技术领域Technical Field
本发明属于包含硫元素的氮的化合物的催化剂技术领域，具体涉及一种含硫氮化碳材料及其制备方法与在光催化产氢方面的应用。The present invention belongs to the technical field of catalysts of nitrogen compounds containing sulfur elements, and specifically relates to a sulfur-containing carbon nitride material and a preparation method thereof and application in photocatalytic hydrogen production.
背景技术Background Art
合理开发资源尤其重要。地球上的水资源丰富，且太阳能取之不竭，用之不尽，所以利用太阳能分解水制氢是解决能源问题的关键途径之一。It is particularly important to develop resources rationally. The water resources on the earth are abundant, and the solar energy is inexhaustible, so using solar energy to decompose water to produce hydrogen is one of the key ways to solve the energy problem.
光催化产氢技术将太阳能转化为氢能，是一种低成本、环保无污染的技术，反应条件温和，适用范围广，具有非常广阔的发展前景。光催化产氢技术需要光催化剂的催化作用，近几十年来，研究人员主要集中于氧化物的半导体光催化材料的研究，该类材料普遍存在易溶于酸碱试剂因而难以改性的特点，从而限制了其应用发展。Photocatalytic hydrogen production technology converts solar energy into hydrogen energy. It is a low-cost, environmentally friendly and pollution-free technology with mild reaction conditions and a wide range of applications. It has a very broad development prospect. Photocatalytic hydrogen production technology requires the catalytic action of photocatalysts. In recent decades, researchers have mainly focused on the research of semiconductor photocatalytic materials of oxides. Such materials are generally soluble in acid and alkali reagents and are therefore difficult to modify, which limits their application development.
近年来，非金属类半导体光催化剂石墨相氮化碳(g-C3N4)材料进入人们视野，由于g-C3N4结构中sp2杂化的C和N原子形成了一定的共轭体系，使其具有优良的热稳定性、化学稳定性等性质，除此以外，g-C3N4还能够吸收可见光，制备工艺简单且成本低廉，在可见光照射和三乙醇胺作为空穴清除剂的情况下能够催化分解水制氢，在光催化产氢领域有大力发展的空间。然而，g-C3N4比表面积低，禁带宽度较宽约为2.72eV，光生电子-空穴易复合以及导电性低等缺点，导致催化活性有限，因而需要对其进行改性。目前可以通过掺杂(金属、非金属、贵金属等)，In recent years, non-metallic semiconductor photocatalyst graphite carbon nitride (gC3 N4 ) materials have come into people's view. Since the sp2 hybridized C and N atoms in the gC3 N4 structure form a certain conjugated system, it has excellent thermal stability, chemical stability and other properties. In addition, gC3 N4 can also absorb visible light, the preparation process is simple and the cost is low. It can catalyze the decomposition of water to produce hydrogen under visible light irradiation and triethanolamine as a hole scavenger, and has room for great development in the field of photocatalytic hydrogen production. However, gC3 N4 has disadvantages such as low specific surface area, wide bandgap of about 2.72eV, easy recombination of photogenerated electrons and holes, and low conductivity, resulting in limited catalytic activity, so it needs to be modified. At present, it can be modified by doping (metal, non-metal, precious metal, etc.),
