技术领域technical field
本发明属于氢能制备领域，涉及氢能的光催化洁净制备技术，即模拟利用太阳能实现光催化分解水廉价制取氢能源技术，特别涉及一种基于镍纳米颗粒助催化剂的光催化体系的构建方法。The invention belongs to the field of hydrogen energy preparation, and relates to the photocatalytic clean preparation technology of hydrogen energy, that is, the technology of simulating the use of solar energy to realize photocatalytic decomposition of water to produce hydrogen energy at low cost, and in particular to the construction of a photocatalytic system based on nickel nanoparticle co-catalyst method.
背景技术Background technique
当今社会科学技术与工业化进程的加速发展使得常规能源供应不足而不断引发能源危机，化石能源的开发和利用带来的环境污染问题也越来越严峻。为了解决能源短缺和环境污染这两大威胁人类生存和发展的难题，寻找可以替代常规能源的清洁无污染可再生能源一直是人们的追求。可再生能源转化利用的基础理论研究，发展高效低成本的可再生能源的优质转化与规模化利用技术，已经成为目前我国能源技术领域最为紧迫的任务。我国拥有非常丰富的可再生能源且开发潜力巨大，目前已经有多种形式的新能源被尝试开发，包括太阳能、水能、风能、海洋能等，但是对于这些新能源的开发，其能量密度、分散性、稳定性、持久性和开发成本等方面都存在着一定的局限性，严重制约着高效低成本的可再生清洁能源的大规模开发和利用。The accelerated development of science, technology and industrialization in today's society has led to insufficient supply of conventional energy, which has continuously triggered energy crises, and the environmental pollution caused by the development and utilization of fossil energy has become more and more serious. In order to solve the two major problems of energy shortage and environmental pollution that threaten human survival and development, it has always been people's pursuit to find clean and non-polluting renewable energy that can replace conventional energy. The basic theoretical research on the conversion and utilization of renewable energy, and the development of high-quality conversion and large-scale utilization technology of high-efficiency and low-cost renewable energy have become the most urgent tasks in the field of energy technology in my country. Our country has very rich renewable energy and has great potential for development. At present, various forms of new energy have been tried to be developed, including solar energy, water energy, wind energy, ocean energy, etc., but for the development of these new energy sources, the energy density, There are certain limitations in terms of dispersion, stability, durability, and development costs, which seriously restrict the large-scale development and utilization of high-efficiency and low-cost renewable clean energy.
比较而言，太阳能的利用无疑是最为行之有效的方法，太阳能具有无限性、普遍性、经济性和清洁性等特点，到目前为止，太阳能的利用已变得越来越广泛，包括光热利用、光电利用和光化学利用等。氢能是理想的二次能源，具有能量密度高，可储存，可运输，无污染等优点，把可再生能源尤其是太阳能转化为氢能，是解决能源与环境问题的理想途径。国际社会一直大力推动形成可持续发展的“氢经济”，氢经济形成的一个关键因素是获得廉价的氢能源，太阳能光催化分解水规模化制氢是最有希望规模化将太阳能转化为氢能的高新技术。In comparison, the utilization of solar energy is undoubtedly the most effective method. Solar energy has the characteristics of infinity, universality, economy and cleanliness. So far, the utilization of solar energy has become more and more extensive, including photothermal utilization, photoelectric utilization and photochemical utilization, etc. Hydrogen energy is an ideal secondary energy source. It has the advantages of high energy density, storability, transportability, and no pollution. Converting renewable energy, especially solar energy, into hydrogen energy is an ideal way to solve energy and environmental problems. The international community has been vigorously promoting the formation of a sustainable "hydrogen economy". A key factor in the formation of the hydrogen economy is to obtain cheap hydrogen energy. Solar photocatalytic water splitting and large-scale hydrogen production are the most promising large-scale conversion of solar energy into hydrogen energy. high-tech.
光催化制备氢气的原理是：在一定能量光的照射下，半导体催化剂受光激发产生电子-空穴对，电子迁移到催化剂表面将水还原为氢气，而空穴被产氢溶液中加入的适当的廉价的牺牲剂所消耗。通常半导体光催化剂都需要负载一定量的贵金属(如铂)作为助催化剂才能实现光催化分解水产氢，从而很大程度上提高了光催化分解水制氢的成本，限制了光催化分解水制氢的工业化发展。因此，实现太阳能光催化分解水制氢的关键技术之一是寻找无毒、廉价、高效、稳定、带隙合适以及具有可见光响应的光催化剂，另一个关键技术是负载无毒、廉价、高效和稳定的助催化剂。The principle of photocatalytic hydrogen production is: under the irradiation of light with a certain energy, the semiconductor catalyst is excited by light to generate electron-hole pairs, and the electrons migrate to the surface of the catalyst to reduce water to hydrogen, while the holes are absorbed by the appropriate hydrogen-producing solution. Consumed by cheap sacrificial agents. Usually, semiconductor photocatalysts need to support a certain amount of noble metals (such as platinum) as co-catalysts to achieve hydrogen production by photocatalytic water splitting, which greatly increases the cost of photocatalytic water splitting for hydrogen production and limits the photocatalytic water splitting for hydrogen production. industrial development. Therefore, one of the key technologies for solar photocatalytic water splitting to produce hydrogen is to find photocatalysts that are non-toxic, cheap, efficient, stable, have a suitable band gap, and respond to visible light. Another key technology is to load non-toxic, cheap, efficient and Stable cocatalyst.
根据现有的研究，金属镍通常被作为一种典型的地表含量丰富的高效的产氢助催化剂而广泛应用到许多光催化剂上，如TiO2,CdS,LaxNa1-xTaO3,g-C3N4等。一般来说，金属镍与半导体催化剂结合后会在二者的接触界面形成肖特基势垒，从而促进光生载流子的分离，另一方面镍具有催化还原H+生成H2的能力。因此，金属镍作为产氢助催化剂能够有效地提高光催化剂的产氢性能，在替代贵金属作为廉价高效的产氢助催化剂方面具有很大的研究潜力。然而，据调研所知，目前半导体光催化负载金属镍的方法有光还原法、化学还原法和溶剂热法等，探索简单方便且普遍适用的金属镍助催化剂、在半导体光催化剂上的负载方法对于光催化分解水制氢的产业化应用具有重大意义。According to the existing research, metallic nickel is usually widely used as a typical surface-abundant and efficient hydrogen-producing co-catalyst in many photocatalysts, such as TiO2 , CdS, Lax Na1-x TaO3 , gC3 N4 etc. Generally speaking, the combination of metal nickel and semiconductor catalyst will form a Schottky barrier at the contact interface between the two, thereby promoting the separation of photogenerated carriers. On the other hand, nickel has the ability to catalyze the reduction of H+ to generate H2 . Therefore, metal nickel as a hydrogen-producing co-catalyst can effectively improve the hydrogen-producing performance of photocatalysts, and has great research potential in replacing noble metals as a cheap and efficient hydrogen-producing co-catalyst. However, according to the survey, the current methods of semiconductor photocatalytic loading of metal nickel include photoreduction method, chemical reduction method and solvothermal method, etc., to explore simple, convenient and universally applicable metal nickel co-catalysts and loading methods on semiconductor photocatalysts It is of great significance for the industrial application of photocatalytic water splitting to produce hydrogen.
