CN110385146A - A kind of Ni0.85Se/PDA/g-C3N4Composite photo-catalyst and its application - Google Patents

A kind of Ni0.85Se/PDA/g-C3N4Composite photo-catalyst and its application Download PDF

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CN110385146A
CN110385146A CN201910731656.3A CN201910731656A CN110385146A CN 110385146 A CN110385146 A CN 110385146A CN 201910731656 A CN201910731656 A CN 201910731656A CN 110385146 A CN110385146 A CN 110385146A
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陈文倩
唐量
陈锦怡
柯书强
吴明红
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Abstract

The invention discloses a kind of Ni0.85Se/PDA/g‑C3N4Composite photo-catalyst and its preparation method and application, the composite photocatalyst material have loaded poly-dopamine (PDA) and Ni using azotized carbon nano piece as carrier, in azotized carbon nano on piece0.85Se nano particle.The composite catalyst has many advantages, such as that environmental-friendly, photo-generated carrier separative efficiency is high, visible absorption region is big；Raw material is easy to get simultaneously, and preparation process is simple, and operation is easy, and has repeatability and higher photocatalytic activity well.By optimizing Ni0.85The loading capacity of Se co-catalyst, hydrogen generating quantity is 3.17 times higher than purity nitrogen carbon nanosheet, compares PDA/g-C3N4Composite catalyst is 2.4 times high.Therefore, there is good application prospect in photodissociation aquatic products hydrogen field.

Description

一种Ni0.85Se/PDA/g-C3N4复合光催化剂及其应用A kind of Ni0.85Se/PDA/g-C3N4 composite photocatalyst and its application

技术领域technical field

本发明属于多元半导体复合材料技术领域，尤其涉及一种Ni0.85Se/PDA/g-C3N4复合光催化剂及其在光解水产氢方向的应用。The invention belongs to the technical field of multiple semiconductor composite materials, and in particular relates to a Ni 0.85 Se/PDA/gC 3 N 4 composite photocatalyst and its application in the direction of photolysis of water to produce hydrogen.

背景技术Background technique

氢能是一种清洁能源。利用半导体催化剂将可持续的太阳能转化为氢能，可以同时减少化石燃料枯竭和环境污染问题。石墨相氮化碳(g-C3N4)是第一种不含金属的半导体聚合物，因其可见光吸收，无毒，低成本，优异的化学和热稳定性，和环境友好性等优点在光催化能源转换领域引起了极大的关注。但是由于氮化碳比表面积较小，光生载流子易复合，可见光区域边缘吸收(吸收波长<455)，导电性较差等限制了氮化碳在光解水制氢领域的实际应用。Hydrogen energy is a clean energy. Using semiconductor catalysts to convert sustainable solar energy into hydrogen energy can simultaneously reduce the problems of fossil fuel depletion and environmental pollution. Graphite carbon nitride (gC 3 N 4 ) is the first metal-free semiconducting polymer, which has been widely used in light due to its visible light absorption, non-toxicity, low cost, excellent chemical and thermal stability, and environmental friendliness. The field of catalytic energy conversion has attracted great attention. However, due to the small specific surface area of carbon nitride, the easy recombination of photogenerated carriers, the edge absorption in the visible light region (absorption wavelength <455), and poor conductivity limit the practical application of carbon nitride in the field of photolysis of water to produce hydrogen.

最近研究表明，通过在氮化碳表面加载碳材料或助催化剂是改善光生电子和空穴分离效率低以及提高可见光吸收，以实现有效光解水产氢活性的最简单，最有效的方法之一。贵金属铂已经被证明是一种出色的助催化剂，但它却存在资源稀缺和价格昂贵等缺点。近年来，过渡金属硫族化合物，如MoS2，NiS，CoS，MoSe2等，已被广泛用作为替代铂的gC3N4的助催化剂。Recent studies have shown that loading carbon materials or co-catalysts on the surface of carbon nitride is one of the simplest and most effective methods to improve the low separation efficiency of photogenerated electrons and holes and enhance the visible light absorption to achieve effective photolysis of water for hydrogen production. The noble metal platinum has been proven to be an excellent co-catalyst, but it has the disadvantages of scarcity and high cost. In recent years , transition metal chalcogenides, such as MoS2, NiS, CoS, MoSe2 , etc., have been widely used as cocatalysts for gC3N4 replacing platinum .

多巴胺是一种来生物小分子，在弱碱性条件下可以自发在任何表面上聚合生成紧密的聚多巴胺(PDA)涂层。PDA作为一种碳材料，本身不具备光解水产氢的能力。但是由于PDA具有出色的光捕获能力，良好的光电导性和丰富的儿茶酚基团，可以有效转移和分离光生载流子。最近的研究表明将PDA作为聚合物纳米涂层用来修饰氮化碳后，可以提高氮化碳的光催化活性。Dopamine is a biologically small molecule that can spontaneously polymerize on any surface under weakly alkaline conditions to form a compact polydopamine (PDA) coating. As a carbon material, PDA itself does not have the ability to photolyze water to produce hydrogen. However, due to the excellent light-harvesting ability, good photoconductivity, and abundant catechol groups of PDA, photogenerated carriers can be efficiently transferred and separated. Recent studies have shown that the photocatalytic activity of carbon nitride can be improved after PDA is used as a polymer nanocoating to modify carbon nitride.

发明内容Contents of the invention

为了克服现有技术所存在的缺陷，本发明提供一种Ni0.85Se/PDA/g-C3N4三元复合光催化剂，用于光解水制氢和有机染料降解，以达到降低催化成本，提高催化效率的目的。In order to overcome the defects existing in the prior art, the present invention provides a Ni 0.85 Se/PDA/gC 3 N 4 ternary composite photocatalyst, which is used for hydrogen production by photolysis of water and degradation of organic dyes, so as to reduce the cost of catalysis and improve purpose of catalytic efficiency.

