CN106622318A - Layered composite photocatalyst using bimetallic nanoparticles as heterojunctions and preparation method thereof - Google Patents

Layered composite photocatalyst using bimetallic nanoparticles as heterojunctions and preparation method thereof Download PDF

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CN106622318A
CN106622318A CN201610980539.7A CN201610980539A CN106622318A CN 106622318 A CN106622318 A CN 106622318A CN 201610980539 A CN201610980539 A CN 201610980539A CN 106622318 A CN106622318 A CN 106622318A
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bimetal nano
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张火利
曹建亮
王燕
陈泽华
贾建波
唐庆杰
马名杰
秦聪
申豆
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Henan University of Technology
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Abstract

The invention discloses a layered composite photocatalyst using bimetallic nanoparticles as heterojunctions. The composite photocatalyst consists of a photocatalysis active component and bimetallic nanoparticles, wherein the bimetallic nanoparticles are uniformly distributed on the photocatalysis active component through an adhesive; the photocatalysis active component is Ti3C2 with a layered structure or an oxidizing product TiO2-xCx, and the adhesive is 0.1-5wt% Nafion perfluorination resin solution, preferably 0.5wt%; the weight percentage of bimetallic nanoparticles and photocatalysis active component is 0.01 to 10.0%; the weight percentage of adhesive and photocatalysis active component is 0.01 to 5.0%. Compared with the prior art, the composite photocatalyst has the advantages that the visible light is more effectively utilized, and the compounding of photo-induced electrons and cavities is inhibited; when the composite photocatalyst is used for photocatalyzing to decompose water to produce hydrogen, the activity is high, and the stability is good.

Description

一种以双金属纳米粒子为异质结的层状复合光催化剂及其制 备方法A layered composite photocatalyst with bimetallic nanoparticles as heterojunction and its preparation preparation method

技术领域technical field

本发明涉及领域，特别是一种以双金属纳米粒子为异质结的层状复合光催化剂及其制备方法。The invention relates to the field, in particular to a layered composite photocatalyst with bimetallic nanoparticles as a heterojunction and a preparation method thereof.

背景技术Background technique

目前由于传统化石能源的储备有限以及使用它们带来的环境问题越来越突出，人们急需寻找新的替代能源。氢能由于其高效性和清洁性而备受重视。各国科学家竞相开发与氢能相关的产品，镍氢电池，氢燃料电池汽车等相关产品正从实验室走向社会，氢能经济即将到来。At present, due to the limited reserves of traditional fossil energy and the environmental problems caused by the use of them are becoming more and more prominent, people urgently need to find new alternative energy. Hydrogen energy is valued for its high efficiency and cleanness. Scientists from all over the world are competing to develop products related to hydrogen energy. Ni-MH batteries, hydrogen fuel cell vehicles and other related products are moving from the laboratory to the society, and the hydrogen energy economy is coming.

传统的制氢方式主要是通过煤、石油、天燃气的裂解产生氢气；或者通过电解水制得氢气；由于在氢气制备的过程中消耗了大量的化石燃料，且造成了区域环境污染和全球的变暖，所以开发出绿色清洁的制氢途径成为氢能源开发的目标之一。太阳能和水是地球上重要的两种可再生性资源，利用太阳能分解水来制备氢气是最清洁的制氢途径，一直是人类开发氢能的梦想。因此，新型光催化剂的研究是未来的发展方向。The traditional way of hydrogen production is mainly to produce hydrogen through the cracking of coal, oil, and natural gas; or to produce hydrogen through electrolysis of water; due to the consumption of a large amount of fossil fuels in the process of hydrogen production, it has caused regional environmental pollution and global harm. Therefore, the development of green and clean hydrogen production methods has become one of the goals of hydrogen energy development. Solar energy and water are two important renewable resources on the earth. Using solar energy to decompose water to produce hydrogen is the cleanest way to produce hydrogen, and it has always been the dream of human beings to develop hydrogen energy. Therefore, research on new photocatalysts is the future direction of development.

中国专利公开号CN102641741A公开了一种以金属镉为核异质结构为壳的复合型光催化剂及制备方法。该复合型光催化剂以金属镉为核，半导体异质结构氧化锌和硫化镉为壳，金属镉的所占摩尔比例在50％-90％，氧化锌所占摩尔比例为5％，硫化镉所占摩尔比例为5％-45％；半导体异质结构氧化锌和硫化镉为壳，是指表面为硫化镉镶嵌着氧化锌颗粒的壳，硫化镉壳的厚度为5-50nm，氧化锌颗粒大小为3-50nm；其制备方法将含镉离子前驱体溶解在去离子水中，然后加入锌粉超声和磁力搅拌条件下，镉离子置换金属锌；水洗后，加入硫化盐水溶液硫化处理，或烘干后使用硫化氢气体硫化处理，得到产物为以金属镉为核，半导体异质结构氧化锌和硫化镉为壳的复合型光催化剂。该复合型光催化剂用于光催化分解水制氢，其具有较高的产氢速率。Chinese Patent Publication No. CN102641741A discloses a composite photocatalyst with metal cadmium as the core heterostructure as the shell and its preparation method. The composite photocatalyst uses metal cadmium as the core, semiconductor heterostructure zinc oxide and cadmium sulfide as the shell, the molar proportion of metal cadmium is 50%-90%, the molar proportion of zinc oxide is 5%, and the molar proportion of cadmium sulfide The molar ratio is 5%-45%; the shell of semiconductor heterostructure zinc oxide and cadmium sulfide refers to the shell whose surface is cadmium sulfide embedded with zinc oxide particles. The thickness of the cadmium sulfide shell is 5-50nm, and the size of the zinc oxide particles is 3-50nm; its preparation method is to dissolve the precursor containing cadmium ion in deionized water, and then add zinc powder under the condition of ultrasonic and magnetic stirring, cadmium ion replaces metal zinc; after washing with water, add sulfide salt solution for vulcanization treatment, or dry After sulfuration treatment with hydrogen sulfide gas, the product obtained is a composite photocatalyst with metal cadmium as the core and semiconductor heterostructure zinc oxide and cadmium sulfide as the shell. The composite photocatalyst is used for photocatalytic water splitting to produce hydrogen, and has a high hydrogen production rate.

