技术领域technical field
本发明涉及电化学检测传感领域，具体为单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极、制备方法。The invention relates to the field of electrochemical detection and sensing, in particular to a film electrode and a preparation method for vertically growing nano-bismuth on the surface of a single-layer carboxylated graphene oxide.
背景技术Background technique
偏二甲肼的英文简称为UDMH，是最常用的一种肼类燃料，具有很好的储存性能和比冲，在火箭发射中被广泛应用，但会使人体出现一些不良症状，如食欲不振、记忆力减退、注意力不集中、肝功能异常。在脱落的助推器中，有大量的UDMH，会造成坠落点附近的水源污染。然而，目前对UDMH在环境中的允许浓度有严格限制，因此，偏二甲肼浓度的大小关系到环境的危害和人员的防护，UDMH的快速检测对环境污染控制以及相关人员安全具有重要的意义。The English abbreviation of unsymmetrical dimethylhydrazine is UDMH. It is the most commonly used hydrazine fuel. It has good storage performance and specific impulse. It is widely used in rocket launches, but it will cause some adverse symptoms in the human body, such as loss of appetite. , memory loss, inattention, abnormal liver function. In the dropped booster, there is a large amount of UDMH, which will pollute the water source near the point of fall. However, there are currently strict restrictions on the allowable concentration of UDMH in the environment. Therefore, the concentration of unsymmetrical dimethylhydrazine is related to the hazards of the environment and the protection of personnel. The rapid detection of UDMH is of great significance to the control of environmental pollution and the safety of related personnel. .
负载钯的单层羧基氧化石墨烯复合薄膜电极，具有环境友好和成本低廉的效果，在UDMH的检测中效率高，在UDMH(1μg/L)中氧化电流峰值最高可达100μA，检测限低(0.012μg/L)，具有良好的电化学检测性能，能够用于快速的电化学检测偏二甲肼。The single-layer carboxylated graphene oxide composite film electrode loaded with palladium has the effect of environmental friendliness and low cost. It has high efficiency in the detection of UDMH, and the peak value of oxidation current in UDMH (1μg/L) can reach up to 100μA, and the detection limit is low ( 0.012μg/L), has good electrochemical detection performance, and can be used for rapid electrochemical detection of unsymmetrical dimethylhydrazine.
然而，钯单质属于贵金属，成本较高，与单层羧基氧化石墨烯复合形成的薄膜电极不利于电极材料作为检测器件的大范围推广应用。However, the simple substance of palladium is a noble metal with high cost, and the thin film electrode formed by compounding with single-layer carboxylated graphene oxide is not conducive to the wide application of electrode materials as detection devices.
发明内容Contents of the invention
针对现有技术中存在的问题，本发明提供单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极、制备方法，铋在地球上大量存在，花状铋负载的单层羧基氧化石墨烯复合薄膜电极环境友好且成本低廉，检测效率高，具有良好的电化学检测性能，能够用于快速的电化学检测偏二甲肼。Aiming at the problems existing in the prior art, the present invention provides a film electrode and a preparation method for vertically growing nanobismuth on the surface of a single-layer carboxylated graphene oxide. The electrode is environmentally friendly and low in cost, has high detection efficiency, has good electrochemical detection performance, and can be used for rapid electrochemical detection of unsymmetrical dimethylhydrazine.
本发明是通过以下技术方案来实现：The present invention is achieved through the following technical solutions:
单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极的制备方法，包括如下步骤：The preparation method of the film electrode of the vertical growth nano-bismuth on the surface of monolayer carboxyl graphene oxide comprises the following steps:
第一步，将五水合硝酸铋粉末溶于超纯水和乙二醇中，五水合硝酸铋粉末和乙二醇的比例为(0.1～0.5)mol：(70～350)mL，之后搅拌，得到前驱液；In the first step, dissolve bismuth nitrate pentahydrate powder in ultrapure water and ethylene glycol, the ratio of bismuth nitrate pentahydrate powder and ethylene glycol is (0.1-0.5) mol: (70-350) mL, and then stir, get the precursor solution;
第二步，将单层羧基氧化石墨烯/玻碳电极或者单层羧基氧化石墨烯/导电玻璃作为工作电极，插入到第一步得到的前驱液中，以-0.25～-0.15V的条件进行恒电位电化学沉积，工作电极上形成复合薄膜；In the second step, the single-layer carboxylated graphene oxide/glassy carbon electrode or single-layer carboxylated graphene oxide/conductive glass is used as the working electrode, inserted into the precursor solution obtained in the first step, and carried out under the condition of -0.25 ~ -0.15V Constant potential electrochemical deposition, forming a composite film on the working electrode;
第三步，将第二步得到的复合物冲洗后再进行干燥，得到单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极。In the third step, the compound obtained in the second step is rinsed and then dried to obtain a thin film electrode with bismuth nanoparticles vertically grown on the surface of the single-layer carboxylated graphene oxide.
优选的，第一步中，先将五水合硝酸铋粉末溶于超纯水中，搅拌10～14h，再加入乙二醇，超纯水和乙二醇的体积比为(30～150)：(70～350)。Preferably, in the first step, the bismuth nitrate pentahydrate powder is first dissolved in ultrapure water, stirred for 10 to 14 hours, and then ethylene glycol is added, and the volume ratio of ultrapure water to ethylene glycol is (30 to 150): (70~350).
优选的，第一步将五水合硝酸铋粉末溶于超纯水和乙二醇之后，搅拌20～24h，得到前驱液。Preferably, in the first step, the bismuth nitrate pentahydrate powder is dissolved in ultrapure water and ethylene glycol, and stirred for 20-24 hours to obtain a precursor solution.
优选的，第二步中，以铂片电极为对电极，以甘汞电极为参比电极。Preferably, in the second step, the platinum plate electrode is used as the counter electrode, and the calomel electrode is used as the reference electrode.
优选的，第二步中，电化学沉积的时间为60～240s。Preferably, in the second step, the electrochemical deposition time is 60-240s.
优选的，第二步中，电化学沉积的采样间隔时间为0.1～0.2s。Preferably, in the second step, the sampling interval of the electrochemical deposition is 0.1-0.2s.
