CN117680168A - A lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology and its preparation method and application - Google Patents

A lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology and its preparation method and application Download PDF

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CN117680168A
CN117680168A CN202311564271.5A CN202311564271A CN117680168A CN 117680168 A CN117680168 A CN 117680168A CN 202311564271 A CN202311564271 A CN 202311564271A CN 117680168 A CN117680168 A CN 117680168A
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lignin
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孙万鹏
张宾朋
刘源
孙春芳
王明锐
孟晓君
范拼搏
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Henan University of Technology
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Abstract

The invention discloses a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-shaped morphology, a preparation method and application thereof, which utilizes lignin carbon induction and pH regulation with rich oxygen functional groups to synthesize the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material BiOX/C with the regular flower-shaped morphology, and the material has the advantages of wide spectral response range, high efficiency, strong stability, and the like, and the separation of photo-generated carriers and cavities is effectively promoted based on the flower-shaped morphology structure and the Z-type heterojunction of the material, so that the material has higher photo-reaction efficiency, and the defects of low quantum efficiency, slow degradation rate, poor stability, easy deactivation and the like of the traditional photocatalytic degradation organic pollutant material are effectively solved. The lignin carbon substrate material takes lignocellulose in agricultural wastes as a carbon source, is environment-friendly, low in production cost, simple and feasible in synthesis method, considerable in yield, mild in reaction condition in the photocatalytic degradation process of organic pollutants, simple and feasible in operation, and wide in application prospect.

Description

一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合 材料及其制备方法和应用A lignin carbon-based bismuth oxyhalide Z-type heterojunction composite with a regular flower-like morphology Materials and their preparation methods and applications

技术领域Technical field

本发明涉及功能材料技术领域，具体涉及一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料及其制备方法和应用。The invention relates to the technical field of functional materials, and specifically relates to a lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology and its preparation method and application.

背景技术Background technique

近年来，资源短缺和环境污染越来越成为威胁人类未来生存与发展的关键问题，能够安全、快速、低能耗、高效率降解各种污染物的新现象、新理论、新技术的开发和利用成为广大科研工作者不断探索的热点。由于具有绿色、温和、节能等优点，近些年来以太阳能为唯一能量来源驱动水体中污染物的去除，逐步成为当下缓解能源短缺和保护水环境最具潜力的策略之一。而作为实现高效水体净化的关键步骤-开发高效、环保、稳定性高、廉价的光响应材料，亦成为当前及未来广大科学家们关注的焦点。In recent years, resource shortages and environmental pollution have increasingly become key issues threatening the future survival and development of mankind. The development and utilization of new phenomena, new theories, and new technologies that can safely, quickly, low-energy-consumption, and efficiently degrade various pollutants It has become a hot spot that the majority of scientific researchers continue to explore. Due to its green, mild, energy-saving and other advantages, in recent years, using solar energy as the only energy source to drive the removal of pollutants in water has gradually become one of the most promising strategies to alleviate energy shortages and protect the water environment. As a key step to achieve efficient water purification, the development of efficient, environmentally friendly, highly stable, and cheap light-responsive materials has become the focus of current and future scientists.

半导体光催化降解处理有机污染的机理是利用空穴强氧化性或者是电子及空穴在水中产生的一些活性物种，如羟基自由基(·OH)及超氧自由基(·O2-)及其次生自由基，这些自由基可以与体系中的有机污染物发生加合、取代、电子转移等一系列反应，通过破坏有机物中存在的C-C键、C-H键等化学键并最终将其转化为CO2和H2O实现有机污染物降解。以TiO2为代表的传统半导体光催化剂虽然具有稳定性高、无毒性及低成本等一系列优点，但是其带隙较宽(如锐钛矿TiO2和金红石相TiO2分别为3.2eV和3.0eV)，只能利用占比较少的紫外光，限制了其实际应用。此外，纳米二氧化钛的光生电子-空穴易复合、纳米颗粒易团聚等缺点也极大的降低了TiO2的光催化活性。因此，开发具备宽光谱响应、高催化活性的光催化材料极具现实意义。The mechanism of semiconductor photocatalytic degradation to treat organic pollution is to utilize the strong oxidation of holes or some active species generated by electrons and holes in water, such as hydroxyl radicals (·OH) and superoxide radicals (·O 2- ) and Secondly, free radicals are generated. These free radicals can undergo a series of reactions such as addition, substitution, and electron transfer with organic pollutants in the system, and finally convert them into CO 2 by destroying chemical bonds such as CC bonds and CH bonds existing in organic matter. and H 2 O to achieve degradation of organic pollutants. Although traditional semiconductor photocatalysts represented by TiO 2 have a series of advantages such as high stability, non-toxicity and low cost, their band gaps are wide (such as 3.2 eV and 3.0 for anatase TiO 2 and rutile phase TiO 2 respectively). eV), can only utilize a small proportion of ultraviolet light, limiting its practical application. In addition, shortcomings such as the easy recombination of photogenerated electrons and holes of nano-titanium dioxide and the easy agglomeration of nanoparticles also greatly reduce the photocatalytic activity of TiO 2 . Therefore, it is of great practical significance to develop photocatalytic materials with wide spectral response and high catalytic activity.

