CN-122010174-A - One-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores and preparation method thereof

CN122010174ACN 122010174 ACN122010174 ACN 122010174ACN-122010174-A

Abstract

The invention discloses a one-dimensional mesoporous bismuth oxide nano rod constructed based on spherical mesopores and a preparation method thereof, belonging to the technical field of one-dimensional mesoporous material synthesis, wherein the method adopts a segmented copolymer single micelle as a soft template, the bismuth oxide nano rod with one-dimensional rod-like morphology and an internal through spherical mesoporous structure is successfully prepared by precisely regulating and controlling the assembly process of the micelle and the precursor and combining a heat treatment process. The preparation method comprises the specific steps of preparing a block copolymer single micelle solution, mixing the block copolymer single micelle solution with a bismuth precursor solution, forming a bismuth oxide@micelle composite precursor under the action of a reducing agent, and removing a template through roasting to obtain the one-dimensional mesoporous bismuth oxide nanorod. The material has the characteristics of adjustable spherical mesoporous aperture, large specific surface area and good pore passage penetrability, shows high activity, high selectivity and good cycling stability in reactions such as photocatalytic CO 2 reduction and the like, and is suitable for the fields of catalysis, energy storage, sensing and the like.

Inventors

ZHAO ZAIWANG
DONG CHUNXIA
ZHAO YUJUAN
LI SHANSHAN
ZHANG DONG
XU ZEPI
WANG XUE
ZHENG SHIZHENG

Assignees

内蒙古大学

Dates

Publication Date: 20260512
Application Date: 20260413

Claims (9)

1. The preparation method of the one-dimensional mesoporous bismuth oxide nanorod constructed based on the spherical mesopores is characterized by comprising the following steps: step one, preparing a block copolymer single micelle solution: The segmented copolymer micelle is taken as a soft template, is dissolved in a solvent, and a thermodynamic control method is adopted to prepare segmented copolymer single micelle solution; preparing a bismuth oxide@micelle composite precursor: firstly, preparing bismuth precursor solution, dropwise adding the bismuth precursor solution into the block copolymer single micelle solution prepared in the step one under the stirring condition, then adding a reducing agent to react for a period of time at a certain temperature, centrifuging, washing and drying after the reaction is finished to obtain a bismuth oxide@micelle composite structure; Step three, template removal and crystallization: Roasting the bismuth oxide@micelle composite structure obtained in the step two in an oxygen atmosphere, and removing the block copolymer single micelle to obtain the one-dimensional mesoporous bismuth oxide nanorod based on spherical mesopores.
2. The preparation method of the one-dimensional mesoporous bismuth oxide nanorod constructed based on the spherical mesopores, as claimed in claim 1, is characterized in that in the first step, the block copolymer is selected from one of polyethylene oxide-polytetravinyl pyridine-polystyrene, polyethylene oxide-polyacrylic acid-polystyrene, polyethylene oxide-polystyrene, polystyrene-polytetravinyl pyridine and polystyrene-polyacrylic acid, and the concentration of the block copolymer in a mixed solution is 0.1-40mg/mL.
3. The method for preparing the one-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores as recited in claim 1, wherein in the first step, the temperature of the thermodynamic control is 20-150 ℃ and the time is controlled to be 0.5-12 hours.
4. The method for preparing the one-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores according to claim 1, wherein in the first step, the solvent is selected from acetic acid, ethanol, water, N-dimethylformamide, N-dimethylformamide/water, tetrahydrofuran and tetrahydrofuran/water.
5. The preparation method of the one-dimensional mesoporous bismuth oxide nanorod based on spherical mesoporous construction, as claimed in claim 1, is characterized in that in the second step, the concentration of the bismuth precursor solution is 2-60mg/mL, and the volume ratio of the block copolymer single micelle solution to the bismuth precursor solution to the reducing agent is 1-6:0.2-4:1-10.
6. The preparation method of the one-dimensional mesoporous bismuth oxide nanorod constructed based on the spherical mesopores, which is disclosed in claim 1, is characterized in that in the second step, the bismuth precursor is one of bismuth nitrate, bismuth chloride, bismuth citrate or bismuth acetate, and the reducing agent is one of formic acid, ascorbic acid, sodium borohydride, citric acid, oxalic acid, sodium nitrite or hydrazine hydrate.
7. The preparation method of the one-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores, as claimed in claim 1, is characterized in that in the second step, the stirring condition is magnetic stirring reaction, the stirring speed is 200-1000r/min, and the reaction time is 0.5-6h; the early stage of the reaction is carried out at normal temperature, the later stage is carried out in an oil bath at 40-80 ℃, and the reaction time is 2-12h; The centrifugal rotating speed is 2000-15000rpm/min, the washing condition and times are that deionized water is washed 1-6 times, 95wt% ethanol solution is washed 1-6 times, the drying temperature is 40-80 ℃, and the drying time is 10-20h.
8. The method for preparing a one-dimensional mesoporous bismuth oxide nano rod constructed based on spherical mesoporous according to claim 1, wherein in the third step, the temperature is raised from room temperature to 350 ℃ at a temperature raising rate of 1-5 ℃ per minute, and the temperature is maintained for 3-5 hours.
9. The one-dimensional mesoporous bismuth oxide nanorod constructed based on the spherical mesopores is characterized by being prepared by the method of any one of claims 1-8, wherein the one-dimensional mesoporous bismuth oxide nanorod is of a one-dimensional rod-shaped structure, the surface and the inside of the one-dimensional mesoporous bismuth oxide nanorod are provided with mutually communicated spherical mesopores, the pore diameter of the spherical mesopores is 15-50nm, and the BET specific surface area of the nanorod is 30-90m 2 /g.