中国专利公开号CN103316693A公开了一种含有助催化剂Cd的光催化剂Cd/CdS及其制备。该光催化剂是将3CdSO4·8H2O和Na2S2O3·5H2O溶于蒸馏水中，搅拌、超声使其充分分散，再在350-500W的氙灯下反应10-25h；然后在500-800W的微波炉中火5-25min，离心，洗涤固体沉淀，烘干，研磨，得到光催化剂Cd/CdS，其应用在光催化产氢反应中。Chinese Patent Publication No. CN103316693A discloses a photocatalyst Cd/CdS containing cocatalyst Cd and its preparation. The photocatalyst is to dissolve 3CdSO 4 8H 2 O and Na 2 S 2 O 3 5 H 2 O in distilled water, stir and ultrasonically disperse them fully, and then react under 350-500W xenon lamp for 10-25h; then Heat it in a 500-800W microwave oven for 5-25 minutes, centrifuge, wash the solid precipitate, dry it, and grind it to obtain the photocatalyst Cd/CdS, which is used in the photocatalytic hydrogen production reaction.

中国专利公开号CN101623644A公开了一种复合空心球CdS-TiO2的制备及在光催化分解水制氢中的应用。该光催化剂制备方法利用Cd(NO3)2·4H2O为镉源和TiCl4为钛源依次采用水热法，二步浸渍法，溶胶凝胶法制得碳核上依次包裹有硫化镉和TiO2的核壳结构C-CdS-TiO2复合材料，然后在马弗炉中于400℃焙烧2h，得到复合空心球CdS-TiO2光催化剂，该催化剂将CdS与TiO2复合，拓宽了TiO2光谱响应范围，将其用于太阳能可见光催化分解水制氢的反应中，与TiO2光催化剂相比，太阳能光能利用率大幅度增加，产氢速率显著提高。Chinese Patent Publication No. CN101623644A discloses the preparation of a composite hollow sphere CdS-TiO 2 and its application in photocatalytic water splitting to produce hydrogen. The photocatalyst preparation method utilizes Cd(NO 3 ) 2 4H 2 O as the cadmium source and TiCl 4 as the titanium source, and sequentially adopts hydrothermal method, two-step impregnation method, and sol-gel method to obtain carbon cores coated with cadmium sulfide and The core-shell structure C-CdS- TiO2 composite material of TiO2 was then calcined in a muffle furnace at 400 °C for 2 h to obtain a composite hollow sphere CdS- TiO2 photocatalyst, which composites CdS with TiO2 to broaden the TiO 2 Spectral response range, it is used in the reaction of solar visible light catalytic water splitting to produce hydrogen, compared with TiO 2 photocatalyst, the utilization rate of solar light energy is greatly increased, and the rate of hydrogen production is significantly improved.

中国专利公开号CN101623645 A公开了一种p-n结空心球NiO-CdS纳米复合材料的制备及在光催化分解水制氢中的应用。该纳米复合材料的制备方法是将Ni(NO3)2·6H2O作为镍源和Cd(NO3)2·4H2O作为镉源，采用水热法合成法，四步浸渍法将n-NiO半导体与p-CdS半导体复合，制备出一种p-n结空心球NiO-CdS复合纳米材料，将其作为太阳能可见光催化分解水制氢的光催化剂，加速了光生电子的输送速率，大幅度提高了制氢产率。Chinese Patent Publication No. CN101623645 A discloses the preparation of a pn junction hollow sphere NiO-CdS nanocomposite material and its application in photocatalytic water splitting to produce hydrogen. The preparation method of the nanocomposite is to use Ni(NO 3 ) 2 ·6H 2 O as nickel source and Cd(NO 3 ) 2 ·4H 2 O as cadmium source, adopt hydrothermal synthesis method, four-step impregnation method to combine n -NiO semiconductor and p-CdS semiconductor are combined to prepare a pn junction hollow sphere NiO-CdS composite nanomaterial, which is used as a photocatalyst for solar visible light catalytic decomposition of water to produce hydrogen, which accelerates the transport rate of photogenerated electrons and greatly improves the hydrogen production rate.

中国专利公开号CN101767021 A公开了一种p-CoO/n-CdS复合半导体光催化剂的制备方法，该复合半导体光催化剂的制备方法是将铵盐、镉盐、硫脲与去离子水混合反应后，经过滤、洗涤、焙烧和研磨得到CdS固体粉末；再将钴盐、氨水与去离子水混合反应，再加入CdS三次固体粉末，经搅拌、超声分散、减压蒸馏、热处理、洗涤、过滤、焙烧和研磨得到p-CoO/n-CdS复合半导体光催化剂，该复合半导体光催化剂可用于光催化降解有机污染物、光催化分解水制氢和制造太阳能电池。Chinese Patent Publication No. CN101767021 A discloses a preparation method of p-CoO/n-CdS composite semiconductor photocatalyst. The preparation method of the composite semiconductor photocatalyst is to mix and react ammonium salt, cadmium salt, thiourea and deionized water , after filtration, washing, roasting and grinding to obtain CdS solid powder; then cobalt salt, ammonia water and deionized water are mixed and reacted, and then CdS solid powder is added three times, after stirring, ultrasonic dispersion, vacuum distillation, heat treatment, washing, filtration, The p-CoO/n-CdS composite semiconductor photocatalyst is obtained by calcining and grinding, and the composite semiconductor photocatalyst can be used for photocatalytic degradation of organic pollutants, photocatalytic water splitting for hydrogen production, and manufacturing of solar cells.

