WO2024088433A1 - Carbon polymer dot composite bismuth oxycarbonate nanosheet material, and preparation method therefor and use thereof - Google Patents

Carbon polymer dot composite bismuth oxycarbonate nanosheet material, and preparation method therefor and use thereof Download PDF

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WO2024088433A1
WO2024088433A1 PCT/CN2023/130437 CN2023130437W WO2024088433A1 WO 2024088433 A1 WO2024088433 A1 WO 2024088433A1 CN 2023130437 W CN2023130437 W CN 2023130437W WO 2024088433 A1 WO2024088433 A1 WO 2024088433A1
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carbon polymer
polymer dot
dot composite
nanosheet material
composite bismuth
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French (fr)
Chinese (zh)
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华英杰
贾仕豪
王崇太
韩慧敏
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海南师范大学
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention belongs to the technical field of nanocomposite materials, and in particular relates to a carbon polymer dot composite bismuth oxycarbonate nanosheet material and a preparation method and application thereof.
  • Photocatalytic technology is a technology that uses semiconductor materials as catalysts to convert harmful substances into harmless substances under light excitation. It has the advantage of efficient removal of pollutants.
  • Bismuth oxycarbonate is a promising semiconductor material with relatively excellent photocatalytic performance, and therefore has attracted widespread attention.
  • Bismuth oxycarbonate has strong light absorption properties, good chemical stability and thermal stability, and can maintain its photocatalytic performance at high temperatures for a long time.
  • Due to its large band gap its photocatalytic activity under visible light irradiation is low, and its conductivity is poor, resulting in low separation efficiency of photogenerated electrons and holes, thus limiting its photocatalytic performance.
  • Carbon polymer dots are a new type of carbon material with the advantages of fluorescence, biocompatibility, non-toxicity, and easy preparation. They are widely used in photocatalysis, bioimaging, drug delivery, chemical sensing and other fields. With the in-depth study of photophysical properties and photocatalytic performance, CPDs have shown great potential in the direction of photocatalysis. Good fluorescence properties enable them to absorb light energy in the visible light region and promote photocatalytic reactions. In addition, CPDs have a high specific surface area and rich functional groups, which can improve the activity and stability of photocatalytic reactions. However, the research on CPDs in the direction of photocatalysis is still in its infancy, and the research on its mechanism and photocatalytic performance needs to be further explored.
  • the present invention proposes a carbon polymer dot composite bismuth oxycarbonate nanosheet material and a preparation method and application thereof.
  • the present invention provides the following technical solutions:
  • a method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material comprises the following steps:
  • the present invention utilizes an in-situ composite method to synthesize N-doped bismuth oxycarbonate and graphite phase carbon nitride composite materials and form an S-type heterojunction, effectively composites bismuth oxycarbonate nanosheets with carbon polymer dots, and forms an effective and environmentally friendly heterojunction of bismuth oxycarbonate nanosheets and polymer dots as a photocatalyst, overcoming the shortcomings of bismuth oxycarbonate's limited visible light response and fewer active sites, generating more photogenerated carriers, and further improving the photocatalytic degradation performance of organic fuels, antibiotics, and phenolic pollutants in environmental water bodies.
  • the mass ratio of CTAB, HMT, BiCl 3 , Na 2 CO 3 and carbon polymer dots is 3:3:10:6:(0.11-0.66);
  • the ethanol solution is obtained by mixing ethanol and water in a volume ratio of 35:2;
  • the ratio of the added amount of CTAB to ethanol is 300 mg:35 ml.
  • ethanol and water in the present invention are used as solvents to provide the best environment for the synthesis of bismuth oxycarbonate, and ctab is a surfactant to make the crystal structure of the product better.
  • the stirring rate is 7000-8000 rpm.
  • the temperature of the in-situ composite reaction is 140° C. and the time is 12 h.
  • the method for preparing the carbon polymer dots comprises the following steps:
  • the carbon polymer dots are obtained by dissolving citric acid and ethylenediamine in water and then performing a hydrothermal reaction, followed by dialysis and freeze drying.
  • the ratio of the added amounts of citric acid, ethylenediamine and water is 5 mmol:335 ⁇ L:10 mL.
  • the temperature of the hydrothermal reaction is 200° C. and the time is 5 hours.
  • the dialysis time is 24 hours.
  • a method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material is disclosed to prepare a carbon polymer dot composite bismuth oxycarbonate nanosheet material.
  • the present invention utilizes an in-situ composite method to prepare composite nanomaterials, which is simpler and easier to prepare in large quantities than traditional methods such as electrostatic adsorption.
  • the present invention utilizes the interaction between N-doped bismuth oxycarbonate and graphite phase carbon nitride to compound bismuth oxycarbonate with carbon polymer dots and form an S-type heterojunction structure, which can broaden the light absorption range, enhance the light absorption intensity, and promote the separation and transfer of photogenerated carriers, thereby improving the photocatalytic degradation of the composite material. Solution performance.
