阅读说明：本技术 一种硫化钼掺杂硫化镉微纳米材料的制备方法及其在光催化产氢中的应用 (A kind of preparation method of molybdenum sulfide doped cadmium sulfide micro Nano material and its application in Photocatalyzed Hydrogen Production ) 是由 郭玉明 丁丽娜 高卫华 王魁 孙萌萌 别亚萌 马晓明 常毅 于 2019-08-05 设计创作，主要内容包括：本发明公开了一种硫化钼掺杂硫化镉微纳米材料的制备方法及其在光催化产氢中的应用,称取0.4mmoL镉盐放入100mL烧杯中,加入100μL巯基化合物搅拌30min,再加入NaOH调整混合体系的pH值为6.0-8.0,滴加4mL、0.25moL/L硫化物溶液至烧杯中,溶液呈黄绿色,然后加入0.0097g钼酸钠和0.0122g硫脲搅拌30min,将上述混合溶液转移至消解式水热反应釜中以3℃/min的升温速率升温至160-200℃恒温24h,再以3℃/min的降温速率降温至30℃,将产物离心洗涤后真空干燥得到目标产物硫化钼掺杂硫化镉微纳米材料。本发明合成的硫化钼掺杂硫化镉微纳米材料在紫外光区和可见光区均有吸收,在光催化产氢领域具有较好的应用前景。(The invention discloses a kind of preparation method of molybdenum sulfide doped cadmium sulfide micro Nano material and its applications in Photocatalyzed Hydrogen Production, 0.4mmoL cadmium salt is weighed to be put into 100mL beaker, 100 μ L sulfhydryl compounds stirring 30min is added, the pH value for adding NaOH adjustment mixed system is 6.0-8.0, 4mL is added dropwise, 0.25moL/L sulfide solution is into beaker, solution is in yellow green, then 0.0097g sodium molybdate is added and 0.0122g thiocarbamide stirs 30min, above-mentioned mixed solution is transferred in resolvent hydrothermal reaction kettle, 160-200 DEG C of constant temperature is warming up to for 24 hours with the heating rate of 3 DEG C/min, 30 DEG C are cooled to again with the rate of temperature fall of 3 DEG C/min, vacuum drying after product centrifuge washing is obtained target to produce Object molybdenum sulfide doped cadmium sulfide micro Nano material.The molybdenum sulfide doped cadmium sulfide micro Nano material that the present invention synthesizes has absorption in ultraviolet region and visible region, Photocatalyzed Hydrogen Production field with good application prospect.)

1. a kind of preparation method of molybdenum sulfide doped cadmium sulfide micro Nano material, it is characterised in that specific steps are as follows: weigh 0.4mmoL cadmium salt is put into 100mL beaker, and 100 μ L sulfhydryl compounds are added and stir 30min, adds NaOH adjustment mixture The pH value of system is 6.0-8.0, and 4mL, 0.25moL/L sulfide solution is added dropwise into beaker, and solution is in yellow green, is then added 0.0097g sodium molybdate and 0.0122g thiocarbamide stir 30min, and above-mentioned mixed solution is transferred in resolvent hydrothermal reaction kettle with 3 DEG C/heating rate of min is warming up to 160-200 DEG C of constant temperature for 24 hours, then is cooled to 30 DEG C with the rate of temperature fall of 3 DEG C/min, by product Vacuum drying obtains target product molybdenum sulfide doped cadmium sulfide micro Nano material after centrifuge washing, and the cadmium salt is cadmium acetate, chlorine Cadmium or cadmium nitrate, the sulfhydryl compound are mercaptoethanol acid, thioacetic acid or mercaptopropionic acid, and the sulfide is thio second Amide, vulcanized sodium or ammonium sulfide.

2. molybdenum sulfide doped cadmium sulfide micro Nano material is in Photocatalyzed Hydrogen Production made from the method according to claim 11 Using, when the optimum mole ratio of Cd and Mo is 10:1 in the molybdenum sulfide doped cadmium sulfide micro Nano material, Photocatalyzed Hydrogen Production efficiency 235.41 μm of ol g can be reached^-1 h^-1。

Technical field

The invention belongs to the synthesis technical fields of catalysis material, and in particular to a kind of molybdenum sulfide doped cadmium sulfide is micro-nano The preparation method of material and its application in Photocatalyzed Hydrogen Production.