优选的，第三步将第二步得到的复合物用超纯水冲洗后再进行干燥。Preferably, in the third step, the complex obtained in the second step is rinsed with ultrapure water and then dried.
进一步，所述的干燥在60～80℃下进行12～18h。Further, the drying is carried out at 60-80° C. for 12-18 hours.
优选的，第二步所述的工作电极按如下过程得到：Preferably, the working electrode described in the second step is obtained as follows:
将单层羧基氧化石墨烯粉末超声分散成1～5mg/mL的水溶液，将10～20μL的水溶液滴涂到玻碳电极或导电玻璃上，干燥后得到工作电极。The single-layer carboxylated graphene oxide powder is ultrasonically dispersed into a 1-5 mg/mL aqueous solution, and 10-20 μL of the aqueous solution is drip-coated on a glassy carbon electrode or conductive glass, and dried to obtain a working electrode.
一种由上述任意一项所述单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极的制备方法得到的单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极。A thin film electrode with bismuth vertically grown on the surface of single-layer carboxylated graphene oxide obtained by the method for preparing a thin-film electrode with bismuth vertically grown on the surface of single-layer carboxylated graphene oxide described in any one of the above.
与现有技术相比，本发明具有以下有益的技术效果：Compared with the prior art, the present invention has the following beneficial technical effects:
本发明单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极的制备方法，先将硝酸铋溶于超纯水和乙二醇中，乙二醇可以活化硝酸铋，通过恒电位电化学沉积能得到形貌为花状的纳米铋。经羧基化的单层氧化石墨烯表面含有大量的羧基，表面的羧基和偏二甲肼中的-NH2结合后会成为电化学检测的活性位点，但单层羧基氧化石墨烯的有效活性面积较低，相比较负载前阻抗较大，负载花状纳米铋(Bi)可以提高羧基氧化石墨烯对偏二甲肼的灵敏度。此外，根据文献中描述纳米铋金属呈现出一些超导性质，说明铋在理论上可以作为电极材料进行应用，因此本发明验证了可以将花状纳米铋和单层羧基氧化石墨烯进行复合作为检测偏二甲肼的电极材料。铋垂直生长在单层羧基氧化石墨烯表面上，形貌如花朵一样，花状的纳米片均匀的负载在层状羧基氧化石墨烯表面，因此活性面积更大，检测性能更优异。The preparation method of the thin film electrode of nano-bismuth vertically grown on the surface of single-layer carboxylated graphene oxide of the present invention firstly dissolves bismuth nitrate in ultrapure water and ethylene glycol, and ethylene glycol can activate bismuth nitrate, and can be obtained by constant potential electrochemical deposition. A flower-like nanobismuth was obtained. The surface of carboxylated single-layer graphene oxide contains a large number of carboxyl groups, and the carboxyl groups on the surface will become active sites for electrochemical detection after combining with-NH2 in unsymmetrical dimethylhydrazine, but the effective activity of single-layer carboxylated graphene oxide The area is lower and the impedance is larger than that before loading. Loading flower-like nanobismuth (Bi) can improve the sensitivity of carboxylated graphene oxide to unsymmetrical dimethylhydrazine. In addition, according to the description in the literature, nano-bismuth metal exhibits some superconducting properties, indicating that bismuth can be used as an electrode material in theory. Therefore, the present invention has verified that flower-shaped nano-bismuth and single-layer carboxylated graphene oxide can be combined as a detection Electrode material for unsymmetrical dimethylhydrazine. Bismuth grows vertically on the surface of single-layer carboxylated graphene oxide, and its shape is like a flower. The flower-like nanosheets are evenly loaded on the surface of layered carboxylated graphene oxide, so the active area is larger and the detection performance is better.
本发明合成的单层羧基氧化石墨烯表面垂直生长纳米铋的薄膜电极，花状纳米铋负载在单层羧基氧化石墨烯上，可以利用其作为检测偏二甲肼的复合传感薄膜，可促使偏二甲肼检测向高灵敏度、非贵金属负载、低成本的方向发展。The film electrode of nanobismuth grown vertically on the surface of the single-layer carboxylated graphene oxide synthesized by the present invention, flower-shaped nanobismuth loaded on the single-layer carboxylated graphene, can be used as a composite sensing film for detecting unsymmetrical dimethylhydrazine, which can promote The detection of unsymmetrical dimethylhydrazine is developing in the direction of high sensitivity, non-precious metal loading, and low cost.
附图说明Description of drawings
图1为本发明实施例1得到的花状纳米铋负载的单层羧基氧化石墨烯的场发射扫描电镜图。Fig. 1 is the field emission scanning electron microscope image of the single-layer carboxylated graphene oxide supported by flower-like nano-bismuth obtained in Example 1 of the present invention.
图2为本发明实施例1得到的花状纳米铋负载的单层羧基氧化石墨烯的透射电镜图。Fig. 2 is a transmission electron microscope image of the single-layer carboxylated graphene oxide supported by flower-shaped nano-bismuth obtained in Example 1 of the present invention.
图3为本发明得到的单层羧基氧化石墨烯和花状纳米铋负载的单层羧基氧化石墨烯的X射线衍射图。Fig. 3 is the X-ray diffraction pattern of the single-layer carboxylated graphene oxide obtained in the present invention and the single-layer carboxylated graphene supported by flower-like nanobismuth.
图4为本发明实施例不同电沉积时间得到的花状纳米铋负载的单层羧基氧化石墨烯对浓度为1μg/L的偏二甲肼检测的循环伏安曲线。Fig. 4 is a cyclic voltammetry curve of flower-shaped nanobismuth-supported single-layer carboxylated graphene oxide with a concentration of 1 μg/L of unsymmetrical dimethylhydrazine obtained at different electrodeposition times in an embodiment of the present invention.
图5为本发明实施例1得到的花状纳米铋负载的单层羧基氧化石墨烯在UDMH＝1μg/L溶液中循环3次的循环伏安扫描曲线。Fig. 5 is a cyclic voltammetry scanning curve of the single-layer carboxylated graphene oxide supported by flower-like nanobismuth obtained in Example 1 of the present invention in a UDMH=1 μg/L solution after 3 cycles.
