技术领域technical field
本发明属于光催化材料技术领域，具体地说涉及一种应用于光催化分解蒸馏水以及天然海水制氢的助催化剂NiMoS与主催化剂CdS纳米棒形成螺旋复合纳米金属硫化物光催化剂及其制备方法和应用。The invention belongs to the technical field of photocatalytic materials, and specifically relates to a helical composite nano-metal sulfide photocatalyst, which is applied to the photocatalytic decomposition of distilled water and hydrogen production from natural seawater, and the main catalyst CdS nanorods to form a helical composite nano-metal sulfide photocatalyst and its preparation method and application.
背景技术Background technique
光催化太阳能转化为可以被人类利用的燃料具有重要意义。氢气作为一种应用广泛的原材料，在合成氨和二氧化碳转化为甲醇以及碳氢化合物方面发挥极大作用。同时天然海水作为一种取之不尽用之不竭的自然资源，其开发和利用具有巨大前景。因此利用半导体光催化剂太阳能分解水制氢引起了国内外的广泛关注。Photocatalytic conversion of solar energy into fuels that can be utilized by humans is of great significance. As a widely used raw material, hydrogen plays an important role in the synthesis of ammonia and the conversion of carbon dioxide into methanol and hydrocarbons. At the same time, as an inexhaustible natural resource, natural seawater has great prospects for its development and utilization. Therefore, the use of semiconductor photocatalysts for solar water splitting to produce hydrogen has attracted widespread attention at home and abroad.
研究调配具有合适能带位置的可见光响应的催化剂是提高可见光催化产氢效率、促进光催化技术进一步发展的研究重点。Researching and deploying visible light-responsive catalysts with suitable energy band positions is the focus of research to improve the efficiency of visible light-catalyzed hydrogen production and promote the further development of photocatalytic technology.
发明内容Contents of the invention
本发明提供一种新型高效光催化产氢助剂、光催化剂及光催化剂的制备方法和应用，不仅大幅提高利用太阳光的制氢效率，而且可充分利用海水制氢，对新能源的开发和利用具有重要意义。The invention provides a new type of high-efficiency photocatalytic hydrogen production additive, photocatalyst and preparation method and application of the photocatalyst, which not only greatly improves the hydrogen production efficiency by utilizing sunlight, but also can make full use of seawater to produce hydrogen, which is beneficial to the development of new energy and Utilization is important.
为解决上述技术问题，本发明采用以下技术方案予以实现：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions to achieve:
一方面，本发明提供一种新型光催化产氢助剂，该光催化产氢助剂为复合纳米层状，化学式为NiMoS。On the one hand, the present invention provides a novel photocatalytic hydrogen production aid, which is in the form of composite nanolayers and has a chemical formula of NiMoS.
另一方面，本发明提供一种通过光催化产氢助剂NiMoS修饰形成的光催化剂，该光催化剂是通过光催化产氢助剂NiMoS包覆在一维棒状CdS主催化剂表面形成的螺旋结构，化学表达式：CdS@NiMoS。NiMoS修饰一维棒状CdS主催化剂形成紧密结合的螺旋结构。On the other hand, the present invention provides a photocatalyst modified by the photocatalytic hydrogen production aid NiMoS, the photocatalyst is a helical structure formed by coating the photocatalytic hydrogen production aid NiMoS on the surface of the one-dimensional rod-shaped CdS main catalyst, Chemical expression: CdS@NiMoS. NiMoS modified one-dimensional rod-like CdS procatalysts to form tightly bound helical structures.
层状纳米MoS2具有类似石墨烯的二维结构，是光解水制氢反应中优良的助剂，其比表面积巨大，可以提供更多的反应活性位；其带隙位置和带隙宽度与CdS纳米棒匹配，可有效复合形成异质结构；其层状结构边缘存在大量不饱和硫原子，能大幅提高催化剂的制氢性能。在MoS2边缘位置引入Ni离子进行调控，形成NiMoS层状结构，进一步提高光催化产氢效率。Layered nano-MoS2 has a two-dimensional structure similar to graphene, and is an excellent additive in the photo-splitting of water to produce hydrogen. Its large specific surface area can provide more reactive sites; its bandgap position and width are the same as The matching of CdS nanorods can effectively compound to form a heterostructure; there are a large number of unsaturated sulfur atoms at the edge of the layered structure, which can greatly improve the hydrogen production performance of the catalyst. The introduction of Ni ions at the edge of MoS2 was regulated to form a NiMoS layered structure, which further improved the efficiency of photocatalytic hydrogen production.
再一方面，本发明提供一种光催化剂的制备方法，包括以下步骤：In another aspect, the present invention provides a method for preparing a photocatalyst, comprising the following steps:
（1）利用溶剂热法合成光催化主催化剂CdS纳米棒；(1) Synthesis of photocatalytic main catalyst CdS nanorods by solvothermal method;
（2）利用水热法合成光催化助剂与主催化剂复合的催化剂CdS@NiMoS。(2) The catalyst CdS@NiMoS, which is a combination of photocatalytic promoter and main catalyst, was synthesized by hydrothermal method.