形貌调控，半导体复合改性以及负载助催化剂等手段对g-C3N4进行改性，调控材料组成或改变比表面积等性质来改善上述缺点，从而提高光催化活性。当对g-C3N4进行硫掺杂时，通过调控g-C3N4组成、电子结构和片层厚薄，可增大比表面积的同时使其产生一定的缺陷，暴露出更多的活性位点，提高光催化产氢的性能。专利CN111185216A公开了将三聚氰胺与三聚硫氰酸混合于溶剂中，再进行水热反应，得到实心管状的复合物，再与尿素煅烧得到中空管状硫掺杂氮化碳/石墨相氮化碳同质结光催化剂的方案。专利CN107930667A公开了一种通过三聚氰胺和三聚硫氰酸分别溶于热水后混合均匀，水热反应后煅烧制备得到硫掺杂的氮化碳的制备方法。这几种公开的制备方法步骤繁琐复杂，需要后处理，成本相对较高。The gC3 N4 is modified by means of morphology control, semiconductor composite modification and loading of co-catalysts, and the above-mentioned shortcomings are improved by controlling the material composition or changing the properties such as specific surface area, thereby improving the photocatalytic activity. When gC3 N4 is sulfur-doped, by controlling the composition, electronic structure and thickness of gC3 N4 , the specific surface area can be increased while causing certain defects, exposing more active sites, and improving the performance of photocatalytic hydrogen production. Patent CN111185216A discloses a scheme of mixing melamine and thiocyanuric acid in a solvent, then performing a hydrothermal reaction to obtain a solid tubular composite, and then calcining with urea to obtain a hollow tubular sulfur-doped carbon nitride/graphite phase carbon nitride homojunction photocatalyst. Patent CN107930667A discloses a method for preparing sulfur-doped carbon nitride by dissolving melamine and thiocyanuric acid in hot water respectively, mixing them evenly, and calcining them after hydrothermal reaction to prepare sulfur-doped carbon nitride. These disclosed preparation methods have complicated steps, require post-processing, and are relatively costly.
由此看来，还需发展一些操作更加简便，能耗成本更低，效果更好的实验方法，从而应用于光催化产氢领域。本发明只采用了三聚硫氰酸和三聚氰胺两种原料，分开称量后不进行直接接触，放入管式炉内直接煅烧即得到含硫氮化碳材料，操作简便，能耗低，且制备的含硫氮化碳材料光电流响应性好，产氢速率达165.4μmol/h，并且有良好的循环产氢稳定性。Therefore, it is necessary to develop some experimental methods with simpler operation, lower energy consumption cost and better effect, so as to apply them to the field of photocatalytic hydrogen production. The present invention uses only two raw materials, thiocyanate and melamine, which are weighed separately without direct contact and directly calcined in a tubular furnace to obtain a sulfur-containing carbon nitride material. The operation is simple, the energy consumption is low, and the prepared sulfur-containing carbon nitride material has good photocurrent responsiveness, a hydrogen production rate of 165.4 μmol/h, and good cyclic hydrogen production stability.
发明内容Summary of the invention
本发明所要解决的技术问题是针对现有技术中存在的上述不足，提供一种含硫氮化碳材料及其制备方法与在光催化产氢方面的应用，所述含硫氮化碳材料比表面积大，对可见光响应敏感，光催化产氢活性高，制备方法简单易操作，重复性好。The technical problem to be solved by the present invention is to provide a sulfur-containing carbon nitride material and a preparation method thereof and application in photocatalytic hydrogen production in view of the above-mentioned deficiencies in the prior art. The sulfur-containing carbon nitride material has a large specific surface area, is sensitive to visible light response, has high photocatalytic hydrogen production activity, and the preparation method is simple and easy to operate with good repeatability.
为解决上述技术问题，本发明提供的技术方案是：In order to solve the above technical problems, the technical solution provided by the present invention is:
提供一种含硫氮化碳材料，其由三聚硫氰酸在与三聚氰胺非直接接触下于惰性气氛下煅烧得到。Provided is a sulfur-containing carbon nitride material, which is obtained by calcining thiocyanuric acid in an inert atmosphere without direct contact with melamine.
按上述方案，所述含硫氮化碳材料比表面积为50～150m2/g。According to the above scheme, the specific surface area of the sulfur-containing carbon nitride material is 50 to 150 m2 /g.