图6a为本发明Bare、MGOCOOH、四种不同沉积时间的电极材料在0.1M氯化钾溶液中的恒电位阻抗图。Fig. 6a is a constant potential impedance diagram of Bare, MGOCOOH and four electrode materials with different deposition times in 0.1M potassium chloride solution of the present invention.
图6b为图6a中虚线处的放大图。Fig. 6b is an enlarged view at the dotted line in Fig. 6a.
图7为本发明实施例1得到的花状纳米铋负载的单层羧基氧化石墨烯的X射线光电子能谱(XPS)的全谱图。Fig. 7 is the full spectrum of X-ray photoelectron spectroscopy (XPS) of the single-layer carboxylated graphene oxide supported by flower-like nanobismuth obtained in Example 1 of the present invention.
图8为本发明实施例1得到的花状纳米铋负载的单层羧基氧化石墨烯XPS谱图中Bi元素的表面化学态。Fig. 8 is the surface chemical state of Bi element in the XPS spectrum of the single-layer carboxylated graphene oxide supported by flower-shaped nano-bismuth obtained in Example 1 of the present invention.
图9为本发明实施例1得到的花状纳米铋负载的单层羧基氧化石墨烯XPS谱图中O元素的1s谱图。Fig. 9 is the 1s spectrum of the O element in the XPS spectrum of the single-layer carboxylated graphene oxide supported by flower-shaped nanobismuth obtained in Example 1 of the present invention.
图10为本发明实施例2得到的花状纳米铋负载的单层羧基氧化石墨烯中偏二甲肼的浓度和氧化电流峰值对应图。Fig. 10 is a graph corresponding to the concentration of unsymmetrical dimethylhydrazine in the single-layer carboxylated graphene oxide supported by flower-like nanobismuth obtained in Example 2 of the present invention and the peak value of the oxidation current.
图11为根据图10拟合的偏二甲肼浓度和氧化电流峰值关系图。Fig. 11 is a graph of the relationship between the concentration of unsymmetrical dimethylhydrazine and the peak value of the oxidation current fitted according to Fig. 10 .
具体实施方式Detailed ways
下面结合具体的实施例对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。The present invention will be further described in detail below in conjunction with specific embodiments, which are explanations of the present invention rather than limitations.
本发明将非贵金属铋负载在单层羧基氧化石墨烯上，得到了一种单层羧基氧化石墨烯表面垂直生长花状纳米铋的薄膜电极，其具体制备过程，包括了如下步骤：In the present invention, the non-precious metal bismuth is loaded on the single-layer carboxylated graphene oxide, and a thin film electrode with flower-shaped nano-bismuth vertically grown on the surface of the single-layer carboxylated graphene oxide is obtained. The specific preparation process includes the following steps:
第一步，取0.1～0.5mol五水合硝酸铋粉末溶于30～150mL的超纯水中，搅拌10～14小时，量取70～350mL的乙二醇加入上述硝酸铋的水溶液中，继续搅拌20～24小时，得到前驱液，乙二醇作为电化学还原过程中的助还原剂，可以降低之后电化学还原铋过程的电势。In the first step, take 0.1-0.5 mol of bismuth nitrate pentahydrate powder and dissolve it in 30-150 mL of ultrapure water, stir for 10-14 hours, measure 70-350 mL of ethylene glycol and add it to the above-mentioned bismuth nitrate aqueous solution, and continue stirring After 20 to 24 hours, the precursor solution is obtained, and ethylene glycol is used as a co-reducing agent in the electrochemical reduction process, which can reduce the potential of the subsequent electrochemical reduction process of bismuth.
第二步，将单层羧基氧化石墨烯/玻碳电极或者单层羧基氧化石墨烯/导电玻璃作为工作电极，插入到第一步得到的前驱液中利用电化学工作站进行电化学沉积60～240s，工作电极上发生恒电位还原反应，铋通过原位电化学还原沉积到单层羧基氧化石墨烯上，其中对电极选择铂片电极，厚度为1mm，面积为1cm2，参比电极选择甘汞电极，电化学工作站具体为美国普林斯顿电化学工作站，这种电化学工作站灵敏度高，噪声小，能得到电流稳定，恒电位的取值范围为-0.25～-0.15V，采样间隔时间的取值范围为0.1～0.2s。In the second step, use a single-layer carboxylated graphene oxide/glassy carbon electrode or a single-layer carboxylated graphene oxide/conductive glass as a working electrode, insert it into the precursor solution obtained in the first step, and use an electrochemical workstation to perform electrochemical deposition for 60-240s , a constant potential reduction reaction occurs on the working electrode, and bismuth is deposited on the single-layer carboxylated graphene oxide through in-situ electrochemical reduction. The counter electrode is a platinum electrode with a thickness of 1 mm and an area of 1 cm2 , and the reference electrode is calomel. The electrode and the electrochemical workstation are specifically the Princeton electrochemical workstation in the United States. This electrochemical workstation has high sensitivity, low noise, and can obtain stable current. The value range of the constant potential is -0.25～-0.15V, and the value range of the sampling interval It is 0.1-0.2s.
第三步，将得到的复合薄膜立即用超纯水冲洗，在60～80℃下干燥12～18h，得到单层羧基氧化石墨烯表面垂直生长花状纳米铋的复合薄膜电极，可进行偏二甲肼的检测。In the third step, the obtained composite film is immediately rinsed with ultrapure water, and dried at 60-80°C for 12-18 hours to obtain a composite film electrode with flower-shaped nanobismuth vertically grown on the surface of a single-layer carboxylated graphene oxide, which can be used for partial bismuth Detection of methylhydrazine.
