阅读说明：本技术 一种碳酸氧铋/碳酸氧镝/氧化铋复合纳米线电极材料及其制备方法 (Bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material and preparation method thereof ) 是由 裴立宅 凌贤长 宇春虎 张勇 樊传刚 于 2021-10-18 设计创作，主要内容包括：本发明公开了一种碳酸氧铋/碳酸氧镝/氧化铋复合纳米线电极材料及其制备方法,属于复合材料技术领域。所述复合纳米线由四方Bi-(2)O-(2)CO-(3)、六方Dy-(2)O-(2)CO-(3)和三斜Bi-(2)O-(3)晶相构成；该复合纳米线的直径为20～100nm、长度大于5μm。该电极材料的制备方法是将三氟甲磺酸镝、铋酸钠、十二烷基磺酸钠与水放入石英玻璃烧瓶内,采用磁力搅拌器搅拌混合均匀,再放置在油浴锅内,于温度150-220℃、保温12-24h,加热过程中蒸发的水通过回流装置回流至烧瓶内,冷却后离心,并用乙醇洗涤。本发明采用一步制备过程,制备过程易于控制,得到的复合纳米线作为电极材料,在电化学传感器领域具有良好的应用前景。(The invention discloses a bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material and a preparation method thereof, belonging to the technical field of composite materials. The composite nanowire is composed of tetragonal Bi 2 O 2 CO 3 Hexagonal Dy 2 O 2 CO 3 And triclinic Bi 2 O 3 Crystal phase composition; the diameter of the composite nanowire is 20-100 nm, and the length of the composite nanowire is larger than 5 mu m. The preparation method of the electrode material comprises the following stepsDysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfate and water are placed in a quartz glass flask, stirred and mixed uniformly by a magnetic stirrer, then placed in an oil bath kettle, kept at the temperature of 150 ℃ and 220 ℃ for 12-24 hours, evaporated water in the heating process flows back to the flask through a reflux device, and is cooled, centrifuged and washed by ethanol. The preparation method adopts a one-step preparation process, the preparation process is easy to control, and the obtained composite nanowire is used as an electrode material and has good application prospect in the field of electrochemical sensors.)

1. The bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material is characterized in that the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is made of tetragonal Bi₂O₂CO₃Hexagonal Dy₂O₂CO₃And triclinic Bi₂O₃Crystal phase composition; the diameter of the composite nanowire is 20-100 nm, and the length of the composite nanowire is larger than 5 mu m.

2. The method for preparing the bismuth subcarbonate/dysprosium subcarbonate/bismuth oxide composite nanowire electrode material as claimed in claim 1, characterized by comprising the steps of:

dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfate and water are placed into a quartz glass flask, stirred and mixed uniformly by a magnetic stirrer, then placed into an oil bath kettle, kept at the temperature of 150 ℃ and 220 ℃ for 12-24 hours, evaporated water in the heating process flows back into the flask through a reflux device, is cooled and centrifuged, and is washed by ethanol to obtain the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire;

the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1: 5;

the weight of the sodium dodecyl sulfate accounts for 3-8% of the weight of the water;

the total weight of the dysprosium trifluoromethanesulfonate and the sodium bismuthate accounts for 1-3% of the weight of the water;

the total amount of the dysprosium trifluoromethanesulfonate, the sodium bismuthate, the sodium dodecyl sulfate and the water accounts for 60-80% of the filling degree of the flask.

3. The method for preparing bismuth subcarbonate/dysprosium subcarbonate/bismuth oxide composite nanowire electrode material according to claim 2,

the weight of the sodium dodecyl sulfate accounts for 3 percent of the weight of the water;

the total weight of the dysprosium trifluoromethanesulfonate and the sodium bismuthate accounts for 1% of the weight of the water;

the total amount of the dysprosium trifluoromethanesulfonate, the sodium bismuthate, the sodium dodecyl sulfate and the water accounts for 60% of the filling degree of the flask.

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to a bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material and a preparation method thereof.

Background

The bismuth-based and dysprosium-based compound belongs to important rare metal materials, and has a good application prospect in the fields of electrochemical sensors, catalysis, lithium ion batteries, supercapacitors and the like for detecting different types of biomolecules due to the large active surface area, good electron transport performance, interface performance, electrocatalytic property, chemical and thermal stability. Bismuth oxycarbonate, dysprosium oxycarbonate and bismuth oxide have attracted research interest as important rare metal materials.