中国专利公开号CN102107904 A公开了一种非模板法制备硫化镉、硫化锌空心纳米方块的方法。该方法是将摩尔比为1:1的无机镉源或无机锌源和硫粉加入到四氢呋喃溶液中，超声分散；再称取摩尔含量与硫粉相同的硼氢化钠，加入到四氢呋喃溶液中，超声分散；得到的溶液滴加到由无机镉源和硫粉加入到四氢呋喃溶液组成的溶液中，超声反应；所得到的反应产物用无水乙醇离心分离；真空干燥,得到最终的黄色产物即为硫化镉空心纳米方块，在光催化分解有毒、有害物质以及光催化分解水制氢反应中，空心纳米结构有利于提高其光催化性能。Chinese Patent Publication No. CN102107904 A discloses a non-template method for preparing cadmium sulfide and zinc sulfide hollow nanocubes. The method is to add an inorganic cadmium source or inorganic zinc source and sulfur powder with a molar ratio of 1:1 into the tetrahydrofuran solution, and ultrasonically disperse; then weigh sodium borohydride with the same molar content as the sulfur powder, and add it to the tetrahydrofuran solution. Ultrasonic dispersion; the obtained solution is added dropwise to a solution composed of an inorganic cadmium source and sulfur powder added to a tetrahydrofuran solution, and ultrasonically reacted; the obtained reaction product is centrifuged with absolute ethanol; vacuum dried, and the final yellow product is Cadmium sulfide hollow nanocubes, in the photocatalytic decomposition of toxic and harmful substances and the photocatalytic water splitting hydrogen production reaction, the hollow nanostructure is conducive to improving its photocatalytic performance.

中国专利公开号CN102489318 A公开了一种多孔纳米p-CuS/n-CdS复合半导体光催化剂的制备方法，该方法按照铜盐、镉盐、含硫化合物、可升华的化合物模板和去离子水的质量百分比为(0.001％-75％)∶(0.00001％-90％)∶(0.001％-85％)∶(0.001％-75％)∶(0.001％-98％)的比例，依次经反应、离心分离、蒸馏水洗涤、超声分散、离心分离、超声处理、减压蒸馏、烘干、焙烧、自然冷却和研磨等过程，得到多孔纳米p-CuS/n-CdS复合半导体光催化剂，其应用于光催化分解水制氢、光催化降解有机污染物。Chinese Patent Publication No. CN102489318 A discloses a method for preparing a porous nanometer p-CuS/n-CdS composite semiconductor photocatalyst. The mass percentage is (0.001%-75%): (0.00001%-90%): (0.001%-85%): (0.001%-75%): (0.001%-98%) ratio, followed by reaction, centrifugation Separation, distilled water washing, ultrasonic dispersion, centrifugal separation, ultrasonic treatment, vacuum distillation, drying, roasting, natural cooling and grinding, etc., to obtain porous nanometer p-CuS/n-CdS composite semiconductor photocatalyst, which is used in photocatalysis Decompose water to produce hydrogen, and photocatalytically degrade organic pollutants.

中国专利公开号CN103316714 A公开了一种光催化分解水制氢用催化剂及其制备方法。该光催化分解水制氢用催化剂CdS/UiO-66或CdS/UiO-66(NH2)是由UiO-66或UiO-66(NH2)与CdS复合而成的，其中，所述CdS与所述UiO-66或UiO-66(NH2)的质量比为100:1-100，CdS/UiO-66以及CdS/UiO-66(NH2)两种原位复合光催化剂具有很高的产氢速率，与单纯CdS相比，产氢速率明显提高。Chinese Patent Publication No. CN103316714 A discloses a catalyst for photocatalytic water splitting to produce hydrogen and a preparation method thereof. The catalyst CdS/UiO-66 or CdS/UiO-66(NH 2 ) for photocatalytic water splitting to produce hydrogen is composed of UiO-66 or UiO-66(NH 2 ) and CdS, wherein the CdS and The mass ratio of the UiO-66 or UiO-66(NH 2 ) is 100:1-100, and the two in-situ composite photocatalysts of CdS/UiO-66 and CdS/UiO-66(NH 2 ) have a high yield Compared with pure CdS, the hydrogen production rate is significantly improved.

中国专利公开号CN103386317 A公开了一种磷酸铋复合氧化石墨烯光催化剂BiPO4/RGO及其制备方法和应用。该光催化剂是磷酸铋BiPO4和氧化石墨烯GO的复合材料，BiPO4具有单斜晶型或六方晶型，GO在制备过程中被部分还原，以还原的氧化石墨烯RGO形式存在；GO与BiPO4的理论质量百分比为0.5～10：100，该磷酸铋复合氧化石墨烯光催化剂BiPO4/RGO应用于光解水制氢。Chinese Patent Publication No. CN103386317 A discloses a bismuth phosphate composite graphene oxide photocatalyst BiPO 4 /RGO and its preparation method and application. The photocatalyst is a composite material of bismuth phosphate BiPO 4 and graphene oxide GO, BiPO 4 has a monoclinic or hexagonal crystal form, GO is partially reduced during the preparation process, and exists in the form of reduced graphene oxide RGO; GO and The theoretical mass percentage of BiPO 4 is 0.5-10:100, and the bismuth phosphate composite graphene oxide photocatalyst BiPO 4 /RGO is applied to photolysis of water to produce hydrogen.

中国专利公开号CN103447024 A公开了一种铋基锶磁性光催化剂的制备方法及其铋基锶磁性光催化剂。该磁性光催化剂以硝酸铋和铁酸锶为原料，用十二烷基苯磺酸钠为分散剂，先制备铋基锶磁性光催化剂的前驱体，再经55-65℃烘干、500-600℃焙烧3-5h得铋基锶磁性光催化剂，其用于降解有机污染物、光催化分解水制氢和太阳能电池等领域中。Chinese Patent Publication No. CN103447024 A discloses a preparation method of a bismuth-based strontium magnetic photocatalyst and the bismuth-based strontium magnetic photocatalyst. The magnetic photocatalyst uses bismuth nitrate and strontium ferrite as raw materials, and sodium dodecylbenzenesulfonate as a dispersant. Firstly, the precursor of bismuth-based strontium magnetic photocatalyst is prepared, and then dried at 55-65°C, 500- Calcined at 600°C for 3-5 hours to obtain a bismuth-based strontium magnetic photocatalyst, which is used in the fields of degradation of organic pollutants, photocatalytic water splitting to produce hydrogen, and solar cells.

上述这些光催化剂虽然均属于复合型光催化剂，但是这些光催化剂分别以传统材料硫化镉、磷酸铋或硝酸铋为基础制备的复合光催化剂，其中，镉元素和铋元素对人体有毒害作用，大量使用容易造成土壤、水体环境的污染。Although the above-mentioned photocatalysts are all composite photocatalysts, these photocatalysts are composite photocatalysts prepared on the basis of traditional materials such as cadmium sulfide, bismuth phosphate or bismuth nitrate. Among them, cadmium and bismuth elements are toxic to the human body, and a large amount of It is easy to cause pollution of soil and water environment.