近些年来，针对这些问题，一系列新型半导体光催化材料不断涌现，包括金属氧化物(Ag2O、ZnO、SnO2、ZrO2)、钒酸盐(BiAlVO7、BiVO4)、钨钼酸盐(Bi2MoO6、Bi2WO6)、卤氧化铋(BiOCl、BiOBr、BiOI)等材料。其中由V-VI-VII主族多组分构成的卤氧铋BiOX(X＝Cl、Br和I)具有由[Bi2O2]2+键与卤素交错结合的层状结构，使得BiOX晶体内部形成了垂直于[Bi2O2]2+和卤素之间的内部电场，可以促进光生电子和空穴的分离，BiOX类半导体具有优异的光催化活性。此外，BiOX类半导体的带隙随着原子序数的增大由4.18eV(BiOF)降低至1.7eV(BiOI)，这也极大的扩展了材料自身的光催化活性范围，此类材料再有机污染物降解领域展现出广阔的应用前景。然而BiOX材料自身也存在不少问题，BiOCl基本无可见光响应，限制了其对太阳光的利用；BiOBr的能带宽度较为合适，但对可见光的吸收范围较窄，需要进一步调控能带结构；BiOI的禁带宽度较窄，光生载流子-空穴容易重新复合，光催化效率较低。In recent years, in response to these problems, a series of new semiconductor photocatalytic materials have been emerging, including metal oxides (Ag 2 O, ZnO, SnO 2 , ZrO 2 ), vanadate (BiAlVO 7 , BiVO 4 ), tungstate molybdate Salt (Bi 2 MoO 6 , Bi 2 WO 6 ), bismuth oxyhalide (BiOCl, BiOBr, BiOI) and other materials. Among them, the bismuth oxyhalide BiOX (X=Cl, Br and I) composed of multi-components of the V-VI-VII main group has a layered structure composed of [Bi 2 O 2 ] 2+ bonds and halogens interlaced, making the BiOX crystal An internal electric field perpendicular to [Bi 2 O 2 ] 2+ and halogen is formed internally, which can promote the separation of photogenerated electrons and holes. BiOX-based semiconductors have excellent photocatalytic activity. In addition, the band gap of BiOX semiconductors decreases from 4.18eV (BiOF) to 1.7eV (BiOI) as the atomic number increases, which also greatly expands the photocatalytic activity range of the material itself. Such materials are no longer subject to organic pollution. The field of biodegradation shows broad application prospects. However, the BiOX material itself also has many problems. BiOCl basically has no visible light response, which limits its use of sunlight; BiOBr has a more suitable energy band width, but its visible light absorption range is narrow, and the energy band structure needs to be further controlled; BiOI The bandgap width is narrow, photogenerated carriers and holes are easy to recombine, and the photocatalytic efficiency is low.

发明内容Contents of the invention

本发明的目的是为解决现有技术中BiOX材料的光催化效率较低的技术问题，提供一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料及其制备方法和应用。The purpose of the present invention is to solve the technical problem of low photocatalytic efficiency of BiOX materials in the prior art, and to provide a lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology and its preparation. Methods and Applications.

本发明为解决上述技术问题的不足，所采用的技术方案是：一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，包括以下步骤：In order to solve the deficiencies in the above technical problems, the technical solution adopted by the present invention is: a preparation method of a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, which includes the following steps:

S1、将模板剂与木质素共同溶于乙二醇中，超声分散混合后加热蒸干，得到原料A；S1. Dissolve the template agent and lignin in ethylene glycol, disperse and mix with ultrasonic, then heat and evaporate to dryness to obtain raw material A;

S2、将原料A在氮气流保护下，以1～5℃/min的升温速率升温至500-1000℃焙烧6-12h，得到前驱体B；S2. Under the protection of nitrogen flow, heat the raw material A to 500-1000°C for 6-12 hours at a heating rate of 1-5°C/min to obtain precursor B;

S3、将前驱体B加入强碱性溶液中加热反应，反应结束后，经洗涤烘干得到木质素碳；S3. Add precursor B to a strong alkaline solution for heating reaction. After the reaction is completed, lignin carbon is obtained by washing and drying;