发明内容Contents of the invention
本发明的目的在于提供了一种基于镍纳米颗粒助催化剂的光催化体系的构建方法。本发明操作简单，适用性广，重复性好，为降低光催化制氢成本和镍在光催化制氢方面的应用提供了一种可靠的方案。The purpose of the present invention is to provide a method for constructing a photocatalytic system based on nickel nanoparticle co-catalyst. The invention has simple operation, wide applicability and good repeatability, and provides a reliable solution for reducing the cost of photocatalytic hydrogen production and the application of nickel in photocatalytic hydrogen production.
为了实现上述目的，本发明采用如下的技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种基于镍纳米颗粒助催化剂的光催化体系的构建方法，包括以下步骤：A method for constructing a photocatalytic system based on a nickel nanoparticle cocatalyst, comprising the following steps:
1)制备助催化剂：金属镍纳米颗粒分散液，制备光催化剂；1) Preparation of co-catalyst: metal nickel nanoparticle dispersion liquid to prepare photocatalyst;
2)将制备的助催化剂加入到含有光催化剂的光催化制氢反应溶液中，进行无贵金属负载的光催化制氢测试；其中，金属镍纳米颗粒的质量占光催化剂的质量分数为0.5～10％，光催化剂与光催化制氢反应溶液的固液比为1mg：4mL。2) Add the prepared co-catalyst to the photocatalytic hydrogen production reaction solution containing the photocatalyst, and carry out the photocatalytic hydrogen production test without noble metal support; wherein, the mass fraction of the metal nickel nanoparticles to the photocatalyst is 0.5-10 %, the solid-to-liquid ratio of the photocatalyst to the photocatalytic hydrogen production reaction solution is 1mg: 4mL.
所述的助催化剂的制备方法如下：The preparation method of described promoter is as follows:
将Ni(NO3)2·6H2O、聚乙烯吡咯烷酮和乙二醇加入到反应器中使其完全溶解，随后加热并搅拌，待温度稳定120℃后向溶液中加入NaBH4，NaBH4的质量是Ni(NO3)2·6H2O中的金属镍质量的18倍；再将反应溶液持续加热并搅拌得到透明的溶液即金属镍纳米颗粒分散液。Add Ni(NO3 )2 ·6H2 O, polyvinylpyrrolidone and ethylene glycol into the reactor to dissolve completely, then heat and stir, and add NaBH4 to the solution after the temperature stabilizes at 120°C. The mass is 18 times that of the metallic nickel in Ni(NO3 )2 ·6H2 O; then the reaction solution is continuously heated and stirred to obtain a transparent solution, that is, metallic nickel nanoparticle dispersion.
所述的光催化剂为石墨相氮化碳粉末、TiO2粉末或CdS粉末。The photocatalyst is graphite phase carbon nitride powder,TiO2 powder or CdS powder.
所述的石墨相氮化碳粉末是通过将尿素在600℃焙烧3h制得。The graphite phase carbon nitride powder is prepared by calcining urea at 600° C. for 3 hours.
所述的CdS粉末是将CdCl2·2.5H2O和硫脲溶于乙二胺中，然后转移到水热釜中在160℃下反应48h，待冷却到室温后将得到的产物洗涤并真空干燥即得到CdS粉末。The CdS powder is prepared by dissolving CdCl2 ·2.5H2 O and thiourea in ethylenediamine, and then transferring it to a hydrothermal kettle to react at 160°C for 48 hours. After cooling to room temperature, the obtained product is washed and vacuum Dry to obtain CdS powder.
步骤2)的具体步骤为：The concrete steps of step 2) are:
a)在反应器中加入光催化剂，然后加入含金属镍纳米颗粒的分散液，以及含牺牲剂的水溶液；a) adding a photocatalyst to the reactor, then adding a dispersion containing metallic nickel nanoparticles, and an aqueous solution containing a sacrificial agent;
b)光照前向反应器中通氮气吹扫直至除去反应器中的氧气；b) nitrogen purging in the reactor before the illumination until the oxygen in the reactor is removed;
c)开磁力搅拌器，然后开氙灯光源。c) Turn on the magnetic stirrer, and then turn on the xenon lamp light source.
所述的氙灯光源为300W Xe灯，λ≥420nm。The xenon lamp light source is a 300W Xe lamp, λ≥420nm.
所述的光催化制氢反应溶液为溶解有牺牲剂的水溶液。The photocatalytic hydrogen production reaction solution is an aqueous solution in which a sacrificial agent is dissolved.
所述的牺牲剂为三乙醇胺或甲醇或Na2S和Na2SO3的混合物，牺牲剂的体积为整个反应体系体积的10～20％。The sacrificial agent is triethanolamine or methanol or a mixture of Na2 S and Na2 SO3 , and the volume of the sacrificial agent is 10-20% of the volume of the entire reaction system.
所述的金属镍纳米颗粒的质量占光催化剂的质量分数为7％。The mass fraction of the said metallic nickel nano-particles in the photocatalyst is 7%.