因此，从避免造成环境污染的角度出发，本发明采用了层状结构的碳化钛Ti3C2或其氧化产物TiO2-xCx作为光催化剂活性组分和双金属纳米粒子开发出了一种以双金属纳米粒子为异质结的层状复合光催化剂。Therefore, from the perspective of avoiding environmental pollution, the present invention adopts layered structure of titanium carbide Ti 3 C 2 or its oxidation product TiO 2-x C x as the photocatalyst active component and bimetallic nanoparticles to develop a A layered composite photocatalyst with bimetallic nanoparticles as a heterojunction.

发明内容Contents of the invention

本发明的目的是要提供一种以双金属纳米粒子为异质结的层状复合光催化剂及其制备方法，将Pd、Au、Ag中的任意两种金属纳米粒子通过电子结构的互相调变获得双金属纳米粒子，再将其均匀复合到光催化材料层状碳化钛或其氧化产物表面可以实现利用可见光进行光催化反应的目的。The purpose of the present invention is to provide a layered composite photocatalyst with bimetallic nanoparticles as a heterojunction and its preparation method. Any two metal nanoparticles in Pd, Au, and Ag can be modulated by electronic structure. Obtaining bimetallic nanoparticles, and then uniformly compounding them on the surface of the photocatalytic material layered titanium carbide or its oxidation product can realize the purpose of photocatalytic reaction using visible light.

为达到上述目的，本发明是按照以下技术方案实施的：一种以双金属纳米粒子为异质结的层状复合光催化剂，该复合光催化剂由光催化活性组分以及通过粘结剂均匀分布在光催化剂活性组分上的双金属纳米粒子组成，所述光催化剂活性组分为层状结构的碳化钛Ti3C2或其氧化产物TiO2-xCx，所述粘结剂为0.1-5wt.％的Nafion全氟化树脂溶液，优选0.5wt.％，所述双金属纳米粒子与光催化剂活性组分的重量百分比为0.01-10.0％，粘结剂与光催化剂活性组分的重量百分比为0.01-5.0％。In order to achieve the above object, the present invention is implemented according to the following technical scheme: a layered composite photocatalyst with bimetallic nanoparticles as a heterojunction, the composite photocatalyst is composed of photocatalytically active components and uniformly distributed through a binder Composition of bimetallic nanoparticles on the photocatalyst active component, the photocatalyst active component is titanium carbide Ti 3 C 2 or its oxidation product TiO 2-x C x with a layered structure, and the binder is 0.1 -5wt.% Nafion perfluorinated resin solution, preferably 0.5wt.%, the weight percentage of the bimetallic nanoparticles and the photocatalyst active component is 0.01-10.0%, the weight of the binding agent and the photocatalyst active component The percentage is 0.01-5.0%.

进一步的，所述碳化钛Ti3C2或其氧化产物TiO2-xCx层状结构中单片层的厚度为1-400nm，优选1-100nm。Further, the thickness of the monolithic layer in the layered structure of titanium carbide Ti 3 C 2 or its oxidation product TiO 2-x C x is 1-400 nm, preferably 1-100 nm.

优选地，所述双金属纳米粒子为Pd-Ag纳米粒子、Pd-Au纳米粒子以及Au-Ag纳米粒子中的至少一种，双金属纳米粒子的形状为球形、粒状、蠕虫状以及核-壳状中的一种，该双金属纳米粒子的尺寸大小为1-50nm，优选尺寸大小在1-20nm。Preferably, the bimetallic nanoparticles are at least one of Pd-Ag nanoparticles, Pd-Au nanoparticles and Au-Ag nanoparticles, and the shapes of the bimetallic nanoparticles are spherical, granular, worm-like and core-shell One of the shapes, the size of the bimetallic nanoparticles is 1-50nm, preferably 1-20nm.

制备以双金属纳米粒子为异质结的层状复合光催化剂的具体方法，包括以下步骤：A specific method for preparing a layered composite photocatalyst with bimetallic nanoparticles as a heterojunction, comprising the following steps:

步骤一、将所述的的水溶性高分子稳定剂溶于去离子水中，充分搅拌溶解后，再分别加入上述双金属纳米粒子含有的两种金属的水溶性金属无机盐溶液，其中，高分子稳定剂：金属无机盐重量比为(1-10):1，调整pH值为6-9并充分混合均匀后，再利用回流搅拌装置保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原1-2h，再在40℃的恒温水浴锅中静置陈化若4-24h，得到含双金属纳米粒子的溶液；Step 1. Dissolve the water-soluble polymer stabilizer in deionized water, stir and dissolve it fully, and then add the water-soluble metal inorganic salt solution of the two metals contained in the above-mentioned bimetallic nanoparticles, wherein the polymer Stabilizer: the metal-inorganic salt weight ratio is (1-10): 1, adjust the pH value to 6-9 and mix well, then use the reflux stirring device to maintain the condition of 80 ℃ with hydrogen containing 1% hydrogen and argon The gas mixture was reduced for 1-2 hours, and then aged in a constant temperature water bath at 40°C for 4-24 hours to obtain a solution containing bimetallic nanoparticles;

步骤二、将所述的光催化剂活性组分和粘结剂加入到步骤一得到的含双金属纳米粒子的溶液中，其中，含双金属纳米粒子的溶液中双金属纳米粒子与光催化剂活性组分的重量百分比为0.01-10.0％，粘结剂与光催化剂活性组分的重量百分比为0.01-5.0％，进行超声分散10-60min，使光催化剂活性组分和粘结剂充分混合均匀后，然后在60-120℃进行真空干燥8-48h，即可得到以双金属纳米粒子为异质结的层状复合光催化剂。Step 2, adding the photocatalyst active component and binder into the solution containing bimetallic nanoparticles obtained in step 1, wherein the bimetallic nanoparticles and the photocatalyst active group in the solution containing bimetallic nanoparticles The weight percentage of the component is 0.01-10.0%, the weight percentage of the binder and the photocatalyst active component is 0.01-5.0%, carry out ultrasonic dispersion for 10-60min, after the photocatalyst active component and the binder are fully mixed, Then carry out vacuum drying at 60-120° C. for 8-48 hours to obtain a layered composite photocatalyst with bimetallic nanoparticles as heterojunctions.