为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:

本发明的第一个方面是提供一种Ni0.85Se/PDA/g-C3N4复合光催化剂，该复合光催化剂料以氮化碳纳米片为载体，在所述氮化碳纳米片上负载聚多巴胺PDA和Ni0.85Se纳米颗粒。The first aspect of the present invention is to provide a Ni 0.85 Se/PDA/gC 3 N 4 composite photocatalyst, the composite photocatalyst material is supported by carbon nitride nanosheets, and polydopamine is loaded on the carbon nitride nanosheets PDA and Ni0.85Se nanoparticles.

进一步地，所述复合光催化剂中Ni0.85Se纳米颗粒的负载量为3wt％～20wt％。更优选为，Ni0.85Se纳米颗粒的负载量为8wt％-12wt％；最优选为，Ni0.85Se纳米颗粒的负载量为10wt％。Further, the loading amount of Ni 0.85 Se nanoparticles in the composite photocatalyst is 3wt%-20wt%. More preferably, the loading amount of Ni 0.85 Se nanoparticles is 8wt%-12wt%; most preferably, the loading amount of Ni 0.85Se nanoparticles is 10wt%.

进一步地，所述复合光催化剂的制备步骤包括：Further, the preparation steps of the composite photocatalyst include:

步骤1)将氮化碳纳米片与弱碱性Tris-HCl缓冲液超声混合后，加入盐酸多巴胺，强力搅拌15～25小时；Step 1) After ultrasonically mixing carbon nitride nanosheets and weakly alkaline Tris-HCl buffer, adding dopamine hydrochloride, and vigorously stirring for 15 to 25 hours;

步骤2)将一定量的Ni0.85Se纳米颗粒与弱碱性Tris-HCl缓冲液超声混合，得到Ni0.85Se均质液；将所述Ni0.85Se均质液滴加至所述步骤1)得到的溶液中，搅拌6～10小时；产物经过抽滤，烘干，研磨后得到Ni0.85Se/PDA/g-C3N4三元复合光催化剂。Step 2) ultrasonically mixing a certain amount of Ni 0.85 Se nanoparticles with a weakly alkaline Tris-HCl buffer solution to obtain a Ni 0.85 Se homogeneous solution; adding the Ni 0.85 Se homogeneous solution dropwise to the step 1) to obtain The solution was stirred for 6-10 hours; the product was suction filtered, dried, and ground to obtain a Ni 0.85 Se/PDA/gC 3 N 4 ternary composite photocatalyst.

进一步地，所述氮化碳纳米片的制备步骤包括：以尿素为原料，经过煅烧和热剥离，制备氮化碳纳米片。Further, the preparation step of the carbon nitride nanosheets includes: using urea as a raw material, calcination and thermal exfoliation to prepare carbon nitride nanosheets.

进一步地，所述Ni0.85Se纳米颗粒的制备步骤包括：以硒粉，硼氢化钠，氯化镍为原料，经过溶剂热反应，制备Ni0.85Se纳米颗粒。Further, the preparation step of the Ni 0.85 Se nanoparticles includes: using selenium powder, sodium borohydride, and nickel chloride as raw materials, and preparing Ni 0.85 Se nanoparticles through solvothermal reaction.

进一步地，所述步骤1)中盐酸多巴胺的用量为氮化碳纳米片质量的8～15％，；更优选为，盐酸多巴胺的用量为氮化碳纳米片质量的10％，聚合时间为20小时。Further, the dosage of dopamine hydrochloride in the step 1) is 8 to 15% of the mass of carbon nitride nanosheets; more preferably, the dosage of dopamine hydrochloride is 10% of the mass of carbon nitride nanosheets, and the polymerization time is 20 Hour.

进一步地，所述弱碱性Tris-HCl缓冲液的pH为8～9；更优选为，pH为8.5。Further, the pH of the weakly alkaline Tris-HCl buffer is 8-9; more preferably, the pH is 8.5.

进一步地，所述步骤2)中，搅拌时间为8小时。Further, in the step 2), the stirring time is 8 hours.

进一步地，所述复合光催化剂的制备步骤具体包括：Further, the preparation step of the composite photocatalyst specifically includes:

步骤1：称取预定量的尿素，以4～6℃/min的升温速率，在520～580℃下煅烧2～6h，待冷却至室温后，研磨成细粉；再将细粉以4～6℃/min的升温速率，在470～530℃下煅烧1～3h，待冷却至室温后得到氮化碳纳米片；Step 1: Weigh a predetermined amount of urea, calcinate at 520-580°C for 2-6 hours at a heating rate of 4-6°C/min, and grind it into fine powder after cooling to room temperature; then grind the fine powder at 4-6°C With a heating rate of 6°C/min, calcining at 470-530°C for 1-3 hours, and obtaining carbon nitride nanosheets after cooling to room temperature;

步骤2：称取预定量的硒粉和硼氢化钠，放入一定量的DMF中，搅拌0.5～2h；再加入预定量的六水合氯化镍，继续搅拌20～40min，在140～180℃下反应18～30h；得到的黑色产物用乙醇和去离子水反复洗涤，在50～70℃下干燥8～16个小时，研磨成粉末，得到Ni0.85Se纳米颗粒。Step 2: Weigh a predetermined amount of selenium powder and sodium borohydride, put it into a certain amount of DMF, and stir for 0.5 to 2 hours; then add a predetermined amount of nickel chloride hexahydrate, and continue to stir for 20 to 40 minutes. reaction at low temperature for 18-30 hours; the obtained black product was repeatedly washed with ethanol and deionized water, dried at 50-70° C. for 8-16 hours, and ground into powder to obtain Ni 0.85 Se nanoparticles.