本发明还提供上述含硫氮化碳材料的制备方法，具体步骤如下：The present invention also provides a method for preparing the above sulfur-containing carbon nitride material, the specific steps of which are as follows:
1)按比例称取三聚硫氰酸、三聚氰胺，备用；1) Weigh thiocyanuric acid and melamine in proportion and set aside;
2)将三聚硫氰酸均匀平铺于1号瓷舟表面，将三聚氰胺均匀平铺于2号瓷舟表面，然后将1号瓷舟放入管式炉恒温区域正中间，2号瓷舟放于管式炉内靠近进气口处，经进气口向管式炉内通入惰性气体，加热进行煅烧，随炉冷却至室温，收集1号瓷舟内样品研磨得到含硫氮化碳材料。2) Spread thiocyanate evenly on the surface of porcelain boat No. 1, spread melamine evenly on the surface of porcelain boat No. 2, then put porcelain boat No. 1 in the middle of the constant temperature area of the tubular furnace, put porcelain boat No. 2 in the tubular furnace near the air inlet, introduce inert gas into the tubular furnace through the air inlet, heat and calcine, cool to room temperature with the furnace, collect the sample in porcelain boat No. 1 and grind it to obtain sulfur-containing carbon nitride material.
按上述方案，步骤1)所述三聚硫氰酸纯度≥95wt％，所述三聚氰胺纯度≥According to the above scheme, the purity of thiocyanuric acid in step 1) is ≥ 95wt%, and the purity of melamine is ≥
99wt％。99wt%.
按上述方案，步骤1)所述三聚硫氰酸与三聚氰胺的质量比为0.5～2：1。According to the above scheme, the mass ratio of thiocyanuric acid to melamine in step 1) is 0.5 to 2:1.
按上述方案，步骤2)所述1号瓷舟与2号瓷舟中心距离为10～20cm。According to the above scheme, in step 2), the center distance between porcelain boat No. 1 and porcelain boat No. 2 is 10 to 20 cm.
按上述方案，步骤2)所述惰性气氛为氮气或氩气，气体纯度为99.99vol％以上，气体流量为60～100mL/min。According to the above scheme, the inert atmosphere in step 2) is nitrogen or argon, the gas purity is above 99.99 vol%, and the gas flow rate is 60-100 mL/min.
按上述方案，步骤2)所述煅烧工艺条件为：室温下以5～15℃/min的升温速率升温至500～600℃，保温3～5h。According to the above scheme, the calcination process conditions in step 2) are: heating to 500-600°C at a heating rate of 5-15°C/min at room temperature and keeping warm for 3-5h.
本发明还包括上述含硫氮化碳材料在光催化产氢方面的应用。The present invention also includes the use of the above sulfur-containing carbon nitride material in photocatalytic hydrogen production.
本发明将三聚硫氰酸与三聚氰胺在非直接接触的状态下于惰性气氛下煅烧得到含硫氮化碳材料，三聚硫氰酸为前驱体，煅烧过程中三聚氰胺产生氨气流动于三聚硫氰酸表面，在三聚硫氰酸聚合产生含硫氮化碳过程中有一定的剥离作用，生成结晶度高并具有一定缺陷的含硫氮化碳材料，测试结果表明该含硫氮化碳材料光催化产氢性能优异。The present invention calcines thiocyanuric acid and melamine in an inert atmosphere in a non-direct contact state to obtain a sulfur-containing carbon nitride material. The thiocyanuric acid is a precursor. During the calcination process, melamine generates ammonia gas that flows on the surface of the thiocyanuric acid, and has a certain stripping effect during the polymerization of thiocyanuric acid to produce sulfur-containing carbon nitride, thereby generating a sulfur-containing carbon nitride material with high crystallinity and certain defects. Test results show that the sulfur-containing carbon nitride material has excellent photocatalytic hydrogen production performance.