  • the present invention has the following advantages and technical effects:
  • the present invention utilizes an in-situ composite method to synthesize a composite material from bismuth oxycarbonate nanosheets and carbon polymer dots to form an effective and environmentally friendly heterojunction of bismuth oxycarbonate composite carbon polymer dots, which overcomes the shortcomings of limited visible light response and fewer active sites of monomer photocatalysts, accelerates charge separation, generates more photogenerated carriers, and improves the spectral response range of the monomer photocatalyst, thereby achieving efficient visible light catalytic oxidation activity and further improving the performance of photocatalytic degradation of organic dyes, antibiotics and phenolic pollutants in environmental water bodies.
  • the method has the advantages of high photocatalytic efficiency, simple and fast method, economy and environmental protection.
  • the present invention controls the proportion of carbon polymer dots when preparing the composite material to obtain a composite material with a suitable energy band structure and optimal photocatalytic activity, thereby effectively improving the photocatalytic performance of the monomer.
  • the present invention utilizes the interaction between N-mixed bismuth oxycarbonate and graphite phase carbon nitride to compound bismuth oxycarbonate with carbon polymer dots and form an S-type heterojunction structure, which can broaden the light absorption range, enhance the light absorption intensity, and promote the separation and transfer of photogenerated carriers, thereby improving the photocatalytic degradation performance of the composite material.
  • the present invention also experimentally verified that the bismuth oxycarbonate and carbon polymer dot composite material maintains good photocatalytic activity in a seawater environment.
  • FIG1 is a schematic diagram of the synthesis process and microstructure of the composite material in Example 1 of the present invention.
  • n-BOC bismuth oxycarbonate nanosheets
  • CPDs carbon polymer dots
  • FIG2 is a schematic diagram of the synthesis process and microstructure of bismuth oxycarbonate nanosheets in Comparative Example 1 of the present invention
  • FIG3 is a TEM image of carbon polymer dots, carbon polymer dots composite bismuth oxycarbonate nanosheet materials, and bismuth oxycarbonate nanosheets obtained in Example 1 of the present invention and Comparative Example 1;
  • FIG4 is a graph showing the photocatalytic degradation performance of the carbon polymer dots composite bismuth oxycarbonate nanosheet materials and bismuth oxycarbonate nanosheets in different proportions obtained in Example 1 of the present invention and Comparative Example 1 for dye RhB (a), antibiotic TC (b) and CIP (c) under visible light;
  • FIG5 is a graph showing the photocatalytic activity of the carbon polymer dot composite bismuth carbonate nanosheet material obtained in Example 1 of the present invention under different anion, cation and pH conditions and the photocatalytic degradation performance of the dye RhB, antibiotic TC and CIP in seawater.
  • the raw materials in the present invention are all purchased from commercial sources.
  • a method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material comprises the following steps:
  • the obtained product was centrifuged in water and ethanol at 7000 rpm for 5 minutes, and the water and ethanol were centrifuged and washed three times each, and then dried in a vacuum drying oven at 60° C. for 12 hours to obtain a carbon polymer dot composite bismuth carbonate nanosheet material, named 0.5wt% CPDs/n-BOC.
  • the difference between this embodiment and embodiment 1 is that the added amount of carbon polymer dots is different, specifically 22 mg, and is named 1wt% CPDs/n-BOC.
  • a method for preparing bismuth oxycarbonate nanosheets comprises the following steps:
  • the obtained product was collected by centrifugation, centrifuged at 7000 rpm for 5 min in water and ethanol, respectively, and washed by centrifugation in water and ethanol three times each, and then dried in a vacuum oven at 60 ° C for 12 h to obtain bismuth carbonate nanosheets, named n-BOC.
  • n-BOC is a two-dimensional nanosheet.
  • the HR-TEM image in the inset of Figure 3 a shows a lattice spacing of 0.295nm, corresponding to the (013) crystal plane of n-BOC.
  • Part b of Figure 3 shows that CPDs are zero-dimensional nanodots with a diameter of about 3-5nm.
  • the HR-TEM inset shows that the lattice spacing is 0.211nm, corresponding to the (100) crystal plane of CPDs.
  • Part c of Figure 3 shows that CPDs are uniformly distributed on the surface of the n-BOC material.
  • the lattice fringe spacings of 0.211 nm and 0.295 nm shown in part d of Figure 3 correspond to the (100) crystal plane of CPDs and the (013) crystal plane of n-BOC, respectively, confirming the successful preparation of the CPD/n-BOC composite material and the tight bonding between CPDs and n-BOC.
  • the photocatalytic degradation of 10 mg/L dye RhB, antibiotic TC and CIP as target pollutants was carried out to evaluate the visible light catalytic oxidation activity of the material prepared by the present invention.
  • the steps are as follows:

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Abstract

A carbon polymer dot composite bismuth oxycarbonate nanosheet material, and a preparation method therefor and the use thereof, which belong to the technical field of nanomaterials. The preparation method comprises the following steps: sequentially dissolving CTAB and HMT in an ethanol solution, then adding BiCl3, Na2CO3 and carbon polymer dots, stirring the mixture, then subjecting the mixture to an in-situ composite reaction, and then washing and drying same to obtain a carbon polymer dot composite bismuth oxycarbonate nanosheet material. Further provided are the carbon polymer dot composite bismuth oxycarbonate nanosheet material prepared by using the preparation method, and the use of same in the photocatalytic degradation of organic dyes, antibiotics or phenolic pollutants in water. The material improves the spectral response range of a photocatalyst, achieves the efficient visible light catalytic oxidation activity, has the advantages of a high photocatalytic efficiency, a simple and rapid method, and economy and environmental protection, etc., and can also maintain a good photocatalytic activity in a seawater environment.