S4、将卤素盐的水溶液以1～10滴/秒的速度逐滴滴加入铋盐和木质素碳的水溶液中，混匀后调节pH至3～7，升温至150～200℃进行反应，反应结束后，经离心、洗涤、干燥及研磨后，即得具有规整花状形貌的木质素碳基卤氧铋复合材料。S4. Add the aqueous solution of the halogen salt to the aqueous solution of the bismuth salt and lignocarbon drop by drop at a rate of 1 to 10 drops/second, mix evenly, adjust the pH to 3 to 7, and raise the temperature to 150 to 200°C for reaction. After completion, after centrifugation, washing, drying and grinding, a lignin carbon-based bismuth oxyhalide composite material with a regular flower-like morphology is obtained.

作为本发明一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法的进一步优化：所述步骤S1中的模板剂为二氧化硅微球，木质素为碱木质素。As a further optimization of the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology of the present invention: the template agent in step S1 is silica microspheres, and the lignin It is alkali lignin.

作为本发明一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法的进一步优化：所述二氧化硅微球与碱木质素的加入质量比为1:1-1:10。As a further optimization of the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology of the present invention: the mass ratio of the silica microspheres to the alkali lignin is 1 :1-1:10.

作为本发明一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法的进一步优化：所述步骤S4中卤素盐为氯化钾、溴化钾、碘化钾中两种的混合物。As a further optimization of the preparation method of the lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology of the present invention: the halogen salt in step S4 is potassium chloride, potassium bromide, and potassium iodide. A mixture of the two.

作为本发明一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法的进一步优化：所述两种卤素盐的用量摩尔比为1:1-10:1。As a further optimization of the preparation method of the lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology of the present invention: the molar ratio of the two halogen salts is 1:1-10: 1.

作为本发明一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法的进一步优化：所述步骤S3中强碱性溶液为氢氧化钠溶液，加热反应的温度为80℃。As a further optimization of the preparation method of the lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology of the present invention: the strong alkaline solution in step S3 is sodium hydroxide solution, and the reaction is heated The temperature is 80℃.

作为本发明一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法的进一步优化：所述步骤S4中使用氨水调节溶液pH值。As a further optimization of the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology of the present invention: in step S4, ammonia water is used to adjust the pH value of the solution.

本发明还提供一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料，该材料由上述方法制备得到。The invention also provides a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, which is prepared by the above method.

本发明还提供一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料在光催化降解有机污染物体系中的应用。The invention also provides an application of a lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology in a system for photocatalytic degradation of organic pollutants.

本发明具有以下有益效果：本发明针对现有卤化铋材料的缺陷，利用具有丰富含氧官能团的木质素碳诱导与pH调控，合成出一种光谱响应范围宽、效率高、稳定性强的具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料BiOX/C，基于材料的花状形貌结构和Z型异质结有效促进光生载流子与空穴的分离，使得该材料具有更高的光反应效率，有效解决了传统光催化降解有机污染物材料量子效率低、降解速率慢、稳定性差、易失活等缺点。且该木质素碳基底材料以农业废弃物中的木质纤维素为碳源，环境友好、生产成本低，合成方法简单易行、产量可观，光催化降解有机污染物过程反应条件温和，操作简单易行，具有广阔的应用前景。The present invention has the following beneficial effects: Aiming at the defects of existing bismuth halide materials, the present invention utilizes lignin carbon induction and pH regulation with rich oxygen-containing functional groups to synthesize a material with wide spectral response range, high efficiency and strong stability. BiOX/C, a lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, effectively promotes the separation of photogenerated carriers and holes based on the material's flower-like morphological structure and Z-type heterojunction. This material has higher photoreaction efficiency and effectively solves the shortcomings of traditional photocatalytic degradation of organic pollutant materials such as low quantum efficiency, slow degradation rate, poor stability, and easy deactivation. Moreover, this lignocarbon-based material uses lignocellulose in agricultural waste as the carbon source, is environmentally friendly, has low production cost, has a simple and easy synthesis method, and has considerable yields. The reaction conditions of the photocatalytic degradation of organic pollutants are mild, and the operation is simple and easy. OK and has broad application prospects.

附图说明Description of the drawings

图1为BiOCl@C、BiOClxBry@C的SEM形貌图；Figure 1 shows the SEM morphology of BiOCl@C and BiOCl x Br y @C;

图2(a)、(b)分别为光催化反应前后BiOCl、BiOCl@C的XRD图谱；Figure 2(a) and (b) show the XRD patterns of BiOCl and BiOCl@C before and after the photocatalytic reaction respectively;

图3分别为PC、BiOCl@C和BiOClxBry@C的紫外-可见漫反射谱图；Figure 3 shows the UV-visible diffuse reflectance spectra of PC, BiOCl@C and BiOCl x Br y @C respectively;

图4为BiOCl、BiOCl@C和BiOBrxCly@C光催化降解有机染料性能图。Figure 4 shows the photocatalytic degradation performance of organic dyes by BiOCl, BiOCl@C and BiOBr x Cl y @C.

