、310nm、320nm、330nm、340nm、350nm、360nm、370nm、380nm、390nm或400nm，优选为300-350nm，进一步优选为300nm。The detection wavelength of the ultraviolet-visible spectrophotometer described in the present invention is 300-500nm, for example detection wavelength can be 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm or 400nm, preferably 300- 350 nm, more preferably 300 nm.
所述方法包括如下步骤：The method comprises the steps of:
(1)配制0.4-10mg/mL纳米晶纤维素溶液与0.4-10mM铅离子溶液，并将两种溶液混合均匀，混合后纳米晶纤维素溶液的终浓度为0.2-5mg/mL，铅离子溶液的终浓度为0.2-5mM；(1) Prepare 0.4-10mg/mL nanocrystalline cellulose solution and 0.4-10mM lead ion solution, and mix the two solutions evenly. After mixing, the final concentration of nanocrystalline cellulose solution is 0.2-5mg/mL, lead ion solution The final concentration is 0.2-5mM;
(2)将硫化氢气体通入步骤(1)得到的混合溶液中，观察溶液颜色变化，并用紫外-可见分光光度计检测，定性的检测硫化氢。(2) Pass hydrogen sulfide gas into the mixed solution obtained in step (1), observe the color change of the solution, and detect with an ultraviolet-visible spectrophotometer to qualitatively detect hydrogen sulfide.
本发明所述方法还可以根据硫化钠浓度所做的标准曲线来定量的检测硫化氢气体的含量。The method of the present invention can also quantitatively detect the content of hydrogen sulfide gas according to the standard curve made by the concentration of sodium sulfide.
作为优选技术方案，本发明所述的方法包括如下步骤：As a preferred technical solution, the method of the present invention comprises the steps of:
(1)配制0.4-10mg/mL纳米晶纤维素溶液与0.4-10mg/mL铅离子溶液，并将两种溶液混合均匀；(1) Prepare 0.4-10mg/mL nanocrystalline cellulose solution and 0.4-10mg/mL lead ion solution, and mix the two solutions evenly;
(2)配制硫化钠溶液，浓度分别为10μM、20μM、40μM、80μM、120μM、160μM和200μM，现配现用；(2) prepare sodium sulfide solution, the concentration is respectively 10 μ M, 20 μ M, 40 μ M, 80 μ M, 120 μ M, 160 μ M and 200 μ M, prepare and use now;
(3)取步骤(1)得到的混合溶液，加入体积比1：1的步骤(2)得到的不同浓度的硫化钠溶液，混匀，混合后纳米晶纤维素溶液的终浓度为0.2-5mg/mL，铅离子溶液的终浓度为0.2-5mM，硫化钠的终浓度为5μM，10μM，20μM，40μM，60μM，80μM，100μM；(3) Take the mixed solution obtained in step (1), add sodium sulfide solutions of different concentrations obtained in step (2) with a volume ratio of 1:1, mix well, and the final concentration of the nanocrystalline cellulose solution after mixing is 0.2-5mg /mL, the final concentration of lead ion solution is 0.2-5mM, the final concentration of sodium sulfide is 5μM, 10μM, 20μM, 40μM, 60μM, 80μM, 100μM;
(4)观察步骤(3)中溶液的颜色变化，并用紫外-可见分光光度计检测，作出标准曲线；(4) observe the color change of solution in step (3), and detect with ultraviolet-visible spectrophotometer, make standard curve;
(5)取1-100mL步骤(1)得到的混合溶液，加入体积比1：1的去离子水，通入待测硫化氢气体，观察溶液的颜色变化，并用紫外-可见分光光度计检测，根据步骤(4)的标准曲线算出硫化氢的浓度。(5) Take 1-100mL of the mixed solution obtained in step (1), add deionized water with a volume ratio of 1:1, pass into the hydrogen sulfide gas to be tested, observe the color change of the solution, and detect it with a UV-Vis spectrophotometer, Calculate the concentration of hydrogen sulfide according to the standard curve of step (4).
步骤(5)所述通入待测气体的反应时间为0.01-3小时，优选为0.02-1小时，例如时间可以是0.02小时、0.5小时、1小时、1.5小时、2小时、2.5小时或3小时。The reaction time of introducing the gas to be tested in step (5) is 0.01-3 hours, preferably 0.02-1 hours, for example, the time can be 0.02 hours, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours. Hour.