步骤3：称取预定量的步骤1制备的氮化碳纳米片，放入弱碱性Tris-HCl缓冲液中，超声使其均质；再加入预定量的盐酸多巴胺，剧烈搅拌15～25h；Step 3: Weigh a predetermined amount of carbon nitride nanosheets prepared in step 1, put them into a weakly alkaline Tris-HCl buffer, and ultrasonically homogenize them; then add a predetermined amount of dopamine hydrochloride, and stir vigorously for 15 to 25 hours;

步骤4：称取预定量的步骤2制备的Ni0.85Se纳米颗粒，放入弱碱性Tris-HCl缓冲液中，间歇超声0.5～2min，得到均质液；将均质液滴加到步骤3的溶液中，剧烈搅拌6～10h；Step 4: Weigh a predetermined amount of Ni 0.85 Se nanoparticles prepared in step 2, put them into weakly alkaline Tris-HCl buffer solution, and ultrasonicate intermittently for 0.5-2 minutes to obtain a homogeneous solution; add the homogeneous solution dropwise to step 3 solution, vigorously stirred for 6 to 10 hours;

步骤5：步骤4获得的产物经过多次抽滤，烘干，研磨后得到聚多巴胺PDA和Ni0.85Se负载的三元复合催化剂Ni0.85Se/PDA/g-C3N4。Step 5: The product obtained in step 4 was filtered several times, dried, and ground to obtain polydopamine PDA and Ni 0.85 Se-supported ternary composite catalyst Ni 0.85 Se/PDA/gC 3 N 4 .

更进一步地，所述复合光催化剂的制备步骤具体包括：Further, the preparation steps of the composite photocatalyst specifically include:

步骤1：称取预定量的尿素，以5℃/min的升温速率，在550℃下煅烧4h，待冷却至室温后，研磨成细粉；再将细粉以5℃/min的升温速率，在500℃下煅烧2h，待冷却至室温后得到氮化碳纳米片；Step 1: Weigh a predetermined amount of urea, calcinate at 550°C for 4 hours at a heating rate of 5°C/min, and grind it into a fine powder after cooling to room temperature; then grind the fine powder at a heating rate of 5°C/min Calcined at 500°C for 2 hours, and obtained carbon nitride nanosheets after cooling to room temperature;

步骤2：称取预定量的硒粉和硼氢化钠，放入一定量的DMF中，搅拌1h；再加入预定量的六水合氯化镍，继续搅拌30min，在160℃下反应24h；得到的黑色产物用乙醇和去离子水反复洗涤，在60℃下干燥12个小时，研磨成粉末，得到Ni0.85Se纳米颗粒。Step 2: Weigh a predetermined amount of selenium powder and sodium borohydride, put it into a certain amount of DMF, and stir for 1 hour; then add a predetermined amount of nickel chloride hexahydrate, continue to stir for 30 minutes, and react at 160°C for 24 hours; The black product was repeatedly washed with ethanol and deionized water, dried at 60 °C for 12 h, and ground into powder to obtain Ni 0.85 Se nanoparticles.

步骤3：称取预定量的步骤1制备的氮化碳纳米片，放入pH＝8.5的Tris-HCl缓冲液中，超声使其均质；再加入预定量的盐酸多巴胺，剧烈搅拌20h；Step 3: Weigh a predetermined amount of carbon nitride nanosheets prepared in step 1, put them into Tris-HCl buffer solution with pH = 8.5, and ultrasonically homogenize them; then add a predetermined amount of dopamine hydrochloride, and stir vigorously for 20 hours;

步骤4：称取预定量的步骤2制备的Ni0.85Se纳米颗粒，放入pH＝8.5的Tris-HCl缓冲液中，间歇超声1min，得到均质液；将均质液滴加到步骤3的溶液中，剧烈搅拌8h；Step 4: Weigh a predetermined amount of Ni 0.85 Se nanoparticles prepared in step 2, put them into Tris-HCl buffer solution with pH = 8.5, and ultrasonicate intermittently for 1 min to obtain a homogeneous solution; add the homogeneous solution dropwise to the solution, vigorously stirred for 8h;

步骤5：步骤4获得的产物经过多次抽滤，烘干，研磨后得到聚多巴胺PDA和Ni0.85Se负载的三元复合催化剂Ni0.85Se/PDA/g-C3N4。Step 5: The product obtained in step 4 was filtered several times, dried, and ground to obtain polydopamine PDA and Ni 0.85 Se-supported ternary composite catalyst Ni 0.85 Se/PDA/gC 3 N 4 .

本发明的第二个方面是提供一种任一上述的Ni0.85Se/PDA/g-C3N4光催化剂在光解水产氢或有机染料降解中的应用。The second aspect of the present invention is to provide an application of any one of the above-mentioned Ni 0.85 Se/PDA/gC 3 N 4 photocatalysts in photolysis of water for hydrogen production or degradation of organic dyes.

进一步地，所述光解水产氢的方法包括如下步骤：称取预定量的复合光催化剂与预定量的三乙醇胺水溶液混合，超声；将混合溶液密闭抽真空，用氙灯模拟太阳光进行光照，以制备氢气。Further, the method for producing hydrogen by photolysis of water includes the following steps: weighing a predetermined amount of composite photocatalyst and mixing with a predetermined amount of triethanolamine aqueous solution, ultrasonication; sealing and vacuumizing the mixed solution, and using a xenon lamp to simulate sunlight for illumination to Produce hydrogen.