本发明的有益效果在于：1、本发明提供的含硫氮化碳材料比表面积大，光吸收能力强，光催化产氢活性高，且循环稳定性优异，具有良好的光催化产氢应用前景。2、本发明只采用三聚硫氰酸和三聚氰胺两种原料，间接利用三聚氰胺产生氨气进行剥离，不直接利用大量氨气气体进行直接接触，危险性降低，安全性好，合成原料简单，且操作步骤少，将按比例称取的两种原料分别放入置于管式炉内且保持一定距离的两瓷舟中一步煅烧即可得到含硫氮化碳材料，成本低。The beneficial effects of the present invention are as follows: 1. The sulfur-containing carbon nitride material provided by the present invention has a large specific surface area, strong light absorption capacity, high photocatalytic hydrogen production activity, and excellent cycle stability, and has good application prospects for photocatalytic hydrogen production. 2. The present invention uses only two raw materials, thiocyanate and melamine, and indirectly uses melamine to generate ammonia for stripping, and does not directly use a large amount of ammonia gas for direct contact, which reduces the danger and has good safety. The synthetic raw materials are simple and the operation steps are few. The two raw materials weighed in proportion are placed in two porcelain boats placed in a tubular furnace and kept at a certain distance, and the sulfur-containing carbon nitride material can be obtained by calcining in one step, which is low in cost.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明对比例1及实施例1-5所制备的含硫氮化碳材料的光催化产氢效果对比图；FIG1 is a comparison diagram of the photocatalytic hydrogen production effects of sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-5 of the present invention;
图2为对比例1及实施例1-3所制备的含硫氮化碳材料的光电流测试图；FIG2 is a photocurrent test diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3;
图3为对比例1及实施例1、4、5所制备的含硫氮化碳材料的光电流测试图；FIG3 is a photocurrent test graph of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5;
图4为实施例4所制备的含硫氮化碳材料在不同波长情况下的产氢对比图；FIG4 is a comparison diagram of hydrogen production of the sulfur-containing carbon nitride material prepared in Example 4 under different wavelengths;
图5为实施例4所制备的含硫氮化碳材料连续20h光催化产氢循环稳定性测试图；FIG5 is a graph showing the stability test of the photocatalytic hydrogen production cycle of the sulfur-containing carbon nitride material prepared in Example 4 for 20 hours;
图6为对比例1及实施例1-3所制备的含硫氮化碳材料的XRD谱图；FIG6 is an XRD spectrum of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3;
图7为对比例1及实施例1、4、5所制备的含硫氮化碳材料的XRD谱图；FIG7 is an XRD spectrum of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5;
图8为对比例1及实施例1-3所制备的含硫氮化碳材料的氮气等温吸附脱附曲线图；FIG8 is a graph showing nitrogen isothermal adsorption and desorption curves of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3;
图9为对比例1及实施例1、4、5所制备的含硫氮化碳材料的氮气等温吸附脱附曲线图；FIG9 is a graph showing nitrogen isothermal adsorption and desorption curves of sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5;
图10为对比例1及实施例1-3所制备的含硫氮化碳材料的孔径分布图；FIG10 is a pore size distribution diagram of sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3;
图11为对比例1及实施例1、4、5所制备的含硫氮化碳材料的孔径分布图；FIG11 is a pore size distribution diagram of sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5;
图12为对比例1及实施例1-3所制备的含硫氮化碳材料的阻抗图；FIG12 is an impedance diagram of sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3;
图13为对比例1及实施例1、4、5所制备的含硫氮化碳材料的阻抗图。FIG13 is an impedance diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5.
具体实施方式DETAILED DESCRIPTION
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图对本发明作进一步详细描述。In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below with reference to the accompanying drawings.
对比例1Comparative Example 1
一种含硫氮化碳材料，具体制备方法如下：A sulfur-containing carbon nitride material, the specific preparation method is as follows:
1)称取2g三聚硫氰酸(纯度95wt％)，备用；1) Weigh 2 g of thiocyanuric acid (purity 95 wt%) and set aside;
2)将三聚硫氰酸固体平铺于瓷舟内，放入管式炉恒温区域正中间，向管式炉内通入氮气(99.99vol％)，设置氮气气流量为80mL/min，然后室温下以10℃/min的升温速率升温至550℃进行煅烧，煅烧时间为3h，自然冷却至室温后研磨成粉末得到含硫氮化碳材料(记为SCN)。2) Spread the thiocyanate solid on a porcelain boat, place it in the middle of the constant temperature zone of a tubular furnace, introduce nitrogen (99.99 vol%) into the tubular furnace, set the nitrogen flow rate to 80 mL/min, then heat the boat to 550°C at a heating rate of 10°C/min at room temperature for calcination for 3 h. After naturally cooling to room temperature, grind into powder to obtain sulfur-containing carbon nitride material (denoted as SCN).