进一步地，制备步骤具体如下：Further, the preparation steps are as follows:
（1）CdS前驱体Cd(S2CNEt2)2的制备：将硝酸镉Cd(NO3)2·4H2O和铜试剂(NaS2CNEt2·3H2O, NaDDTC)按1:2的摩尔比分别溶于适量水中，然后在磁力搅拌下将铜试剂水溶液缓慢滴加至Cd(NO3)2水溶液中，即得到CdS前驱体Cd(DDTC)2，将产物洗涤并真空干燥；(1) Preparation of CdS precursor Cd(S2 CNEt2 )2 : cadmium nitrate Cd(NO3 )2 4H2 O and copper reagent (NaS2 CNEt2 3H2 O, NaDDTC) were mixed at a ratio of 1:2 The molar ratios were dissolved in an appropriate amount of water, and then the copper reagent aqueous solution was slowly added dropwise to the Cd(NO3 )2 aqueous solution under magnetic stirring to obtain the CdS precursor Cd(DDTC)2 , and the product was washed and vacuum-dried;
（2）CdS纳米棒的制备：高压釜中加入乙二胺至其容积的70-80%，然后向其中加入Cd(DDTC)2，将其在120-200 ℃下反应6-48 h，即得到CdS纳米棒，将产物洗涤并真空干燥；(2) Preparation of CdS nanorods: Add ethylenediamine to the autoclave to 70-80% of its volume, then add Cd(DDTC)2 to it, and react it at 120-200 °C for 6-48 h, that is Obtain CdS nanorods, the product is washed and vacuum-dried;
（3）CdS@NiMoS的水热法制备：在含有15-25 mL蒸馏水的烧杯中加入80-150 mg CdS纳米棒，并在另一含有15-25 mL蒸馏水的烧杯中分别加入Na2MoO4、Ni(NO3)2与足量硫脲，控制助剂NiMoS与CdS的比例范围在0.01-0.25:1；烧杯中的反应物超声分解后混合均匀，将混合液转移到高压釜中，在180-220 ℃下反应5-25 h；即得到CdS@NiMoS螺旋结构复合催化剂，将产物洗涤并真空干燥。(3) Hydrothermal preparation of CdS@NiMoS: add 80-150 mg CdS nanorods to a beaker containing 15-25 mL distilled water, and add Na2 MoO4 to another beaker containing 15-25 mL distilled water , Ni(NO3 )2 and a sufficient amount of thiourea, the ratio of NiMoS and CdS is controlled in the range of 0.01-0.25:1; the reactants in the beaker are ultrasonically decomposed and mixed evenly, and the mixed solution is transferred to an autoclave, and the React at 180-220 °C for 5-25 h; the CdS@NiMoS helical structure composite catalyst is obtained, and the product is washed and vacuum-dried.
其中,助剂NiMoS中的各元素的来源分别是Ni(NO3)2、Na2MoO4和硫脲，Among them, the sources of the elements in the additive NiMoS are Ni(NO3 )2 , Na2 MoO4 and thiourea, respectively.
Ni、Mo的物质的量与最终产品中的物质的量是一致的，硫脲是硫源。The amounts of Ni and Mo are consistent with those in the final product, and thiourea is the source of sulfur.
本发明制备方法具有工艺简单，成本低廉，重复性好的特点，能够制备组成可控、性能高效的太阳光制氢光催化剂。The preparation method of the invention has the characteristics of simple process, low cost and good repeatability, and can prepare a solar hydrogen production photocatalyst with controllable composition and high performance.
上述光催化剂和光催化产氢助剂在光催化制氢方面的应用。Application of the above photocatalyst and photocatalytic hydrogen production assistant in photocatalytic hydrogen production.
上述光催化剂和光催化产氢助剂在光催化天然海水产氢方面的应用，可以实现对海洋资源的开发和利用。The application of the above-mentioned photocatalyst and photocatalytic hydrogen production aid in photocatalytic natural seawater hydrogen production can realize the development and utilization of marine resources.
上述可见光催化助剂在模拟太阳光制氢方面有良好的应用效果。是符合新能源需求的新型光催化材料。该光催化产氢助剂可大幅度提高主催化剂的光催化产氢性能，该助剂修饰主催化剂所得新型光催化剂的表达式为CdS@NiMoS。The above-mentioned visible light catalytic promoter has a good application effect in simulating solar hydrogen production. It is a new type of photocatalytic material that meets the needs of new energy sources. The photocatalytic hydrogen production assistant can greatly improve the photocatalytic hydrogen production performance of the main catalyst, and the expression of the novel photocatalyst obtained by modifying the main catalyst with the assistant is CdS@NiMoS.