Description

一种碳聚合物点复合碳酸氧铋纳米片材料及其制备方法与应用A carbon polymer dot composite bismuth carbonate nanosheet material and its preparation method and application 技术领域Technical Field
本发明属于纳米复合材料技术领域，尤其涉及一种碳聚合物点复合碳酸氧铋纳米片材料及其制备方法与应用。The invention belongs to the technical field of nanocomposite materials, and in particular relates to a carbon polymer dot composite bismuth oxycarbonate nanosheet material and a preparation method and application thereof.
背景技术Background technique
随着人类社会的快速发展和城市化进程，各种有害物质逐渐被释放到大气、水和土壤中，导致环境污染日益严重。特别是化学污染物的排放，严重威胁到人类健康和生态系统的稳定。因此，高效、低成本地去除有害污染物已成为当前环境保护领域亟待解决的问题。在众多的治理技术中，光催化技术因其高效、无需添加化学试剂和对环境友好等特点受到广泛关注，光催化技术是一种以半导体材料作催化剂，在光激发下将有害物质转化为无害物质的技术，其具有高效去除污染物的优点。With the rapid development of human society and the process of urbanization, various harmful substances are gradually released into the atmosphere, water and soil, leading to increasingly serious environmental pollution. In particular, the emission of chemical pollutants seriously threatens human health and the stability of the ecosystem. Therefore, the efficient and low-cost removal of harmful pollutants has become an urgent problem to be solved in the current field of environmental protection. Among the many treatment technologies, photocatalytic technology has attracted widespread attention due to its high efficiency, no need to add chemical reagents and environmental friendliness. Photocatalytic technology is a technology that uses semiconductor materials as catalysts to convert harmful substances into harmless substances under light excitation. It has the advantage of efficient removal of pollutants.
碳酸氧铋是一种有前景的半导体材料，具有相对优异的光催化性能，因此受到广泛的关注。碳酸氧铋具有较强的光吸收性能、良好的化学稳定性和热稳定性，能够在长期较高的温度下保持自身光催化性能。但由于带隙较大，其在可见光照射下的光催化活性较低，且导电性较差，导致光生电子和空穴的分离效率较低，从而限制光催化性能。Bismuth oxycarbonate is a promising semiconductor material with relatively excellent photocatalytic performance, and therefore has attracted widespread attention. Bismuth oxycarbonate has strong light absorption properties, good chemical stability and thermal stability, and can maintain its photocatalytic performance at high temperatures for a long time. However, due to its large band gap, its photocatalytic activity under visible light irradiation is low, and its conductivity is poor, resulting in low separation efficiency of photogenerated electrons and holes, thus limiting its photocatalytic performance.
碳聚合物点(CPDs)作为一种新型的碳材料，具有荧光性、生物相容性、无毒性、易制备等优点，在光催化、生物成像、药物输送、化学传感等领域有广泛应用。随着对光物理性质和光催化性能的深入研究，CPDs在光催化方向展现出巨大的潜力。良好荧光性质可使其在可见光区域内吸收光能，促进光催化反 应的进行。此外，CPDs具有高比表面积和丰富的官能团，可提高光催化反应的活性和稳定性。然而，CPDs在光催化方向的研究仍处于起步阶段，对其机理和光催化性能的研究需要深入探究。Carbon polymer dots (CPDs) are a new type of carbon material with the advantages of fluorescence, biocompatibility, non-toxicity, and easy preparation. They are widely used in photocatalysis, bioimaging, drug delivery, chemical sensing and other fields. With the in-depth study of photophysical properties and photocatalytic performance, CPDs have shown great potential in the direction of photocatalysis. Good fluorescence properties enable them to absorb light energy in the visible light region and promote photocatalytic reactions. In addition, CPDs have a high specific surface area and rich functional groups, which can improve the activity and stability of photocatalytic reactions. However, the research on CPDs in the direction of photocatalysis is still in its infancy, and the research on its mechanism and photocatalytic performance needs to be further explored.
因此，如何提供一种利用碳聚合物点结合碳酸氧铋，并提高产品光催化性能的方法是本领域技术人员亟需解决的技术问题。Therefore, how to provide a method for utilizing carbon polymer dots to bind bismuth oxycarbonate and improve the photocatalytic performance of the product is a technical problem that those skilled in the art urgently need to solve.
发明内容Summary of the invention
为解决上述技术问题，本发明提出了一种碳聚合物点复合碳酸氧铋纳米片材料及其制备方法与应用。In order to solve the above technical problems, the present invention proposes a carbon polymer dot composite bismuth oxycarbonate nanosheet material and a preparation method and application thereof.