实施例1Example 1
一种含硫氮化碳材料，具体制备方法如下：A sulfur-containing carbon nitride material, the specific preparation method is as follows:
1)称取2g三聚硫氰酸(纯度95wt％)和3g三聚氰胺(纯度99wt％)，备用；1) Weigh 2 g of thiocyanuric acid (purity 95 wt%) and 3 g of melamine (purity 99 wt%) and set aside;
2)将三聚硫氰酸平铺于1号瓷舟，放入管式炉恒温区域正中间，将三聚氰胺平铺于2号瓷舟，放入管式炉内靠近进气口处，1号瓷舟与2号瓷舟中心距离为15cm，向管式炉内通入氮气(99.99vol％)，设置氮气气流量为80mL/min，然后室温下以10℃/min的升温速率升温至550℃进行煅烧，煅烧时间为3h，自然冷却至室温后研磨成粉末得到含硫氮化碳材料(记为A)。2) Spread thiocyanate on porcelain boat No. 1, and place it in the middle of the constant temperature area of the tubular furnace; spread melamine on porcelain boat No. 2, and place it in the tubular furnace near the air inlet. The center distance between porcelain boat No. 1 and porcelain boat No. 2 is 15 cm. Nitrogen (99.99 vol%) is introduced into the tubular furnace, and the nitrogen flow rate is set to 80 mL/min. Then, the temperature is increased to 550°C at a heating rate of 10°C/min at room temperature for calcination. The calcination time is 3 h. After naturally cooling to room temperature, the mixture is ground into powder to obtain sulfur-containing carbon nitride material (denoted as A).
实施例2Example 2
一种含硫氮化碳材料，其制备方法与实施例1相似，不同之处在于步骤2)设置氮气气流量为100mL/min，所得产物记为B。A sulfur-containing carbon nitride material, the preparation method of which is similar to that of Example 1, except that in step 2) the nitrogen gas flow rate is set to 100 mL/min, and the obtained product is recorded as B.
实施例3Example 3
一种含硫氮化碳材料，其制备方法与实施例1相似，不同之处在于步骤2)设置氮气气流量为60mL/min，所得产物记为C。A sulfur-containing carbon nitride material, the preparation method of which is similar to that of Example 1, except that in step 2), the nitrogen gas flow rate is set to 60 mL/min, and the obtained product is recorded as C.
实施例4Example 4
一种含硫氮化碳材料，其制备方法与实施例1相似，不同之处在于步骤2)1号瓷舟与2号瓷舟中心距离为10cm，所得产物记为D。A sulfur-containing carbon nitride material, the preparation method of which is similar to that of Example 1, except that in step 2), the center distance between porcelain boat No. 1 and porcelain boat No. 2 is 10 cm, and the obtained product is recorded as D.
实施例5Example 5
一种含硫氮化碳材料，其制备方法与实施例1相似，不同之处在于步骤2)1号瓷舟与2号瓷舟中心距离为20cm，所得产物记为E。A sulfur-containing carbon nitride material, the preparation method of which is similar to that of Example 1, except that in step 2), the center distance between porcelain boat No. 1 and porcelain boat No. 2 is 20 cm, and the obtained product is recorded as E.