本发明的新型纳米光催化产氢助剂NiMoS复合主催化剂CdS纳米棒的光产氢性能研究，方法如下：Research on the photohydrogen production performance of the novel nano photocatalytic hydrogen production aid NiMoS composite main catalyst CdS nanorods of the present invention, the method is as follows:
称取10-50 mg光催化剂，将其分散在40-80 mL蒸馏水中，然后分别加入 Na2SO3和Na2S作为光催化牺牲剂，在磁搅拌下，用300 W氙灯作为可见光光源，进行光还原水分解产氢实验，反应间隔相同时间进行一次测样，每种样品连续进行3-5次产氢分析，用气相色谱进行定性分析，确定产物的含量。反应结束后将催化剂回收。Weigh 10-50mg photocatalyst, disperse it in 40-80 mL distilled water, then add Na2SO3 andNa2S respectively as photocatalytic sacrificial agent, under magnetic stirring, use300 W xenon lamp as visible light source, The photoreduction water splitting hydrogen production experiment was carried out, and the reaction interval was the same as the sample, and each sample was continuously analyzed for hydrogen production 3-5 times, and the gas chromatography was used for qualitative analysis to determine the content of the product. After the reaction, the catalyst is recovered.
因此，本发明基于水热溶剂热法一体化反应，通过调节不同前驱体的种类以及加入比例，实现了新型光产氢助催化剂的组成调控。催化剂的制备采用水热溶剂热法一体化合成的技术：首先在乙二胺体系中合成了尺寸均匀，形貌规则的CdS纳米棒，然后通过水热环境使Na2MoO4、Ni(NO3)2与硫脲反应合成相应层状硫化物NiMoS，并与纳米棒状CdS形成异质结构。Therefore, the present invention is based on the integrated reaction of hydrothermal solvothermal method, and realizes the composition control of the novel photohydrogen production cocatalyst by adjusting the types and addition ratios of different precursors. The preparation of the catalyst adopts the integrated synthesis technology of hydrothermal solvothermal method: first, CdS nanorods with uniform size and regular shape are synthesized in the ethylenediamine system, and then Na2 MoO4 , Ni(NO3 )2 reacted with thiourea to synthesize the corresponding layered sulfide NiMoS, and formed a heterostructure with nanorod-like CdS.
本发明所制备的催化剂具有较强的可见光吸收，大幅度提高了太阳能利用率，在模拟太阳光制氢方面表现出很高的活性及稳定性，并在海水制氢中表现出优异性能。这些特征表明该类催化剂在新能源开发领域具有较高的应用价值。The catalyst prepared by the invention has strong visible light absorption, greatly improves the utilization rate of solar energy, exhibits high activity and stability in hydrogen production by simulating sunlight, and exhibits excellent performance in hydrogen production from seawater. These characteristics indicate that this type of catalyst has high application value in the field of new energy development.
所述异质结构复合金属硫化物光催化剂最优选的组成为：Mo的最佳负载量为15%，表达为CdS@15%MoS2；Ni的最佳负载量为1%，表达为CdS@1%NiMoS。上述方法制得的复合光催化剂中的助剂添加量已经验证为最佳配比，即首先在CdS纳米棒基础上找到MoS2的最佳产氢负载量；在最优化MoS2用量的基础上，调节Ni离子的加入比例以得到最佳光催化制氢效果的CdS@NiMoS复合光催化剂。上述催化剂结合了不同半导体的特性，各种硫化物的复合使该复合催化剂具有合适的能带位置；同时，催化材料边缘的不饱和硫键及螺旋结构可提供大量活性位点，有利于氢离子吸附，因此是具有优异性能的新型复合光催化材料。The most preferred composition of the heterostructure composite metal sulfide photocatalyst is: the optimal loading of Mo is 15%, expressed as CdS@15%MoS2 ; the optimal loading of Ni is 1%, expressed as CdS@ 1%NiMoS. The amount of additives added to the composite photocatalyst prepared by the above method has been verified as the optimal ratio, that is, firstly, the optimalhydrogen production loading of MoS2 is found on the basis of CdS nanorods; on the basis of optimizing the amount of MoS2 , adjusting the addition ratio of Ni ions to obtain the CdS@NiMoS composite photocatalyst with the best photocatalytic hydrogen production effect. The above-mentioned catalyst combines the characteristics of different semiconductors, and the combination of various sulfides makes the composite catalyst have a suitable energy band position; at the same time, the unsaturated sulfur bond and helical structure at the edge of the catalytic material can provide a large number of active sites, which is beneficial to hydrogen ions. adsorption, so it is a novel composite photocatalytic material with excellent properties.