关于第二步中所提到的工作电极按如下过程得到：The working electrode mentioned in the second step is obtained as follows:
将单层氧化石墨烯纳米片和去离子水加入到烧杯中超声分散，其中单层氧化石墨烯纳米片和去离子水的比例为(50～100)mg：100mL，具体分散的时间为3～8h，然后依次加入氢氧化钾溶液和氯乙酸混匀，该氢氧化钾溶液的浓度为0.025mol/L，其与去离子水的体积比为1:10，而氯乙酸与去离子水的比例为0.01mol:100mL，用浓度为0.1mol/L的氢氧化钠溶液调节混合液的pH为6～8，得到含单层羧基氧化石墨烯的分散液；Add single-layer graphene oxide nanosheets and deionized water into a beaker for ultrasonic dispersion, wherein the ratio of single-layer graphene oxide nanosheets and deionized water is (50-100) mg: 100mL, and the specific dispersion time is 3~ 8h, then add potassium hydroxide solution and chloroacetic acid and mix in turn, the concentration of the potassium hydroxide solution is 0.025mol/L, its volume ratio to deionized water is 1:10, and the ratio of chloroacetic acid to deionized water 0.01mol: 100mL, with a concentration of 0.1mol/L sodium hydroxide solution to adjust the pH of the mixed solution is 6 ~ 8, to obtain a dispersion containing monolayer carboxyl graphene oxide;
以超纯水洗涤的方式，以90000～13000rpm/min的转速离心上一步得到的分散液3～5次，每次5～10min，分离位于底层的固体物，在50～70℃下真空干燥12～24h，最后研磨得到黑色的单层羧基氧化石墨烯粉末。Wash with ultra-pure water, centrifuge the dispersion obtained in the previous step at a speed of 90,000-13,000 rpm/min for 3-5 times, each time for 5-10 minutes, separate the solids at the bottom, and dry them under vacuum at 50-70°C for 12 ~24h, and finally grind to obtain a black single-layer carboxylated graphene oxide powder.
将单层羧基氧化石墨烯粉末超声分散成1～5mg/mL的水溶液，呈深黑色，再利用微量注射器，将10～20μL的水溶液滴涂到玻碳电极或导电玻璃上，烘干后得到工作电极。The single-layer carboxylated graphene oxide powder is ultrasonically dispersed into a 1-5 mg/mL aqueous solution, which is dark black, and then using a micro-syringe, 10-20 μL of the aqueous solution is drip-coated on the glassy carbon electrode or conductive glass, and the work is obtained after drying. electrode.
实施例1Example 1
本发明一种花状纳米铋负载单层羧基氧化石墨烯复合薄膜电极的制备方法，包括如下步骤：A method for preparing a flower-shaped nano-bismuth-loaded single-layer carboxyl graphene oxide composite film electrode of the present invention comprises the following steps:
第一步，将4.8g五水合硝酸铋粉末溶解在30mL去离子水中，搅拌10小时，再加入70mL乙二醇继续搅拌24h，得到混合溶液，其中铋的浓度为0.1mol L-1；In the first step, dissolve 4.8 g of bismuth nitrate pentahydrate powder in 30 mL of deionized water, stir for 10 hours, then add 70 mL of ethylene glycol and continue stirring for 24 hours to obtain a mixed solution, in which the concentration of bismuth is 0.1 mol L-1 ;
第二步，将工作电极插入到第一步得到的混合溶液中，参比电极选择甘汞电极，对电极选择厚度为1mm和面积为1cm2的铂片电极，在美国普林斯顿电化学工作站中进行恒电位还原反应，恒电位为-0.2V，采样间隔为0.1s，时间为60s。In the second step, insert the working electrode into the mixed solution obtained in the first step, select the calomel electrode as the reference electrode, and select the platinum plate electrode with a thickness of 1mm and an area of1cm2 as the counter electrode, and carry out at the Princeton Electrochemical Workstation in the United States For the constant potential reduction reaction, the constant potential is -0.2V, the sampling interval is 0.1s, and the time is 60s.
第三步，将得到的复合薄膜立即用超纯水冲洗，在70℃下干燥16h，，花状纳米铋负载的单层羧基氧化石墨烯复合薄膜附着在玻碳电极上，得到花状纳米铋负载的单层羧基氧化石墨烯复合薄膜电极，记为Bi/MGOCOOH-1。In the third step, the obtained composite film was immediately rinsed with ultrapure water, dried at 70°C for 16 hours, and the single-layer carboxylated graphene oxide composite film loaded with flower-shaped nanobismuth was attached to a glassy carbon electrode to obtain flower-shaped nanobismuth The supported single-layer carboxylated graphene oxide composite film electrode is denoted as Bi/MGOCOOH-1.
第二步中所提到的工作电极按如下过程得到：The working electrode mentioned in the second step is obtained as follows:
将单层氧化石墨烯纳米片和去离子水加入到烧杯中超声分散6h，其中单层氧化石墨烯纳米片为80mg，去离子水为100mL，然后依次加入氢氧化钾溶液和氯乙酸混匀，氢氧化钾溶液的浓度为0.025mol/L，体积为10mL，氯乙酸为0.01mol，用浓度为0.1mol/L的氢氧化钠溶液调节混合液的pH为7，得到含单层羧基氧化石墨烯的分散液；Add single-layer graphene oxide nanosheets and deionized water into a beaker for ultrasonic dispersion for 6h, wherein the single-layer graphene oxide nanosheets are 80mg, deionized water is 100mL, and then add potassium hydroxide solution and chloroacetic acid and mix well. The concentration of potassium hydroxide solution is 0.025mol/L, the volume is 10mL, chloroacetic acid is 0.01mol, and the pH of the mixed solution is adjusted to 7 with a concentration of 0.1mol/L sodium hydroxide solution to obtain a single-layer carboxyl group-containing graphene oxide. the dispersion liquid;
以超纯水洗涤的方式，以10000rpm/min的转速离心上一步得到的分散液4次，每次8min，分离位于底层的固体物，在60℃下真空干燥18h，最后研磨得到黑色的单层羧基氧化石墨烯粉末。Wash with ultra-pure water, centrifuge the dispersion obtained in the previous step at a speed of 10,000 rpm/min for 4 times, each time for 8 minutes, separate the solid at the bottom layer, dry it in vacuum at 60°C for 18 hours, and finally grind to obtain a black monolayer Carboxylated graphene oxide powder.
将单层羧基氧化石墨烯粉末超声分散成3mg/mL的深黑色水溶液，再利用微量注射器，将15μL的水溶液滴涂到玻碳电极上，烘干后得到工作电极。The single-layer carboxylated graphene oxide powder was ultrasonically dispersed into a 3 mg/mL dark black aqueous solution, and then 15 μL of the aqueous solution was drip-coated on the glassy carbon electrode using a micro-syringe, and the working electrode was obtained after drying.