光催化产氢性能测试：将20mg的对比例1及实施例1-5所制备的含硫氮化碳材料分别加入到6份含有10wt％三乙醇胺的100mL去离子水溶液中，每份溶液中加入0.33mL的H2PtCl4溶液(基于20mg的光催化剂负载Pt的质量分数为3wt％，H2PtCl4在光催化体系中起到助催化剂的作用)，混合溶液超声分散30min后，在光反应器(Labsolar-6A，光源为插有420nm截止滤光片的300W氙灯)中光照4h进行测试，对比例1及实施例1-5所制备的含硫氮化碳材料的可见光光催化产氢效果对比图如图1所示，可以看出对比例1及实施例1-5所制备的含硫氮化碳材料产H2速率分别为：SCN 62.9μmol/h，A 144.9μmol/h，B 127.1μmol/h，C108.1μmol/h，D 165.4μmol/h，E 119.9μmol/h，其中A至E的光催化产氢速率高于SCN，D的光催化产氢速率最高。光电流测试：将对比例1及实施例1-5所制备的含硫氮化碳材料分别配制为1.0g/L的水分散液，每份水分散液吸取8μL滴涂到玻碳电极(直径3mm)表面，采用辰华电化学工作站，在>420nm的光照条件下，放入0.5mol/L的Na2SO4溶液中进行光电流测试。光电流能够反映材料的光催化性能，光电流越高，越能促进光生载流子的分离，材料的光催化效果越好，对比例1及实施例1-3所制备的含硫氮化碳材料的光电流测试图如图2所示，对比例1及实施例1、4、5所制备的含硫氮化碳材料的光电流测试图如图3所示，测试结果表明SCN光电流最小，对比实施例1-3可看出，保持瓷舟距离为15cm不变，调整气流量时实施例1所制备的A光电流最大。对比实施例1、4、5可看出，保持气流量为80mL/min不变，调整瓷舟距离时实施例4所制备的D光电流最大。Photocatalytic hydrogen production performance test: 20 mg of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-5 were added to 6 portions of 100 mL of deionized water solution containing 10 wt% triethanolamine, and 0.33 mL of H2 PtCl4 solution was added to each solution (the mass fraction of Pt loaded on 20 mg of the photocatalyst is 3 wt%, and H2 PtCl4 plays the role of a co-catalyst in the photocatalytic system). After the mixed solution was ultrasonically dispersed for 30 min, it was illuminated in a photoreactor (Labsolar-6A, the light source was a 300 W xenon lamp with a 420 nm cutoff filter) for 4 h for testing. The visible light photocatalytic hydrogen production effect comparison diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-5 is shown in FIG1 . It can be seen that the H2 production rates of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-5 are: SCN 62.9 μmol/h, A 144.9 μmol/h, B 127.1μmol/h, C 108.1μmol/h, D 165.4μmol/h, E 119.9μmol/h, among which the photocatalytic hydrogen production rates of A to E are higher than SCN, and the photocatalytic hydrogen production rate of D is the highest. Photocurrent test: The sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-5 were respectively prepared into 1.0g/L aqueous dispersions, and 8μL of each aqueous dispersion was dripped onto the surface of a glassy carbon electrode (3mm in diameter). A Chenhua electrochemical workstation was used to place the samples in a 0.5mol/L Na2 SO4 solution under >420nm illumination conditions for photocurrent test. The photocurrent can reflect the photocatalytic performance of the material. The higher the photocurrent, the more it can promote the separation of photogenerated carriers, and the better the photocatalytic effect of the material. The photocurrent test graph of the sulfur-containing carbon nitride material prepared by Comparative Example 1 and Examples 1-3 is shown in Figure 2, and the photocurrent test graph of the sulfur-containing carbon nitride material prepared by Comparative Example 1 and Examples 1, 4, and 5 is shown in Figure 3. The test results show that the SCN photocurrent is the smallest. It can be seen from the comparison of Examples 1-3 that the photocurrent of A prepared in Example 1 is the largest when the porcelain boat distance is kept at 15 cm and the gas flow rate is adjusted. It can be seen from the comparison of Examples 1, 4, and 5 that the photocurrent of D prepared in Example 4 is the largest when the gas flow rate is kept at 80 mL/min and the porcelain boat distance is adjusted.