与现有技术相比，本发明的优点和积极效果是：本发明通过简便的水热反应制备螺旋结构新型光催化产氢助剂复合纳米粒子，并有效应用于光解蒸馏水制氢及光解海水制氢，特别是光解海水制氢应用前景广泛。Compared with the prior art, the advantages and positive effects of the present invention are: the present invention prepares helical structure novel photocatalytic hydrogen production additive composite nanoparticles through a simple hydrothermal reaction, and is effectively applied to photolysis of distilled water for hydrogen production and photolysis Hydrogen production from seawater, especially hydrogen production from seawater by photolysis, has broad application prospects.
附图说明Description of drawings
图1为实施例1-3制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS与传统催化剂CdS及CdS@MoS2的扫描电镜SEM照片对比；Figure 1 is a comparison of the scanning electron microscope SEM photos of CdS@NiMoS obtained by modifying the CdS main catalyst with the new photocatalytic hydrogen production additive NiMoS prepared in Example 1-3, and the traditional catalyst CdS and CdS@MoS2 ;
图2为实施例2-3制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS与传统催化剂CdS@MoS2的透射电镜TEM照片对比；Figure 2 is a comparison of the transmission electron microscope TEM photos of CdS@NiMoS obtained by modifying the CdS main catalyst with the new photocatalytic hydrogen production additive NiMoS prepared in Example 2-3 and the traditional catalyst CdS@MoS2 ;
图3为实施例1-4制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS与传统催化剂CdS及CdS@MoS2的模拟太阳光制氢产率比较图；Figure 3 is a comparison chart of simulated solar hydrogen production yields of CdS@NiMoS obtained from the new photocatalytic hydrogen production additive NiMoS modified CdS main catalyst prepared in Examples 1-4 and traditional catalysts CdS and CdS@MoS2 ;
图4为实施例3制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS分别光解蒸馏水制氢和光解海水制氢的产率比较图；Fig. 4 is a comparison chart of the yields of CdS@NiMoS obtained from CdS@NiMoS modified by the new photocatalytic hydrogen production additive NiMoS prepared in Example 3 to produce hydrogen from distilled water and hydrogen from seawater;
图5为实施例3制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS的光催化制氢稳定性测试图；Fig. 5 is a photocatalytic hydrogen production stability test diagram of CdS@NiMoS obtained by modifying the CdS main catalyst with the new photocatalytic hydrogen production additive NiMoS prepared in Example 3;
图6为实施例3制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS在光催化产氢前后的X射线衍射（XRD）图；Fig. 6 is the X-ray diffraction (XRD) pattern of CdS@NiMoS obtained by modifying the CdS main catalyst with the new photocatalytic hydrogen production additive NiMoS prepared in Example 3 before and after photocatalytic hydrogen production;
图7为实施例3制备的新型光催化产氢助剂NiMoS修饰CdS主催化剂所得CdS@NiMoS在光催化产氢前后的SEM照片。Figure 7 is the SEM photographs of CdS@NiMoS obtained by modifying the CdS main catalyst with the new photocatalytic hydrogen production assistant NiMoS prepared in Example 3 before and after photocatalytic hydrogen production.
具体实施方式Detailed ways
本发明针对现有技术的不足，提供了CdS@NiMoS太阳光制氢纳米光催化剂的制备方法。Aiming at the deficiencies of the prior art, the present invention provides a preparation method of CdS@NiMoS nanometer photocatalyst for solar hydrogen production.
本发明的可见光驱动催化剂由助催化剂（NiMoS）与主催化剂（CdS）构成，通过水热溶剂热法将这几种半导体复合。The visible light-driven catalyst of the present invention is composed of a cocatalyst (NiMoS) and a main catalyst (CdS), and these semiconductors are compounded by a hydrothermal solvothermal method.
（1）CdS前驱体Cd(S2CNEt2)2的制备：将硝酸镉Cd(NO3)2·4H2O和铜试剂(NaS2CNEt2·3H2O, DDTC)按1:2的摩尔比分别溶于适量水中，然后在磁力搅拌下将铜试剂水溶液缓慢滴加至Cd(NO3)2水溶液中，即得到CdS前驱体Cd(DDTC)2，将产物洗涤并真空干燥；(1) Preparation of CdS precursor Cd(S2 CNEt2 )2 : cadmium nitrate Cd(NO3 )2 4H2 O and copper reagent (NaS2 CNEt2 3H2 O, DDTC) were mixed at a ratio of 1:2 The molar ratios were dissolved in an appropriate amount of water, and then the copper reagent aqueous solution was slowly added dropwise to the Cd(NO3 )2 aqueous solution under magnetic stirring to obtain the CdS precursor Cd(DDTC)2 , and the product was washed and vacuum-dried;
（2）CdS纳米棒的制备：高压釜中加入乙二胺至其容积的70-80%，然后向其中加入Cd(DDTC)2，将其在120-200 ℃下反应6-48 h，即得到CdS纳米棒，将产物洗涤并真空干燥；(2) Preparation of CdS nanorods: Add ethylenediamine to the autoclave to 70-80% of its volume, then add Cd(DDTC)2 to it, and react it at 120-200 °C for 6-48 h, that is Obtain CdS nanorods, the product is washed and vacuum-dried;
（3）CdS@NiMoS的水热法制备：在含有15-25 mL蒸馏水的烧杯中加入80-150mgCdS纳米棒，并在另一含有15-25 mL蒸馏水的烧杯中分别加入Na2MoO4、Ni(NO3)2与足量硫脲，控制助剂NiMoS与CdS的比例范围在0.01-0.25:1；烧杯中的反应物经超声分解后混合均匀。将混合液转移到高压釜中，在180-220 ℃下反应5-25 h；即得到CdS@NiMoS螺旋结构复合光催化剂，将产物洗涤并真空干燥。(3) Hydrothermal preparation of CdS@NiMoS: Add 80-150 mg of CdS nanorods to a beaker containing 15-25 mL of distilled water, and add Na2 MoO4 , Ni (NO3 )2 and a sufficient amount of thiourea, the ratio of NiMoS to CdS is controlled in the range of 0.01-0.25:1; the reactants in the beaker are ultrasonically decomposed and mixed evenly. The mixed solution was transferred to an autoclave, and reacted at 180-220 °C for 5-25 h; the CdS@NiMoS helical structure composite photocatalyst was obtained, and the product was washed and vacuum-dried.