将待测气体通入检测溶液中，观察溶液颜色随时间变化，发现体系在较长时间内是稳定的。Pass the gas to be tested into the detection solution, observe the color change of the solution with time, and find that the system is stable for a long time.
作为优选技术方案，本发明所述的方法包括如下步骤：As a preferred technical solution, the method of the present invention comprises the steps of:
(1)配制4mg/mL纳米晶纤维素溶液与4mg/mL铅离子溶液，并按体积比1:1将两种溶液混合均匀；(1) Prepare 4mg/mL nanocrystalline cellulose solution and 4mg/mL lead ion solution, and mix the two solutions evenly by volume ratio 1:1;
(2)配制硫化钠溶液，浓度分别为10μM、20μM、40μM、80μM、120μM、160μM和200μM；(2) preparing sodium sulfide solution, the concentrations are respectively 10 μM, 20 μM, 40 μM, 80 μM, 120 μM, 160 μM and 200 μM;
(3)取步骤(1)得到的混合溶液，加入体积比1:1的步骤(2)得到的不同浓度的硫化钠溶液，混匀，此时纳米晶纤维素溶液的终浓度为1mg/mL，铅离子溶液的终浓度为1mM，硫化钠的终浓度为5μM，10μM，20μM，40μM，60μM，80μM，100μM；(3) Take the mixed solution obtained in step (1), add the sodium sulfide solutions of different concentrations obtained in step (2) with a volume ratio of 1:1, and mix well. At this time, the final concentration of the nanocrystalline cellulose solution is 1mg/mL , the final concentration of lead ion solution is 1 mM, the final concentration of sodium sulfide is 5 μM, 10 μM, 20 μM, 40 μM, 60 μM, 80 μM, 100 μM;
(4)观察步骤(3)中溶液的颜色变化，并用紫外-可见分光光度计检测，作出标准曲线；(4) observe the color change of solution in step (3), and detect with ultraviolet-visible spectrophotometer, make standard curve;
(5)取步骤(1)得到的混合溶液，加入体积比1:1的去离子水，通入待测硫化氢气体，反应0.01-1小时，观察溶液颜色变化，并用紫外-可见分光光度计检测，根据步骤(4)的标准曲线算出硫化氢的浓度。(5) Take the mixed solution obtained in step (1), add deionized water with a volume ratio of 1:1, pass into the hydrogen sulfide gas to be measured, react for 0.01-1 hour, observe the color change of the solution, and use a UV-visible spectrophotometer Detect, calculate the concentration of hydrogen sulfide according to the standard curve of step (4).
对于本领域技术人员来说，即使不明了本发明的检测原理，同样能够实施、再现本发明，即本发明的检测原理是否清楚明了，都不影响本发明的实施和再现。本发明的一种基于纳米晶纤维素的铅离子检测和去除方法，本发明的检测原理在于：For those skilled in the art, even if they do not understand the detection principle of the present invention, they can also implement and reproduce the present invention, that is, whether the detection principle of the present invention is clear does not affect the implementation and reproduction of the present invention. A method for detecting and removing lead ions based on nanocrystalline cellulose of the present invention, the detection principle of the present invention is:
本发明利用硫离子与铅离子生成硫化铅的反应检测硫化氢，纳米晶纤维素(NCC)起到分散硫化铅的作用。首先配制NCC溶液，当加入醋酸铅后，铅离子通过静电作用分散在NCC表面，此时溶液为无色，当通入硫化氢气体后，溶液中生成微米级的硫化铅颗粒，NCC分散在颗粒当中，溶液颜色呈现为淡黄色或褐色。NCC可以起到稳定硫化铅的作用，使得溶液颜色稳定。The invention detects hydrogen sulfide by utilizing the reaction of sulfur ions and lead ions to generate lead sulfide, and the nanocrystalline cellulose (NCC) plays the role of dispersing the lead sulfide. First prepare the NCC solution. When lead acetate is added, the lead ions are electrostatically dispersed on the surface of the NCC. At this time, the solution is colorless. When hydrogen sulfide gas is introduced, micron-sized lead sulfide particles are formed in the solution, and NCC is dispersed in the particles. , the solution color is pale yellow or brown. NCC can play the role of stabilizing lead sulfide, making the solution color stable.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1)本发明的检测方法具有很好的选择性，由于本发明都无法检测二氧化硫、氨气、空气、二氧化碳、甲烷和乙烯等气体，唯独能检测二氧化硫；1) The detection method of the present invention has good selectivity, because the present invention cannot detect gases such as sulfur dioxide, ammonia, air, carbon dioxide, methane and ethylene, only can detect sulfur dioxide;
2)本发明的检测方法检测快速，溶液的颜色在几秒种就能由无色转变为淡黄色或褐色，而且在一定时间内保持稳定；2) The detection method of the present invention detects quickly, and the color of the solution can be changed from colorless to light yellow or brown in a few seconds, and remains stable within a certain period of time;
3)本发明的检测方法灵敏度高，能检测到的硫化氢气体的最低浓度为1mg/m3；3) The detection method of the present invention has high sensitivity, and the minimum concentration of hydrogen sulfide gas that can be detected is 1 mg/m 3 ;
4)本发明的检测方法所需试剂少，操作简单，便于推广应用。4) The detection method of the present invention requires few reagents, is simple to operate, and is convenient for popularization and application.