Background technique

In 21 century, energy and environment problem has become the theme of World Focusing, at present the energy used in human society If petroleum, coal, oil gas belong to non-renewable resources, storage is limited on the earth, in the exploitation that recent decades have been over And utilization, since the reserves of coal and petroleum on earth are limited, and they are all the non-renewable energy, thus coal and Petroleum has been unable to meet the industrial requirement of sustainable development.In addition, the burning of coal and petroleum can generate many poisonous and hazardous objects Matter seriously pollutes environment.It is understood that combustion of fossil fuel can release a large amount of carbon dioxide, present greenhouse effects is caused to get over Come more serious, therefore there is an urgent need to develop novel renewable and clean environment type new energy.The appearance of photocatalysis hydrogen production technology Solution is provided to solve energy shortage and problem of environmental pollution, catalyst can be by the reducing hydrogen ions Cheng Qing in water Gas, and water is generated again after combustion of hydrogen, there is no any pollution to environment.In addition, tellurian water resource is very rich, institute To there is enough hydrogen sources, and sunlight can provide light source for photochemical catalyst, therefore photocatalysis hydrogen production technology both solved Problem of energy crisis in turn avoids the pollution to environment, therefore the research and development of photochemical catalyst also suddenly become current international hot topic and grind Study carefully one of field.

Cadmium sulfide (CdS) is a kind of extensive photochemical catalyst of research, but some defects existing for CdS itself limit CdS Application in terms of Photocatalyzed Hydrogen Production.The compound rate of one side CdS photogenerated charge itself is very fast, and photocatalysis generates the work of hydrogen Property is lower.Therefore in order to improve the activity of CdS Photocatalyzed Hydrogen Production, it is necessary in the area load noble metal of CdS, such as Pt, with Its Photocatalyzed Hydrogen Production activity is improved, but noble metal is expensive.The MoS of two-dimensional structure₂Because its suitable band structure and compared with Narrow forbidden bandwidth (about 1.9eV) is considered as optimal candidate co-catalyst.And it is reported that MoS₂No matter in electricity There is very high catalytic effect in terms of catalyzing manufacturing of hydrogen or photocatalysis hydrogen production.

Summary of the invention

The technical problem to be solved by the present invention is to provide a kind of environmentally protective and simple process molybdenum sulfide doped cadmium sulfides The preparation method of micro Nano material, molybdenum sulfide doped cadmium sulfide micro Nano material made from this method are produced with good photocatalysis Hydrogen activity, can as photochemical catalyst by the reducing hydrogen ions in water at hydrogen.

The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of micro-nano material of molybdenum sulfide doped cadmium sulfide The preparation method of material, it is characterised in that specific steps are as follows: weigh 0.4mmoL cadmium salt and be put into 100mL beaker, 100 μ L mercaptos are added Based compound stirs 30min, and the pH value for adding NaOH adjustment mixed system is 6.0-8.0, and 4mL, 0.25moL/L vulcanization is added dropwise For object solution into beaker, solution is in yellow green, and 0.0097g sodium molybdate is then added and 0.0122g thiocarbamide stirs 30min, will be upper It states mixed solution and is transferred in resolvent hydrothermal reaction kettle and 160-200 DEG C of constant temperature is warming up to for 24 hours with the heating rate of 3 DEG C/min, 30 DEG C are cooled to the rate of temperature fall of 3 DEG C/min again, vacuum drying after product centrifuge washing is obtained into target product molybdenum sulfide and is mixed Miscellaneous cadmium sulfide micro Nano material, the cadmium salt are cadmium acetate, caddy or cadmium nitrate, and the sulfhydryl compound is mercaptoethanol Acid, thioacetic acid or mercaptopropionic acid, the sulfide are thioacetamide, vulcanized sodium or ammonium sulfide.

Application of the molybdenum sulfide doped cadmium sulfide micro Nano material of the present invention in Photocatalyzed Hydrogen Production, the molybdenum sulfide are mixed When the optimum mole ratio of Cd and Mo is 10:1 in miscellaneous cadmium sulfide micro Nano material, Photocatalyzed Hydrogen Production efficiency can reach 235.41 μ mol g^-1 h^-1。

Compared with the prior art, the invention has the following beneficial effects: the micro-nano material of molybdenum sulfide doped cadmium sulfide in the present invention The synthesis process of material is simple and low in cost, and the molybdenum sulfide doped cadmium sulfide micro Nano material of synthesis is not soluble in water, urges conducive to light The recycling and recycling of agent；The molybdenum sulfide doped cadmium sulfide micro Nano material of synthesis has in ultraviolet region and visible region Absorb, Photocatalyzed Hydrogen Production field with good application prospect.

Detailed description of the invention

Fig. 1 is the scanning electron microscope (SEM) photograph of molybdenum sulfide doped cadmium sulfide micro Nano material made from embodiment 1；

Fig. 2 is the scanning electron microscope (SEM) photograph of molybdenum sulfide doped cadmium sulfide micro Nano material made from embodiment 1；

Fig. 3 is the Powder XRD pattern of molybdenum sulfide doped cadmium sulfide micro Nano material made from embodiment 1；

Fig. 4 is that the uv-vis spectra of molybdenum sulfide doped cadmium sulfide micro Nano material made from embodiment 1 absorbs map.

Specific embodiment

Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.