新型复合纳米光产氢助剂复合主催化剂CdS纳米棒形成CdS@NiMoS光催化剂的光产氢性能研究，方法如下：称取10-50 mg光催化剂，将其分散在40-80 mL蒸馏水中，然后分别加入Na2SO3和Na2S作为光催化牺牲剂，在磁搅拌下，用300 W氙灯作为可见光光源，进行光还原水分解产氢实验，反应间隔相同时间进行一次测样，每种样品连续进行3-5次产氢分析，用气相色谱进行定性分析，确定产物的含量。反应结束后将催化剂回收。Research on the photohydrogen production performance of CdS@NiMoS photocatalyst formed by the new composite nano-photohydrogen production aid and composite main catalyst CdS nanorods, the method is as follows: Weigh 10-50 mg photocatalyst, disperse it in 40-80 mL distilled water, Then Na2 SO3 and Na2 S were added as photocatalytic sacrificial agents, and under magnetic stirring, a 300 W xenon lamp was used as a visible light source to carry out the photoreduction water splitting hydrogen production experiment. The sample is continuously analyzed for hydrogen production 3-5 times, and qualitatively analyzed by gas chromatography to determine the content of the product. After the reaction, the catalyst is recovered.
下面结合附图和具体实施例对本发明作进一步详细的说明。The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.
实施例1Example 1
具有光催化产氢性能的纳米光催化剂CdS纳米棒的制备与性能测试。Preparation and performance test of nanophotocatalyst CdS nanorods with photocatalytic hydrogen production performance.
（1）CdS前驱体Cd(S2CNEt2)2的制备：(1) Preparation of CdS precursor Cd(S2 CNEt2 )2 :
称取一定量Cd(NO3)2˙4H2O溶于50-80 mL水中，称取足量铜试剂（NaS2CNEt2·3H2O, DDTC）溶于40-50 mL水中；然后在磁力搅拌下将铜试剂水溶液缓慢滴加至Cd(NO3)2水溶液中，在室温下磁力搅拌5-20 min，经过真空抽滤装置，即得到CdS前驱体Cd(DDTC)2，用蒸馏水和乙醇分别洗涤3次并真空干燥6-10 h，即可得到白色产物待用；Weigh a certain amount of Cd(NO3 )2 ˙4H2 O and dissolve it in 50-80 mL of water, weigh a sufficient amount of copper reagent (NaS2 CNEt2 ·3H2 O, DDTC) and dissolve it in 40-50 mL of water; then in Slowly add the copper reagent aqueous solution to the Cd(NO3 )2 aqueous solution under magnetic stirring, magnetically stir at room temperature for 5-20 min, and pass through a vacuum filtration device to obtain the CdS precursor Cd(DDTC)2 . After washing with ethanol three times and drying in vacuum for 6-10 h, a white product can be obtained for use;
（2）CdS纳米棒的制备：(2) Preparation of CdS nanorods:
在高压釜中加入1.0-2.0 g Cd(DDTC)2，然后向其中加入70-80 mL无水乙二胺，将其在120-200 ℃下反应6-48 h，将产物离心并用蒸馏水和乙醇分别洗涤3次，真空干燥6-10 h，即得到黄色CdS纳米棒。Add 1.0-2.0 g Cd(DDTC)2 to the autoclave, then add 70-80 mL of anhydrous ethylenediamine to it, react it at 120-200 °C for 6-48 h, centrifuge the product and wash it with distilled water and ethanol After washing three times and drying in vacuum for 6-10 h, yellow CdS nanorods were obtained.
