阅读说明：本技术 一种氧化镨/氧化铋/镨酸铋复合纳米片及其合成方法 (Praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet and synthetic method thereof ) 是由 裴立宅 凌贤长 黄剑峰 张勇 樊传刚 于 2021-10-18 设计创作，主要内容包括：本发明公开了一种氧化镨/氧化铋/镨酸铋复合纳米片及其合成方法,属于纳米材料技术领域。所述复合纳米片由六方Pr-(2)O-(3)、四方Bi-(2)O-(3)和斜方Bi-(1.35)Pr-(0.65)O-(3)晶相构成,纳米片的厚度为20～100nm、尺寸为250nm～2μm。合成方法是将水、硝酸镨、铋酸钠、十六烷基三甲基溴化铵依次加入石英玻璃烧瓶内,再放入水浴锅于100℃保温12-24h,加热过程中蒸发的水通过回流装置回流到烧瓶内,冷却后获得液态前驱物；将液态前驱物放入反应容器内密封,于200-250℃保温24-48h。本发明合成过程简单、无需复杂设备、易于控制；制备的复合纳米片作为电极材料,在电化学传感器件领域具有良好的应用潜力。(The invention discloses a praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet and a synthesis method thereof, and belongs to the technical field of nano materials. The composite nano sheet consists of hexagonal Pr 2 O 3 Bi of tetragonal form 2 O 3 And rhombus Bi 1.35 Pr 0.65 O 3 The nano-sheet is composed of a crystal phase, the thickness of the nano-sheet is 20-100 nm, and the size of the nano-sheet is 250 nm-2 mu m. The synthesis method comprises the steps of sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, then putting the quartz glass flask into a water bath kettle, keeping the temperature at 100 ℃ for 12-24h, and introducing water for evaporation in the heating processRefluxing the mixture into the flask through a reflux device, and cooling the mixture to obtain a liquid precursor; the liquid precursor is put into a reaction container for sealing, and the temperature is kept at 200-250 ℃ for 24-48 h. The synthetic process is simple, does not need complex equipment and is easy to control; the prepared composite nanosheet is used as an electrode material, and has good application potential in the field of electrochemical sensing devices.)

1. The praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet is characterized in that the composite nanosheet is made of hexagonal Pr₂O₃Bi of tetragonal form₂O₃And rhombus Bi_1.35Pr_0.65O₃Crystal phase composition; the thickness of the composite nano sheet is 20-100 nm, and the size of the whole nano sheet is 250 nm-2 mu m.

2. The method for synthesizing praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheets as set forth in claim 1, characterized by comprising the steps of:

(1) sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, putting the flask into a water bath kettle, preserving the temperature for 12-24 hours at the temperature of 100 ℃, refluxing the water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a liquid precursor;

(2) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 250 ℃ for 24-48h, cooling, centrifuging, and washing with ethanol to obtain praseodymium oxide/bismuth praseodymium carbonate composite nanosheets;

the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1: 1;

the weight of the hexadecyl trimethyl ammonium bromide accounts for 3-6% of the weight of the water;

the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2-4% of the weight of the water;

the total amount of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 70-90% of the filling degree of the reaction container.

3. The method for synthesizing praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheets as defined in claim 2, wherein:

the weight of the hexadecyl trimethyl ammonium bromide accounts for 3 percent of the weight of the water;

the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2 percent of the weight of the water;

the total amount of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 70 percent of the filling degree of the reaction container.

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to a praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet and a synthetic method thereof.

Background

The praseodymium-containing and bismuth-containing nano composite is an important rare metal material, and has a good application prospect in the fields of electrochemical sensors, catalysis, lithium ion batteries, supercapacitors and the like due to the large active surface area, good electron transport performance, interface performance and catalytic characteristic. Praseodymium oxide, bismuth praseodymium oxide and bismuth oxide have attracted research interest as important rare metal materials.