附图说明Description of drawings
图1是本发明硫化氢气体检测原理图。Fig. 1 is a schematic diagram of hydrogen sulfide gas detection in the present invention.
图2是本发明方法与不同浓度硫化钠反应的颜色图。Fig. 2 is the color map that the inventive method reacts with different concentrations of sodium sulfide.
图3是本发明对不同浓度硫化钠紫外分光光度计检测结果。Fig. 3 is the detection result of the present invention to different concentrations of sodium sulfide ultraviolet spectrophotometer.
图4是本发明300nm吸光度与硫化钠浓度线性关系。Fig. 4 is the linear relationship between 300nm absorbance and sodium sulfide concentration of the present invention.
图5是本发明方法与不同气体反应的颜色图。Figure 5 is a color map of the reaction of the method of the present invention with different gases.
图6是本发明方法与不同气体反应300nm下吸光度比较。Fig. 6 is a comparison of absorbance at 300 nm between the method of the present invention and different gas reactions.
图7是本发明硫化钠反应体系随时间变化检测图。Fig. 7 is a time-dependent detection diagram of the sodium sulfide reaction system of the present invention.
图8是本发明NCC形貌及有无NCC存在时硫化铅的TEM图。Fig. 8 is the TEM image of NCC morphology of the present invention and lead sulfide with or without the presence of NCC.
具体实施方式detailed description
为更进一步阐述本发明所采取的技术手段及其效果，以下结合附图并通过具体实施方式来进一步说明本发明的技术方案，但本发明并非局限在实施例范围内。In order to further illustrate the technical means and effects adopted by the present invention, the technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and through specific implementation methods, but the present invention is not limited within the scope of the embodiments.
实施例1：Example 1:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制0.4mg/mL的纳米晶纤维素溶液与0.4mM的醋酸铅溶液，并将他们按体积份数1:1混合；(1) Prepare 0.4mg/mL nanocrystalline cellulose solution and 0.4mM lead acetate solution, and mix them 1:1 by volume;
(2)向步骤(1)中的溶液通入硫化氢气体。(2) Pass hydrogen sulfide gas into the solution in step (1).
(3)观察溶液颜色变化，并用紫外-可见分光光度计在300nm下检测溶液的吸光值。(3) Observe the color change of the solution, and detect the absorbance value of the solution at 300 nm with an ultraviolet-visible spectrophotometer.
实施例2：Example 2:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制10mg/mL的纳米晶纤维素溶液与10mM的醋酸铅溶液，并将他们按体积份数1:1混合；(1) Prepare 10mg/mL nanocrystalline cellulose solution and 10mM lead acetate solution, and mix them 1:1 by volume;
(2)向步骤(1)中的溶液通入硫化氢气体。(2) Pass hydrogen sulfide gas into the solution in step (1).
(3)观察溶液颜色变化，并用紫外-可见分光光度计在300nm下检测溶液的吸光值。(3) Observe the color change of the solution, and detect the absorbance value of the solution at 300 nm with an ultraviolet-visible spectrophotometer.
实施例3：Example 3:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制4mg/mL的纳米晶纤维素溶液与4mM的醋酸铅溶液，并将他们按体积份数1:1混合；(1) Prepare 4mg/mL nanocrystalline cellulose solution and 4mM lead acetate solution, and mix them 1:1 by volume;
(2)向步骤(1)中的溶液通入硫化氢气体。(2) Pass hydrogen sulfide gas into the solution in step (1).
(3)观察溶液颜色变化，并用紫外-可见分光光度计在300nm下检测溶液的吸光值。(3) Observe the color change of the solution, and detect the absorbance value of the solution at 300 nm with an ultraviolet-visible spectrophotometer.