实施例2Example 2
本发明一种花状纳米铋负载单层羧基氧化石墨烯复合薄膜电极的制备方法，包括如下步骤：A method for preparing a flower-shaped nano-bismuth-loaded single-layer carboxyl graphene oxide composite film electrode of the present invention comprises the following steps:
第一步，将9.6g五水合硝酸铋粉末溶解在40mL去离子水中，搅拌10小时，再加入80mL乙二醇继续搅拌22h，得到混合溶液；In the first step, dissolve 9.6g of bismuth nitrate pentahydrate powder in 40mL of deionized water, stir for 10 hours, then add 80mL of ethylene glycol and continue stirring for 22h to obtain a mixed solution;
第二步，将工作电极插入到第一步得到的混合溶液中，参比电极选择甘汞电极，对电极选择厚度为1mm和面积为1cm2的铂片电极，在美国普林斯顿电化学工作站中进行恒电位还原反应，恒电位为-0.2V，采样间隔为0.1s，时间为120s。In the second step, insert the working electrode into the mixed solution obtained in the first step, select the calomel electrode as the reference electrode, and select the platinum plate electrode with a thickness of 1mm and an area of1cm2 as the counter electrode, and carry out at the Princeton Electrochemical Workstation in the United States For the constant potential reduction reaction, the constant potential is -0.2V, the sampling interval is 0.1s, and the time is 120s.
第三步，将得到的复合薄膜立即用超纯水冲洗，在80℃下干燥12h，花状纳米铋负载的单层羧基氧化石墨烯复合薄膜附着在玻碳电极上，得到花状纳米铋负载的单层羧基氧化石墨烯复合薄膜电极，记为Bi/MGOCOOH-2。In the third step, the obtained composite film was immediately rinsed with ultrapure water, dried at 80°C for 12 hours, and the single-layer carboxylated graphene oxide composite film loaded with flower-like nanobismuth was attached to a glassy carbon electrode to obtain a flower-shaped nanobismuth-loaded The single-layer carboxylated graphene oxide composite film electrode, denoted as Bi/MGOCOOH-2.
第二步中所提到的工作电极按如下过程得到：The working electrode mentioned in the second step is obtained as follows:
将单层氧化石墨烯纳米片和去离子水加入到烧杯中超声分散5h，其中单层氧化石墨烯纳米片为50mg，去离子水为100mL，然后依次加入氢氧化钾溶液和氯乙酸混匀，氢氧化钾溶液的浓度为0.025mol/L，体积为10mL，氯乙酸为0.01mol，用浓度为0.1mol/L的氢氧化钠溶液调节混合液的pH为7.5，得到含单层羧基氧化石墨烯的分散液；Add single-layer graphene oxide nanosheets and deionized water into a beaker for ultrasonic dispersion for 5h, wherein the single-layer graphene oxide nanosheets are 50mg, deionized water is 100mL, and then add potassium hydroxide solution and chloroacetic acid and mix well. The concentration of potassium hydroxide solution is 0.025mol/L, the volume is 10mL, chloroacetic acid is 0.01mol, and the pH of the mixed solution is adjusted to 7.5 with a concentration of 0.1mol/L sodium hydroxide solution to obtain a single-layer carboxylated graphene oxide the dispersion liquid;
以超纯水洗涤的方式，以12000rpm/min的转速离心上一步得到的分散液5次，每次7min，分离位于底层的固体物，在50℃下真空干燥20h，最后研磨得到黑色的单层羧基氧化石墨烯粉末。Wash with ultrapure water, centrifuge the dispersion obtained in the previous step at a speed of 12000rpm/min for 5 times, 7min each time, separate the solid at the bottom layer, dry in vacuum at 50°C for 20h, and finally grind to obtain a black monolayer Carboxylated graphene oxide powder.
将单层羧基氧化石墨烯粉末超声分散成2mg/mL的深黑色水溶液，再利用微量注射器，将20μL的水溶液滴涂到玻碳电极上，烘干后得到工作电极。The single-layer carboxylated graphene oxide powder was ultrasonically dispersed into a 2 mg/mL dark black aqueous solution, and then 20 μL of the aqueous solution was drip-coated on the glassy carbon electrode using a micro-syringe, and the working electrode was obtained after drying.
实施例3Example 3
本发明一种花状纳米铋负载单层羧基氧化石墨烯复合薄膜电极的制备方法，包括如下步骤：A method for preparing a flower-shaped nano-bismuth-loaded single-layer carboxyl graphene oxide composite film electrode of the present invention comprises the following steps:
第一步，将4.8g五水合硝酸铋粉末溶解在30mL去离子水中，搅拌10小时，再加入70mL乙二醇继续搅拌24h，得到混合溶液；In the first step, dissolve 4.8g of bismuth nitrate pentahydrate powder in 30mL of deionized water, stir for 10 hours, then add 70mL of ethylene glycol and continue stirring for 24h to obtain a mixed solution;
第二步，将工作电极插入到第一步得到的混合溶液中，铋的浓度为0.1mol L-1，参比电极选择甘汞电极，对电极选择厚度为1mm和面积为1cm2的铂片电极，在美国普林斯顿电化学工作站中进行恒电位还原反应，恒电位为-0.2V，采样间隔为0.1s，时间为180s。In the second step, the working electrode is inserted into the mixed solution obtained in the first step, the concentration of bismuth is 0.1mol L-1 , the reference electrode is a calomel electrode, and the counter electrode is a platinum sheet with a thickness of 1 mm and an area of 1 cm2 The electrode was subjected to a constant potential reduction reaction in an electrochemical workstation in Princeton, USA, with a constant potential of -0.2V, a sampling interval of 0.1s, and a time of 180s.
第三步，将得到的复合薄膜立即用超纯水冲洗，在70℃下干燥16h，，花状纳米铋负载的单层羧基氧化石墨烯复合薄膜附着在玻碳电极上，得到花状纳米铋负载的单层羧基氧化石墨烯复合薄膜电极，记为Bi/MGOCOOH-3。In the third step, the obtained composite film was immediately rinsed with ultrapure water, dried at 70°C for 16 hours, and the single-layer carboxylated graphene oxide composite film loaded with flower-shaped nanobismuth was attached to a glassy carbon electrode to obtain flower-shaped nanobismuth The supported single-layer carboxylated graphene oxide composite thin film electrode is denoted as Bi/MGOCOOH-3.