为实现上述目的，本发明提供了以下技术方案：To achieve the above object, the present invention provides the following technical solutions:
一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，包括如下步骤：A method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material comprises the following steps:
将CTAB、HMT依次溶解至乙醇溶液中后，再加入BiCl3、Na2CO3和碳聚合物点进行搅拌，然后进行高压水热反应，再经洗涤、干燥，得到纳米片状的碳酸氧铋。After CTAB and HMT are dissolved in ethanol solution in sequence, BiCl 3 , Na 2 CO 3 and carbon polymer dots are added and stirred, and then a high-pressure hydrothermal reaction is carried out, and then washed and dried to obtain nano-sheet-shaped bismuth oxycarbonate.
有益效果：本发明利用原位复合法合成N杂碳酸氧铋与石墨相氮化碳复合材料并形成S型异质结，有效地将碳酸氧铋纳米片与碳聚合物点进行复合，形成一种有效的、环保的碳酸氧铋纳米片与聚合物点的光催化剂的异质结，克服了碳酸氧铋可见光响应有限和活性位点较少的缺点，产生更多的光生载流子，并进一步提高光催化降解环境水体有机燃料、抗生素和酚类污染物性能。Beneficial effects: The present invention utilizes an in-situ composite method to synthesize N-doped bismuth oxycarbonate and graphite phase carbon nitride composite materials and form an S-type heterojunction, effectively composites bismuth oxycarbonate nanosheets with carbon polymer dots, and forms an effective and environmentally friendly heterojunction of bismuth oxycarbonate nanosheets and polymer dots as a photocatalyst, overcoming the shortcomings of bismuth oxycarbonate's limited visible light response and fewer active sites, generating more photogenerated carriers, and further improving the photocatalytic degradation performance of organic fuels, antibiotics, and phenolic pollutants in environmental water bodies.
优选的，所述CTAB、HMT、BiCl3、Na2CO3和碳聚合物点的质量比为3：3：10：6：(0.11-0.66)；Preferably, the mass ratio of CTAB, HMT, BiCl 3 , Na 2 CO 3 and carbon polymer dots is 3:3:10:6:(0.11-0.66);
所述乙醇溶液为乙醇和水以体积比35:2混合得到； The ethanol solution is obtained by mixing ethanol and water in a volume ratio of 35:2;
所述CTAB与乙醇的添加量之比为300mg：35ml。The ratio of the added amount of CTAB to ethanol is 300 mg:35 ml.
有益效果：本发明中的乙醇和水是作为溶剂提供碳酸氧铋的合成最佳环境，ctab是表面活性剂使生成物晶体结构更佳。Beneficial effects: The ethanol and water in the present invention are used as solvents to provide the best environment for the synthesis of bismuth oxycarbonate, and ctab is a surfactant to make the crystal structure of the product better.
优选的，所述搅拌的速率为7000～8000rpm。Preferably, the stirring rate is 7000-8000 rpm.
有益效果：上述搅拌条件下可以快速充分搅拌均匀。Beneficial effect: The above stirring conditions can quickly and fully stir evenly.
优选的，所述原位复合反应的温度为140℃，时间为12h。Preferably, the temperature of the in-situ composite reaction is 140° C. and the time is 12 h.
有益效果：在上述反应条件下生成的半导体晶型最佳。Beneficial effect: The semiconductor crystal form generated under the above reaction conditions is optimal.
优选的，所述碳聚合物点的制备方法包括以下步骤：Preferably, the method for preparing the carbon polymer dots comprises the following steps:
将柠檬酸和乙二胺溶解于水后进行水热反应，再经透析、冷冻干燥，即得所述碳聚合物点。The carbon polymer dots are obtained by dissolving citric acid and ethylenediamine in water and then performing a hydrothermal reaction, followed by dialysis and freeze drying.
优选的，所述柠檬酸、乙二胺和水的添加量之比为5mmol：335μL：10mL。Preferably, the ratio of the added amounts of citric acid, ethylenediamine and water is 5 mmol:335 μL:10 mL.
优选的，所述水热反应的温度为200℃，时间为5h。Preferably, the temperature of the hydrothermal reaction is 200° C. and the time is 5 hours.
优选的，所述透析的时间为24h。Preferably, the dialysis time is 24 hours.
一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法制备得到的碳聚合物点复合碳酸氧铋纳米片材料。A method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material is disclosed to prepare a carbon polymer dot composite bismuth oxycarbonate nanosheet material.
有益效果：本发明利用原位复合的方法对复合纳米材料进行制备，相比传统的静电吸附等方法更简单且更容易大量制备。Beneficial effect: The present invention utilizes an in-situ composite method to prepare composite nanomaterials, which is simpler and easier to prepare in large quantities than traditional methods such as electrostatic adsorption.
一种碳聚合物点复合碳酸氧铋纳米片材料在光催化降解水中有机染料、抗生素或酚类污染物中的应用。Application of a carbon polymer dot composite bismuth oxycarbonate nanosheet material in photocatalytic degradation of organic dyes, antibiotics or phenolic pollutants in water.