The invention patent of China 'method for preparing porous flaky large-particle praseodymium oxide' (the patent number of the invention of China: ZL201210382926.2) reports that ammonium bicarbonate, ammonia water, praseodymium nitrate and hydrogen peroxide are used as raw materials, and after aging is carried out for 24-48 hours, heat preservation is carried out for 4 hours at 900-1200 ℃, so that the porous flaky praseodymium oxide with the particle size of 20-35 mu m is prepared. The invention patent of China (national invention patent: ZL201410024527.8) reports that neodymium praseodymium chloride and ammonium bicarbonate are used as raw materials, aged for 10-15 hours and calcined to prepare neodymium praseodymium oxide with the particle size of 30-40 mu m. Praseodymium nitrate, cerium nitrate and aluminum oxide are used as raw materials, and the temperature is kept at 500 ℃ for 2 hours to prepare the praseodymium oxide/cerium oxide/aluminum oxide composite catalyst (Q.J.jin, Y.S.Shen, S.M.Zhu.praseodynium oxide modified CeO₂/Al₂O₃catalyst for selective catalytic reduction of NO by NH₃Chinese Journal of Chemistry 34(2016)1283-1290.) this composite catalyst is effective in catalyzing the reduction of NO. The praseodymium oxide is compounded with the praseodymium bismuth oxide and the bismuth praseodymate to form the praseodymium oxide/praseodymium bismuth oxide/bismuth oxide composite nano material, so that the catalytic active sites in the material can be increased, the material can be used as an electrode material to measure biomolecules in a solution, and the material has a good application prospect in the aspect of electrochemical sensors.

Disclosure of Invention

The invention aims to provide a praseodymium oxide/bismuth praseodylate composite nano sheet.

The praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet is formed by hexagonal Pr₂O₃Bi of tetragonal form₂O₃And rhombus Bi_1.35Pr_0.65O₃Crystal phase composition; the thickness of the composite nano sheet is 20-100 nm, and the size of the whole nano sheet is 250 nm-2 mu m.

The invention also provides a preparation method of the praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet, which comprises the following specific steps:

(1) sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, putting the flask into a water bath kettle, preserving the temperature for 12-24h at the temperature of 100 ℃, refluxing the water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a liquid precursor.

(2) And (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 250 ℃ for 24-48h, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth praseodylate composite nano-sheet.

The molar ratio of the praseodymium nitrate to the sodium bismuthate is 1: 1; the weight of the hexadecyl trimethyl ammonium bromide accounts for 3-6% of the weight of the water; the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2-4% of the weight of the water; the total amount of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 70-90% of the filling degree of the reaction container (flask).

As an optimization, the weight of the hexadecyl trimethyl ammonium bromide accounts for 3 percent of the weight of the water; the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2 percent of the weight of the water; the total amount of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 70 percent of the filling degree of the reaction container.

The scientific principle of the invention is as follows:

the method adopts the two-step synthesis process, firstly, through a water bath process, praseodymium nitrate and sodium bismuthate are slowly decomposed in an aqueous solution to form a uniform liquid precursor, praseodymium nitrate and sodium bismuthate are continuously decomposed in the aqueous solution to generate praseodymium oxide, bismuth oxide and other substances in a sealed container at a certain temperature and under a certain pressure, part of praseodymium oxide and bismuth oxide react to generate praseodymium bismuth oxide, the praseodymium bismuth oxide and the bismuth oxide reach supersaturation in water to be separated out to form crystal nuclei, hexadecyl trimethyl ammonium bromide is adsorbed on the surfaces of the crystal nuclei, and the formation of the praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nano-sheets is promoted.

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

1. the synthesis process is simple, complex equipment is not needed, the control is easy, the obtained praseodymium oxide/bismuth oxide/praseodymium bismuth acid composite nano-sheet is low in cost, and conditions are provided for the practical application of the praseodymium oxide/bismuth oxide/praseodymium bismuth acid composite nano-sheet.

2. The invention has easily obtained raw materials, adopts nontoxic praseodymium nitrate, sodium bismuthate, hexadecyl trimethyl ammonium bromide and water, and has no pollution to the environment in the raw materials and the synthesis process.

3. The praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet 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 and has good application potential in the field of electrochemical sensing devices.

Drawings

FIG. 1 is an X-ray diffraction (XRD) pattern of a praseodymium oxide/bismuth praseodymium carboxylate composite nanosheet synthesized in example 1;

according to the JCPDS PDF card, the obtained praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nano sheet can be searched out from hexagonal Pr₂O₃(JCPDS card number: 47-1111) and tetragonal Bi₂O₃(JCPDS card number: 24-0050) and rhombic Bi_1.35Pr_0.65O₃(JCPDS card number: 41-0305) crystal phase.

Fig. 2 is Scanning Electron Microscope (SEM) images of low magnification (fig. 2(a)) and high magnification (fig. 2(b)) of the praseodymium oxide/bismuth praseodymium carboxylate composite nanosheets synthesized in example 1;

the product is formed by praseodymium oxide/bismuth oxide/praseodymium bismuth composite nanosheets, the thickness of the nanosheets is 20-100 nm, and the size of the whole nanosheets is 250 nm-2 microns.