第二步中所提到的工作电极按如下过程得到：The working electrode mentioned in the second step is obtained as follows:
将单层氧化石墨烯纳米片和去离子水加入到烧杯中超声分散6h，其中单层氧化石墨烯纳米片为80mg，去离子水为100mL，然后依次加入氢氧化钾溶液和氯乙酸混匀，氢氧化钾溶液的浓度为0.025mol/L，体积为10mL，氯乙酸为0.01mol，用浓度为0.1mol/L的氢氧化钠溶液调节混合液的pH为7，得到含单层羧基氧化石墨烯的分散液；Add single-layer graphene oxide nanosheets and deionized water into a beaker for ultrasonic dispersion for 6h, wherein the single-layer graphene oxide nanosheets are 80mg, deionized water is 100mL, and then add potassium hydroxide solution and chloroacetic acid and mix well. The concentration of potassium hydroxide solution is 0.025mol/L, the volume is 10mL, chloroacetic acid is 0.01mol, and the pH of the mixed solution is adjusted to 7 with a concentration of 0.1mol/L sodium hydroxide solution to obtain a single-layer carboxyl group-containing graphene oxide. the dispersion liquid;
以超纯水洗涤的方式，以9000rpm/min的转速离心上一步得到的分散液3次，每次8min，分离位于底层的固体物，在60℃下真空干燥18h，最后研磨得到黑色的单层羧基氧化石墨烯粉末。Wash with ultra-pure water, centrifuge the dispersion obtained in the previous step at a speed of 9000rpm/min for 3 times, each time for 8min, separate the solid at the bottom layer, dry in vacuum at 60°C for 18h, and finally grind to obtain a black single layer Carboxylated graphene oxide powder.
将单层羧基氧化石墨烯粉末超声分散成5mg/mL的深黑色水溶液，再利用微量注射器，将10μL的水溶液滴涂到玻碳电极上，烘干后得到工作电极。The single-layer carboxylated graphene oxide powder was ultrasonically dispersed into a 5 mg/mL dark black aqueous solution, and then 10 μL of the aqueous solution was drip-coated on the glassy carbon electrode using a micro-syringe, and the working electrode was obtained after drying.
实施例4Example 4
本发明一种花状纳米铋负载单层羧基氧化石墨烯复合薄膜电极的制备方法，包括如下步骤：A method for preparing a flower-shaped nano-bismuth-loaded single-layer carboxyl graphene oxide composite film electrode of the present invention comprises the following steps:
第一步，将4.8g五水合硝酸铋粉末溶解在30mL去离子水中，搅拌10小时，再加入70mL乙二醇继续搅拌24h，得到混合溶液；In the first step, dissolve 4.8g of bismuth nitrate pentahydrate powder in 30mL of deionized water, stir for 10 hours, then add 70mL of ethylene glycol and continue stirring for 24h to obtain a mixed solution;
第二步，将工作电极插入到第一步得到的混合溶液中，铋的浓度为0.1mol L-1，参比电极选择甘汞电极，对电极选择厚度为1mm和面积为1cm2的铂片电极，在美国普林斯顿电化学工作站中进行恒电位还原反应，恒电位为-0.2V，采样间隔为0.1s，时间为240s。In the second step, the working electrode is inserted into the mixed solution obtained in the first step, the concentration of bismuth is 0.1mol L-1 , the reference electrode is a calomel electrode, and the counter electrode is a platinum sheet with a thickness of 1 mm and an area of 1 cm2 The electrode was subjected to a constant potential reduction reaction in an electrochemical workstation in Princeton, USA, with a constant potential of -0.2V, a sampling interval of 0.1s, and a time of 240s.
第三步，将得到的复合薄膜立即用超纯水冲洗，在70℃下干燥16h，，花状纳米铋负载的单层羧基氧化石墨烯复合薄膜附着在玻碳电极上，得到花状纳米铋负载的单层羧基氧化石墨烯复合薄膜电极，记为Bi/MGOCOOH-4。In the third step, the obtained composite film was immediately rinsed with ultrapure water, dried at 70°C for 16 hours, and the single-layer carboxylated graphene oxide composite film loaded with flower-shaped nanobismuth was attached to a glassy carbon electrode to obtain flower-shaped nanobismuth The supported single-layer carboxylated graphene oxide composite film electrode is denoted as Bi/MGOCOOH-4.
第二步中所提到的工作电极按如下过程得到：The working electrode mentioned in the second step is obtained as follows:
将单层氧化石墨烯纳米片和去离子水加入到烧杯中超声分散6h，其中单层氧化石墨烯纳米片为80mg，去离子水为100mL，然后依次加入氢氧化钾溶液和氯乙酸混匀，氢氧化钾溶液的浓度为0.025mol/L，体积为10mL，氯乙酸为0.01mol，用浓度为0.1mol/L的氢氧化钠溶液调节混合液的pH为7，得到含单层羧基氧化石墨烯的分散液；Add single-layer graphene oxide nanosheets and deionized water into a beaker for ultrasonic dispersion for 6h, wherein the single-layer graphene oxide nanosheets are 80mg, deionized water is 100mL, and then add potassium hydroxide solution and chloroacetic acid and mix well. The concentration of potassium hydroxide solution is 0.025mol/L, the volume is 10mL, chloroacetic acid is 0.01mol, and the pH of the mixed solution is adjusted to 7 with a concentration of 0.1mol/L sodium hydroxide solution to obtain a single-layer carboxyl group-containing graphene oxide. the dispersion liquid;
以超纯水洗涤的方式，以10000rpm/min的转速离心上一步得到的分散液4次，每次8min，分离位于底层的固体物，在60℃下真空干燥18h，最后研磨得到黑色的单层羧基氧化石墨烯粉末。Wash with ultra-pure water, centrifuge the dispersion obtained in the previous step at a speed of 10,000 rpm/min for 4 times, each time for 8 minutes, separate the solid at the bottom layer, dry it in vacuum at 60°C for 18 hours, and finally grind to obtain a black monolayer Carboxylated graphene oxide powder.