与现有技术相比，本发明采用上述技术方案具有以下有益效果：Compared with the prior art, the present invention adopts the above-mentioned technical solution and has the following beneficial effects:

(1)本发明原料易得，制备过程简单，操作容易，无毒，而且具有很好的重复性，有利于此项技术的推广和应用。(1) The raw materials of the present invention are easy to obtain, the preparation process is simple, the operation is easy, non-toxic, and has good repeatability, which is beneficial to the popularization and application of this technology.

(2)本发明中，聚多巴胺(PDA)的复合不仅显著的提高了氮化碳纳米片在可见光区域的吸收范围和光生载流子分离效率，同时在其聚合过程中可以充当粘结剂紧密的固定硒化镍纳米颗粒。(2) In the present invention, the composite of polydopamine (PDA) not only significantly improves the absorption range of carbon nitride nanosheets in the visible light region and the separation efficiency of photogenerated carriers, but also acts as a binder during the polymerization process. immobilized nickel selenide nanoparticles.

(3)本发明中Ni0.85Se/PDA/g-C3N4三元复合光催化剂具有优异的光解水产氢活性。通过优化Ni0.85Se的加载量，加载10％质量比的Ni0.85Se纳米颗粒的三元催化剂具有最好的催化活性，H2产生量比纯氮化碳纳米片高3.17倍，比PDA/g-C3N4复合催化剂高2.4倍。(3) The Ni 0.85 Se/PDA/gC 3 N 4 ternary composite photocatalyst in the present invention has excellent photolysis activity for hydrogen production. By optimizing the loading amount of Ni 0.85 Se, the three-way catalyst loaded with 10% by mass of Ni 0.85 Se nanoparticles had the best catalytic activity, and the H2 generation was 3.17 times higher than that of pure carbon nitride nanosheets, and higher than that of PDA/gC 3 N 4 composite catalyst is 2.4 times higher.

附图说明Description of drawings

图1为本发明一实施例中Ni0.85Se/PDA/g-C3N4三元复合催化剂的制备流程示意图；Fig. 1 is the schematic flow chart of the preparation process of Ni 0.85 Se/PDA/gC 3 N 4 ternary composite catalyst in an embodiment of the present invention;

图2为依据本发明实施例3制备的10Ni0.85Se/PDA/g-C3N4催化剂的TEM图；Fig. 2 is the TEM picture of the 10Ni 0.85 Se/PDA/gC 3 N 4 catalyst prepared according to Example 3 of the present invention;

图3为依据本发明实施例与对比例所制备CN,PDA/CN和不同Ni0.85Se负载量的三元催化剂的XRD图；Fig. 3 is the XRD figure of CN prepared according to the embodiment of the present invention and comparative example, PDA/CN and the three-way catalyst of different Ni 0.85 Se loads;

图4为本发明一实施例中制得的Ni0.85Se的XRD图；Fig. 4 is the XRD figure of the Ni0.85Se that makes in an embodiment of the present invention;

图5为依据本发明实施例3与对比例所制备的CN,PDA/CN和10Ni0.85Se-PDA/CN催化剂的固体荧光光谱图；Fig. 5 is the solid fluorescence spectrogram of CN prepared according to the embodiment of the present invention 3 and comparative example, PDA/CN and 10Ni 0.85 Se-PDA/CN catalyst;

图6为依据本发明实施例3与对比例所制备的CN,PDA/CN和10Ni0.85Se-PDA/CN催化剂的固体紫外光谱图；Fig. 6 is the solid ultraviolet spectrogram of CN prepared according to the embodiment of the present invention 3 and comparative example, PDA/CN and 10Ni 0.85 Se-PDA/CN catalyst;

图7为依据本发明实施例与对比例制备的CN,PDA/CN和不同Ni0.85Se负载量的三元催化剂进行光解水的产氢图。Fig. 7 is a hydrogen production graph of photolysis of water by CN, PDA/CN and three-way catalysts with different Ni 0.85 Se loadings prepared according to the examples and comparative examples of the present invention.

具体实施方式Detailed ways

本发明涉及一种Ni0.85Se/PDA/g-C3N4复合光催化剂及其制备方法和应用，该复合光催化剂料以氮化碳纳米片为载体，在所述氮化碳纳米片上负载聚多巴胺PDA和Ni0.85Se纳米颗粒；其中，所述复合光催化剂中Ni0.85Se纳米颗粒的负载量为3wt％～20wt％。下述实施例中Ni0.85Se/PDA/g-C3N4三元复合催化剂的制备流程如图1所示。The invention relates to a Ni 0.85 Se/PDA/gC 3 N 4 composite photocatalyst and its preparation method and application. The composite photocatalyst material uses carbon nitride nanosheets as a carrier, and polydopamine is loaded on the carbon nitride nanosheets PDA and Ni0.85Se nanoparticles; wherein, the loading amount of Ni0.85Se nanoparticles in the composite photocatalyst is 3wt%-20wt%. The preparation process of the Ni 0.85 Se/PDA/gC 3 N 4 ternary composite catalyst in the following examples is shown in FIG. 1 .

下面结合附图和实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。The specific implementation manners of the present invention will be further described below in conjunction with the drawings and examples. The following examples are only used to illustrate the technical solution of the present invention more clearly, but not to limit the protection scope of the present invention.

下述实施例中的实验方法，如无特殊说明，均为常规方法；下述实施例中所用的原料、试剂等，如无特殊说明，均可从公开商业途径获得。The experimental methods in the following examples, unless otherwise specified, are conventional methods; the raw materials, reagents, etc. used in the following examples, unless otherwise specified, can be obtained from open commercial channels.