有益效果：本发明利用N杂碳酸氧铋与石墨相氮化碳之间的相互作用，将碳酸氧铋与碳聚合物点进行复合并形成S型异质结结构，能够拓宽光吸收范围，增强光吸收强度，促进光生载流子的分离和转移，从而提升复合材料光催化降 解性能。Beneficial effects: The present invention utilizes the interaction between N-doped bismuth oxycarbonate and graphite phase carbon nitride to compound bismuth oxycarbonate with carbon polymer dots and form an S-type heterojunction structure, which can broaden the light absorption range, enhance the light absorption intensity, and promote the separation and transfer of photogenerated carriers, thereby improving the photocatalytic degradation of the composite material. Solution performance.
与现有技术相比，本发明具有如下优点和技术效果：Compared with the prior art, the present invention has the following advantages and technical effects:
本发明利用原位复合法将碳酸氧铋纳米片与碳聚合物点合成复合材料，形成一种有效的、环保的碳酸氧铋复合碳聚合物点的异质结，克服了单体光催化剂可见光响应有限和活性位点较少的缺点，加速电荷分离，产生更多的光生载流子，改善单体光催化剂的光谱响应范围，从而实现高效的可见光催化氧化活性，并进一步提高光催化降解环境水体有机染料、抗生素和酚类污染物性能，具有光催化效率高、方法简单快捷和经济环保等优点。The present invention utilizes an in-situ composite method to synthesize a composite material from bismuth oxycarbonate nanosheets and carbon polymer dots to form an effective and environmentally friendly heterojunction of bismuth oxycarbonate composite carbon polymer dots, which overcomes the shortcomings of limited visible light response and fewer active sites of monomer photocatalysts, accelerates charge separation, generates more photogenerated carriers, and improves the spectral response range of the monomer photocatalyst, thereby achieving efficient visible light catalytic oxidation activity and further improving the performance of photocatalytic degradation of organic dyes, antibiotics and phenolic pollutants in environmental water bodies. The method has the advantages of high photocatalytic efficiency, simple and fast method, economy and environmental protection.
本发明在制备复合材料时通过控制碳聚合物点的比例，得到具有合适能带结构、拥有最佳光催化活性的复合材料，有效提高了单体的光催化性能。并且，本发明利用N杂碳酸氧铋与石墨相氮化碳之间的相互作用，将碳酸氧铋与碳聚合物点进行复合并形成S型异质结结构，能够拓宽光吸收范围，增强光吸收强度，促进光生载流子的分离和转移，从而提升复合材料光催化降解性能。最后，本发明还通过实验探证了碳酸氧铋与碳聚合物点复合材料在海水环境中保持良好的光催化活性。The present invention controls the proportion of carbon polymer dots when preparing the composite material to obtain a composite material with a suitable energy band structure and optimal photocatalytic activity, thereby effectively improving the photocatalytic performance of the monomer. In addition, the present invention utilizes the interaction between N-mixed bismuth oxycarbonate and graphite phase carbon nitride to compound bismuth oxycarbonate with carbon polymer dots and form an S-type heterojunction structure, which can broaden the light absorption range, enhance the light absorption intensity, and promote the separation and transfer of photogenerated carriers, thereby improving the photocatalytic degradation performance of the composite material. Finally, the present invention also experimentally verified that the bismuth oxycarbonate and carbon polymer dot composite material maintains good photocatalytic activity in a seawater environment.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
构成本申请的一部分的附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:
图1是本发明实施例1中复合材料的合成流程与微观结构示意图；FIG1 is a schematic diagram of the synthesis process and microstructure of the composite material in Example 1 of the present invention;
其中，n-BOC：碳酸氧铋纳米片；CPDs：碳聚合物点；Wherein, n-BOC: bismuth oxycarbonate nanosheets; CPDs: carbon polymer dots;
图2是本发明对比例1中碳酸氧铋纳米片的合成流程与微观结构示意图； FIG2 is a schematic diagram of the synthesis process and microstructure of bismuth oxycarbonate nanosheets in Comparative Example 1 of the present invention;
图3为本发明实施例1和对比例1所得碳聚合物点、碳聚合物点复合碳酸氧铋纳米片材料和碳酸氧铋纳米片的TEM图像；FIG3 is a TEM image of carbon polymer dots, carbon polymer dots composite bismuth oxycarbonate nanosheet materials, and bismuth oxycarbonate nanosheets obtained in Example 1 of the present invention and Comparative Example 1;
图4为本发明实施例1和对比例1所得不同比例的碳聚合物点复合碳酸氧铋纳米片材料和碳酸氧铋纳米片在可见光下对染料RhB(a)、抗生素TC(b)和CIP(c)光催化降解性能图；FIG4 is a graph showing the photocatalytic degradation performance of the carbon polymer dots composite bismuth oxycarbonate nanosheet materials and bismuth oxycarbonate nanosheets in different proportions obtained in Example 1 of the present invention and Comparative Example 1 for dye RhB (a), antibiotic TC (b) and CIP (c) under visible light;
图5为本发明实施例1所得碳聚合物点复合碳酸氧铋纳米片材料在不同阴离子、阳离子和酸碱度条件下的光催化活性与对海水中染料RhB，抗生素TC和CIP光催化降解性能图。FIG5 is a graph showing the photocatalytic activity of the carbon polymer dot composite bismuth carbonate nanosheet material obtained in Example 1 of the present invention under different anion, cation and pH conditions and the photocatalytic degradation performance of the dye RhB, antibiotic TC and CIP in seawater.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和具体实施方式对本发明作进一步详细的说明。In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.