具体实施方式Detailed ways

为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容并不局限于下面的实施例。In order to better understand the present invention, the content of the present invention will be further explained below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，包括以下步骤：A method for preparing a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, including the following steps:

S1、将模板剂与木质素共同溶于乙二醇中，超声分散混合后加热蒸干，得到原料A。S1. Dissolve the template agent and lignin in ethylene glycol, disperse and mix with ultrasonic, then heat and evaporate to dryness to obtain raw material A.

模板剂可以选用二氧化硅微球，木质素选用碱木质素，二氧化硅微球与碱木质素的加入质量比为1:1-1:10。The template agent can be silica microspheres, and the lignin can be alkali lignin. The mass ratio of silica microspheres to alkali lignin is 1:1-1:10.

S2、将原料A在氮气流保护下，以1～5℃/min的升温速率升温至500-1000℃焙烧6-12h，得到前驱体B。S2. Under the protection of nitrogen flow, heat the raw material A to 500-1000°C and roast it for 6-12 hours at a heating rate of 1-5°C/min to obtain the precursor B.

S3、将前驱体B加入强碱性溶液中加热反应，反应结束后，经洗涤烘干得到木质素碳。S3. Add precursor B to a strong alkaline solution and heat for reaction. After the reaction is completed, lignin carbon is obtained by washing and drying.

强碱性溶液为氢氧化钠溶液，加热反应的温度为80℃。The strong alkaline solution is sodium hydroxide solution, and the temperature of the heating reaction is 80°C.

S4、将卤素盐的水溶液以1～10滴/秒的速度逐滴滴加入铋盐和木质素碳的水溶液中，混匀后调节pH(氨水)至3～7，升温至150～200℃进行反应，反应结束后，经离心、洗涤、干燥及研磨后，即得具有规整花状形貌的木质素碳基卤氧铋复合材料。S4. Add the aqueous solution of halogen salt to the aqueous solution of bismuth salt and lignin carbon drop by drop at a speed of 1 to 10 drops/second. After mixing, adjust the pH (ammonia water) to 3 to 7, and raise the temperature to 150 to 200°C. After the reaction, after centrifugation, washing, drying and grinding, a lignin carbon-based bismuth oxyhalide composite material with a regular flower-like morphology is obtained.

卤素盐为氯化钾、溴化钾、碘化钾中两种的混合物，卤素盐的用量摩尔比为1:1-10:1。The halogen salt is a mixture of potassium chloride, potassium bromide and potassium iodide, and the molar ratio of the halogen salt is 1:1-10:1.

<实施例1><Example 1>

将5g二氧化硅微球和5g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以5℃/min升温至800℃，焙烧12h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 5g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 800°C at 5°C/min, and roasted for 12 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A；将6mmol氯化钾(KCl)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以5滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用氨水调节PH为3，继续搅拌30min。随后将混合溶液转移至水热釜中，200℃反应12h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到木质素碳基卤氧铋材料3％BiOCl@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047g of lignocarbon to 30 mL of deionized water, stir for 30 min, and prepare solution A; add 6 mmol of potassium chloride (KCl) to 30 mL. In ionized water, stir for 30 minutes to prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 5 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 3 with ammonia water and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200°C for 12 hours. After natural cooling, centrifuge at 10,000 r/min, dry at 80°C for 12 hours, cool to room temperature and grind to obtain lignin carbon-based bismuth oxyhalide material 3% BiOCl@C, which is sealed and stored.

图1中的SEM图所示为实施例1制备的复合材料。从图中可以看出，所有产物均可以观察到大量规整的花状结构，其直径在3-5μm的范围内变动。高倍率的SEM图揭示该催化剂花状表面的精细结构，该催化剂由纳米片组成，这些纳米片紧密的结合在一起，形成了花状的结构。The SEM image in Figure 1 shows the composite material prepared in Example 1. As can be seen from the figure, a large number of regular flower-like structures can be observed in all products, and their diameters vary within the range of 3-5 μm. High-magnification SEM images reveal the fine structure of the catalyst's flower-like surface. The catalyst is composed of nanosheets that are tightly combined to form a flower-like structure.