Fig. 3 is a Transmission Electron Microscope (TEM) image (fig. 3(a)) and a high-resolution TEM (hrtem) image (fig. 3(b)) of the praseodymium oxide/bismuth praseodylate composite nanosheets synthesized in example 1;

the figure shows that the product is composed of praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheets, the nanosheets are of polycrystalline structures, the interplanar distances are 0.33nm, 0.55nm and 0.46nm, and the interplanar distances respectively correspond to hexagonal Pr₂O₃{100} crystal face of crystal phase, tetragonal Bi₂O₃{110} crystal face of crystal phase and orthorhombic Bi_1.35Pr_0.65O₃Interplanar spacing of the {006} crystallographic plane of the crystalline phase.

Fig. 4 is an electrochemical Cyclic Voltammetry (CV) curve of praseodymium oxide/bismuth oxide/praseodymium bismuth compound nanosheets synthesized in example 1 as a glassy carbon electrode modification material in cysteine and 0.1M potassium chloride buffer solutions of different concentrations, and an inset in the upper left corner is a CV peak current-cysteine concentration relationship curve;

and calculating the detection limit of the cysteine in the glassy carbon electrode modified by the praseodymium oxide/bismuth oxide/praseodymium bismuth composite nanosheet to be 0.28 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

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 3% of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2% of the weight of the water, the total filling degree of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 70% of the flask, placing the flask into a water bath, keeping the temperature at 100 ℃ for 12h, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth praseodymium bismuth oxide acid bismuth liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 200 ℃ for 24 hours, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth praseodylate composite nanosheet.

Example 2

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 6% of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 4% of the weight of the water, the total filling degree of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 90% of the flask, placing the flask into a water bath, keeping the temperature for 24 hours at 100 ℃, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth praseodymium bismuth oxide/bismuth silicate liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 250 ℃ for 48 hours, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth praseodylate composite nanosheet.

Example 3

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 4% of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2.3% of the weight of the water, the total weight of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 75% of the filling degree of the flask, putting the flask into a water bath kettle, keeping the temperature at 100 ℃ for 14h, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth oxide/praseodymium silicate liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 210 ℃ for 28h, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet.

Example 4

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 5% of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 2.6% of the weight of the water, the total weight of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 80% of the filling degree of the flask, putting the flask into a water bath kettle, keeping the temperature at 100 ℃ for 18h, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth oxide/praseodymium silicate liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 220 ℃ for 32 hours, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth praseodylate composite nanosheet.

Example 5

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 5% of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 3% of the weight of the water, the total filling degree of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 83% of the flask, placing the flask into a water bath, keeping the temperature for 20 hours at 100 ℃, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth praseodymium bismuth oxide/bismuth silicate liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 230 ℃ for 36 hours, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth oxide/praseodymium carbonate composite nanosheet.

Example 6

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 3.5 percent of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 3.2 percent of the weight of the water, and the total weight of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 86 percent of the filling degree of the flask, putting the flask into a water bath, keeping the temperature at 100 ℃ for 22 hours, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth oxide/praseodymium oxide/bismuth acid bismuth liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 240 ℃ for 40h, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth praseodylate composite nanosheet.

Example 7

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 4.5 percent of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 3.5 percent of the weight of the water, and the total weight of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 88 percent of the filling degree of the flask, putting the flask into a water bath, keeping the temperature at 100 ℃ for 23 hours, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth oxide/praseodymium oxide/bismuth oxide acid bismuth liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 215 ℃ for 44 hours, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth oxide/praseodymium bismuth oxide composite nanosheet.

Example 8

(1) Sequentially adding water, praseodymium nitrate, sodium bismuthate and hexadecyl trimethyl ammonium bromide into a quartz glass flask, wherein the molar ratio of the praseodymium nitrate to the sodium bismuthate is 1:1, the weight of the hexadecyl trimethyl ammonium bromide accounts for 5.5 percent of the weight of the water, the total weight of the praseodymium nitrate and the sodium bismuthate accounts for 3.8 percent of the weight of the water, and the total weight of the praseodymium nitrate, the sodium bismuthate, the hexadecyl trimethyl ammonium bromide and the water accounts for 89 percent of the filling degree of the flask, putting the flask into a water bath, keeping the temperature at 100 ℃ for 23.5 hours, refluxing water evaporated in the heating process into the flask through a reflux device, and cooling to obtain a praseodymium oxide/bismuth oxide/praseodymium oxide/bismuth acid bismuth liquid precursor;

(2) and (3) putting the liquid precursor into a reaction container, sealing the reaction container, keeping the temperature at 235 ℃ for 46h, cooling, centrifuging, and washing with ethanol to obtain the praseodymium oxide/bismuth oxide/praseodymium carbonate composite nanosheet.