本发明中的原料均通过市售途径购买获得。The raw materials in the present invention are all purchased from commercial sources.
实施例1Example 1
一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，如图1所示，包括以下步骤：A method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material, as shown in FIG1 , comprises the following steps:
(1)碳聚合物点的制备(1) Preparation of carbon polymer dots
将5mmol柠檬酸和335μL乙二胺溶解在10mL去离子水中，搅拌30min后，将混合溶液转移至25mL反应釜，在200℃下加热5h，冷却至室温后，将 产物透析24h，得到碳聚合物点溶液，经过冷冻干燥，得到碳聚合物点固体。5 mmol of citric acid and 335 μL of ethylenediamine were dissolved in 10 mL of deionized water. After stirring for 30 min, the mixed solution was transferred to a 25 mL reactor and heated at 200 °C for 5 h. After cooling to room temperature, The product was dialyzed for 24 hours to obtain a carbon polymer dot solution, which was then freeze-dried to obtain a carbon polymer dot solid.
(2)复合材料的制备(2) Preparation of composite materials
将35mL乙醇和2mL去离子水混合均匀后加入300mg CTAB，直到其完全溶解，然后加入300mg HMT保持7000～8000rpm的速率搅拌直至溶液透明，再将1g BiCl3，600mg Na2CO3和11mg的CPDs搅拌1h，得到前体混合物，再将前体混合物转移至50mL高压釜140℃下加热12h，反应结束后，将所得产物分别在水和乙醇中7000rpm离心5min，且水和乙醇离心洗涤各三次，再于60℃真空干燥箱中干燥12h，即得碳聚合物点复合碳酸氧铋纳米片材料，命名为0.5wt％CPDs/n-BOC。35 mL of ethanol and 2 mL of deionized water were mixed evenly, and 300 mg of CTAB was added until it was completely dissolved. Then 300 mg of HMT was added and stirred at a rate of 7000-8000 rpm until the solution was transparent. Then 1 g of BiCl 3 , 600 mg of Na 2 CO 3 and 11 mg of CPDs were stirred for 1 hour to obtain a precursor mixture. The precursor mixture was transferred to a 50 mL autoclave and heated at 140° C. for 12 hours. After the reaction was completed, the obtained product was centrifuged in water and ethanol at 7000 rpm for 5 minutes, and the water and ethanol were centrifuged and washed three times each, and then dried in a vacuum drying oven at 60° C. for 12 hours to obtain a carbon polymer dot composite bismuth carbonate nanosheet material, named 0.5wt% CPDs/n-BOC.
实施例2Example 2
本实施例与实施例1的区别在于，碳聚合物点的加入量不同，具体为22mg，命名为1wt％CPDs/n-BOC。The difference between this embodiment and embodiment 1 is that the added amount of carbon polymer dots is different, specifically 22 mg, and is named 1wt% CPDs/n-BOC.
实施例3Example 3
本实施例与实施例1的区别在于，碳聚合物点的加入量不同，具体为66mg，命名为3wt％CPDs/n-BOC。The difference between this embodiment and embodiment 1 is that the added amount of carbon polymer dots is different, specifically 66 mg, named 3wt% CPDs/n-BOC.
对比例1Comparative Example 1
一种碳酸氧铋纳米片制备的制备方法，如图2所示，包括以下步骤：A method for preparing bismuth oxycarbonate nanosheets, as shown in FIG2 , comprises the following steps:
在35mL乙醇和2mL去离子水混合溶液中加入300mg CTAB，直到完全溶解，然后加入300mg HMT并保持7000～8000rpm的速率搅拌直至溶液变得透明。接着，将1g BiCl3和600mg Na2CO3溶解在上述体系中，得到前体混合物，再将前体混合物转移至50mL高压反应釜中，在140℃下加热12h。离心收集所得产物，分别在水和乙醇中7000rpm离心5min，且水和乙醇离心洗涤各三次，再于60℃真空干燥箱中干燥12h，得到碳酸氧铋纳米片，命名为n-BOC。 300 mg CTAB was added to a mixed solution of 35 mL ethanol and 2 mL deionized water until it was completely dissolved, and then 300 mg HMT was added and stirred at a rate of 7000-8000 rpm until the solution became transparent. Next, 1 g BiCl 3 and 600 mg Na 2 CO 3 were dissolved in the above system to obtain a precursor mixture, which was then transferred to a 50 mL autoclave and heated at 140 ° C for 12 h. The obtained product was collected by centrifugation, centrifuged at 7000 rpm for 5 min in water and ethanol, respectively, and washed by centrifugation in water and ethanol three times each, and then dried in a vacuum oven at 60 ° C for 12 h to obtain bismuth carbonate nanosheets, named n-BOC.