<实施例2><Example 2>

将5g二氧化硅微球和5g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以5℃/min升温至800℃，焙烧12h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 5g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 800°C at 5°C/min, and roasted for 12 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A。将3mmol溴化钾(KBr)、3mmol氯化钾(KCl)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以2滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用氨水调节PH为3，继续搅拌30min。随后将混合溶液转移至水热釜中，200℃反应12h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料3％BiOCl0.5Br0.5@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047 g of lignocarbon to 30 mL of deionized water, stir for 30 min, and prepare solution A. Add 3 mmol potassium bromide (KBr) and 3 mmol potassium chloride (KCl) to 30 mL of deionized water, stir for 30 min, and prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 2 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 3 with ammonia water and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200°C for 12 hours. After natural cooling, centrifuge at 10000r/min, dry at 80°C for 12h, cool to room temperature and grind to obtain a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology 3% BiOCl 0.5 Br 0.5 @C , sealed and stored.

<实施例3><Example 3>

将5g二氧化硅微球和25g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以2℃/min升温至1000℃，焙烧6h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 25g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 1000°C at 2°C/min and roasted for 6 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A。将3mmol溴化钾(KBr)、3mmol碘化钾(KI)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以10滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用氨水调节PH为3，继续搅拌30min。随后将混合溶液转移至水热釜中，150℃反应12h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料3％BiOBr0.5I0.5@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047 g of lignocarbon to 30 mL of deionized water, stir for 30 min, and prepare solution A. Add 3 mmol potassium bromide (KBr) and 3 mmol potassium iodide (KI) to 30 mL of deionized water, stir for 30 min, and prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 10 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 3 with ammonia water and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 150°C for 12 hours. After natural cooling, centrifuge at 10000r/min, dry at 80°C for 12h, cool to room temperature and grind to obtain a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology 3% BiOBr 0.5 I 0.5 @C , sealed and stored.

<实施例4><Example 4>

将5g二氧化硅微球和50g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以1℃/min升温至500℃，焙烧8h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 50g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 500°C at 1°C/min and roasted for 8 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A。将3mmol氯化钾(KCl)、3mmol碘化钾(KI)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以10滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用氨水调节PH为3，继续搅拌30min。随后将混合溶液转移至水热釜中，180℃反应10h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料3％BiOCl0.5I0.5@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047 g of lignocarbon to 30 mL of deionized water, stir for 30 min, and prepare solution A. Add 3 mmol potassium chloride (KCl) and 3 mmol potassium iodide (KI) to 30 mL of deionized water, stir for 30 min, and prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 10 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 3 with ammonia water and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 180°C for 10 h. After natural cooling, centrifuge at 10000r/min, dry at 80°C for 12h, cool to room temperature and grind to obtain a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology 3% BiOCl 0.5 I 0.5 @C , sealed and stored.

<对比例1><Comparative Example 1>

将5g二氧化硅微球和5g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以30℃/min升温至800℃，焙烧12h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 5g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 800°C at 30°C/min and roasted for 12 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A。将3mmol溴化钾(KBr)、3mmol氯化钾(KCl)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以2滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用氨水调节PH为3，继续搅拌30min。随后将混合溶液转移至水热釜中，200℃反应12h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料3％BiOCl0.5Br0.5@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047 g of lignin carbon into 30 mL of deionized water, stir for 30 min, and prepare solution A. Add 3 mmol potassium bromide (KBr) and 3 mmol potassium chloride (KCl) to 30 mL of deionized water, stir for 30 minutes, and prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 2 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 3 with ammonia water and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200°C for 12 hours. After natural cooling, centrifuge at 10000r/min, dry at 80℃ for 12h, cool to room temperature and grind to obtain a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology 3% BiOCl 0.5 Br 0.5 @C , sealed and stored.

<对比例2><Comparative Example 2>

将5g二氧化硅微球和5g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以5℃/min升温至800℃，焙烧12h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 5g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 800°C at 5°C/min, and roasted for 12 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A。将3mmol溴化钾(KBr)、3mmol氯化钾(KCl)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以20滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用氨水调节PH为3，继续搅拌30min。随后将混合溶液转移至水热釜中，200℃反应12h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料3％BiOCl0.5Br0.5@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047 g of lignocarbon to 30 mL of deionized water, stir for 30 min, and prepare solution A. Add 3 mmol potassium bromide (KBr) and 3 mmol potassium chloride (KCl) to 30 mL of deionized water, stir for 30 minutes, and prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 20 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 3 with ammonia water and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200°C for 12 hours. After natural cooling, centrifuge at 10000r/min, dry at 80°C for 12h, cool to room temperature and grind to obtain a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology 3% BiOCl 0.5 Br 0.5 @C , sealed and stored.