相对于现有技术，本发明具有如下效果：Compared with the prior art, the present invention has the following effects:
本发明的基于镍纳米颗粒助催化剂的光催化体系的构建方法，首先制备了分散性能良好的非贵金属镍纳米颗粒作为助催化剂，该金属镍纳米颗粒分散在溶液中不会发生团聚和沉降；然后在光催化制氢过程中将含一定量金属镍纳米颗粒的分散液直接加到含不同光催化剂(如TiO2,CdS,g-C3N4)的制氢溶液中，实现了光催化制氢反应且表现出高效的光催化制氢性能。金属镍纳米颗粒与光催化剂之间的作用机理可解释为：金属镍纳米颗粒通过与光催化剂相互接触而被吸附到光催化剂的表面上，金属镍纳米颗粒与光催化剂在接触面会产生肖特基势垒，能够有效促进光生载流子的高效分离。一般地，在光照条件下，半导体光催化剂价带上产生的光生电子受光激发跃迁到导带上，同时价带上留下光生空穴，负载在半导体光催化剂表面的金属镍纳米颗粒能够捕捉光生电子并作为光催化制氢的活性位点与水中的H+反应而生成氢气，导带上的空穴与溶液里的牺牲剂发生反应而被消耗，该过程有效地促进了光生载流子的分离，抑制了光生电子-空穴的复合，促进了光催化制氢反应的进行。本发明操作简单，适用性广，重复性好，为降低光催化制氢成本和镍在光催化制氢方面的应用提供了一种可靠的方案。由本发明方法直接将助催化剂和光催化剂混合，得到在光催化剂上负载金属镍的方法操作简单且容易重复，对不同的光催化剂具有普遍适用性，另外这种直接混合的方法具有良好的效果，采用该方法在不同光催化剂上负载金属镍纳米颗粒进行光催化制氢均取得了良好的效果。The construction method of the photocatalytic system based on the nickel nanoparticle co-catalyst of the present invention first prepares the non-precious metal nickel nano-particles with good dispersion performance as the co-catalyst, and the metal nickel nano-particles are dispersed in the solution without agglomeration and sedimentation; then In the process of photocatalytic hydrogen production, the dispersion liquid containing a certain amount of metal nickel nanoparticles is directly added to the hydrogen production solution containing different photocatalysts (such as TiO2 , CdS, gC3 N4 ) to realize the photocatalytic hydrogen production reaction And it exhibits efficient photocatalytic hydrogen production performance. The mechanism of action between the metal nickel nanoparticles and the photocatalyst can be explained as follows: the metal nickel nanoparticles are adsorbed on the surface of the photocatalyst through contact with the photocatalyst, and the metal nickel nanoparticles and the photocatalyst will generate Schottky Potential barriers can effectively promote the efficient separation of photogenerated carriers. Generally, under light conditions, the photogenerated electrons generated on the valence band of the semiconductor photocatalyst are excited by light and jump to the conduction band, leaving photogenerated holes in the valence band, and the metal nickel nanoparticles loaded on the surface of the semiconductor photocatalyst can capture the photogenerated electrons. The electrons act as active sites for photocatalytic hydrogen production and react with H+ in water to generate hydrogen gas, and the holes on the conduction band react with the sacrificial agent in the solution to be consumed, which effectively promotes the photogenerated charge carriers. The separation inhibits the recombination of photogenerated electrons and holes, and promotes the photocatalytic hydrogen production reaction. The invention has simple operation, wide applicability and good repeatability, and provides a reliable scheme for reducing the cost of photocatalytic hydrogen production and the application of nickel in photocatalytic hydrogen production. By the method of the present invention, the co-catalyst and the photocatalyst are directly mixed to obtain the method of loading metal nickel on the photocatalyst, which is simple to operate and easy to repeat, and has universal applicability to different photocatalysts. In addition, this direct mixing method has a good effect. This method has achieved good results in photocatalytic hydrogen production by loading metal nickel nanoparticles on different photocatalysts.
进一步，金属镍纳米颗粒质量为光催化剂质量的7％时制氢活性达到最大。Furthermore, the hydrogen production activity reaches the maximum when the mass of the metallic nickel nanoparticles is 7% of the mass of the photocatalyst.
附图说明Description of drawings
图1是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的X射线衍射(XRD)图；Fig. 1 is the X-ray diffraction (XRD) figure of recovery sample after graphite phase carbon nitride and metal nickel nano particle dispersion liquid react in photocatalytic hydrogen production solution;
图2是透射电镜照片，其中(a)是金属镍纳米颗粒的透射电镜照片，(b)是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的透射电镜照片；Figure 2 is a transmission electron microscope photograph, wherein (a) is a transmission electron microscope photograph of metallic nickel nanoparticles, and (b) is the transmission of the recovered sample after the graphite phase carbon nitride and metallic nickel nanoparticle dispersion react in the photocatalytic hydrogen production solution Electron microscope photo;
图3是X射线光电子能谱(XPS)图，其中(a)是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的XPS图；其中(b)是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的Ni2p轨道的高分辨XPS图；Fig. 3 is an X-ray photoelectron spectrum (XPS) figure, wherein (a) is the XPS figure of the graphite phase carbon nitride and metal nickel nanoparticle dispersion liquid in the photocatalytic hydrogen production solution and reclaims the sample; wherein (b) is High-resolution XPS map of the Ni2p orbital of the recovered sample after the graphite phase carbon nitride and metal nickel nanoparticle dispersion reacted in the photocatalytic hydrogen production solution;
图4是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的荧光光谱；Fig. 4 is the fluorescence spectrum of the recovered sample after the graphite phase carbon nitride and metal nickel nanoparticle dispersion react in the photocatalytic hydrogen production solution;
图5是石墨相氮化碳和不同质量浓度的金属镍纳米颗粒分散液在光催化制氢溶液中混合的制氢速率图，制氢条件：光催化剂为50.0mg，助催化剂为不同质量浓度的金属镍纳米颗粒分散液，反应液为含10vol％三乙醇胺(TEOA)或含20vol％甲醇(MeOH)的200mL水溶液，光源为300W Xe灯(λ≥420nm)。Figure 5 is a diagram of the hydrogen production rate of graphitic carbon nitride and metal nickel nanoparticle dispersions of different mass concentrations mixed in the photocatalytic hydrogen production solution. Metallic nickel nanoparticle dispersion, the reaction solution is 200mL aqueous solution containing 10vol% triethanolamine (TEOA) or 20vol% methanol (MeOH), and the light source is a 300W Xe lamp (λ≥420nm).
图6是不同光催化剂和金属镍纳米颗粒分散液(金属镍纳米颗粒质量为光催化剂质量的7％)在不同牺牲剂溶液中的光催化制氢速率图。Fig. 6 is a photocatalytic hydrogen production rate diagram of different photocatalysts and metal nickel nanoparticle dispersions (the mass of metal nickel nanoparticles is 7% of the photocatalyst mass) in different sacrificial agent solutions.