实施例1Example 1

本实施例为Ni0.85Se负载量为3wt％的Ni0.85Se/PDA/g-C3N4三元复合光催化剂的一种较佳的制备方法，其包括如下步骤：This embodiment is a better preparation method of Ni0.85Se /PDA/ gC3N4 ternary composite photocatalyst with Ni0.85Se loading of 3wt%, which includes the following steps:

步骤1：称取约30克的尿素于50毫升带盖的坩埚中，以5℃/min的升温速率，在550℃下煅烧4h，待冷却至室温后，用研钵研磨成细粉。再将细粉放入不带盖的坩埚中，以5℃/min的升温速率，在500℃下煅烧2h，待冷却至室温后得到氮化碳纳米片。Step 1: Weigh about 30 grams of urea into a 50 ml crucible with a lid, calcinate at 550 °C for 4 hours at a heating rate of 5 °C/min, and grind it into a fine powder with a mortar after cooling to room temperature. Then put the fine powder into a crucible without a cover, calcinate at 500° C. for 2 h at a heating rate of 5° C./min, and obtain carbon nitride nanosheets after cooling to room temperature.

步骤2：称取0.316g硒粉，0.190g硼氢化钠，放入65mL的DMF中，磁力搅拌1h。再加入0.808g氯化镍(六水合)，继续搅拌30min。将其转移到100mL的反应釜中，在160℃下反应24h。得到的黑色产物用乙醇和去离子水反复洗涤，在60℃下干燥12个小时，用研钵研磨成粉末，得到Ni0.85Se纳米颗粒。Step 2: Weigh 0.316g of selenium powder and 0.190g of sodium borohydride, put them into 65mL of DMF, and stir magnetically for 1h. Then add 0.808g of nickel chloride (hexahydrate), and continue stirring for 30min. It was transferred to a 100mL reactor and reacted at 160°C for 24h. The obtained black product was repeatedly washed with ethanol and deionized water, dried at 60 °C for 12 h, and ground into powder with a mortar to obtain Ni 0.85 Se nanoparticles.

步骤3：准确称量0.1g氮化碳，放入40mL Tris-HCl缓冲液(pH＝8.5)中，在超声波清洁器中以100Hz的频率超声0.5h。再加入10mg盐酸多巴胺，剧烈搅拌20h。Step 3: Accurately weigh 0.1 g of carbon nitride, put it into 40 mL of Tris-HCl buffer solution (pH=8.5), and sonicate at a frequency of 100 Hz for 0.5 h in an ultrasonic cleaner. Add 10 mg of dopamine hydrochloride and stir vigorously for 20 h.

步骤4：准确称量3mg步骤2中得到的Ni0.85Se纳米颗粒，放入20mL Tris-HCl缓冲液(pH＝8.5)中，用超声棒以300W的功率间歇超声1min，得到均质液。将均质液滴加到步骤3的溶液中，剧烈搅拌8h。Step 4: Accurately weigh 3 mg of Ni 0.85 Se nanoparticles obtained in Step 2, put them into 20 mL of Tris-HCl buffer solution (pH=8.5), and intermittently sonicate for 1 min with an ultrasonic rod at a power of 300 W to obtain a homogeneous solution. Add the homogeneous solution dropwise to the solution in step 3, and stir vigorously for 8h.

步骤5：产物经过多次抽滤，烘干，研磨后得到3％wt Ni0.85Se负载的三元复合催化剂，命名为3Ni0.85Se-PDA/CN。Step 5: The product was subjected to multiple times of suction filtration, drying, and grinding to obtain a three-way composite catalyst supported by 3%wt Ni 0.85 Se, which was named 3Ni 0.85 Se-PDA/CN.

实施例2Example 2

本实施例为Ni0.85Se负载量为5wt％的Ni0.85Se/PDA/g-C3N4三元复合光催化剂的一种较佳的制备方法，其包括如下步骤：This embodiment is a better preparation method of Ni0.85Se /PDA/ gC3N4 ternary composite photocatalyst with Ni0.85Se loading of 5wt%, which includes the following steps:

步骤1～3与实施例1相同。Steps 1-3 are the same as in Example 1.

步骤4：准确称量5mg步骤2中得到的Ni0.85Se纳米颗粒，放入20mL Tris-HCl缓冲液(pH＝8.5)中，用超声棒以300W的功率间歇超声1min，得到均质液。将均质液滴加到步骤3的溶液中，剧烈搅拌8h。Step 4: Accurately weigh 5 mg of the Ni 0.85 Se nanoparticles obtained in Step 2, put them into 20 mL of Tris-HCl buffer solution (pH=8.5), and intermittently sonicate for 1 min at a power of 300 W with an ultrasonic rod to obtain a homogeneous solution. Add the homogeneous solution dropwise to the solution in step 3, and stir vigorously for 8h.

步骤5：产物经过多次抽滤，烘干，研磨后得到5％wt Ni0.85Se负载的三元复合催化剂，命名为5Ni0.85Se-PDA/CN。Step 5: The product was subjected to multiple times of suction filtration, drying, and grinding to obtain a ternary composite catalyst supported by 5%wt Ni 0.85 Se, which was named 5Ni 0.85 Se-PDA/CN.

实施例3Example 3

本实施例为Ni0.85Se负载量为10wt％的Ni0.85Se/PDA/g-C3N4三元复合光催化剂的一种较佳的制备方法，其包括如下步骤：This embodiment is a better preparation method of Ni0.85Se /PDA/ gC3N4 ternary composite photocatalyst with Ni0.85Se loading of 10wt%, which includes the following steps:

步骤1～3与实施例1相同。Steps 1-3 are the same as in Example 1.