<对比例3><Comparative Example 3>

将5g二氧化硅微球和5g碱木质素加入50ml乙二醇中，超声混合30min后，不断搅拌加热蒸干。在氮气流保护下，以5℃/min升温至800℃，焙烧12h，得到木质素质碳前驱体。将前驱体加入50ml浓氢氧化钠溶液中，在80℃条件下搅拌6h，离心洗涤至中性，烘干研磨，即得木质素碳，密封保存。Add 5g of silica microspheres and 5g of alkali lignin into 50ml of ethylene glycol, mix with ultrasonic for 30 minutes, then stir and heat to evaporate to dryness. Under the protection of nitrogen flow, the temperature was raised to 800°C at 5°C/min, and roasted for 12 hours to obtain the lignin carbon precursor. Add the precursor to 50 ml of concentrated sodium hydroxide solution, stir for 6 hours at 80°C, centrifuge and wash until neutral, dry and grind to obtain lignin carbon, which is sealed and stored.

将6mmol的五水硝酸铋(Bi(NO3)3·5H2O)和0.047g木质素碳加入30mL去离子水中，搅拌30min，配制成溶液A。将3mmol溴化钾(KBr)、3mmol氯化钾(KCl)加入30mL去离子水中，搅拌30min，配制成溶液B。搅拌结束后，将B溶液倒入分液漏斗中，使之以2滴/秒的速度逐滴加入到A溶液中，搅拌至均匀后形成混合溶液，用调节PH为10，继续搅拌30min。随后将混合溶液转移至水热釜中，200℃反应12h。自然冷却后，10000r/min离心后80℃干燥12h，冷却至室温并研磨，得到具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料3％BiOCl0.5Br0.5@C，密封保存。Add 6 mmol of bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.047 g of lignocarbon to 30 mL of deionized water, stir for 30 min, and prepare solution A. Add 3 mmol potassium bromide (KBr) and 3 mmol potassium chloride (KCl) to 30 mL of deionized water, stir for 30 minutes, and prepare solution B. After stirring, pour solution B into the separatory funnel and add it drop by drop to solution A at a rate of 2 drops/second. Stir until uniform to form a mixed solution. Adjust the pH to 10 and continue stirring for 30 minutes. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200°C for 12 hours. After natural cooling, centrifuge at 10000r/min, dry at 80°C for 12h, cool to room temperature and grind to obtain a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology 3% BiOCl 0.5 Br 0.5 @C , sealed and stored.

<光催化性能检测><Photocatalytic Performance Test>

分别称取20mg的BiOCl、实施例1和2以及对比例1-3制备得到的复合材料，放入特质石英反应器中，在避光条件下，分别加入50ml亚甲基蓝MB溶液和罗丹明RhB(20mg/L)。室温条件下，将反应器转移至500W氙灯光照下，光照3h，每20min取样一次。采用普析T6新世纪型紫外-可见分光光度计检测样品，测定664nm吸收波长时各个样品的吸光度。Weigh 20 mg of BiOCl, the composite materials prepared in Examples 1 and 2, and Comparative Examples 1-3 respectively, put them into a special quartz reactor, and under light-proof conditions, add 50 ml of methylene blue MB solution and rhodamine RhB (20 mg). /L). At room temperature, the reactor was transferred to a 500W xenon lamp for 3 hours, and samples were taken every 20 minutes. Use Puji T6 New Century UV-Visible Spectrophotometer to detect the samples and measure the absorbance of each sample at the absorption wavelength of 664nm.

图2(a、b)分别显示BiOCl及3％BiOCl@C光催化降解MB和RhB 3h前后XRD谱图，如图所示，反应前后BiOCl及3％BiOCl@C晶型结构并未发生变化，这说明卤氧化铋材料PbFCl型结构的稳定性。Figure 2 (a, b) respectively shows the XRD spectra before and after the photocatalytic degradation of MB and RhB by BiOCl and 3% BiOCl@C for 3h. As shown in the figure, the crystal structure of BiOCl and 3% BiOCl@C has not changed before and after the reaction. This illustrates the stability of the PbFCl type structure of the bismuth oxyhalide material.