Description

One-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores and preparation method thereof Technical Field The invention belongs to the technical field of one-dimensional mesoporous material synthesis, and particularly relates to a one-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores and a preparation method thereof. Background The one-dimensional nano material has a plurality of excellent characteristics, such as high aspect ratio, high conductivity, high-efficiency mass transfer, excellent mechanical deformation and other structural characteristics, so that a conductive infiltration network can be constructed with a small amount of material, and the one-dimensional nano material can be widely applied to the research fields of photoelectrocatalysis, energy storage, sensors, adsorption, biological medicine and the like. In order to further improve the performance of the bismuth oxide material, the introduction of a porous structure, particularly a mesoporous structure, is one of effective strategies. The mesoporous structure can obviously increase the specific surface area of the material, expose more active sites and provide a channel for the transmission of reactants and ions. At present, common methods for preparing the porous bismuth oxide material comprise a template-free method, a hard template method, a hydrothermal induction method, a microwave auxiliary method and the like. However, the methods often have the limitations of no template method, such as disordered pore structure and uneven morphology, hard template method, such as difficult template removal, easy collapse of pore channels, high cost, hydrothermal induction method, such as harsh reaction conditions and low pore regulation precision, and microwave auxiliary method, such as high equipment cost, poor heating uniformity, and difficulty in considering morphology and structure stability. The soft template method, in particular to a micelle formed by self-assembly of amphiphilic block copolymers, is an effective way for preparing ordered mesoporous materials. However, the soft template method is applied to the controllable preparation of the one-dimensional bismuth oxide nano rod, and meanwhile, uniform and through spherical mesopores are built in and on the surface of the soft template method, so that related reports are less, and the technical challenges are faced. Therefore, a novel method for simply, conveniently and controllably preparing the bismuth oxide material with one-dimensional nanorod morphology and internally through spherical mesopores is developed, and has important significance for fully playing the structural advantages of the bismuth oxide material and expanding the application of the bismuth oxide material in the fields of efficient catalysis, energy storage and the like. Disclosure of Invention Aiming at the defect that bismuth oxide materials with one-dimensional morphology and internal through spherical mesoporous structures are difficult to prepare in the prior art, the invention aims to provide the one-dimensional mesoporous bismuth oxide nanorod constructed based on spherical mesopores and a preparation method thereof. The surface and the interior of the nano rod are provided with spherical double-sided through pore passages, the specific surface area and the pore volume of the one-dimensional nano rod can be improved, and the application range of the one-dimensional mesoporous nano rod is greatly expanded by the special pore passages. The invention is realized by the following technical scheme: the preparation method of the one-dimensional mesoporous bismuth oxide nanorod based on spherical mesoporous construction specifically comprises the following steps: step one, preparing a block copolymer single micelle solution: the segmented copolymer micelle is taken as a soft template, is dissolved in a solvent, and a thermodynamic control method is adopted to prepare segmented copolymer single micelle solution; preparing a bismuth oxide@micelle composite precursor: firstly, preparing bismuth precursor solution, dropwise adding the bismuth precursor solution into the block copolymer single micelle solution prepared in the step one under the stirring condition, then adding a reducing agent to react for a period of time at a certain temperature, centrifuging, washing and drying after the reaction is finished to obtain a bismuth oxide@micelle composite structure; Step three, template removal and crystallization: Roasting the bismuth oxide@micelle composite structure obtained in the step two in an oxygen atmosphere, and removing the block copolymer single micelle to obtain the one-dimensional mesoporous bismuth oxide nanorod based on spherical mesopores. Further, in the first step, the block copolymer is selected from one of polyethylene oxide-polytetravinyl pyridine-polystyrene, polyethylene oxide-polyacrylic acid-polystyrene, polyethylene oxide-polystyrene,