图7是石墨相氮化碳和金属镍纳米颗粒分散液的光催化制氢稳定性测试图，其中(a)石墨相氮化碳和金属镍纳米颗粒分散液(金属镍纳米颗粒质量为光催化剂质量的7％)在三乙醇胺牺牲剂溶液中光催化制氢稳定性测试图；其中(b)石墨相氮化碳和金属镍纳米颗粒分散液(金属镍纳米颗粒质量为光催化剂质量的7％)在甲醇牺牲剂溶液中可见光催化制氢稳定性测试图；制氢条件：光催化剂为50.0mg，助催化剂为不同质量浓度的金属镍纳米颗粒分散液，反应液为含10vol％三乙醇胺或含20vol％甲醇的200mL水溶液，光源为300WXe灯(λ≥420nm)。Fig. 7 is the photocatalytic hydrogen production stability test figure of graphite phase carbon nitride and metallic nickel nanoparticle dispersion liquid, wherein (a) graphite phase carbon nitride and metallic nickel nanoparticle dispersion liquid (the mass of metallic nickel nanoparticle is photocatalyst 7% of mass) photocatalytic hydrogen production stability test figure in triethanolamine sacrificial agent solution; Wherein (b) graphite phase carbon nitride and metal nickel nanoparticle dispersion liquid (metal nickel nanoparticle quality is 7% of photocatalyst quality ) Stability test chart of visible light catalytic hydrogen production in methanol sacrificial agent solution; hydrogen production conditions: photocatalyst is 50.0mg, cocatalyst is metal nickel nanoparticle dispersion liquid with different mass concentrations, and reaction solution is containing 10vol% triethanolamine or containing 200mL aqueous solution of 20vol% methanol, the light source is 300WXe lamp (λ≥420nm).
具体实施方式detailed description
本发明一种基于镍纳米颗粒助催化剂的光催化体系的构建方法，包括以下步骤：A method for constructing a photocatalytic system based on a nickel nanoparticle co-catalyst of the present invention comprises the following steps:
步骤一：制备金属镍纳米颗粒分散液。将17.5mg的Ni(NO3)2·6H2O，100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4(NaBH4的质量是金属镍质量的18倍)，将反应溶液持续加热并搅拌2h后得到透明的溶液即金属镍纳米颗粒分散液，理论上分散液中金属镍纳米颗粒的质量为3.5mg，占50mg光催化剂的质量分数为7％，记作Ni7，同样的步骤制备镍纳米颗粒的质量分别为0.5mg，2.5mg和5.0mg的分散液，记作Ni1，Ni5和Ni10。作为对比，将100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4，将反应溶液持续加热并搅拌2h后得到透明的溶液记作Ni0。Step 1: preparing a metal nickel nanoparticle dispersion. Add 17.5mg of Ni(NO3 )2 6H2 O, 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and dissolve completely, then place the three-necked flask at 120 Heat and stir in an oil bath at ℃, add 63.0 mg of NaBH4 (the mass of NaBH4 is 18 times the mass of nickel metal) to the solution after the temperature stabilizes, and continue heating and stirring the reaction solution for 2 hours to obtain a transparent solution. Metallic nickel nanoparticle dispersion liquid, the quality of metallic nickel nanoparticle in the dispersion liquid is theoretically 3.5mg, accounts for the mass fraction of 50mg photocatalyst and is 7%, is denoted as Ni7, the quality of the same step preparation nickel nanoparticle is respectively 0.5mg , 2.5mg and 5.0mg of the dispersion, denoted as Ni1, Ni5 and Ni10. As a comparison, 100.0 mg of polyvinylpyrrolidone (PVP K30) and 20 mL of ethylene glycol were added to a 125 mL three-necked flask and completely dissolved, and then the three-necked flask was heated and stirred in an oil bath at 120° C. After stabilization, 63.0 mg of NaBH4 was added to the solution, and the reaction solution was continuously heated and stirred for 2 hours to obtain a transparent solution, which was recorded as Ni0.
步骤二：制备不同的光催化剂。石墨相氮化碳(g-C3N4)粉末：通过将10g尿素在600℃焙烧3h制得；TiO2粉末：选取商业购买的P25；CdS粉末：将20.25mmol CdCl2·2.5H2O和60.75mmol的硫脲溶于60mL乙二胺中，然后转移到100mL水热釜中在160℃下反应48h，待冷却到室温后将得到的产物洗涤并真空干燥即得到CdS粉末。Step 2: Prepare different photocatalysts. Graphite phase carbon nitride (gC3 N4 ) powder: prepared by roasting 10 g of urea at 600°C for 3 h; TiO2 powder: choose commercially purchased P25; CdS powder: mix 20.25 mmol CdCl2 ·2.5H2 O and 60.75 One mmol of thiourea was dissolved in 60mL of ethylenediamine, and then transferred to a 100mL hydrothermal kettle to react at 160°C for 48h. After cooling to room temperature, the obtained product was washed and vacuum-dried to obtain CdS powder.
步骤三：将步骤一制备的金属镍纳米颗粒分散液加入到含有步骤二中制备的光催化剂的光催化制氢反应溶液中，进行无贵金属负载的光催化制氢测试。具体步骤如下：Step 3: Add the metal nickel nanoparticle dispersion prepared in step 1 into the photocatalytic hydrogen production reaction solution containing the photocatalyst prepared in step 2, and conduct a photocatalytic hydrogen production test without noble metal support. Specific steps are as follows:
1)在容积为250mL的反应器中加入50.0mg光催化剂，然后加入含一定量金属镍纳米颗粒的分散液，以及含不同种类和浓度牺牲剂的200mL水溶液；1) Add 50.0mg photocatalyst to a reactor with a volume of 250mL, then add a dispersion containing a certain amount of metallic nickel nanoparticles, and 200mL aqueous solutions containing different types and concentrations of sacrificial agents;
2)光照前向反应器中通氮气吹扫15min，以除去反应器中的氧气；2) Purging the reactor with nitrogen gas for 15 minutes before lighting to remove the oxygen in the reactor;
3)开磁力搅拌器，然后开氙灯光源。3) Turn on the magnetic stirrer, and then turn on the xenon lamp light source.
下面结合附图及具体实施方式对本发明作详细描述：The present invention is described in detail below in conjunction with accompanying drawing and specific embodiment:
实施例1：Example 1:
步骤1：将100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4，将反应溶液持续加热并搅拌2h后得到透明的溶液记作Ni0。Step 1: Add 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and dissolve completely, then place the three-necked flask in a 120°C oil bath and heat and stir until the temperature After stabilization, 63.0 mg of NaBH4 was added to the solution, and the reaction solution was continuously heated and stirred for 2 hours to obtain a transparent solution, which was recorded as Ni0.