优选地，所述步骤一中水溶性高分子稳定剂为甲基纤维素、羧甲基纤维素、聚乙烯吡咯烷酮以及聚丙烯酰胺中的至少一种。Preferably, the water-soluble polymer stabilizer in step 1 is at least one of methylcellulose, carboxymethylcellulose, polyvinylpyrrolidone and polyacrylamide.

优选地，所述步骤一中双金属纳米粒子含有的两种金属的水溶性金属无机盐为两种金属的硝酸盐、醋酸盐或氯化物。Preferably, the water-soluble metal inorganic salts of the two metals contained in the bimetallic nanoparticles in the first step are nitrates, acetates or chlorides of the two metals.

与现有的用于光催化分解水产氢的复合光催化剂相比，由于Pd、Au和Ag纳米粒子的局域表面等离子体共振效应能影响其光通量和传导电子，在金属颗粒的表面，传导电子经光照射产生了较多能参与化学反应的高能电子，双金属纳米粒子的性质不是原有性能的“1+1”式的简单叠加，而是拥有新的功能特性，将Pd、Au、Ag中的任意两种金属纳米粒子通过电子结构的互相调变，使其光电性能产生质变，使用双金属纳米粒子作为光催化剂异质结具有表面等离子体共振效应和界面肖特基效应，能更有效的利用可见光和抑制光生电子和空穴的复合，提高光催化效率，再将其均匀复合到光催化材料层状碳化钛或氧化产物表面可以实现利用可见光进行光催化反应，本发明使用的原料均为环境友好型材料，制得的复合光催化剂应用于光催化分解水产氢活性高、稳定性好。Compared with the existing composite photocatalysts for photocatalytic decomposition of water to produce hydrogen, due to the local surface plasmon resonance effect of Pd, Au and Ag nanoparticles can affect their luminous flux and conduction electrons, on the surface of metal particles, conduction electrons After light irradiation, more high-energy electrons that can participate in chemical reactions are produced. The properties of bimetallic nanoparticles are not a simple superposition of the original performance of the "1+1" formula, but have new functional characteristics. Pd, Au, Ag Any two kinds of metal nanoparticles in the photocatalyst have surface plasmon resonance effect and interface Schottky effect, which can be more effective The use of visible light and the suppression of the recombination of photogenerated electrons and holes can improve the photocatalytic efficiency, and then evenly compound it on the surface of photocatalytic material layered titanium carbide or oxidation products to realize the photocatalytic reaction using visible light. The raw materials used in the present invention are all As an environment-friendly material, the prepared composite photocatalyst has high activity and good stability when applied to photocatalytic decomposition of water to produce hydrogen.

附图说明Description of drawings

图1为层状Ti3C2材料的SEM照片。Figure 1 is a SEM photo of layered Ti 3 C 2 material.

图2为层状Ti3C2材料单片层的TEM照片。Figure 2 is a TEM photograph of a single layer of layered Ti 3 C 2 material.

图3为层状Ti3C2材料的XRD谱图。Fig. 3 is the XRD spectrum of the layered Ti 3 C 2 material.

图4为层状TiO2-xCx材料的SEM照片。Fig. 4 is the SEM photo of the layered TiO 2-x C x material.

图5为以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层的TEM照片。Fig. 5 is a TEM photograph of a monolithic layer of a layered Ti 3 C 2 composite photocatalyst with Pd-Ag bimetallic nanoparticles as a heterojunction.

图6(a)为以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层的EDX谱图(a)，图6(b)为以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层的STEM照片。Figure 6(a) is the EDX spectrum (a) of the monolithic layer of layered Ti 3 C 2 composite photocatalyst with Pd-Ag bimetallic nanoparticles as the heterojunction, and Figure 6(b) is the EDX spectrum with Pd-Ag STEM image of monolithic layered Ti3C2 composite photocatalyst with bimetallic nanoparticles as heterojunction.

具体实施方式detailed description

下面结合具体实施例对本发明作进一步描述，在此发明的示意性实施例以及说明用来解释本发明，但并不作为对本发明的限定。The present invention will be further described below in conjunction with specific embodiments. The exemplary embodiments and descriptions of the present invention are used to explain the present invention, but not as a limitation to the present invention.

实施例1Example 1

称取15mg甲基纤维素溶于40mL去离子水中，充分搅拌溶解后，再分别加入2mL的含Pd为2mg/mL的硝酸钯水溶液和3mL的含Au为2.4mg/mL的氯金酸水溶液，调整pH值至7.5，经充分混合均匀后，再利用回流搅拌装置保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原1h后，再在40℃的恒温水浴锅中静置陈化4h，得到含Pd-Au双金属的纳米粒子的溶液；Weigh 15mg of methylcellulose and dissolve it in 40mL of deionized water. After fully stirring and dissolving, add 2mL of palladium nitrate aqueous solution containing 2mg/mL of Pd and 3mL of chloroauric acid aqueous solution containing 2.4mg/mL of Au respectively. Adjust the pH value to 7.5, and after fully mixing, use the reflux stirring device to maintain the condition of 80 ℃ and reduce it with a mixture of hydrogen and argon containing 1% hydrogen for 1 hour, and then statically place it in a constant temperature water bath at 40 ℃. Place and age for 4h to obtain a solution containing Pd-Au bimetallic nanoparticles;

在得到的含双金属纳米粒子的溶液中，加入500mg层状Ti3C2和2mL的0.5wt.％全氟磺酸树脂溶液，进行超声分散30min，使其充分混合均匀后，然后保持在80℃进行真空干燥24h，可得到以Pd-Au双金属纳米粒子为异质结的层状Ti3C2复合光催化剂A。In the obtained solution containing bimetallic nanoparticles, add 500mg of layered Ti 3 C 2 and 2mL of 0.5wt.% perfluorosulfonic acid resin solution, carry out ultrasonic dispersion for 30min, make it fully mixed, and then keep it at 80 °C for 24 hours in vacuum, the layered Ti 3 C 2 composite photocatalyst A with Pd-Au bimetallic nanoparticles as heterojunction can be obtained.