实施例4：Example 4:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制4mg/mL的纳米晶纤维素溶液与8mM的硝酸铅溶液，并将他们按体积份数1:2混合；(1) Prepare 4mg/mL nanocrystalline cellulose solution and 8mM lead nitrate solution, and mix them 1:2 by volume;
(2)向步骤(1)中的溶液通入硫化氢气体。(2) Pass hydrogen sulfide gas into the solution in step (1).
(3)观察溶液颜色变化，并用紫外-可见分光光度计在300nm下检测溶液的吸光值。(3) Observe the color change of the solution, and detect the absorbance value of the solution at 300 nm with an ultraviolet-visible spectrophotometer.
实施例5：Example 5:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制4mg/mL的纳米晶纤维素溶液与4mM的醋酸铅溶液，并将他们按体积份数1:1混合；(1) Prepare 4mg/mL nanocrystalline cellulose solution and 4mM lead acetate solution, and mix them 1:1 by volume;
(2)配制硫化钠溶液，浓度分别为10μM、20μM、40μM、80μM、120μM、160μM和200μM，现配现用；(2) prepare sodium sulfide solution, the concentration is respectively 10 μ M, 20 μ M, 40 μ M, 80 μ M, 120 μ M, 160 μ M and 200 μ M, prepare and use now;
(3)取100μL纳米晶纤维素与醋酸铅的混合溶液，加入100μL上述不同浓度的硫化钠溶液，混匀，硫化钠的终浓度为5μM，10μM，20μM，40μM，60μM，80μM和100μM；(3) Take 100 μL of the mixed solution of nanocrystalline cellulose and lead acetate, add 100 μL of the above-mentioned sodium sulfide solution of different concentrations, mix well, and the final concentration of sodium sulfide is 5 μM, 10 μM, 20 μM, 40 μM, 60 μM, 80 μM and 100 μM;
(4)观察溶液颜色变化，并用紫外-可见分光光度计检测溶液吸光度的变化；(4) Observe the color change of the solution, and detect the change of the absorbance of the solution with an ultraviolet-visible spectrophotometer;
(5)取溶液300nm处的吸光度作图，发现吸光度与硫化钠浓度间有很好的线性关系。(5) Take the absorbance at 300nm of the solution and make a graph, and find that there is a good linear relationship between the absorbance and the concentration of sodium sulfide.
从图2能看出随着硫化钠浓度的升高，溶液的颜色加深，图3中同样随着硫化钠浓度升高，分光光度计检测值也随之升高，图4硫化钠标准曲线线性相关性好，所得的硫化钠标准曲线为Y＝0.25394+0.01126X(R2＝0.99871)。As can be seen from Fig. 2 along with the raising of sodium sulfide concentration, the color of solution deepens, and in Fig. 3 equally along with the raising of sodium sulfide concentration, spectrophotometer detection value also raises thereupon, Fig. 4 sodium sulfide standard curve linearity The correlation is good, and the obtained sodium sulfide standard curve is Y=0.25394+0.01126X (R 2 =0.99871).
实施例6：Embodiment 6:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制2mg/mL的NCC溶液与2mM的醋酸铅溶液，并将它们等体积混合；(1) Prepare 2mg/mL NCC solution and 2mM lead acetate solution, and mix them in equal volumes;
(2)向步骤(1)中的溶液通入硫化氢气体、二氧化硫、氨气、甲烷、乙烯、二氧化碳、氮气、氩气和空气，并准备一个空白对照。(2) Pass hydrogen sulfide gas, sulfur dioxide, ammonia, methane, ethylene, carbon dioxide, nitrogen, argon and air into the solution in step (1), and prepare a blank control.
(3)观察溶液颜色变化，并用紫外-可见分光光度计检测溶液吸光度的变化。(3) Observe the color change of the solution, and detect the change of the absorbance of the solution with an ultraviolet-visible spectrophotometer.
从图5、图6明显看出检测体系只对硫化氢气体产生颜色变化，而对二氧化硫只有很低的吸收率，其他气体基本不会反应，所以该方法能稳定的检测硫化氢气体而不受别的气体影响。It is obvious from Figure 5 and Figure 6 that the detection system only produces color changes for hydrogen sulfide gas, but has a very low absorption rate for sulfur dioxide, and basically does not react to other gases, so this method can stably detect hydrogen sulfide gas without being affected. effects of other gases.