步骤2：通过将10g尿素在600℃焙烧3h制得g-C3N4；Step 2: Prepare gC3 N4 by roasting 10 g of urea at 600°C for 3 hours;
步骤3：选取制备的g-C3N4作为光催化剂，三乙醇胺作为制氢牺牲剂，向反应溶液中加入Ni0分散液进行光催化制氢反应。具体步骤如下：Step 3: Select the prepared gC3 N4 as the photocatalyst, triethanolamine as the sacrificial agent for hydrogen production, and add Ni0 dispersion liquid into the reaction solution to carry out the photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL的反应器中加入50.0mg的g-C3N4光催化剂，加入Ni0分散液，以及总体积为200mL的三乙醇胺含量为10vol％的水溶液作为牺牲剂；(1) Add 50.0 mg of gC3 N4 photocatalyst into a reactor with a volume of 250 mL, add NiO dispersion liquid, and an aqueous solution with a total volume of 200 mL of triethanolamine content of 10 vol% as a sacrificial agent;
(2)光照前向反应器中通氮气吹扫15min，以除去反应器中的氧气；(2) Nitrogen was purged in the reactor for 15 minutes before illumination to remove the oxygen in the reactor;
(3)开磁力搅拌器，然后开氙灯光源，加420nm截止滤光片；(3) Turn on the magnetic stirrer, then turn on the xenon lamp light source, and add a 420nm cut-off filter;
实施例2：Example 2:
步骤1：将100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4，将反应溶液持续加热并搅拌2h后得到透明的溶液记作Ni0。Step 1: Add 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and dissolve completely, then place the three-necked flask in a 120°C oil bath and heat and stir until the temperature After stabilization, 63.0 mg of NaBH4 was added to the solution, and the reaction solution was continuously heated and stirred for 2 hours to obtain a transparent solution, which was recorded as Ni0.
步骤2：通过将10g尿素在600℃焙烧3h制得g-C3N4；Step 2: Prepare gC3 N4 by roasting 10 g of urea at 600°C for 3 hours;
步骤3：选取制备的g-C3N4作为光催化剂，甲醇作为制氢牺牲剂，向反应溶液中加入Ni0分散液进行光催化制氢反应。具体步骤如下：Step 3: Select the prepared gC3 N4 as a photocatalyst, methanol as a sacrificial agent for hydrogen production, and add Ni0 dispersion liquid to the reaction solution to carry out photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL的反应器中加入50.0mg的g-C3N4光催化剂，加入Ni0分散液，以及总体积为200mL的甲醇含量为20vol％的水溶液作为牺牲剂；(1) Add 50.0 mg of gC3 N4 photocatalyst into a reactor with a volume of 250 mL, add NiO dispersion liquid, and an aqueous solution with a total volume of 200 mL of methanol content of 20 vol% as a sacrificial agent;
(2)光照前向反应器中通氮气吹扫15min，以除去反应器中的氧气；(2) Nitrogen was purged in the reactor for 15 minutes before illumination to remove the oxygen in the reactor;
(3)开磁力搅拌器，然后开氙灯光源，加420nm截止滤光片；(3) Turn on the magnetic stirrer, then turn on the xenon lamp light source, and add a 420nm cut-off filter;
实施例3：Example 3:
步骤1：将100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4，将反应溶液持续加热并搅拌2h后得到透明的溶液记作Ni0。Step 1: Add 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and dissolve completely, then place the three-necked flask in a 120°C oil bath and heat and stir until the temperature After stabilization, 63.0 mg of NaBH4 was added to the solution, and the reaction solution was continuously heated and stirred for 2 hours to obtain a transparent solution, which was recorded as Ni0.
步骤2：购买商业的P25作为TiO2光催化剂；Step 2: Purchase commercial P25 asTiO2 photocatalyst;
步骤3：选取制备的TiO2作为光催化剂，甲醇作为制氢牺牲剂，向反应溶液中加入Ni0分散液进行光催化制氢反应。具体步骤如下：Step 3: Select the prepared TiO2 as a photocatalyst, methanol as a sacrificial agent for hydrogen production, and add NiO dispersion liquid to the reaction solution for photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL的反应器中加入50.0mg的TiO2光催化剂，加入Ni0分散液，以及总体积为200mL的甲醇含量为20vol％的水溶液作为牺牲剂；(1) In a reactor with a volume of 250mL, add 50.0mg ofTiO photocatalyst, add NiO dispersion, and a total volume of 200mL of methanol content of 20vol% aqueous solution as a sacrificial agent;
(2)光照前向反应器中通氮气吹扫15min，以除去反应器中的氧气；(2) Nitrogen was purged in the reactor for 15 minutes before illumination to remove the oxygen in the reactor;
(3)开磁力搅拌器，然后开氙灯光源，不加420nm截止滤光片；(3) Turn on the magnetic stirrer, then turn on the xenon lamp light source, without adding the 420nm cut-off filter;
实施例4：Example 4:
步骤1：将100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4，将反应溶液持续加热并搅拌2h后得到透明的溶液记作Ni0。Step 1: Add 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and dissolve completely, then place the three-necked flask in a 120°C oil bath and heat and stir until the temperature After stabilization, 63.0 mg of NaBH4 was added to the solution, and the reaction solution was continuously heated and stirred for 2 hours to obtain a transparent solution, which was recorded as Ni0.