实施例2Example 2

称取10mg甲基纤维素溶于40mL去离子水中，充分搅拌溶解后，再分别加入1mL的含Pd为2mg/mL的硝酸钯水溶液和4mL的含Ag为2mg/mL的硝酸银水溶液，调整pH值至7.5，经充分的混合均匀后，再利用回流搅拌装置保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原1h后，再在40℃的恒温水浴锅中静置陈化4h，得到含Pd-Ag双金属的纳米粒子的溶液；Weigh 10 mg of methyl cellulose and dissolve it in 40 mL of deionized water. After fully stirring and dissolving, add 1 mL of palladium nitrate aqueous solution containing 2 mg/mL of Pd and 4 mL of silver nitrate aqueous solution containing 2 mg/mL of Ag to adjust the pH value to 7.5, after fully mixing evenly, and then using the reflux stirring device to maintain the condition of 80 ° C with a hydrogen-containing 1% mixture of hydrogen and argon for 1 hour, and then let it stand in a constant temperature water bath at 40 ° C Aging for 4h to obtain a solution containing Pd-Ag bimetallic nanoparticles;

在得到的含双金属纳米粒子的溶液中，加入500mg层状Ti3C2和2mL的0.5wt.％全氟磺酸树脂溶液，进行超声分散30min，使其充分混合均匀后，然后保持在80℃进行真空干燥24h，可得到以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂B。In the obtained solution containing bimetallic nanoparticles, add 500mg of layered Ti 3 C 2 and 2mL of 0.5wt.% perfluorosulfonic acid resin solution, carry out ultrasonic dispersion for 30min, make it fully mixed, and then keep it at 80 °C for 24 hours in vacuum, the layered Ti 3 C 2 composite photocatalyst B with Pd-Ag bimetallic nanoparticles as heterojunction can be obtained.

实施例3Example 3

称取20mg甲基纤维素溶于40mL去离子水中，充分搅拌溶解后，再分别加入4mL的含Au为2.4mg/mL的氯金酸水溶液和5mL的含Ag为2mg/mL的硝酸银水溶液，调整pH值至7.5，经充分混合均匀后，再利用回流搅拌装置保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原2h后，再在40℃的恒温水浴锅中静置陈化4h，得到含Au-Ag双金属的纳米粒子的溶液；Weigh 20 mg of methyl cellulose and dissolve it in 40 mL of deionized water. After fully stirring and dissolving, add 4 mL of chloroauric acid aqueous solution containing 2.4 mg/mL of Au and 5 mL of silver nitrate aqueous solution containing 2 mg/mL of Ag. Adjust the pH value to 7.5, and after fully mixing, use the reflux stirring device to maintain the condition of 80 ℃ and reduce it with a mixture of hydrogen and argon containing 1% hydrogen for 2 hours, and then statically place it in a constant temperature water bath at 40 ℃. Place and age for 4h to obtain a solution containing Au-Ag bimetallic nanoparticles;

在得到的含双金属纳米粒子的溶液中，加入500mg层状Ti3C2和2mL的0.5wt.％全氟磺酸树脂溶液，进行超声分散30min，使其充分混合均匀后，然后保持在80℃进行真空干燥24h，可得到以Au-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂C。In the obtained solution containing bimetallic nanoparticles, add 500mg of layered Ti3C2 and 2mL of 0.5wt.% perfluorosulfonic acid resin solution, carry out ultrasonic dispersion for 30min, make it fully mixed, and then keep it at 80 °C for 24 hours in vacuum, the layered Ti 3 C 2 composite photocatalyst C with Au-Ag bimetallic nanoparticles as heterojunction can be obtained.

实施例4Example 4

称取20mg甲基纤维素溶于40mL去离子水中，充分搅拌溶解后，再分别加入5mL的含Pd为2mg/mL的硝酸钯水溶液和4mL的含Au为2.4mg/mL的氯金酸水溶液，调整pH值至7.5，经充分混合均匀后，再利用回流搅拌装置保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原2h后，再在40℃的恒温水浴锅中静置陈化4h，得到含Pd-Au双金属的纳米粒子的溶液；Weigh 20 mg of methyl cellulose and dissolve it in 40 mL of deionized water. After fully stirring and dissolving, add 5 mL of aqueous palladium nitrate containing 2 mg/mL of Pd and 4 mL of aqueous chloroauric acid containing 2.4 mg/mL of Au. Adjust the pH value to 7.5, and after fully mixing, use the reflux stirring device to maintain the condition of 80 ℃ and reduce it with a mixture of hydrogen and argon containing 1% hydrogen for 2 hours, and then statically place it in a constant temperature water bath at 40 ℃. Place and age for 4h to obtain a solution containing Pd-Au bimetallic nanoparticles;

在得到的含双金属纳米粒子的溶液中，加入500mg层状TiO2-xCx和2mL的0.5wt.％全氟磺酸树脂溶液，进行超声分散30min，使其充分混合均匀后，然后保持在80℃进行真空干燥24h，可得到以Pd-Au双金属纳米粒子为异质结的层状TiO2-xCx复合光催化剂D。In the obtained solution containing bimetallic nanoparticles, add 500 mg of layered TiO 2-x C x and 2 mL of 0.5wt.% perfluorosulfonic acid resin solution, carry out ultrasonic dispersion for 30 min, make it fully mixed, and then keep After vacuum drying at 80°C for 24h, the layered TiO 2-x C x composite photocatalyst D with Pd-Au bimetallic nanoparticles as heterojunction can be obtained.

实施例5Example 5

称取20mg甲基纤维素溶于40mL去离子水中，充分搅拌溶解后，再分别加入4mL的含Au为2.4mg/mL的氯金酸水溶液和5mL的含Ag为2mg/mL的硝酸银水溶液，调整pH值至7.5，经充分混合均匀后，再利用回流搅拌装置中保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原2h后，再在40℃恒温水浴锅中静置陈化4h，得到含Au-Ag双金属的纳米粒子的溶液；Weigh 20 mg of methyl cellulose and dissolve it in 40 mL of deionized water. After fully stirring and dissolving, add 4 mL of chloroauric acid aqueous solution containing 2.4 mg/mL of Au and 5 mL of silver nitrate aqueous solution containing 2 mg/mL of Ag. Adjust the pH value to 7.5, after fully mixing, and then use the reflux stirring device to maintain 80 °C under the condition of 1% hydrogen and argon for 2 hours, and then statically place in a 40 °C constant temperature water bath. Place and age for 4h to obtain a solution containing Au-Ag bimetallic nanoparticles;

在得到的含双金属纳米粒子的溶液中，加入500mg层状TiO2-xCx和2mL的0.5wt.％全氟磺酸树脂溶液，进行超声分散30min，使其充分混合均匀后，然后保持在80℃进行真空干燥24h，可得到以Au-Ag双金属纳米粒子为异质结的层状TiO2-xCx复合光催化剂E。In the obtained solution containing bimetallic nanoparticles, add 500 mg of layered TiO 2-x C x and 2 mL of 0.5wt.% perfluorosulfonic acid resin solution, carry out ultrasonic dispersion for 30 min, make it fully mixed, and then keep After vacuum drying at 80°C for 24h, the layered TiO 2-x C x composite photocatalyst E with Au-Ag bimetallic nanoparticles as heterojunction can be obtained.