实施例7：Embodiment 7:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制4mg/mL的NCC溶液与4mM的醋酸铅溶液，并将它们等体积混合；(1) Prepare 4mg/mL NCC solution and 4mM lead acetate solution, and mix them in equal volumes;
(2)取100μL NCC与醋酸铅的混合溶液，加入100μL 100μM的硫化钠溶液；(2) Take 100 μL of the mixed solution of NCC and lead acetate, and add 100 μL of 100 μM sodium sulfide solution;
(3)观察0分钟、3分钟、6分钟、15分钟、30分钟和60分钟溶液颜色变化，并用紫外-可见分光光度计在300nm下检测各时间段溶液吸光值。(3) Observe the color change of the solution in 0 minutes, 3 minutes, 6 minutes, 15 minutes, 30 minutes and 60 minutes, and use a UV-visible spectrophotometer to detect the absorbance of the solution in each time period at 300 nm.
从图7可以看出，本发明的检测方法是非常稳定的，在1小时之内，检测值没有发生改变。It can be seen from Fig. 7 that the detection method of the present invention is very stable, and the detection value does not change within 1 hour.
实施例8：Embodiment 8:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制4mg/mL的NCC溶液与4mM的醋酸铅溶液，并将它们与水按体积比1：1：2混合；(1) Prepare 4mg/mL NCC solution and 4mM lead acetate solution, and mix them with water at a volume ratio of 1:1:2;
(2)向步骤(1)中的溶液通入5mg/m3的硫化氢气体。(2) The solution in step (1) is passed into 5mg/m The hydrogen sulfide gas.
(3)观察溶液颜色变化，并用紫外-可见分光光度计检测溶液吸光度的变化。(3) Observe the color change of the solution, and detect the change of the absorbance of the solution with an ultraviolet-visible spectrophotometer.
(4)测定吸收液在300nm处的吸光度，并从标准曲线上读取对应的浓度值。(4) Measure the absorbance of the absorbing solution at 300nm, and read the corresponding concentration value from the standard curve.
实施例9：Embodiment 9:
本实施例具体检测方法如下：The concrete detection method of this embodiment is as follows:
(1)配制4mg/mL的NCC溶液与4mM的醋酸铅溶液，并将它们与水按体积比1：1：2混合；(1) Prepare 4mg/mL NCC solution and 4mM lead acetate solution, and mix them with water at a volume ratio of 1:1:2;
(2)向步骤(1)中的溶液通入1mg/m3的硫化氢气体。(2) To the solution in the step (1), 1 mg/ m hydrogen sulfide gas is fed.
(3)观察溶液颜色变化，并用紫外-可见分光光度计检测溶液吸光度的变化。(3) Observe the color change of the solution, and detect the change of the absorbance of the solution with an ultraviolet-visible spectrophotometer.
(4)测定吸收液在300nm处的吸光度，并从标准曲线上读取对应的浓度值。(4) Measure the absorbance of the absorbing solution at 300nm, and read the corresponding concentration value from the standard curve.
图8展示了本发明NCC形貌及有无NCC存在时硫化铅的TEM图，铅离子通过静电作用分散在NCC表面，通入硫化氢气体后，溶液中生成微米级的硫化铅颗粒，NCC分散在颗粒当中。Figure 8 shows the NCC morphology of the present invention and the TEM image of lead sulfide when NCC exists or not. Lead ions are dispersed on the NCC surface by electrostatic action. After hydrogen sulfide gas is introduced, micron-sized lead sulfide particles are generated in the solution, and NCC is dispersed. among the particles.
综上所述，本发明的方法可以定性和定量的检测硫化氢气体，且快速准确，在长时间内保持稳定。同时，本发明的检测方法专一性强，能特异性的检测硫化氢气体。通过不同浓度的硫化氢气体的检测，本发明的方法可以准确的检测硫化氢气体的浓度，最低能检测到1mg/m3的硫化氢气体。In summary, the method of the present invention can detect hydrogen sulfide gas qualitatively and quantitatively, quickly and accurately, and keep stable for a long time. At the same time, the detection method of the invention has strong specificity and can specifically detect hydrogen sulfide gas. Through the detection of hydrogen sulfide gas with different concentrations, the method of the invention can accurately detect the concentration of hydrogen sulfide gas, and the hydrogen sulfide gas of 1 mg/ m3 can be detected at least.
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention can only be implemented depending on the above-mentioned detailed methods. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.
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