（3）纳米光催化剂CdS的光产氢性能研究：(3) Research on photohydrogen production performance of nano-photocatalyst CdS:
称取10-50 mg光催化剂，将其分散在40-80 mL蒸馏水中，然后分别加入Na2SO3和Na2S作为光催化牺牲剂，在磁力搅拌下，用300 W氙灯作为可见光光源，进行光还原水分解产氢实验，反应间隔相同时间进行一次测样，每种样品连续进行3-5次产氢分析，用气相色谱进行定性分析，确定产物的含量。反应结束后将催化剂回收。Weigh 10-50mg photocatalyst, disperse it in 40-80 mL distilled water, then add Na2SO3 andNa2S respectively as photocatalytic sacrificial agent, under magnetic stirring, use300 W xenon lamp as visible light source, The photoreduction water splitting hydrogen production experiment was carried out, and the reaction interval was the same as the sample, and each sample was continuously analyzed for hydrogen production 3-5 times, and the gas chromatography was used for qualitative analysis to determine the content of the product. After the reaction, the catalyst is recovered.
实施例2Example 2
具有优异光催化产氢性能的纳米光催化剂CdS@MoS2螺旋结构的制备与性能测试。Preparation and performance test of nano-photocatalyst CdS@MoS2 helical structure with excellent photocatalytic hydrogen production performance.
在含有15-25 mL蒸馏水的烧杯中加入80-150 mg CdS纳米棒，并在另一含有15-25 mL蒸馏水的烧杯中分别加入Na2MoO4·2H2O和足量CN2H4S；烧杯中的反应物经超声分解后混合均匀。将混合液转移到50 mL高压釜中，在180-220 ℃下反应5-25 h；将产物离心并用蒸馏水和乙醇分别洗涤3次，真空干燥6-10h，即得到CdS@MoS2螺旋结构复合催化剂。对比一系列不同Mo/Cd用量比的反应液：0、5%、10%、15%、20%、25%，得到最佳Mo负载量的CdS@MoS2催化剂，即Mo/Cd的最佳用量比为15%。实验中加入2.5 mL浓度5%的氯铂酸溶液，对其光催化性能进行检测，并与传统负载Pt助剂的CdS纳米棒的光催化性能进行对比。Add 80-150 mg CdS nanorods to a beaker containing 15-25 mL of distilled water, and add Na2 MoO4 2H2 O and sufficient amount of CN2 H4 S to another beaker containing 15-25 mL of distilled water ; The reactants in the beaker were homogeneously mixed after ultrasonic decomposition. The mixture was transferred to a 50 mL autoclave and reacted at 180-220 °C for 5-25 h; the product was centrifuged and washed three times with distilled water and ethanol respectively, and dried in vacuum for 6-10 h to obtain a CdS@MoS2 helical structure composite catalyst. Comparing a series of reaction solutions with different Mo/Cd ratios: 0, 5%, 10%, 15%, 20%, 25%, the CdS@MoS2 catalyst with the best Mo loading was obtained, that is, the best Mo/Cd The dosage ratio is 15%. In the experiment, 2.5 mL of 5% chloroplatinic acid solution was added to detect its photocatalytic performance, and compared with the photocatalytic performance of CdS nanorods loaded with Pt additives.
所得光催化剂模拟太阳光制氢过程与实施例1相同。The obtained photocatalyst simulates the solar hydrogen production process and is the same as in Example 1.
实施例3Example 3
具有优异光催化产氢性能的纳米光催化剂CdS@NiMoS的制备与性能测试。Preparation and performance test of nano-photocatalyst CdS@NiMoS with excellent photocatalytic hydrogen production performance.
对具有最佳制氢性能的光催化剂，即Mo/Cd用量比为15%的最佳负载量下，对Ni离子掺杂进行研究。向含有15-25 mL蒸馏水的烧杯中加入80-150 mg CdS纳米棒，并向另一含有15-25 mL蒸馏水的烧杯中分别加入Na2MoO4·2H2O、Ni(NO3)2·6H2O和足量CN2H4S；烧杯中的反应物经超声分解后混合均匀。将混合液转移到50 mL高压釜中，在180-220 ℃下反应5-25 h；将产物离心并用蒸馏水和乙醇分别洗涤3次，真空干燥6-10 h，即得到新型光催化剂CdS@NiMoS。对比一系列不同Ni/Cd用量比的反应液：0、1%、5%、10%、15%，得到最佳Ni负载量的CdS@NiMoS催化剂，即Ni的最佳负载量为1%。The photocatalyst with the best hydrogen production performance, that is, the optimum loading of Mo/Cd with a ratio of 15%, was studied on Ni ion doping. Add 80-150 mg CdS nanorods to a beaker containing 15-25 mL distilled water, and add Na2 MoO4 ·2H2 O, Ni(NO3 )2 · 6H2 O and a sufficient amount of CN2 H4 S; the reactants in the beaker were ultrasonically decomposed and mixed evenly. The mixture was transferred to a 50 mL autoclave and reacted at 180-220 °C for 5-25 h; the product was centrifuged and washed three times with distilled water and ethanol respectively, and dried in vacuum for 6-10 h to obtain the new photocatalyst CdS@NiMoS . A series of reaction solutions with different Ni/Cd ratios: 0, 1%, 5%, 10%, and 15% were compared to obtain the CdS@NiMoS catalyst with the optimal Ni loading, that is, the optimal Ni loading was 1%.