实施例6Example 6

称取20mg甲基纤维素溶于40mL去离子水中，充分搅拌溶解后，再分别加入5mL的含Pd为2mg/mL的硝酸钯水溶液和5mL的含Ag为2mg/mL的硝酸银水溶液，调整pH值至7.5，经充分的混合均匀后，再利用回流搅拌装置保持80℃条件下用含氢气为1％的氢气和氩气的混合气还原2h后，再在40℃的恒温水浴锅中静置陈化4h，得到含Pd-Ag双金属的纳米粒子的溶液；Weigh 20mg of methylcellulose and dissolve it in 40mL of deionized water. After fully stirring and dissolving, add 5mL of palladium nitrate aqueous solution containing 2mg/mL of Pd and 5mL of silver nitrate aqueous solution of 2mg/mL of Ag to adjust the pH value to 7.5, after fully mixing evenly, and then use the reflux stirring device to maintain the condition of 80 ℃ with the hydrogen containing 1% hydrogen and argon mixed gas for 2 hours, and then let it stand in a constant temperature water bath at 40 ℃ Aging for 4h to obtain a solution containing Pd-Ag bimetallic nanoparticles;

在得到的含双金属纳米粒子的溶液中，加入500mg层状TiO2-xCx和2mL的0.5wt.％全氟磺酸树脂溶液，进行超声分散30min，使其充分混合均匀后，然后保持在80℃进行真空干燥24h，可得到以Pd-Ag双金属纳米粒子为异质结的层状TiO2-xCx复合光催化剂F。In the obtained solution containing bimetallic nanoparticles, add 500 mg of layered TiO 2-x C x and 2 mL of 0.5wt.% perfluorosulfonic acid resin solution, carry out ultrasonic dispersion for 30 min, make it fully mixed, and then keep After vacuum drying at 80°C for 24h, the layered TiO 2-x C x composite photocatalyst F with Pd-Ag bimetallic nanoparticles as heterojunction can be obtained.

检测实验：Detection experiment:

取Ti3C2材料在高倍扫面电子显微镜下得到Ti3C2材料的SEM照片，如图1所示，Ti3C2材料在高倍扫面电子显微镜下显示为层状结构，其层状结构中单片层的厚度为小于100nm，取TiO2-xCx材料在高倍扫面电子显微镜下得到TiO2-xCx材料的SEM照片，如图4所示，TiO2-xCx材料在高倍扫面电子显微镜下显示为层状结构，其层状结构中单片层的厚度为小于100nm；取层状Ti3C2材料的单片层在高倍透射电子显微镜下得到层状Ti3C2材料的单片层的TEM照片，如图2所示，层状Ti3C2材料的单片层显示为薄片状结构；将层状Ti3C2材料在X-射线下衍射得到层状Ti3C2材料的XRD谱图，如图3所示，层状Ti3C2材料在X-射线衍射谱图中，显示为Ti3C2谱峰；Take the Ti 3 C 2 material and obtain the SEM photo of the Ti 3 C 2 material under the high-power scanning electron microscope, as shown in Figure 1, the Ti 3 C 2 material shows a layered structure under the high-power scanning electron microscope, and its layered The thickness of the monolithic layer in the structure is less than 100nm. Take the TiO 2-x C x material and obtain the SEM photo of the TiO 2-x C x material under a high-power scanning electron microscope. As shown in Figure 4, the TiO 2-x C x The material shows a layered structure under a high-power scanning electron microscope, and the thickness of a single layer in the layered structure is less than 100nm; take a single layer of the layered Ti 3 C 2 material and obtain a layered Ti under a high-power transmission electron microscope. The TEM photo of the monolithic layer of the 3 C 2 material, as shown in Figure 2, the monolithic layer of the layered Ti 3 C 2 material shows a thin sheet structure; the layered Ti 3 C 2 material is obtained by diffraction under X-rays The XRD spectrum of the layered Ti 3 C 2 material, as shown in Figure 3, the layered Ti 3 C 2 material is shown as a Ti 3 C 2 peak in the X-ray diffraction spectrum;

取上述实施例2或6中制得的以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层，在高倍透射电子显微镜下得到以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层的TEM照片，如图5所示，Pd-Ag双金属纳米粒子在高倍透射电子显微镜下显示为小于50nm的粒状或蠕虫状，并且层状的以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层上可以清楚的看到Pd-Ag双金属纳米粒子异质结均匀的分布在Ti3C2薄片上；如图6所示为以Pd-Ag双金属纳米粒子为异质结的层状Ti3C2复合光催化剂的单片层的EDX谱图6(a)和STEM照片6(b)，通过对图6(b)中矩形框内的区域1进行线扫描能谱分析，得出的谱图为图6(a)，从图6(a)中可知，得到的异质结是Pd与Ag的纳米粒子结构。Get the monolithic layer of the layered Ti3C2 composite photocatalyst with the Pd-Ag bimetallic nanoparticles obtained in the above-mentioned embodiment 2 or 6 as the heterojunction, and obtain the Pd-Ag bimetallic photocatalyst under the high power transmission electron microscope. The TEM photo of the monolithic layer of the layered Ti 3 C 2 composite photocatalyst with metal nanoparticles as heterojunction, as shown in Figure 5, the Pd-Ag bimetallic nanoparticles are shown as granular particles smaller than 50nm under the high-power transmission electron microscope. Or worm-like, and layered layered Ti 3 C 2 composite photocatalyst with Pd-Ag bimetallic nanoparticles as the heterojunction can clearly see the Pd-Ag bimetallic nanoparticle heterojunction Evenly distributed on the Ti 3 C 2 flakes; as shown in Figure 6, the EDX spectrum of the monolithic layer of the layered Ti 3 C 2 composite photocatalyst with Pd-Ag bimetallic nanoparticles as the heterojunction 6(a ) and STEM photo 6(b), through the line-scan energy spectrum analysis of the area 1 in the rectangular box in Figure 6(b), the obtained spectrum is Figure 6(a), from Figure 6(a) we can see , the resulting heterojunction is a nanoparticle structure of Pd and Ag.