步骤4：准确称量10mg步骤2中得到的Ni0.85Se纳米颗粒，放入20mL Tris-HCl缓冲液(pH＝8.5)中，用超声棒以300W的功率间歇超声1min，得到均质液。将均质液滴加到步骤3的溶液中，剧烈搅拌8h。Step 4: Accurately weigh 10 mg of Ni 0.85 Se nanoparticles obtained in Step 2, put them into 20 mL of Tris-HCl buffer solution (pH=8.5), and ultrasonicate intermittently at 300 W for 1 min with an ultrasonic rod to obtain a homogeneous solution. Add the homogeneous solution dropwise to the solution in step 3, and stir vigorously for 8h.

步骤5：产物经过多次抽滤，烘干，研磨后得到10％wt Ni0.85Se负载的三元复合催化剂，命名为10Ni0.85Se-PDA/CN。Step 5: The product was subjected to multiple times of suction filtration, drying, and grinding to obtain a ternary composite catalyst supported by 10%wt Ni 0.85 Se, which was named 10Ni 0.85 Se-PDA/CN.

实施例4Example 4

本实施例为Ni0.85Se负载量为20wt％的Ni0.85Se/PDA/g-C3N4三元复合光催化剂的一种较佳的制备方法，其包括如下步骤：This embodiment is a better preparation method of Ni0.85Se /PDA/ gC3N4 ternary composite photocatalyst with Ni0.85Se loading of 20wt%, which includes the following steps:

步骤1～3与实施例1相同。Steps 1-3 are the same as in Example 1.

步骤4：准确称量20mg步骤2中得到的Ni0.85Se纳米颗粒，放入20mL Tris-HCl缓冲液(pH＝8.5)中，用超声棒以300W的功率间歇超声1min，得到均质液。将均质液滴加到步骤3的溶液中，剧烈搅拌8h。Step 4: Accurately weigh 20 mg of Ni 0.85 Se nanoparticles obtained in Step 2, put them into 20 mL of Tris-HCl buffer solution (pH=8.5), and intermittently sonicate for 1 min at a power of 300 W with an ultrasonic rod to obtain a homogeneous solution. Add the homogeneous solution dropwise to the solution in step 3, and stir vigorously for 8h.

步骤5：产物经过多次抽滤，烘干，研磨后得到20％wt Ni0.85Se负载的三元复合催化剂，命名为20Ni0.85Se-PDA/CN。Step 5: The product was subjected to multiple times of suction filtration, drying, and grinding to obtain a ternary composite catalyst supported by 20%wt Ni 0.85 Se, which was named 20Ni 0.85 Se-PDA/CN.

对比例1Comparative example 1

本对比例为无负载的氮化碳纳米片的制备方法，其包括如下步骤：This comparative example is the preparation method of unloaded carbon nitride nanosheets, which comprises the following steps:

称取约30克的尿素于50毫升带盖的坩埚中，以5℃/min的升温速率，在550℃下煅烧4h，待冷却至室温后，用研钵研磨成细粉。再将细粉放入不带盖的坩埚中，以5℃/min的升温速率，在500℃下煅烧2h，待冷却至室温后得到氮化碳纳米片，命名为CN。Weigh about 30 g of urea into a 50 ml crucible with a lid, calcinate at 550 °C for 4 h at a heating rate of 5 °C/min, and grind it into a fine powder with a mortar after cooling to room temperature. Then put the fine powder into a crucible without a cover, and calcined at 500 °C for 2 h at a heating rate of 5 °C/min, and after cooling to room temperature, carbon nitride nanosheets were obtained, named CN.

对比例2Comparative example 2

本对比例为仅负载PDA的氮化碳纳米片的制备方法，其包括如下步骤：This comparative example is the preparation method of the carbon nitride nanosheet of only loading PDA, and it comprises the steps:

步骤1：称取约30克的尿素于50毫升带盖的坩埚中，以5℃/min的升温速率，在550℃下煅烧4h，待冷却至室温后，用研钵研磨成细粉。再将细粉放入不带盖的坩埚中，以5℃/min的升温速率，在500℃下煅烧2h，待冷却至室温后得到氮化碳纳米片。Step 1: Weigh about 30 grams of urea into a 50 ml crucible with a lid, calcinate at 550 °C for 4 hours at a heating rate of 5 °C/min, and grind it into a fine powder with a mortar after cooling to room temperature. Then put the fine powder into a crucible without a cover, calcinate at 500° C. for 2 h at a heating rate of 5° C./min, and obtain carbon nitride nanosheets after cooling to room temperature.

步骤2：准确称量0.1g氮化碳，放入40mL Tris-HCl缓冲液(pH＝8.5)中，在超声波清洁器中以100Hz的频率超声0.5h。再加入10mg盐酸多巴胺，剧烈磁力搅拌20h。再加入20mLTris-Hcl缓冲液(pH＝8.5)，继续搅拌8h。产物经过抽滤，烘干，研磨后得到聚多巴胺/氮化碳复合催化剂，命名为PDA/CN。Step 2: Accurately weigh 0.1 g of carbon nitride, put it into 40 mL of Tris-HCl buffer solution (pH=8.5), and sonicate at a frequency of 100 Hz for 0.5 h in an ultrasonic cleaner. Then 10 mg of dopamine hydrochloride was added, and vigorously magnetically stirred for 20 h. Add 20 mL of Tris-Hcl buffer (pH=8.5) and continue stirring for 8 h. The product was suction filtered, dried, and ground to obtain a polydopamine/carbon nitride composite catalyst named PDA/CN.