步骤2：CdS粉末制备：将20.25mmol CdCl2·2.5H2O和60.75mmol的硫脲溶于60mL乙二胺，然后转移到100mL水热釜中在160℃下反应48h，待冷却到室温后将得到的产物洗涤并真空干燥即得到CdS粉末；Step 2: CdS powder preparation: Dissolve 20.25mmol CdCl2 ·2.5H2 O and 60.75mmol thiourea in 60mL ethylenediamine, then transfer to a 100mL hydrothermal kettle and react at 160°C for 48h, after cooling to room temperature The obtained product is washed and vacuum-dried to obtain CdS powder;
步骤3：选取制备的CdS作为光催化剂，甲醇作为制氢牺牲剂，向反应溶液中加入Ni0分散液进行光催化制氢反应。具体步骤如下：Step 3: Select the prepared CdS as a photocatalyst, methanol as a sacrificial agent for hydrogen production, and add NiO dispersion liquid to the reaction solution to carry out photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL反应器中加入50.0mg的CdS光催化剂，加入Ni0分散液，以及含0.35M Na2S和0.25M Na2SO3的200mL水溶液作为牺牲剂溶液；(1) Add 50.0 mg of CdS photocatalyst into a 250 mL reactor, add Ni0 dispersion, and 200 mL of aqueous solution containing 0.35M Na2 S and 0.25M Na2 SO3 as a sacrificial agent solution;
(2)光照前向反应器中通氮气吹扫15min，以除去反应器中的氧气；(2) Nitrogen was purged in the reactor for 15 minutes before illumination to remove the oxygen in the reactor;
(3)开磁力搅拌器，然后开氙灯光源，加420nm截止滤光片；(3) Turn on the magnetic stirrer, then turn on the xenon lamp light source, and add a 420nm cut-off filter;
实施例5：Example 5:
步骤1：制备金属镍纳米颗粒分散液，将17.5mg的Ni(NO3)2·6H2O，100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4(NaBH4的质量是金属镍质量的18倍)，将反应溶液持续加热并搅拌2h后得到透明的溶液即金属镍纳米颗粒分散液，理论上分散液中金属镍纳米颗粒的质量为3.5mg，占50mg光催化剂的质量分数为7％，记作Ni7，同样的步骤制备镍纳米颗粒的质量分别为0.5mg，2.5mg和5.0mg的分散液，记作Ni1，Ni5和Ni10；Step 1: Prepare metal nickel nanoparticle dispersion, add 17.5mg of Ni(NO3 )2 6H2 O, 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and completely Dissolve, then place the three-necked flask in a 120°C oil bath to heat and stir, and add 63.0 mg of NaBH4 (the quality of NaBH4 is 18 times that of metal nickel) to the solution after the temperature stabilizes, and the reaction solution After continuous heating and stirring for 2 hours, a transparent solution is obtained, that is, a dispersion of metallic nickel nanoparticles. Theoretically, the mass of metallic nickel nanoparticles in the dispersion is 3.5 mg, which accounts for 7% of the mass fraction of 50 mg of photocatalyst, which is recorded as Ni7, and the same Steps to prepare the quality of nickel nanoparticles are 0.5mg, 2.5mg and 5.0mg dispersion, denoted as Ni1, Ni5 and Ni10;
步骤2：通过将10g尿素在600℃焙烧3h制得g-C3N4；Step 2: Prepare gC3 N4 by roasting 10 g of urea at 600°C for 3 hours;
步骤3：选取制备的g-C3N4作为光催化剂，三乙醇胺作为产氢牺牲剂，向反应溶液中分别加入Ni1，Ni5，Ni7和Ni10分散液进行光催化制氢反应。具体步骤如下：Step 3: Select the prepared gC3 N4 as the photocatalyst, and triethanolamine as the sacrificial agent for hydrogen production, and respectively add Ni1, Ni5, Ni7 and Ni10 dispersions into the reaction solution to carry out the photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL反应器中加入50.0mg石墨相氮化碳作为光催化剂，分别加入Ni1，Ni5，Ni7和Ni10分散液作为助催化剂，以及含10vol％三乙醇胺的总体积200mL水溶液作为牺牲剂溶液；(1) Add 50.0mg graphitic carbon nitride as a photocatalyst in a reactor with a volume of 250mL, add Ni1, Ni5, Ni7 and Ni10 dispersions as cocatalysts, and a total volume of 200mL aqueous solution containing 10vol% triethanolamine as a sacrifice agent solution;
(2)光照前向反应器中通氮气吹扫15min，以除去溶液中的氧气；(2) Purging nitrogen into the reactor for 15 minutes before lighting to remove oxygen in the solution;
(3)开磁力搅拌器，开氙灯光源，加420nm截止滤光片；(3) Turn on the magnetic stirrer, turn on the xenon lamp light source, and add a 420nm cut-off filter;
实施例6：Embodiment 6:
步骤1：制备金属镍纳米颗粒分散液，将17.5mg的Ni(NO3)2·6H2O，100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，待温度稳定后向溶液中加入63.0mg的NaBH4(NaBH4的质量是金属镍质量的18倍)，将反应溶液持续加热并搅拌2h后得到透明的溶液即金属镍纳米颗粒分散液，理论上分散液中金属镍纳米颗粒的质量为3.5mg，占50mg光催化剂的质量分数为7％，记作Ni7，同样的步骤制备镍纳米颗粒的质量分别为0.5mg，2.5mg和5.0mg的分散液，记作Ni1，Ni5和Ni10；Step 1: Prepare metal nickel nanoparticle dispersion, add 17.5mg of Ni(NO3 )2 6H2 O, 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and completely Dissolve, then place the three-necked flask in a 120°C oil bath to heat and stir, and add 63.0 mg of NaBH4 (the quality of NaBH4 is 18 times that of metal nickel) to the solution after the temperature stabilizes, and the reaction solution After continuous heating and stirring for 2 hours, a transparent solution is obtained, that is, a dispersion of metallic nickel nanoparticles. Theoretically, the mass of metallic nickel nanoparticles in the dispersion is 3.5 mg, which accounts for 7% of the mass fraction of 50 mg of photocatalyst, which is recorded as Ni7, and the same Steps to prepare the quality of nickel nanoparticles are 0.5mg, 2.5mg and 5.0mg dispersion, denoted as Ni1, Ni5 and Ni10;
步骤2：通过将10g尿素在600℃焙烧3h制得g-C3N4；Step 2: Prepare gC3 N4 by roasting 10 g of urea at 600°C for 3 hours;
步骤3：选取制备的g-C3N4作为光催化剂，甲醇作为产氢牺牲剂，向反应溶液中分别加入Ni1，Ni5，Ni7和Ni10分散液进行光催化制氢反应。具体步骤如下：Step 3: Select the prepared gC3 N4 as the photocatalyst, methanol as the sacrificial agent for hydrogen production, and add Ni1, Ni5, Ni7 and Ni10 dispersion liquids to the reaction solution to carry out the photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL反应器中加入50.0mg的g-C3N4作为光催化剂，分别加入Ni1，Ni5，Ni7和Ni10分散液做助催化剂，以及总体积200mL的三乙醇胺含量为10vol％的水溶液作为牺牲剂；(1) Add 50.0 mg of gC3 N4 as a photocatalyst to a 250 mL reactor, add Ni1, Ni5, Ni7 and Ni10 dispersions as co-catalysts, and an aqueous solution with a total volume of 200 mL of triethanolamine containing 10 vol%. as a sacrificial agent;