The invention patent of China 'preparation method of bismuth oxycarbonate photocatalyst' (the patent number of the invention of China: ZL201210037356.3) discloses a nano-sheet and microsphere bismuth oxycarbonate, the raw materials of the bismuth oxycarbonate are bismuth source (bismuth citrate or bismuth ammonium citrate) and soluble carbonate (sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate). The invention patent of the state (the invention patent of the state: ZL201410494219.1) reports that tetrabutyl titanate and bismuth nitrate are used as raw materials, potassium hydroxide is added to control the pH value of the solution, and the bismuth carbonate micron flower is prepared. The invention patent of the nation (invention patent number: ZL201910555108.X) reports that bismuth oxide/bismuth oxycarbonate/bismuth molybdate composite photocatalytic material is prepared by introducing bismuth oxycarbonate and bismuth oxide nanosheets on the surface of the bismuth molybdate photocatalytic material through sodium carbonate assistance and roasting. The bismuth subcarbonate, the dysprosium subcarbonate and the bismuth oxide are compounded to form the bismuth subcarbonate/dysprosium subcarbonate/bismuth oxide composite nano material, so that catalytic active sites in the material can be increased, the bismuth subcarbonate/bismuth oxide composite nano material can be used as an electrode material to measure biomolecules in a solution, and the bismuth subcarbonate/bismuth oxide composite nano material has good application potential in the aspect of electrochemical sensors.

Disclosure of Invention

The invention aims to provide a bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material.

The invention relates to a bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material, wherein the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is made of tetragonal Bi₂O₂CO₃Hexagonal Dy₂O₂CO₃And triclinic Bi₂O₃Crystal phase composition; the diameter of the nanowire is 20-100 nm, and the length of the nanowire is larger than 5 mu m.

The invention also provides a preparation method of the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire electrode material, which comprises the following specific steps:

dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfate and water are placed into a quartz glass flask, stirred and mixed uniformly by a magnetic stirrer, then placed into an oil bath pot, kept at the temperature of 150 ℃ and 200 ℃ for 12-24h, evaporated water in the heating process flows back into the flask through a reflux device, cooled and centrifuged, and washed by ethanol, so that the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is obtained.

The molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1: 5; the weight of the sodium dodecyl sulfate accounts for 3-8% of the weight of the water; the total weight of the dysprosium trifluoromethanesulfonate and the sodium bismuthate accounts for 1-3% of the weight of the water; the total amount of the dysprosium trifluoromethanesulfonate, the sodium bismuthate, the sodium dodecyl sulfate and the water accounts for 60-80% of the filling degree of the flask.

As an optimization, the weight of the sodium dodecyl sulfate accounts for 3% of the weight of the water; the total weight of the dysprosium trifluoromethanesulfonate and the sodium bismuthate accounts for 1% of the weight of the water; the total amount of the dysprosium trifluoromethanesulfonate, the sodium bismuthate, the sodium dodecyl sulfate and the water accounts for 60% of the filling degree of the flask.

The scientific principle of the invention is as follows:

according to the preparation method, the sodium bismuthate has a strong oxidation effect, the sodium bismuthate, dysprosium trifluoromethanesulfonate and water react to generate bismuth oxycarbonate, dysprosium oxycarbonate and bismuth oxide by uniformly heating in an oil bath at a certain temperature, the bismuth oxycarbonate, the dysprosium oxycarbonate and the bismuth oxide are supersaturated in the water and precipitate to form crystal nuclei, the sodium dodecyl sulfate is adsorbed on the surfaces of the crystal nuclei, and the formation of the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is promoted under the combined action of a certain temperature gradient formed in a container after water subjected to evaporation and condensation flows back and the sodium dodecyl sulfate.

Compared with the prior art, the invention has the following technical effects:

1. the preparation method adopts a one-step preparation process, the preparation process is easy to control, the repeatability is good, the cost of the obtained bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is low, and conditions are provided for the practical application of the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire;

2. the raw materials used by the invention are dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfate and water, and no toxic or harmful gas is generated, so that the environment is not polluted;

3. the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire has a large number of catalytic active sites, can be used as an electrode material, can be used for highly sensitively measuring biomolecules such as cysteine in an aqueous solution, and has a good application prospect in the field of electrochemical sensors.

Drawings

FIG. 1 is an X-ray diffraction (XRD) pattern of the bismuth oxycarbonate/dysprosium carbonate/bismuth oxide composite nanowires prepared in example 1;

according to the JCPDS PDF card, the obtained bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire can be searched to be composed of tetragonal Bi₂O₂CO₃(JCPDS card number: 41-1488), hexagonal Dy₂O₂CO₃(JCPDS card number: 26-0588) and triclinic Bi₂O₃(JCPDS card number: 50-1088) crystal phase.

Fig. 2 is Scanning Electron Microscope (SEM) images of low magnification (fig. 2(a)) and high magnification (fig. 2(b)) of the bismuth oxycarbonate/dysprosium carbonate/bismuth oxide composite nanowires prepared in example 1;

the figure shows that the product is composed of bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowires, the diameters of the nanowires are 20-100 nm, and the lengths of the nanowires are more than 5 mu m.