图4为实施例4所制备的含硫氮化碳材料在不同波长情况下的产氢对比图，其中，配制数份光催化剂溶液，每份光催化剂溶液的制备方法为：将20mg实施例4制备的含硫氮化碳材料D加入到含有10wt％三乙醇胺的100mL去离子水溶液中，并加入0.33mL的H2PtCl4溶液(基于20mg的光催化剂负载Pt的质量分数为3wt％)，混合溶液超声分散30min后得到。将配制的光催化剂溶液置于光反应器(Labsolar-6A，光源为300W氙灯)中光照4h进行产氢测试，光的波长分别为，365nm、420nm、450nm、500nm、550nm以及截止420nm(即>420nm)，从图4可以看出，在各波长光照情况下均有一定的产氢效果。FIG4 is a comparison diagram of hydrogen production of sulfur-containing carbon nitride material prepared in Example 4 under different wavelength conditions, wherein several portions of photocatalyst solutions are prepared, and the preparation method of each portion of photocatalyst solution is as follows: 20 mg of sulfur-containing carbon nitride material D prepared in Example 4 is added to 100 mL of deionized water solution containing 10 wt% triethanolamine, and 0.33 mL of H2 PtCl4 solution (based on the mass fraction of 20 mg of photocatalyst loaded Pt is 3 wt%) is added, and the mixed solution is obtained after ultrasonic dispersion for 30 min. The prepared photocatalyst solution is placed in a photoreactor (Labsolar-6A, the light source is a 300 W xenon lamp) and illuminated for 4 hours to conduct a hydrogen production test, and the wavelengths of the light are 365 nm, 420 nm, 450 nm, 500 nm, 550 nm and cut-off 420 nm (i.e. > 420 nm), respectively. It can be seen from FIG4 that there is a certain hydrogen production effect under each wavelength illumination condition.
测试含硫氮化碳材料催化产氢循环稳定性：将20mg实施例4制备的含硫氮化碳材料D加入到含有10wt％三乙醇胺的100mL去离子水溶液中，并加入0.33mL的H2PtCl4(基于20mg的光催化剂负载Pt的质量分数为3wt％)，混合溶液超声分散30min后，在光反应器(Labsolar-6A，光源为插有420nm截止滤光片的300W氙灯)中进行循环产氢稳定性测试，每4h停一次，测试5个周期共20h，实施例4所制备的含硫氮化碳材料连续20h光催化产氢循环稳定性测试图如图5所示，从图发现该含硫氮化碳材料循环稳定性良好。Testing the cyclic stability of catalytic hydrogen production by the sulfur-containing carbon nitride material: 20 mg of the sulfur-containing carbon nitride material D prepared in Example 4 was added to 100 mL of a deionized water solution containing 10 wt % of triethanolamine, and 0.33 mL of H2 PtCl4 (based on the mass fraction of 3 wt % of the photocatalyst loaded Pt of 20 mg) was added. After the mixed solution was ultrasonically dispersed for 30 min, a cyclic hydrogen production stability test was carried out in a photoreactor (Labsolar-6A, the light source was a 300 W xenon lamp with a 420 nm cutoff filter). The test was stopped every 4 h, and 5 cycles were tested for a total of 20 h. The test graph of the cyclic stability of photocatalytic hydrogen production of the sulfur-containing carbon nitride material prepared in Example 4 for 20 h is shown in FIG5 . It can be found from the figure that the sulfur-containing carbon nitride material has good cyclic stability.