图3中卤氧化铋材料3％BiOCl@C(实施例1)和3％BiOCl0.5Br0.5@C(实施例2)样品的紫外-可见漫反射谱图中，3％BiOCl@C和3％BiOCl0.5Br0.5@C样品在整个可见光区域显示出较强的光吸收。图中样品木质素碳材料在整个可见光区域未显示出较强的光吸收。通过数据分析可知3％BiOCl@C的禁带宽度Eg＝3.14eV、3％BiOCl0.5Br0.5@C的禁带宽度Eg＝2.92eV，两种材料的禁带宽度均小于BiOCl，表明花状结构和Z型异质结的形成增强了材料的可见光响应。In Figure 3, the UV-visible diffuse reflectance spectra of the bismuth oxyhalide material 3% BiOCl@C (Example 1) and 3% BiOCl 0.5 Br 0.5 @C (Example 2) samples, 3% BiOCl@C and 3% The BiOCl 0.5 Br 0.5 @C sample shows strong light absorption in the entire visible light region. The sample lignocarbon material in the picture does not show strong light absorption in the entire visible light region. Through data analysis, it can be seen that the bandgap width of 3% BiOCl@C is Eg=3.14eV, and the bandgap width of 3%BiOCl 0.5 Br 0.5@C is Eg=2.92eV. The bandgap widths of both materials are smaller than BiOCl, indicating a flower-like structure. The formation of Z-shaped heterojunction enhances the visible light response of the material.

图4所示，3％BiOCl0.5Br0.5@C(实施例2)催化剂显著提高对有机染料的降解率，该催化剂对MB和RhB的降解率分别为96.8％和81.3％；3％BiOCl@C(实施例1)对MB的降解率为83.6％、对RhB的降解率为62.7％。As shown in Figure 4, the 3% BiOCl 0.5 Br 0.5 @C (Example 2) catalyst significantly improves the degradation rate of organic dyes. The degradation rates of MB and RhB by this catalyst are 96.8% and 81.3% respectively; 3% BiOCl@C (Example 1) The degradation rate of MB was 83.6% and the degradation rate of RhB was 62.7%.

当体系中未加入木质素碳和溴元素时，BiOCl对MB和RhB的降解率分别为37.3％和46.2％，降解效果不明显。When no lignin carbon and bromine were added to the system, the degradation rates of MB and RhB by BiOCl were 37.3% and 46.2% respectively, and the degradation effect was not obvious.

这说明在花状结构和Z型异质结的共同作用使该催化剂性能提升，其原因可以归因于以下两方面。一方面材料的规整花状结构实现了BiOX纳米片的空间分离，而且增加了材料比表面积，极大提高了BiOX材料与污染物的相接触面积，强化了光催化反应。其次，当两种卤素盐混合水热后形成BiOXnY1-n型化合物，两种类似结构半导体间产生Z型异质结，促进光生电子-空穴分离，拓展了材料的可见光响应，两种作用协同起效使得催化剂达到最佳的光催化性能。This shows that the combined effect of the flower-like structure and Z-shaped heterojunction improves the performance of the catalyst, and the reasons can be attributed to the following two aspects. On the one hand, the regular flower-like structure of the material realizes the spatial separation of BiOX nanosheets, increases the specific surface area of the material, greatly increases the contact area between the BiOX material and pollutants, and strengthens the photocatalytic reaction. Secondly, when two halogen salts are mixed with water and heated to form a BiOX n Y 1-n compound, a Z-type heterojunction is generated between two similar-structured semiconductors, which promotes the separation of photogenerated electrons and holes and expands the visible light response of the material. These effects work synergistically to enable the catalyst to achieve optimal photocatalytic performance.

对比例1催化剂对MB和RhB的降解率分别为72.6％和66.4％。对比例2催化剂对MB和RhB的降解率分别为78.2％和68.3％。对比例3催化剂对MB和RhB的降解率分别为46.6％和62.5％。The degradation rates of MB and RhB by the catalyst of Comparative Example 1 were 72.6% and 66.4% respectively. The degradation rates of MB and RhB by the catalyst of Comparative Example 2 were 78.2% and 68.3% respectively. The degradation rates of MB and RhB by the catalyst of Comparative Example 3 were 46.6% and 62.5% respectively.

对比例1-3中催化剂对MB和RhB的降解率与实施例2相比均有所下降，这说明采用控制升温速率的中温焙烧可以有效保留木质素特有的丰富含氧官能团，而后结合控制滴加速度和PH调控，使得木质素表面含氧官能团形成给电子的羟基与吸电子的卤素离子相互吸引，从而实现BiOX纳米片的空间分离，形成花状形貌，提高光生电子-空穴复合的能垒。The degradation rates of MB and RhB by the catalysts in Comparative Examples 1-3 have decreased compared with Example 2, which shows that the medium-temperature roasting with controlled heating rate can effectively retain the rich oxygen-containing functional groups unique to lignin, and then combined with the controlled drop rate Acceleration and pH control make the oxygen-containing functional groups on the surface of lignin form electron-donating hydroxyl groups and electron-withdrawing halogen ions to attract each other, thereby achieving spatial separation of BiOX nanosheets, forming a flower-like morphology, and improving the energy of photogenerated electron-hole recombination. base.