将单层羧基氧化石墨烯粉末超声分散成3mg/mL的深黑色水溶液，再利用微量注射器，将15μL的水溶液滴涂到玻碳电极上，烘干后得到工作电极。The single-layer carboxylated graphene oxide powder was ultrasonically dispersed into a 3 mg/mL dark black aqueous solution, and then 15 μL of the aqueous solution was drip-coated on the glassy carbon electrode using a micro-syringe, and the working electrode was obtained after drying.
对比例comparative example
步骤1，取空白的玻碳电极，在3mm的铝粉中采用横8进行打磨，先用超纯水进行粗洗，之后在超纯水中超声清洗30s，循环三次，放置烘箱中干燥；Step 1, take a blank glassy carbon electrode, grind it in 3mm aluminum powder with horizontal 8, first rough wash it with ultrapure water, then ultrasonically clean it in ultrapure water for 30s, cycle three times, and place it in an oven to dry;
步骤2，将清洗干净的玻碳电极放置在浓度为1μg/L的偏二甲肼溶液中，采用循环伏安法对其进行检测。Step 2, place the cleaned glassy carbon electrode in the unsymmetrical dimethylhydrazine solution with a concentration of 1 μg/L, and detect it by cyclic voltammetry.
图1是使用普林斯顿电化学工作站采用恒电位还原得到的非贵金属花状纳米铋负载的单层羧基氧化石墨烯的场发射扫描电镜图，可以看到花状的纳米片均匀的负载在层状羧基氧化石墨烯表面。Figure 1 is a field emission scanning electron microscope image of a non-precious metal flower-like nanobismuth-loaded single-layer carboxylated graphene oxide obtained by constant potential reduction on a Princeton electrochemical workstation. It can be seen that the flower-like nanosheets are uniformly loaded on the layered carboxyl group Graphene oxide surface.
从图2的透射电镜图可以看到，铋负载在单层羧基氧化石墨烯得到的花状纳米铋，相比较纳米粒子结构能够吸附更多的偏二甲肼，传递更多的电荷，进而提高了电极对偏二甲肼检测的灵敏度。It can be seen from the transmission electron microscope image in Figure 2 that the flower-like nanobismuth obtained by loading bismuth on a single-layer carboxylated graphene oxide can absorb more unsymmetrical dimethylhydrazine and transfer more charges than the nanoparticle structure, thereby improving The sensitivity of the electrode to the detection of unsymmetrical dimethylhydrazine was improved.
图3是花状纳米铋负载的单层羧基氧化石墨烯的X射线衍射(XRD)图，可以证明成功的合成了目标材料，根据峰归属发现37.9°和39.6°出的尖峰归属于铋的(1 0 4)和(1 10)晶面。与不负载铋的单层羧基氧化石墨烯进行对比，随着电沉积的时间增加，(1 0 4)与(1 1 0)晶面的比值不断减小，说明花状纳米铋(1 0 4)晶面在检测过程中起到主要的作用。沉积时间为120s时的晶面结构最稳定。Fig. 3 is the X-ray diffraction (XRD) pattern of the single-layer carboxyl graphene oxide of flower-like nano-bismuth load, can prove that the target material has been successfully synthesized, and find that the peaks at 37.9° and 39.6° belong to bismuth ( 1 0 4) and (1 10) planes. Compared with the single-layer carboxylated graphene oxide without bismuth, as the electrodeposition time increases, the ratio of (1 0 4) to (1 1 0) crystal planes decreases continuously, indicating that the flower-like nanobismuth (1 0 4 ) facets play a major role in the detection process. The crystal plane structure is the most stable when the deposition time is 120s.
图4为玻碳电极、单层羧基氧化石墨烯和四种不同时间沉积的花状纳米铋负载的单层羧基氧化石墨烯电极对浓度为1μg/L的偏二甲肼(UDMH)在检测时的循环伏安曲线，UDMH的氧化峰电位在0.25V左右，还原峰在-0.5左右，经过扫描6个不同的电极，电化学沉积时间为120s时(即Bi/MGOCOOH-2)的复合电极在偏二甲肼溶液中的氧化峰电位、还原峰电位有最明显的电流响应，而其他几个电极在偏二甲肼溶液中无电流或者电流响应弱，因此沉积时间为120s的花状纳米铋负载的单层羧基氧化石墨烯具有优异的检测活性。Figure 4 shows the detection of glassy carbon electrode, single-layer carboxylated graphene oxide and four kinds of flower-shaped nano-bismuth-loaded single-layer carboxylated graphene electrodes with a concentration of 1 μg/L. The cyclic voltammetry curve shows that the oxidation peak potential of UDMH is about 0.25V, and the reduction peak is about -0.5. After scanning 6 different electrodes, the composite electrode when the electrochemical deposition time is 120s (that is, Bi/MGOCOOH-2) is at The oxidation peak potential and reduction peak potential in the unsymmetrical dimethylhydrazine solution have the most obvious current response, while the other electrodes have no current or weak current response in the unsymmetrical dimethylhydrazine solution, so the flower-shaped nano-bismuth with a deposition time of 120s The supported monolayer carboxylated graphene oxide has excellent detection activity.
对花状纳米铋负载的单层羧基氧化石墨烯电极经过3次的循环伏安扫描，得到图5。从图5可以看到，在0.25V的氧化峰电流值相差不大，花状纳米铋负载的单层羧基氧化石墨烯电极对于偏二甲肼检测的重复性很高，表明花状纳米铋负载的单层羧基氧化石墨烯电极具有良好的稳定性。The single-layer carboxylated graphene oxide electrode supported by flower-shaped nanobismuth was subjected to three cyclic voltammetry scans, and Figure 5 was obtained. It can be seen from Figure 5 that the oxidation peak current value at 0.25V is not much different, and the single-layer carboxylated graphene oxide electrode loaded with flower-shaped nanobismuth has a high repeatability for the detection of unsymmetrical dimethylhydrazine, indicating that the flower-shaped nanobismuth loaded The single-layer carboxylated graphene oxide electrode has good stability.