图6为对比例1及实施例1-3所制备的含硫氮化碳材料的XRD谱图，图7为对比例1及实施例1、4、5所制备的含硫氮化碳材料的XRD谱图。由图6，图7可知，在样品的XRD图谱中有两个主峰，13°左右对应的(100)平面的峰代表材料单元环的层内结构堆叠。大约27.1°处的另一个峰对应于共轭芳族单元的层间堆叠，其归属为(002)平面。比较相应峰的位置和强度，SCN的相应(002)面峰强度最低，实施例1-5制备的材料峰强有所提高，表明引入三聚氰胺作为氨气来源合成的含硫氮化碳材料结构更加有序，具有更高的结晶度，实施例1-5制备的材料的(002)晶面均发生了一定的移动，导致层间距变小，载流子的迁移路径变少，从而提高了载流子的分离效率。FIG6 is an XRD spectrum of the sulfur-containing carbon nitride material prepared in Comparative Example 1 and Examples 1-3, and FIG7 is an XRD spectrum of the sulfur-containing carbon nitride material prepared in Comparative Example 1 and Examples 1, 4, and 5. As shown in FIG6 and FIG7, there are two main peaks in the XRD spectrum of the sample, and the peak of the (100) plane corresponding to about 13° represents the intralayer structure stacking of the material unit ring. Another peak at about 27.1° corresponds to the interlayer stacking of the conjugated aromatic unit, which is attributed to the (002) plane. Comparing the positions and intensities of the corresponding peaks, the corresponding (002) plane peak intensity of SCN is the lowest, and the peak intensity of the material prepared in Examples 1-5 is improved, indicating that the structure of the sulfur-containing carbon nitride material synthesized by introducing melamine as a source of ammonia is more ordered and has a higher degree of crystallinity. The (002) crystal planes of the materials prepared in Examples 1-5 have all moved to a certain extent, resulting in a smaller interlayer spacing and fewer carrier migration paths, thereby improving the separation efficiency of carriers.
图8为对比例1及实施例1-3所制备的含硫氮化碳材料的氮气等温吸附脱附曲线图，图9为对比例1及实施例1、4、5所制备的含硫氮化碳材料的氮气等温吸附脱附曲线图，图10为对比例1及实施例1-3所制备的含硫氮化碳材料的孔径分布图，图11为对比例1及实施例1、4、5所制备的含硫氮化碳材料的孔径分布图。由图8，图9可知，典型的N2吸附脱附等温线表明该类含硫氮化碳材料样品具有中孔结构，其中样品D的比表面积最大，达到了135.75m2/g，比表面积大可以暴露更多的活性位点，从而提升光催化产氢活性。由图10，图11孔径分布图表明类含硫氮化碳材料样品中含有介孔。FIG8 is a nitrogen isothermal adsorption-desorption curve of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3, FIG9 is a nitrogen isothermal adsorption-desorption curve of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5, FIG10 is a pore size distribution diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3, and FIG11 is a pore size distribution diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5. As shown in FIG8 and FIG9, the typicalN2 adsorption-desorption isotherms indicate that the sulfur-containing carbon nitride material samples have a mesoporous structure, among which the specific surface area of sample D is the largest, reaching 135.75m2 /g. The large specific surface area can expose more active sites, thereby improving the photocatalytic hydrogen production activity. The pore size distribution diagrams of FIG10 and FIG11 indicate that the sulfur-containing carbon nitride material samples contain mesopores.
图12为对比例1及实施例1-3所制备的含硫氮化碳材料的阻抗图，图13为对比例1及实施例1、4、5所制备的含硫氮化碳材料的阻抗图。由图12，图13可知，与对比例SCN相比，实施例1-5制备的含硫氮化碳材料具有更小的半圆弧，样品D半圆弧最小，这表明SCN具有最高的载流子迁移阻力，D的载流子迁移阻力相对最小，迁移效率高，电子传输能力更强。Figure 12 is an impedance diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1-3, and Figure 13 is an impedance diagram of the sulfur-containing carbon nitride materials prepared in Comparative Example 1 and Examples 1, 4, and 5. As shown in Figures 12 and 13, compared with the comparative example SCN, the sulfur-containing carbon nitride materials prepared in Examples 1-5 have a smaller semicircle, and the semicircle of sample D is the smallest, which indicates that SCN has the highest carrier migration resistance, D has the smallest carrier migration resistance, has high migration efficiency, and has a stronger electron transmission capability.
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