为了验证本催化剂的稳定性，进行了长时间制氢反应，观察其产氢速率，并对反应后的催化剂回收进行SEM和XRD表征，以比较光催化反应前后催化剂的形貌及组成是否稳定。In order to verify the stability of the catalyst, a long-term hydrogen production reaction was carried out to observe the hydrogen production rate, and the recovery of the catalyst after the reaction was characterized by SEM and XRD to compare whether the morphology and composition of the catalyst before and after the photocatalytic reaction were stable.
为了探究本催化剂的光催化海水产氢性能，在中国黄海西海岸——唐岛湾随机量取一定量海水，经沉降后直接用于光催化制氢反应。选取具有最佳产氢性能的光催化剂，比较其光解海水制氢与光解蒸馏水产氢的差别。In order to explore the photocatalytic seawater hydrogen production performance of this catalyst, a certain amount of seawater was randomly taken from Tangdao Bay on the west coast of the Yellow Sea in China, and was directly used for photocatalytic hydrogen production reaction after sedimentation. Select the photocatalyst with the best hydrogen production performance, and compare the difference between its photolysis of seawater for hydrogen production and photolysis of distilled water for hydrogen production.
所得光催化剂模拟太阳光制氢过程与实施例1相同。The obtained photocatalyst simulates the solar hydrogen production process and is the same as in Example 1.
实施例4Example 4
光催化产氢纳米光催化剂CdS与光催化助剂MoS2、NiMoS物理混合物的制备与光催化产氢性能测试。Preparation of photocatalytic hydrogen production nano-photocatalyst CdS and photocatalytic additives MoS2 , NiMoS physical mixture and photocatalytic hydrogen production performance test.
为验证新型光催化助剂MoS2与NiMoS经化学负载至CdS纳米棒表面后形成异质结构且可促进光催化性能，本实验特别合成了未经CdS纳米棒负载的单相催化助剂MoS2及NiMoS。按最佳制氢用量比将上述单相催化助剂与主催化剂CdS进行物理混合，并探究其光催化产氢性能。In order to verify that the new photocatalytic promoter MoS2 and NiMoS are chemically loaded on the surface of CdS nanorods to form a heterogeneous structure and can promote photocatalytic performance, a single-phase catalytic promoter MoS2 without CdS nanorods was specially synthesized in this experiment. and NiMoS. According to the optimal hydrogen production ratio, the above-mentioned single-phase catalytic promoter was physically mixed with the main catalyst CdS, and its photocatalytic hydrogen production performance was explored.
所得光催化剂模拟太阳光制氢过程与实施例1相同。The obtained photocatalyst simulates the solar hydrogen production process and is the same as in Example 1.
图1为实施例1-3的SEM照片，其中图(A)、(B)为纯相CdS纳米棒催化剂；图(C)、(D)为CdS@MoS2螺旋结构纳米棒催化剂；图(E)、(F)为CdS@NiMoS新型纳米棒。由图可知，大量纳米片状助催化剂负载生长在CdS纳米棒表面，形成界面良好的异质结构。该结构可以促进电子传输、提供大量反应活性位点、抑制CdS的光腐蚀，对提高产氢性能具有重要作用。Fig. 1 is the SEM photograph of embodiment 1-3, and wherein figure (A), (B) are pure phase CdS nanorod catalysts; Figure (C), (D) are CdS@MoS2 helical structure nanorod catalysts; Figure ( E), (F) are new nanorods of CdS@NiMoS. It can be seen from the figure that a large number of nanosheet co-catalysts are supported and grown on the surface of CdS nanorods, forming a heterostructure with a good interface. This structure can promote electron transport, provide a large number of reactive active sites, and inhibit the photocorrosion of CdS, which plays an important role in improving the hydrogen production performance.
图2为实施例2-3的TEM照片，其中图(A)、(B)为CdS@MoS2螺旋结构纳米棒催化剂；图(C)、(D)为CdS@NiMoS新型纳米棒催化剂。图中可见明显的纳米层状结构NiMoS的晶格条纹，说明光产氢助剂已成功负载至主催化剂CdS纳米棒表面。Figure 2 is the TEM photograph of Example 2-3, in which Figures (A) and (B) are CdS@MoS2 helical nanorod catalysts; Figures (C) and (D) are CdS@NiMoS new nanorod catalysts. The obvious lattice fringes of nano-layered NiMoS can be seen in the figure, indicating that the photohydrogen generation additive has been successfully loaded on the surface of the main catalyst CdS nanorods.