以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above. Those skilled in the art can make various variations or modifications within the scope of the claims, which does not affect the essence of the present invention.

Claims (10)

1.一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于，包括以下步骤：1. A method for preparing a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, which is characterized by comprising the following steps: S1、将模板剂与木质素共同溶于乙二醇中，超声分散混合后加热蒸干，得到原料A；S1. Dissolve the template agent and lignin in ethylene glycol, disperse and mix with ultrasonic, then heat and evaporate to dryness to obtain raw material A; S2、将原料A在氮气流保护下，以1～5℃/min的升温速率升温至500-1000℃焙烧6-12h，得到前驱体B；S2. Under the protection of nitrogen flow, heat the raw material A to 500-1000°C for 6-12 hours at a heating rate of 1-5°C/min to obtain precursor B; S3、将前驱体B加入强碱性溶液中加热反应，反应结束后，经洗涤烘干得到木质素碳；S3. Add precursor B to a strong alkaline solution for heating reaction. After the reaction is completed, lignin carbon is obtained by washing and drying; S4、将卤素盐的水溶液以1～10滴/秒的速度逐滴滴加入铋盐和木质素碳的水溶液中，混匀后调节pH至3～7，升温至150～200℃进行反应，反应结束后，经离心、洗涤、干燥及研磨后，即得具有规整花状形貌的木质素碳基卤氧铋复合材料。S4. Add the aqueous solution of the halogen salt to the aqueous solution of the bismuth salt and lignocarbon drop by drop at a rate of 1 to 10 drops/second, mix evenly, adjust the pH to 3 to 7, and raise the temperature to 150 to 200°C for reaction. After completion, after centrifugation, washing, drying and grinding, a lignin carbon-based bismuth oxyhalide composite material with a regular flower-like morphology is obtained. 2.如权利要求1所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：所述步骤S1中的模板剂为二氧化硅微球，木质素为碱木质素。2. A method for preparing a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 1, characterized in that: the template agent in step S1 is dioxide Silicon microspheres, lignin is alkali lignin. 3.如权利要求2所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：所述二氧化硅微球与碱木质素的加入质量比为1:1-1:10。3. A method for preparing a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 2, characterized in that: the silica microspheres and alkali lignin The mass ratio of adding is 1:1-1:10. 4.如权利要求1所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：所述步骤S4中卤素盐为氯化钾、溴化钾或碘化钾。4. A method for preparing a lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 1, characterized in that: the halogen salt in step S4 is potassium chloride , potassium bromide or potassium iodide. 5.如权利要求1所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：所述步骤S4中卤素盐为氯化钾、溴化钾和碘化钾中任意两种的混合物。5. A method for preparing a lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 1, characterized in that: the halogen salt in step S4 is potassium chloride , a mixture of any two of potassium bromide and potassium iodide. 6.如权利要求5所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：两种卤素盐的用量摩尔比为1:1-10:1。6. The preparation method of a lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 5, characterized in that: the molar ratio of the two halogen salts is 1: 1-10:1. 7.如权利要求1所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：所述步骤S3中强碱性溶液为氢氧化钠溶液，加热反应的温度为80℃。7. A method for preparing a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 1, characterized in that: the strong alkaline solution in step S3 is hydrogen Sodium oxide solution is heated to a reaction temperature of 80°C. 8.如权利要求1所述一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料的制备方法，其特征在于：所述步骤S4中使用氨水调节溶液pH值。8. A method for preparing a lignocarbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology as claimed in claim 1, characterized in that: in step S4, ammonia is used to adjust the pH value of the solution . 9.一种具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料，由权利要求1-8中任一权利要求所述方法制备得到。9. A lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, prepared by the method of any one of claims 1-8. 10.如权利要求9所述具有规整花状形貌的木质素碳基卤氧铋Z型异质结复合材料在光催化降解有机污染物体系中的应用。10. Application of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology in the photocatalytic degradation of organic pollutants systems as claimed in claim 9.
CN202311564271.5A 2023-11-22 2023-11-22 A lignin-carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology and its preparation method and application Pending CN117680168A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115779889A (en) * 2022-11-10 2023-03-14 中国林业科学研究院林产化学工业研究所 A kind of lignin carbon/bismuth molybdate composite photocatalyst and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115779889A (en) * 2022-11-10 2023-03-14 中国林业科学研究院林产化学工业研究所 A kind of lignin carbon/bismuth molybdate composite photocatalyst and its preparation method and application
CN115779889B (en) * 2022-11-10 2024-05-03 中国林业科学研究院林产化学工业研究所 A lignin carbon/bismuth molybdate composite photocatalyst and its preparation method and application

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