(2)光照前向反应器中通氮气吹扫15min，以除去溶液中的氧气；(2) Purging nitrogen into the reactor for 15 minutes before lighting to remove oxygen in the solution;
(3)开磁力搅拌器，开氙灯光源，加420nm截止滤光片；(3) Turn on the magnetic stirrer, turn on the xenon lamp light source, and add a 420nm cut-off filter;
实施例7：Embodiment 7:
步骤1：制备金属镍纳米颗粒分散液，将17.5mg的Ni(NO3)2·6H2O，100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，温度稳定后向溶液中加入63.0mg的NaBH4(NaBH4的质量是金属镍质量的18倍)，将反应溶液持续加热并搅拌2h后得到透明的溶液即金属镍纳米颗粒分散液，理论上分散液中金属镍纳米颗粒的质量为3.5mg，占50mg光催化剂的质量分数为7％，记作Ni7；Step 1: Prepare metal nickel nanoparticle dispersion, add 17.5mg of Ni(NO3 )2 6H2 O, 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and completely Dissolve, then place the three-necked flask in a 120°C oil bath to heat and stir, add 63.0mg of NaBH4 (the quality of NaBH4 is 18 times that of metal nickel) after the temperature stabilizes, and continue After heating and stirring for 2 hours, a transparent solution is obtained, that is, a dispersion of metallic nickel nanoparticles. Theoretically, the mass of metallic nickel nanoparticles in the dispersion is 3.5 mg, accounting for 7% of the mass fraction of 50 mg of photocatalyst, which is recorded as Ni7;
步骤2：购买商业的P25作为TiO2光催化剂；Step 2: Purchase commercial P25 asTiO2 photocatalyst;
步骤3：选取TiO2作为光催化剂，甲醇作为产氢牺牲剂，向反应溶液中加入Ni7分散液进行光催化制氢反应。具体步骤如下：Step 3: SelectTiO2 as the photocatalyst, methanol as the sacrificial agent for hydrogen production, and add Ni7 dispersion liquid to the reaction solution for photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL反应器中加入50.0mg的TiO2作为光催化剂，加入Ni7分散液作为助催化剂，以及含20vol％甲醇的200mL水溶液作为牺牲剂溶液；(1) Add 50.0 mg ofTiO in a 250 mL reactor as a photocatalyst, add Ni7 dispersion as a cocatalyst, and 200 mL of aqueous solution containing 20 vol% methanol as a sacrificial agent solution;
(2)光照前向反应器中通氮气吹扫15min，以除去溶液中的氧气；(2) Purging nitrogen into the reactor for 15 minutes before lighting to remove oxygen in the solution;
(3)开磁力搅拌器，开氙灯光源，不加420nm截止滤光片；(3) Turn on the magnetic stirrer, turn on the xenon lamp light source, and do not add the 420nm cut-off filter;
实施例8：Embodiment 8:
步骤1：制备金属镍纳米颗粒分散液，将17.5mg的Ni(NO3)2·6H2O，100.0mg的聚乙烯吡咯烷酮(PVP K30)和20mL乙二醇加入到125mL三颈烧瓶中并完全溶解，随后再将三颈烧瓶置于120℃油浴锅中加热并搅拌，温度稳定后向溶液中加入63.0mg的NaBH4(NaBH4的质量是金属镍质量的18倍)，将反应溶液持续加热并搅拌2h后得到透明的溶液即金属镍纳米颗粒分散液，理论上分散液中金属镍纳米颗粒的质量为3.5mg，占50mg光催化剂的质量分数为7％，记作Ni7；Step 1: Prepare metal nickel nanoparticle dispersion, add 17.5mg of Ni(NO3 )2 6H2 O, 100.0mg of polyvinylpyrrolidone (PVP K30) and 20mL of ethylene glycol into a 125mL three-necked flask and completely Dissolve, then place the three-necked flask in a 120°C oil bath to heat and stir, add 63.0mg of NaBH4 (the quality of NaBH4 is 18 times that of metal nickel) after the temperature stabilizes, and continue After heating and stirring for 2 hours, a transparent solution is obtained, that is, a dispersion of metallic nickel nanoparticles. Theoretically, the mass of metallic nickel nanoparticles in the dispersion is 3.5 mg, accounting for 7% of the mass fraction of 50 mg of photocatalyst, which is recorded as Ni7;
步骤2：CdS粉末制备：将20.25mmol CdCl2·2.5H2O和60.75mmol的硫脲溶于60mL乙二胺，然后转移到100mL水热釜中在160℃下反应48h，待冷却到室温后将得到的产物洗涤并真空干燥即得到CdS粉末；Step 2: CdS powder preparation: Dissolve 20.25mmol CdCl2 ·2.5H2 O and 60.75mmol thiourea in 60mL ethylenediamine, then transfer to a 100mL hydrothermal kettle and react at 160°C for 48h, after cooling to room temperature The obtained product is washed and vacuum-dried to obtain CdS powder;
步骤3：选取CdS作为光催化剂，Na2S和Na2SO3作为产氢牺牲剂，向反应溶液中加入Ni7分散液进行光催化制氢反应。具体步骤如下：Step 3: Select CdS as the photocatalyst, Na2 S and Na2 SO3 as hydrogen production sacrificial agents, add Ni7 dispersion liquid to the reaction solution for photocatalytic hydrogen production reaction. Specific steps are as follows:
(1)在容积为250mL反应器中加入50.0mg的CdS作为光催化剂，加入Ni7分散液做助催化剂，以及含0.35M Na2S和0.25M Na2SO3的200mL水溶液作为牺牲剂溶液；(1) Add 50.0mg of CdS as a photocatalyst into a 250mL reactor, add Ni7 dispersion as a cocatalyst, and 200mL aqueous solution containing 0.35M Na2 S and 0.25M Na2 SO3 as a sacrificial agent solution;
(2)光照前向反应器中通氮气吹扫15min，以除去溶液中的氧气；(2) Purging nitrogen into the reactor for 15 minutes before lighting to remove oxygen in the solution;
(3)开磁力搅拌器，开氙灯光源，加420nm截止滤光片；(3) Turn on the magnetic stirrer, turn on the xenon lamp light source, and add a 420nm cut-off filter;
实施例1-4得到的是作为对比的g-C3N4,TiO2和CdS在无金属镍作为助催化剂的情况下的光催化制氢结果；实施例5得到的是以石墨相氮化碳为光催化剂，在三乙醇胺产氢牺牲剂溶液中加入不同质量浓度的金属镍纳米颗粒分散液的光催化制氢性能；实施例6得到的是以石墨相氮化碳为光催化剂，在甲醇产氢牺牲剂溶液中加入不同质量浓度的金属镍纳米颗粒分散液的光催化制氢性能；实施例7得到的是以TiO2为光催化剂，在甲醇产氢牺牲剂溶液中加入金属镍纳米颗粒分散液(金属镍纳米颗粒质量为光催化剂质量的7％)的光催化制氢性能；实施例8得到的是以CdS为光催化剂，在Na2S和Na2SO3产氢牺牲剂溶液中加入金属镍纳米颗粒分散液(金属镍纳米颗粒质量为光催化剂质量的7％)的光催化制氢性能。