将实施例1-6制备的复合光催化剂用于光催化分解水产氢，反应条件如下：The composite photocatalyst prepared in Examples 1-6 is used for photocatalytic decomposition of water to produce hydrogen, and the reaction conditions are as follows:

分别取上述实施例1-6所制备的复合光催化剂分别放入不同的石英瓶中，加入300mL的蒸馏水，再加入4g硫化钠与2g亚硫酸钠溶于其中作为光催化牺牲剂，实验使用的光源为500W氙灯模拟太阳光，光强为100mW·cm-2，反应前需先通入氮气进行吹扫30min，然后，开始光催化连续反应48h，收集所产生的气体，测量其体积并用气相色谱分析气体组成，实施例1-6制备的复合光催化剂产氢量见表1：Put the composite photocatalysts prepared in the above examples 1-6 into different quartz bottles, add 300mL of distilled water, and then add 4g of sodium sulfide and 2g of sodium sulfite to dissolve them as photocatalytic sacrificial agents. The light source used in the experiment is A 500W xenon lamp simulates sunlight, and the light intensity is 100mW·cm -2 . Before the reaction, nitrogen gas should be introduced for purging for 30 minutes. Then, the photocatalytic continuous reaction should be started for 48 hours. The generated gas was collected, its volume was measured, and the gas was analyzed by gas chromatography. Composition, the composite photocatalyst hydrogen production capacity that embodiment 1-6 prepares is shown in Table 1:

表1光催化产氢反应结果Table 1 Photocatalytic hydrogen production reaction results

从表1中可知，在实施例1-6中贵金属Pd、Au和Ag相互组合还原后获得双金属纳米粒子纳米粒子，其作为异质结分别负载到层状Ti3C2或层状TiO2-xCx材料上获得的复合光催化剂均有光催化分解水产氢的效果。It can be seen from Table 1 that in Examples 1-6, the noble metals Pd, Au and Ag are combined and reduced to obtain bimetallic nanoparticles nanoparticles, which are respectively loaded on layered Ti3C2 or layered TiO2 as a heterojunction The composite photocatalysts obtained on -x C x materials all have the effect of photocatalytically decomposing water to produce hydrogen.

本发明的技术方案不限于上述具体实施例的限制，凡是根据本发明的技术方案做出的技术变形，均落入本发明的保护范围之内。The technical solution of the present invention is not limited to the limitations of the above-mentioned specific embodiments, and any technical deformation made according to the technical solution of the present invention falls within the protection scope of the present invention.

Claims (6)

1. a kind of lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions, it is characterised in that：The composite photocatalyst Agent is evenly distributed on the bimetal nano particles in photocatalyst activity component by photocatalytic activity component and by binding agent Composition, the photocatalyst activity component is the titanium carbide Ti of layer structure3C2Or its oxidation product TiO2-xCx, the binding agent For the weight of the Nafion perfluorinated resin solution of 0.1-5wt.%, the bimetal nano particles and photocatalyst activity component Percentage is 0.01-10.0%, and binding agent is 0.01-5.0% with the percentage by weight of photocatalyst activity component.
2. the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions according to claim 1, its feature exists In：The titanium carbide Ti3C2Or its oxidation product TiO2-xCxThe thickness of monolithic layer is 1-400nm in layer structure.
3. the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions according to claim 1, its feature exists In：The bimetal nano particles are at least in Pd-Ag nano-particles, Pd-Au nano-particles and Au-Ag nano-particles Kind, being shaped as bimetal nano particles is spherical, granular, the one kind in vermiform and core-shell structure copolymer shape, the bimetal nano particles Size be 1-50nm.
4. a kind of lamellar composite photochemical catalyst system with bimetal nano particles as hetero-junctions as described in claim 1-3 is arbitrary Preparation Method, it is characterised in that comprise the following steps：
Step one, described water soluble polymer stabilizer is dissolved in deionized water, after being sufficiently stirred for dissolving, then is separately added into The water-soluble metal inorganic salt solution of two kinds of metals that above-mentioned bimetal nano particles contain, wherein, macromolecule stabilizer：Metal Inorganic salts weight ratio is (1-10):1, adjustment pH value be 6-9 and be sufficiently mixed it is uniform after, recycling is refluxed device and keeps 80 1-2h is reduced with the gaseous mixture of the hydrogen and argon gas that hydrogen is 1% under the conditions of DEG C, then is stood in 40 DEG C of thermostat water bath If ageing 4-24h, obtains the solution containing bimetal nano particles；
Step 2, described photocatalyst activity component and binding agent be added to step one obtains containing bimetal nano particles Solution in, wherein, the weight of bimetal nano particles and photocatalyst activity component in the solution containing bimetal nano particles Percentage is 0.01-10.0%, and binding agent is 0.01-5.0% with the percentage by weight of photocatalyst activity component, carries out ultrasound Dispersion 10-60min, after photocatalyst activity component and binding agent is sufficiently mixed uniformly, then carries out vacuum at 60-120 DEG C It is dried 8-48h, you can obtain the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions.
5. the lamellar composite photochemical catalyst preparation method with bimetal nano particles as hetero-junctions according to claim 4, It is characterized in that：Water soluble polymer stabilizer is methylcellulose, carboxymethylcellulose calcium, polyvinyl pyrrole in the step one At least one in alkanone and polyacrylamide.
6. the lamellar composite photochemical catalyst preparation method with bimetal nano particles as hetero-junctions according to claim 4, It is characterized in that：The water-soluble metal inorganic salts of two kinds of metals that bimetal nano particles contain are two kinds of gold in the step one The nitrate of category, acetate or chloride.
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