Fig. 3 is a Transmission Electron Microscope (TEM) image (fig. 3(a)) and a high-resolution TEM (hrtem) image (fig. 3(b)) of the bismuth oxycarbonate/dysprosium carbonate/bismuth oxide composite nanowire prepared in example 1;

as can be seen from the figure, the product is composed of bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowires, the nanowires have a polycrystalline structure, the interplanar distances are 0.68nm, 0.72nm and 0.76nm, and the interplanar distances respectively correspond to tetragonal Bi₂O₂CO₃{002} crystal face of crystal phase, triclinic Bi₂O₃{100} crystal plane and hexagonal Dy of crystal phase₂O₂CO₃The interplanar spacing of the {002} crystallographic planes of the crystalline phase.

Fig. 4 is an electrochemical Cyclic Voltammetry (CV) curve of the bismuth subcarbonate/dysprosium subcarbonate/bismuth oxide composite nanowire prepared in example 1 as a glassy carbon electrode modification material in 0.1M potassium chloride buffer solution containing cysteine at different concentrations, and a graph with a relationship curve of CV peak current and cysteine concentration is inserted in the lower right corner;

and calculating the detection limit of cysteine of the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire modified glassy carbon electrode to be 0.21 mu M according to the signal-to-noise ratio of 3(S/N is 3), wherein the linear detection range is 0.001-2 mM.

Detailed Description

The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.

Example 1

Dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water are placed in a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 3% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 1% of the weight of water, the total filling degree of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 60% of the flask, the mixture is stirred and mixed uniformly by a magnetic stirrer, then the mixture is placed in an oil bath pot, the temperature is kept at 150 ℃ for 12h, evaporated water in the heating process flows back into the flask through a reflux device, the mixture is cooled and centrifuged, and the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is obtained after washing with ethanol.

Example 2

Dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water are placed in a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 8% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 3% of the weight of water, the total filling degree of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 80% of the flask, the mixture is stirred and mixed uniformly by a magnetic stirrer, then the mixture is placed in an oil bath pot, the temperature is kept at 200 ℃ for 24h, evaporated water in the heating process flows back into the flask through a reflux device, the mixture is cooled and centrifuged, and the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is obtained after washing with ethanol.

Example 3

Dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water are placed in a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 4% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 2% of the weight of water, the total filling degree of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 62% of the flask, the mixture is stirred and mixed uniformly by a magnetic stirrer, then the mixture is placed in an oil bath pot, the temperature is kept at 155 ℃ for 14h, evaporated water in the heating process flows back into the flask through a reflux device, the mixture is cooled and centrifuged, and the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire is obtained after washing with ethanol.

Example 4

Placing dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water into a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 5% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 1.5% of the weight of water, the total filling degree of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 65% of the flask, stirring and mixing uniformly by a magnetic stirrer, placing the mixture in an oil bath, keeping the temperature at 160 ℃ for 16h, refluxing evaporated water in the heating process into the flask by a reflux device, cooling and centrifuging, and washing by ethanol to obtain the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire.

Example 5

Placing dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water into a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 6% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 1.8% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 68% of the filling degree of the flask, stirring and mixing uniformly by a magnetic stirrer, placing the mixture into an oil bath, keeping the temperature at 170 ℃ for 18h, refluxing evaporated water in the heating process into the flask by a reflux device, cooling and centrifuging, and washing by ethanol to obtain the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire.

Example 6

Placing dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water into a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 7% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 2.2% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 72% of the filling degree of the flask, stirring and mixing uniformly by a magnetic stirrer, placing the mixture into an oil bath, keeping the temperature at 180 ℃ for 20h, refluxing evaporated water in the heating process into the flask by a reflux device, cooling and centrifuging, and washing by ethanol to obtain the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire.

Example 7

Placing dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water into a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 7.5% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 2.5% of the weight of water, and the total weight of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 74% of the filling degree of the flask, stirring and mixing uniformly by a magnetic stirrer, placing the mixture in an oil bath, keeping the temperature for 22h at 190 ℃, refluxing water evaporated in the heating process into the flask by a reflux device, cooling and centrifuging, and washing by ethanol to obtain the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire.

Example 8

Dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water are placed into a quartz glass flask, wherein the molar ratio of dysprosium trifluoromethanesulfonate to sodium bismuthate is 1:5, the weight of sodium dodecyl sulfate accounts for 7.8% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate and sodium bismuthate accounts for 2.8% of the weight of water, the total weight of dysprosium trifluoromethanesulfonate, sodium bismuthate, sodium dodecyl sulfonate and water accounts for 76% of the filling degree of the flask, the mixture is stirred and mixed uniformly by a magnetic stirrer and then placed in an oil bath pot, the temperature is kept at 185 ℃ for 23h, water evaporated in the heating process flows back into the flask through a reflux device, the cooling and centrifugation are carried out, and ethanol is used for washing to obtain the bismuth oxycarbonate/dysprosium oxycarbonate/bismuth oxide composite nanowire.