性能表征实施例Performance Characterization Examples

取本发明实施例1～4，对比例1～2制备的催化剂的进行表征，具体包括：The characterization of the catalysts prepared in Examples 1 to 4 of the present invention and Comparative Examples 1 to 2 specifically includes:

(1)10Ni0.85Se-PDA/CN的透射电镜表征(1) TEM characterization of 10Ni 0.85 Se-PDA/CN

具体地，图2示出了依据实施例3制备的10Ni0.85Se-PDA/CN三元复合光催化剂的透射电镜图，可见PDA涂层均匀包覆在层状g-C3N4上，许多黑色的Ni0.85Se纳米颗粒被沉积在其表面。Specifically, Figure 2 shows the transmission electron microscope image of the 10Ni 0.85 Se-PDA/CN ternary composite photocatalyst prepared according to Example 3. It can be seen that the PDA coating is evenly coated on the layered gC 3 N 4 , and many black Ni 0.85 Se nanoparticles were deposited on its surface.

(2)CN，PDA/CN和不同Ni0.85Se负载量的三元催化剂的X射线衍射表征(2) X-ray diffraction characterization of CN, PDA/CN and three-way catalysts with different Ni 0.85 Se loadings

具体地，图3清楚地示出了实施例1～4，对比例1～2制备的CN、PDA/CN和不同Ni0.85Se负载量的三元催化剂的X射线衍射表征的粉末的XRD图；可见所有的XRD图谱呈现出相似的图形，具有最典型的石墨相氮化碳的特征峰。在图3中所有三元复合催化剂样品的XRD图谱均未检测到PDA或Ni0.85Se，这可能是由于负载的Ni0.85Se纳米颗粒含量低、PDA结晶度较低。Specifically, Fig. 3 clearly shows the XRD pattern of the powder characterized by X-ray diffraction of CN, PDA/CN prepared in Comparative Examples 1-2 and the three-way catalyst with different Ni 0.85 Se loadings in Examples 1-4; It can be seen that all XRD patterns show similar patterns, with the most typical characteristic peaks of graphite phase carbon nitride. No PDA or Ni 0.85 Se was detected in the XRD patterns of all ternary composite catalyst samples in Fig. 3, which may be due to the low content of supported Ni 0.85 Se nanoparticles and the low crystallinity of PDA.

(3)Ni0.85Se的X射线衍射表征(3) X-ray diffraction characterization of Ni 0.85 Se

具体地，图4清楚地示出了依据实施例1制备的Ni0.85Se的粉末的XRD图；可见，实测XRD图谱与标准卡片完美地匹配，从而表明所制备的Ni0.85Se的纯度高。Specifically, Fig. 4 clearly shows the XRD pattern of the Ni 0.85 Se powder prepared according to Example 1; it can be seen that the measured XRD pattern perfectly matches the standard card, thus indicating that the prepared Ni 0.85 Se has a high purity.

(4)CN，PDA/CN和10Ni0.85Se-PDA/CN的固体荧光表征(4) Solid-state fluorescence characterization of CN, PDA/CN and 10Ni 0.85 Se-PDA/CN

具体地，图5示出了依据实施例3制备的10Ni0.85Se-PDA/CN三元复合光催化剂和对比例1～2所制备的CN和PDA/CN的固体荧光光谱图，可见10Ni0.85Se-PDA/CN催化剂荧光发射强度最低，表明该催化剂光生载流子的分离效率最快。Specifically, Figure 5 shows the solid-state fluorescence spectra of the 10Ni 0.85 Se-PDA/CN ternary composite photocatalyst prepared according to Example 3 and the CN and PDA/CN prepared in Comparative Examples 1-2. It can be seen that 10Ni 0.85 Se -PDA/CN catalyst has the lowest fluorescence emission intensity, indicating that the catalyst has the fastest separation efficiency of photogenerated carriers.

(5)CN，PDA/CN和10Ni0.85Se-PDA/CN的固体紫外表征(5) Solid UV characterization of CN, PDA/CN and 10Ni 0.85 Se-PDA/CN

具体地，图6所制备的CN和PDA/CN的固体紫外光谱图，可见PDA的负载显著提高了CN在可见光区域(λ>420nm)的光吸收，同时10wt％Ni0.85Se的负载进一步地提高了PDA/CN的可见光吸收。Specifically, the solid-state UV spectra of CN and PDA/CN prepared in Figure 6, it can be seen that the loading of PDA significantly improves the light absorption of CN in the visible light region (λ>420nm), and the loading of 10wt% Ni 0.85 Se further improves Visible light absorption of PDA/CN.

应用实施例Application example

本应用实施例将依据实施例1～4、对比例1～2作为光催化剂进行光解水，以制备氢气，具体包括以下步骤：This application example uses Examples 1-4 and Comparative Examples 1-2 as photocatalysts to photolyze water to produce hydrogen, specifically including the following steps:

步骤1，称取50mg的光催化剂并加入到玻璃反应瓶中；Step 1, weigh 50 mg of photocatalyst and add it into a glass reaction vial;

步骤2，向该玻璃反应瓶中加入50mL 10％的三乙醇胺水溶液，超声一段时间；Step 2, add 50mL of 10% triethanolamine aqueous solution to the glass reaction bottle, and sonicate for a period of time;

步骤3，将该玻璃反应瓶连接到连通气相色谱仪的多通道反应器，密闭抽真空，用300W氙灯模拟太阳光进行光照，以制备氢气。Step 3, connect the glass reaction bottle to a multi-channel reactor connected to a gas chromatograph, seal and evacuate, and use a 300W xenon lamp to simulate sunlight for illumination to prepare hydrogen.