技术效果：Technical effect:
1.形貌分析1. Morphology Analysis
为验证本发明对比例1所得碳酸氧铋纳米片与实施例1所得碳聚合物点复合碳酸氧铋纳米片材料的形貌与晶相特征，将实施例1所得样品用透射电子显微镜(型号：JEOL JSM-2010)进行拍照，结果见图3。可看出，n-BOC是一个二维纳米片状。图3中a插图中的HR-TEM图像显示0.295nm的晶格间距，与n-BOC的(013)晶面相对应。图3中b部分显示CPDs是零维纳米点状，直径约为3-5nm，HR-TEM插图显示晶格间距为0.211nm，对应于CPDs的(100)晶面。图3中c部分显示CPDs均匀地分布在n-BOC材料的表面。图3中d部分中显示的0.211nm和0.295nm的晶格条纹间距分别与CPDs的(100)晶面和n-BOC的(013)晶面应，证实CPD/n-BOC复合材料的成功制备，且CPDs和n-BOC紧密结合。In order to verify the morphology and crystal phase characteristics of the bismuth oxycarbonate nanosheets obtained in Comparative Example 1 of the present invention and the carbon polymer dot composite bismuth oxycarbonate nanosheet materials obtained in Example 1, the sample obtained in Example 1 was photographed with a transmission electron microscope (model: JEOL JSM-2010), and the results are shown in Figure 3. It can be seen that n-BOC is a two-dimensional nanosheet. The HR-TEM image in the inset of Figure 3 a shows a lattice spacing of 0.295nm, corresponding to the (013) crystal plane of n-BOC. Part b of Figure 3 shows that CPDs are zero-dimensional nanodots with a diameter of about 3-5nm. The HR-TEM inset shows that the lattice spacing is 0.211nm, corresponding to the (100) crystal plane of CPDs. Part c of Figure 3 shows that CPDs are uniformly distributed on the surface of the n-BOC material. The lattice fringe spacings of 0.211 nm and 0.295 nm shown in part d of Figure 3 correspond to the (100) crystal plane of CPDs and the (013) crystal plane of n-BOC, respectively, confirming the successful preparation of the CPD/n-BOC composite material and the tight bonding between CPDs and n-BOC.
2.性能检测2. Performance testing
以10mg/L染料RhB、抗生素TC和CIP为目标污染物进行光催化降解，以评价本发明所制备材料的可见光催化氧化活性。其步骤如下：The photocatalytic degradation of 10 mg/L dye RhB, antibiotic TC and CIP as target pollutants was carried out to evaluate the visible light catalytic oxidation activity of the material prepared by the present invention. The steps are as follows:
(1)取50mg样品置于光催化反应器中，在250W氙灯下光降解100mL RhB(λ>400nm)。(1) Take 50 mg of sample and place it in a photocatalytic reactor to photodegrade 100 mL of RhB (λ>400 nm) under a 250 W xenon lamp.
(2)采用流动冷却水系统使温度维持在30℃以避免热催化。氙灯照射前，将溶液磁搅拌30min，使光催化剂在材料表面达到吸附-脱附平衡。开灯后，在15min的时间间隔内，取3mL溶液，离心并通过0.2μm聚醚砜过滤去除颗粒，用于后续分析。用紫外-可见分光光度计在最大吸收波长554、358和276nm下测定目标污染物的浓度变化。 (2) A flowing cooling water system was used to maintain the temperature at 30 °C to avoid thermal catalysis. Before xenon lamp irradiation, the solution was magnetically stirred for 30 min to allow the photocatalyst to reach adsorption-desorption equilibrium on the material surface. After turning on the lamp, 3 mL of the solution was taken at intervals of 15 min, centrifuged and filtered through 0.2 μm polyethersulfone to remove particles for subsequent analysis. The concentration changes of the target pollutants were measured using a UV-visible spectrophotometer at the maximum absorption wavelengths of 554, 358 and 276 nm.
测试结果如图4所示，从图4可以看出，1wt％CPDs/n-BOC降解各种污染物都具有最佳性能。The test results are shown in FIG4 . As can be seen from FIG4 , 1 wt % CPDs/n-BOC has the best performance in degrading various pollutants.