图3为实施例1-4的光催化制氢图，其中CdS@MoS2一列为不同MoS2负载量的CdS@MoS2、CdS与MoS2物理混合物与负载Pt的CdS的产氢速率比较。由图可知，与物理混合CdS与MoS2及负载贵金属Pt相比，CdS化学负载MoS2后光催化性能显著提高；且MoS2负载量15%时此催化剂具有最佳产氢性能。CdS@NiMoS一列为不同NiMoS负载量的CdS@NiMoS及CdS与NiMoS物理混合物产氢速率比较。由图可知，负载Ni后，催化剂的光催化产氢速率显著提高，当NiMoS负载量为1%时此催化剂具有最佳产氢性能。Fig. 3 is the photocatalytic hydrogen production diagram of Examples 1-4, in which the CdS@MoS2 column is the comparison of the hydrogen production rate of CdS@MoS2 with different MoS2 loadings, the physical mixture of CdS and MoS2 and the Pt-loaded CdS. It can be seen from the figure that compared with the physical mixture of CdS and MoS2 and supported noble metal Pt, the photocatalytic performance of CdS chemically loaded with MoS2 is significantly improved; and the catalyst has the best hydrogen production performance when the MoS2 loading is 15%. The column of CdS@NiMoS is the comparison of the hydrogen production rate of CdS@NiMoS with different NiMoS loadings and the physical mixture of CdS and NiMoS. It can be seen from the figure that after Ni is loaded, the photocatalytic hydrogen production rate of the catalyst is significantly improved, and the catalyst has the best hydrogen production performance when the NiMoS loading is 1%.
图4为实施例3的CdS@1%NiMoS光催化蒸馏水-海水制氢图，可知该催化剂光解海水制氢产率与光解蒸馏水的能力相当，说明此催化剂用于海水制氢具有巨大潜力。Figure 4 is the CdS@1%NiMoS photocatalytic distilled water-seawater hydrogen production diagram of Example 3. It can be seen that the hydrogen production rate of the catalyst by photolysis of seawater is equivalent to the ability of photolysis of distilled water, indicating that this catalyst has great potential for hydrogen production from seawater .
图5为实施例3的长时间光催化制氢图，可知经过长时间反应后，催化剂仍然具有良好的产氢性能，说明该催化剂稳定性良好。Figure 5 is the long-time photocatalytic hydrogen production diagram of Example 3. It can be seen that after a long time of reaction, the catalyst still has good hydrogen production performance, indicating that the catalyst has good stability.
图6-7为实施例3的XRD图和SEM照片，可知经长时间制氢后，CdS@1%NiMoS光催化剂的形貌和结构基本未发生改变，证实该催化剂具有良好的结构及性能稳定性。Figures 6-7 are the XRD patterns and SEM photos of Example 3. It can be seen that the morphology and structure of the CdS@1%NiMoS photocatalyst have not changed substantially after hydrogen production for a long time, confirming that the catalyst has a good structure and stable performance sex.
本发明的光催化剂的制备方法通过两步水热技术实现了螺旋复合纳米光催化剂的合成，首先在乙二胺体系中合成了尺寸均匀、形貌规则的CdS纳米棒，然后通过水热加压使Na2MoO4、Ni(NO3)2与硫脲反应合成相应层状硫化物NiMoS，并与纳米棒状CdS形成异质结构CdS@NiMoS。该催化剂表现出优异的光催化产氢性能，而且海水制氢产率可达19.147 mmol·g-1·h-1，为新能源开发提供了新的催化剂研发思路。The preparation method of the photocatalyst of the present invention realizes the synthesis of the helical composite nano-photocatalyst through the two-step hydrothermal technology. First, CdS nanorods with uniform size and regular shape are synthesized in the ethylenediamine system, and then pressurized by hydrothermal The corresponding layered sulfide NiMoS was synthesized by reacting Na2 MoO4 , Ni(NO3 )2 and thiourea, and formed heterostructure CdS@NiMoS with nanorod CdS. The catalyst exhibits excellent photocatalytic hydrogen production performance, and the hydrogen production rate from seawater can reach 19.147 mmol·g-1 ·h-1 , which provides a new catalyst research and development idea for the development of new energy.
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention to other forms. Any skilled person who is familiar with this profession may use the technical content disclosed above to change or modify the equivalent of equivalent changes. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still belong to the protection scope of the technical solution of the present invention.
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| CN201510308310.4ACN104959153B (en) | 2015-06-08 | 2015-06-08 | The preparation method and application of Photocatalyzed Hydrogen Production auxiliary agent, photochemical catalyst and photochemical catalyst |
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| CN118751268B (en)* | 2024-06-13 | 2025-09-23 | 宁德师范学院 | A Ni3Mo3N-CdS composite photocatalyst and its preparation method and application |
| Publication number | Publication date |
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| CN104959153B (en) | 2018-03-02 |
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| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20180302 Termination date:20200608 |