参见图7，可见，一种Ni0.85Se-PDA/CN三元复合材料作为光催化剂，且三乙醇胺作为空穴牺牲剂的条件下，光催化活性均得到了提高。通过优化硒化镍助催化剂的加载量，10Ni0.85Se-PDA/CN具有最好的催化活性，氢气产生量比纯氮化碳纳米片高3.17倍，比PDA/CN复合催化剂高2.4倍。由此可见，本发明实施例所制备的Ni0.85Se/PDA/g-C3N4三元催化剂的光催化活性较高，而且其在无需任何光敏剂和铂助催化剂的条件下就能够将水分解为氢气。Referring to Fig. 7, it can be seen that the photocatalytic activity of a Ni 0.85 Se-PDA/CN ternary composite material is used as a photocatalyst and triethanolamine is used as a hole sacrificial agent. By optimizing the loading of nickel selenide cocatalyst, 10Ni 0.85 Se-PDA/CN has the best catalytic activity, and the hydrogen generation is 3.17 times higher than that of pure carbon nitride nanosheets, and 2.4 times higher than that of PDA/CN composite catalyst. It can be seen that the photocatalytic activity of the Ni 0.85 Se/PDA/gC 3 N 4 ternary catalyst prepared in the example of the present invention is relatively high, and it can decompose water without any photosensitizer and platinum co-catalyst for hydrogen.

以上对本发明的具体实施例进行了详细描述，但其只作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。The specific embodiments of the present invention have been described in detail above, but they are only examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, equivalent changes and modifications made without departing from the spirit and scope of the present invention shall fall within the scope of the present invention.

Claims (9)

1. a kind of Ni0.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that the composite photo-catalyst material is with carbonitride Nanometer sheet is carrier, loads poly-dopamine PDA and Ni in the azotized carbon nano on piece0.85Se nano particle.
2. a kind of Ni according to claim 10.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that described Ni in composite photo-catalyst0.85The load capacity of Se nano particle is 3wt%~20wt%.
3. a kind of Ni according to claim 10.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that described multiple The preparation step of light combination catalyst includes:
Dopamine hydrochloride, strength is added by after azotized carbon nano piece and alkalescent Tris-HCl buffer ultrasonic mixing in step 1) Stirring 15~25 hours；
Step 2) is by a certain amount of Ni0.85Se nano particle and alkalescent Tris-HCl buffer ultrasonic mixing, obtain Ni0.85Se Homogenizing fluid；By the Ni0.85Se homogenizing fluid is added dropwise in the solution that the step 1) obtains, and is stirred 6~10 hours；Product passes through It filters, drying obtains Ni after grinding0.85Se/PDA/g-C3N4Three-element composite photocatalyst.
4. a kind of Ni according to claim 30.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that the nitrogen The preparation step for changing carbon nanosheet includes: using urea as raw material, by calcining and hot soarfing from preparing azotized carbon nano piece.
5. a kind of Ni according to claim 30.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that described Ni0.85The preparation step of Se nano particle includes: with selenium powder, sodium borohydride, and nickel chloride is raw material, by solvent thermal reaction, system Standby Ni0.85Se nano particle.
6. a kind of Ni according to claim 30.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that described The dosage of Dopamine hydrochloride is the 8~15% of azotized carbon nano tablet quality in step 1), and polymerization pH is 8~9, polymerization time 15 ~25h.
7. a kind of Ni according to claim 30.85Se/PDA/g-C3N4Composite photo-catalyst, which is characterized in that described multiple The preparation step of light combination catalyst specifically includes:
Step 1: the urea of predetermined amount is weighed, with the heating rate of 4~6 DEG C/min, 2~6h is calcined at 520~580 DEG C, to After being cooled to room temperature, it is ground into fine powder；Again by fine powder with the heating rate of 4~6 DEG C/min, calcine 1 at 470~530 DEG C~ 3h obtains azotized carbon nano piece after being cooled to room temperature；
Step 2: weighing the selenium powder and sodium borohydride of predetermined amount, be put into a certain amount of DMF, stir 0.5~2h；It adds predetermined The Nickel dichloride hexahydrate of amount continues 20~40min of stirring, and 18~30h is reacted at 140~180 DEG C；Obtained black product is used Ethyl alcohol and deionized water are washed repeatedly, and dry 8~16 hours, grind into powder obtain Ni at 50~70 DEG C0.85Se nanometers Particle.
Step 3: weighing azotized carbon nano piece prepared by the step 1 of predetermined amount, be put into alkalescent Tris-HCl buffer, ultrasound Make its homogeneous；The Dopamine hydrochloride for adding predetermined amount, is vigorously stirred 15~25h；
Step 4: weighing Ni prepared by the step 2 of predetermined amount0.85Se nano particle is put into alkalescent Tris-HCl buffer, 0.5~2min of ultrasound of having a rest, obtains homogenizing fluid；Homogenizing fluid is added drop-wise in the solution of step 3,6~10h is vigorously stirred；
Step 5: for the product that step 4 obtains by repeatedly filtering, drying obtains poly-dopamine PDA and Ni after grinding0.85Se load Ternary complex catalyst Ni0.85Se/PDA/g-C3N4。
8. a kind of such as Ni according to any one of claims 1 to 70.85Se/PDA/g-C3N4Composite photo-catalyst is in photodissociation aquatic products Application in hydrogen or degradation of organic dyes.
9. application according to claim 8, which is characterized in that the method for the photodissociation aquatic products hydrogen includes the following steps: to claim The composite photo-catalyst of predetermined amount is taken to mix with the triethanolamine aqueous solution of predetermined amount, ultrasound；It vacuumizes mixed solution is closed, Illumination is carried out with xenon lamp simulated solar irradiation, to prepare hydrogen.
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