3.自然水体性能检测3. Natural water performance testing
探究性能最佳的1wt％CPDs/n-BOC光催化剂在真实海水环境中对有机污染物是否同样拥有良好的光催化活性。进行以下工作，考察不同无机离子对光催化性能的影响(图5中a-b)。，其中，SW和DW分别代表海水和去离子水。具体操作为将光催化实验所用去离子水换成1.0mmol/L的不同无机离子溶液后进行光催化实验，实验结果表明，该催化剂对RhB的光催化降解性能不受大多数无机离子的显著抑制。此外，还通过调节溶液的pH值来研究其对光催化性能的影响(图5中c部分)。结果表明，1wt％CPDs/n-BOC具有所有合成样品中最好的pH稳定性，在pH＝13时性能仅下降18％。之后在真实的海洋环境中评估催化剂的光催化性能实验中(图5中d-f)，该催化剂同样表现出良好的光催化活性，性能下降仅在2-4％之间。这些数据表明1wt％CPDs/n-BOC是一种具有实用前景的光催化剂。It is investigated whether the best performing 1wt% CPDs/n-BOC photocatalyst also has good photocatalytic activity against organic pollutants in a real seawater environment. The following work was carried out to investigate the effects of different inorganic ions on the photocatalytic performance (a-b in Figure 5). , where SW and DW represent seawater and deionized water, respectively. The specific operation is to replace the deionized water used in the photocatalytic experiment with 1.0mmol/L different inorganic ion solutions and then conduct photocatalytic experiments. The experimental results show that the photocatalytic degradation performance of the catalyst for RhB is not significantly inhibited by most inorganic ions. In addition, the effect of the pH value of the solution on the photocatalytic performance was studied by adjusting its pH value (part c in Figure 5). The results show that 1wt% CPDs/n-BOC has the best pH stability among all synthesized samples, and the performance only decreases by 18% at pH = 13. Later, in the photocatalytic performance experiment of the catalyst evaluated in a real marine environment (d-f in Figure 5), the catalyst also showed good photocatalytic activity, and the performance decrease was only between 2-4%. These data indicate that 1wt% CPDs/n-BOC is a photocatalyst with practical prospects.
以上，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应该以权利要求的保护范围为准。 The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the technical field within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims (10)

  1. 一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，包括如下步骤：A method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material, characterized in that it comprises the following steps:
    将CTAB、HMT依次溶解至乙醇溶液中后，再加入BiCl3、Na2CO3和碳聚合物点进行搅拌，然后进行原位复合反应，再经洗涤、干燥，得到碳聚合物点复合碳酸氧铋纳米片材料。After CTAB and HMT are dissolved in ethanol solution in sequence, BiCl 3 , Na 2 CO 3 and carbon polymer dots are added and stirred, and then an in-situ composite reaction is carried out. After washing and drying, a carbon polymer dot composite bismuth carbonate nanosheet material is obtained.
  2. 根据权利要求1所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，所述CTAB、HMT、BiCl3、Na2CO3和碳聚合物点的质量比为3：3：10：6：(0.11-0.66)。The method for preparing a carbon polymer dot composite bismuth carbonate nanosheet material according to claim 1 is characterized in that the mass ratio of CTAB, HMT, BiCl 3 , Na 2 CO 3 and carbon polymer dot is 3:3:10:6:(0.11-0.66).
  3. 根据权利要求1所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，所述搅拌的速率为7000～8000rpm。The method for preparing a carbon polymer dot composite bismuth carbonate nanosheet material according to claim 1 is characterized in that the stirring rate is 7000-8000 rpm.
  4. 根据权利要求1所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，所述原位复合反应的温度为140℃，时间为12h。The method for preparing a carbon polymer dot composite bismuth carbonate nanosheet material according to claim 1 is characterized in that the temperature of the in-situ composite reaction is 140° C. and the time is 12 hours.
  5. 根据权利要求1所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，所述碳聚合物点的制备方法包括以下步骤：The method for preparing a carbon polymer dot composite bismuth carbonate nanosheet material according to claim 1 is characterized in that the method for preparing the carbon polymer dot comprises the following steps:
    将柠檬酸和乙二胺溶解于水后进行水热反应，再经透析、冷冻干燥，即得所述碳聚合物点。The carbon polymer dots are obtained by dissolving citric acid and ethylenediamine in water and then performing a hydrothermal reaction, followed by dialysis and freeze drying.
  6. 根据权利要求5所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，所述柠檬酸、乙二胺和水的添加量之比为5mmol：335μL：10mL。The method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material according to claim 5 is characterized in that the ratio of the added amounts of citric acid, ethylenediamine and water is 5 mmol:335 μL:10 mL.
  7. 根据权利要求5所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法，其特征在于，所述水热反应的温度为200℃，时间为5h。The method for preparing a carbon polymer dot composite bismuth oxycarbonate nanosheet material according to claim 5 is characterized in that the temperature of the hydrothermal reaction is 200° C. and the time is 5 hours.
  8. 根据权利要求5所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备 方法，其特征在于，所述透析的时间为24h。Preparation of a carbon polymer dot composite bismuth carbonate nanosheet material according to claim 5 The method is characterized in that the dialysis time is 24 hours.
  9. 如权利要求1-8任一项所述的一种碳聚合物点复合碳酸氧铋纳米片材料的制备方法制备得到的碳聚合物点复合碳酸氧铋纳米片材料。The carbon polymer dot composite bismuth carbonate nanosheet material prepared by the method for preparing a carbon polymer dot composite bismuth carbonate nanosheet material as described in any one of claims 1 to 8.
  10. 如权利要求9所述的一种碳聚合物点复合碳酸氧铋纳米片材料在光催化降解水中有机染料、抗生素或酚类污染物中的应用。 The use of a carbon polymer dot composite bismuth oxycarbonate nanosheet material as claimed in claim 9 in the photocatalytic degradation of organic dyes, antibiotics or phenolic pollutants in water.
PCT/CN2023/130437 2023-11-06 2023-11-08 Carbon polymer dot composite bismuth oxycarbonate nanosheet material, and preparation method therefor and use thereof WO2024088433A1 (en)

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