图6a是Bare(即玻碳电极)、MGOCOOH、四种不同沉积时间的铋负载的单层羧基氧化石墨烯电极在1.0M KCl溶液中的阻抗图，其中从图6b可以看到，Bi/MGOCOOH-2的阻抗直径最小，说明电化学沉积时间在120s时的电子转移效率最高。随着电沉积时间的增加，表面负载过多的铋反而会抑制电子的转移。Figure 6a is the impedance diagram of Bare (ie, glassy carbon electrode), MGOCOOH, bismuth-loaded single-layer carboxygraphene oxide electrode in 1.0M KCl solution with four different deposition times, where it can be seen from Figure 6b that Bi/MGOCOOH -2 has the smallest impedance diameter, indicating that the electron transfer efficiency is the highest when the electrochemical deposition time is 120s. With the increase of electrodeposition time, too much bismuth loaded on the surface will inhibit the transfer of electrons.
图7是花状纳米铋负载的单层羧基氧化石墨烯的X射线光电子能谱(XPS)的全谱图，可以看到其由元素C、O和铋组成。根据分峰以及元素含量分析得到C:O元素比例为21.4％:78.6％，另外铋的含量太低未检测出来。Figure 7 is the full spectrum of X-ray photoelectron spectroscopy (XPS) of flower-like nanobismuth-supported single-layer carboxylated graphene oxide, which can be seen to be composed of elements C, O and bismuth. According to peak division and element content analysis, the C:O element ratio is 21.4%:78.6%, and the content of bismuth is too low to be detected.
图8是XPS谱图中Bi元素的表面化学态，并通过CasaXPS软件进行分峰处理，显示158.8和164.84eV处的双峰结合能分别对应于Bi-4f 5/2和Bi-4f 7/2的电子轨道，被分配到Bi+3电子态，这是因为XPS仅仅能检测表面的电子轨道。Figure 8 is the surface chemical state of the Bi element in the XPS spectrum, and the peaks are processed by CasaXPS software, showing that the doublet binding energies at 158.8 and 164.84eV correspond to Bi-4f 5/2 and Bi-4f 7/2 respectively The electronic orbitals of , are assigned to the Bi+3 electronic state, because XPS can only detect the electronic orbitals on the surface.
图9是根据O1s谱图分析得到的O1s两个特征峰，其中531.6eV分配给了C-O键，533eV结合能峰为O-H键的特征峰，并未存在Bi-O键的特征峰，因此说明成功的合成了铋负载的单层羧基氧化石墨烯电极材料。Figure 9 shows the two characteristic peaks of O1s obtained from the analysis of the O1s spectrum, of which 531.6eV is assigned to the C-O bond, the 533eV binding energy peak is the characteristic peak of the O-H bond, and there is no characteristic peak of the Bi-O bond, so it shows success Bismuth-supported single-layer carboxylated graphene oxide electrode material was synthesized.
根据图10得到的沉积时间为120s的花状纳米铋负载的单层羧基氧化石墨烯中偏二甲肼浓度和氧化电流峰值的曲线，拟合得到得到图11所示的直线段，相应的表达式为y(10-6)＝1.625×x+0.9222，结合最低检测限公式LOD＝3σ/s，可以计算出偏二甲肼LOD＝1.71×10-5μg/L，电极灵敏度更高。The deposition time obtained according to Fig. 10 is the curve of unsymmetrical dimethylhydrazine concentration and oxidation current peak value in the single-layer carboxylated graphene oxide of flower-shaped nano-bismuth load of 120s, fitting obtains the straight line segment shown in Fig. 11, corresponding expression The formula is y(10-6 )=1.625×x+0.9222, combined with the minimum detection limit formula LOD=3σ/s, it can be calculated that unsymmetrical dimethylhydrazine LOD=1.71×10-5 μg/L, the electrode sensitivity is higher.
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| CN202310629169.2ACN116626129A (en) | 2023-05-30 | 2023-05-30 | Thin film electrode for vertically growing nano bismuth on surface of single-layer carboxyl graphene oxide and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104475752A (en)* | 2014-12-09 | 2015-04-01 | 孚派特环境科技（苏州）有限公司 | Graphene/bismuth composite material and modifying method of screen printed electrode |
| CN107941875A (en)* | 2017-11-25 | 2018-04-20 | 于世金 | The detection method and detecting electrode material of a kind of electrochemistry of uric acid in urine |
| CN112924534A (en)* | 2021-02-02 | 2021-06-08 | 广东省农业科学院农业质量标准与监测技术研究所 | Preparation method of nano bismuth/graphene composite material and application of nano bismuth/graphene composite material in MALDI-MS |
| US20210332489A1 (en)* | 2020-04-27 | 2021-10-28 | Iowa State University Research Foundation, Inc. | Laser-induced graphene electrodes adaptable for electrochemical sensing and catalysis |
| CN115950934A (en)* | 2022-12-13 | 2023-04-11 | 中国人民解放军火箭军工程大学 | Palladium/single-layer carboxylated graphene oxide composite thin film electrode and its preparation method and application in detection of hydrazine fuels |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104475752A (en)* | 2014-12-09 | 2015-04-01 | 孚派特环境科技（苏州）有限公司 | Graphene/bismuth composite material and modifying method of screen printed electrode |
| CN107941875A (en)* | 2017-11-25 | 2018-04-20 | 于世金 | The detection method and detecting electrode material of a kind of electrochemistry of uric acid in urine |
| US20210332489A1 (en)* | 2020-04-27 | 2021-10-28 | Iowa State University Research Foundation, Inc. | Laser-induced graphene electrodes adaptable for electrochemical sensing and catalysis |
| CN112924534A (en)* | 2021-02-02 | 2021-06-08 | 广东省农业科学院农业质量标准与监测技术研究所 | Preparation method of nano bismuth/graphene composite material and application of nano bismuth/graphene composite material in MALDI-MS |
| CN115950934A (en)* | 2022-12-13 | 2023-04-11 | 中国人民解放军火箭军工程大学 | Palladium/single-layer carboxylated graphene oxide composite thin film electrode and its preparation method and application in detection of hydrazine fuels |
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