下面针对上述实施例的方法进行测试得到的结果进行如下分析：What embodiment 1-4 obtains is the photocatalytic hydrogen production result of gC3 N4 , TiO2 and CdS in the absence of metallic nickel as a cocatalyst; what embodiment 5 obtains is based on graphite phase carbon nitride Photocatalyst, the photocatalytic hydrogen production performance of adding different mass concentrations of metal nickel nanoparticle dispersion liquid in triethanolamine hydrogen production sacrificial agent solution; what embodiment 6 obtains is to use graphitic phase carbon nitride as photocatalyst, produces hydrogen in methanol The photocatalytic hydrogen production performance of adding different mass concentrations of metal nickel nanoparticle dispersions in the sacrificial agent solution; Example 7 obtained withTiO2 as the photocatalyst, adding metal nickel nanoparticle dispersions in the methanol hydrogen production sacrificial agent solution (Metal nickel nanoparticle quality is 7% of photocatalyst quality) photocatalytic hydrogen production performance; What embodiment 8 obtains is to be photocatalyst with CdS, in Na2 S and Na2 SO3 add metal The photocatalytic hydrogen production performance of the nickel nanoparticle dispersion (the mass of the metallic nickel nanoparticle is 7% of the mass of the photocatalyst). The results obtained by testing the method of the above-mentioned embodiment are analyzed as follows:
图1展示了石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的X射线衍射(XRD)图，从图中可知，石墨相氮化碳的晶体结构并没有随着金属镍纳米颗粒的加入而发生变化，由于金属镍纳米颗粒的含量少且尺寸小，所以XRD并未检测到其衍射峰。Figure 1 shows the X-ray diffraction (XRD) pattern of the sample recovered after the reaction of graphite phase carbon nitride and metal nickel nanoparticle dispersion in the photocatalytic hydrogen production solution. From the figure, it can be seen that the crystal structure of graphite phase carbon nitride is not There is no change with the addition of metal nickel nanoparticles. Due to the small content and small size of metal nickel nanoparticles, no diffraction peaks were detected by XRD.
图2是透射电镜照片，其中(a)是金属镍纳米颗粒的透射电镜照片，(b)是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的透射电镜照片。从图中可知，金属镍纳米颗粒尺寸不大于5nm，而且没有发生团聚。Figure 2 is a transmission electron microscope photograph, wherein (a) is a transmission electron microscope photograph of metallic nickel nanoparticles, and (b) is the transmission of the recovered sample after the graphite phase carbon nitride and metallic nickel nanoparticle dispersion react in the photocatalytic hydrogen production solution Electron microscope photo. It can be seen from the figure that the size of metallic nickel nanoparticles is not greater than 5nm, and no agglomeration occurs.
图3是X射线光电子能谱(XPS)图，从图中可知，镍的状态为金属镍。Figure 3 is an X-ray photoelectron spectrum (XPS) diagram, from which it can be seen that the state of nickel is metallic nickel.
图4是石墨相氮化碳和金属镍纳米颗粒分散液在光催化制氢溶液中反应后回收样品的荧光光谱，从图中可知，金属镍纳米颗粒有利于促进石墨相氮化碳的光生载流子的分离，极大地抑制了电子-空穴的复合。Figure 4 is the fluorescence spectrum of the sample recovered after the reaction of graphite phase carbon nitride and metal nickel nanoparticle dispersion in the photocatalytic hydrogen production solution. It can be seen from the figure that metal nickel nanoparticles are beneficial to promote the photogenerated loading of graphite phase carbon nitride The separation of flow carriers greatly suppresses the electron-hole recombination.
图5是石墨相氮化碳和不同质量浓度的金属镍纳米颗粒分散液在光催化制氢溶液中混合的制氢速率图，从图中可知，金属镍纳米颗粒质量为光催化剂质量的7％时制氢活性达到最高,其中三乙醇胺含量为10vol％的水溶液作为牺牲剂的产氢体系中最高活性为440.8μmol h-1gcat-1，甲醇含量为20vol％的水溶液作为牺牲剂的产氢体系中最高活性为130.4μmol h-1gcat-1，而在无金属镍纳米颗粒负载的情况下氮化碳在两种牺牲剂体系中均没有光催化产氢活性。Figure 5 is a diagram of the hydrogen production rate of graphitic carbon nitride and metal nickel nanoparticle dispersions with different mass concentrations mixed in the photocatalytic hydrogen production solution. It can be seen from the figure that the mass of metallic nickel nanoparticles is 7% of the mass of the photocatalyst When the hydrogen production activity reaches the highest, the highest activity in the hydrogen production system is 440.8μmol h-1 gcat-1 when the aqueous solution with the content of 10vol% triethanolamine is used as the sacrificial agent, and the hydrogen production system with the aqueous solution with the content of 20vol% methanol is used as the sacrificial agent The highest activity in the system is 130.4μmol h-1 gcat-1 , and carbon nitride has no photocatalytic hydrogen production activity in the two sacrificial systems without the support of metal nickel nanoparticles.
图6是不同光催化剂和金属镍纳米颗粒分散液(金属镍纳米颗粒质量为光催化剂质量的7％)在不同牺牲剂溶液中的光催化制氢的速率图。说明这种加入金属镍纳米颗粒分散液直接和光催化剂混合的方法具有良好的效果且适用性广，重复性好。Fig. 6 is a graph of the rate of photocatalytic hydrogen production of different photocatalysts and metallic nickel nanoparticle dispersions (the mass of metallic nickel nanoparticles is 7% of the mass of the photocatalyst) in different sacrificial agent solutions. It shows that this method of adding metal nickel nanoparticle dispersion and directly mixing with photocatalyst has good effect, wide applicability and good repeatability.
图7是石墨相氮化碳和金属镍纳米颗粒分散液的光催化制氢稳定性测试图，不论是在三乙醇胺牺牲剂溶液还是甲醇牺牲剂溶液中，石墨相氮化碳和金属镍纳米颗粒分散液的光催化制氢均保持了良好的稳定性。Figure 7 is a photocatalytic hydrogen production stability test diagram of graphite phase carbon nitride and metal nickel nanoparticle dispersion liquid, whether in triethanolamine sacrificial agent solution or methanol sacrificial agent solution, graphite phase carbon nitride and metal nickel nanoparticle The photocatalytic hydrogen production from the dispersion maintained good stability.
以上的具体实施方式仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神及原则之内所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific implementation above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the present invention within the scope of protection.
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