CN111377482A - Application of barium-doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production - Google Patents
Application of barium-doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 90
- 239000001257 hydrogen Substances 0.000 title claims abstract description 89
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 230000001699 photocatalysis Effects 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 claims description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims description 9
- 239000011684 sodium molybdate Substances 0.000 claims description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
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- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 229910052961 molybdenite Inorganic materials 0.000 description 12
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 10
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- 150000002431 hydrogen Chemical class 0.000 description 3
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- 229910003203 NH3BH3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及一种钡掺杂硫化钼材料于自供能压电增强制氢中的应用，特别涉及钡掺杂硫化钼材料于光催化自供能压电增强制氢中的应用，属于新能源领域。The invention relates to the application of a barium-doped molybdenum sulfide material in self-powered piezoelectric enhanced hydrogen production, in particular to the application of a barium-doped molybdenum sulfide material in photocatalytic self-powered piezoelectric enhanced hydrogen production, belonging to the field of new energy.
背景技术Background technique
随着人类社会的快速发展，人们对能源的需求日益增长，化石燃料的枯竭造成能源短缺。氢能因其燃烧值高，不产生二次污染等优点受到人们的广泛关注。但是，氢气容易发生爆炸，压缩氢气的成本比较高，因此如何安全有效而又经济地制取氢气和使用氢气一直是氢能源和氢经济需要解决的技术难题。氨硼烷(NH3BH3)是一种主要的储氢材料，其氢含量高达19.6wt％，在常温常压下呈固体，具有较高的稳定性，并且安全无毒性，容易携带。因此，与气态或液态氢相比，NH3BH3被认为是一种更有效和更安全的氢能储存方式。但是，NH3BH3在自然条件下释放氢气十分缓慢。为了快速释放氢气，人们开发了一些含有贵金属的催化剂，如铂、钯、铑、金等。然而，贵金属的成本高和丰度低，因此它们的应用十分有限。这就需要研究开发一种既安全、又经济、且环保、并能高效释放氢气的新技术。With the rapid development of human society, people's demand for energy is increasing, and the exhaustion of fossil fuels has caused energy shortages. Hydrogen energy has attracted widespread attention due to its high combustion value and no secondary pollution. However, hydrogen is prone to explosion and the cost of compressing hydrogen is relatively high. Therefore, how to produce and use hydrogen safely, effectively and economically has always been a technical problem to be solved by hydrogen energy and hydrogen economy. Ammonia borane (NH 3 BH 3 ) is a major hydrogen storage material with a hydrogen content of up to 19.6 wt %. It is solid at normal temperature and pressure, has high stability, is safe, non-toxic, and easy to carry. Therefore, compared with gaseous or liquid hydrogen, NH3BH3 is considered to be a more efficient and safer way to store hydrogen energy. However, NH 3 BH 3 releases hydrogen very slowly under natural conditions. In order to release hydrogen rapidly, some catalysts containing precious metals, such as platinum, palladium, rhodium, and gold, have been developed. However, the high cost and low abundance of noble metals make their applications very limited. This requires research and development of a new technology that is safe, economical, environmentally friendly, and can release hydrogen efficiently.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供钡掺杂硫化钼材料于自供能压电增强制氢中的应用，以克服现有技术中的不足。The purpose of the present invention is to provide the application of barium-doped molybdenum sulfide material in self-powered piezoelectric enhanced hydrogen production to overcome the deficiencies in the prior art.
为实现前述发明目的，本发明采用的技术方案包括：In order to realize the foregoing invention purpose, the technical scheme adopted in the present invention includes:
本发明实施例中提供一种钡掺杂硫化钼压电增强材料(Ba-MoS2)在红外光照射下自供能压电增强制氢中的用途。The embodiments of the present invention provide the use of a barium-doped molybdenum sulfide piezoelectric enhancement material (Ba-MoS 2 ) in self-powered piezoelectric enhanced hydrogen production under infrared light irradiation.
进一步的，所述钡掺杂硫化钼材料包括对近红外光具有响应的硫化钼MoS2材料以及掺杂在硫化钼内部及表面的二价钡离子。Further, the barium-doped molybdenum sulfide material includes a molybdenum sulfide MoS 2 material that is responsive to near-infrared light and divalent barium ions doped inside and on the surface of the molybdenum sulfide.
进一步的，所述二价钡离子的质量为所述硫化钼材料质量的10.0wt％-35.0wt％。Further, the mass of the divalent barium ions is 10.0wt%-35.0wt% of the mass of the molybdenum sulfide material.
进一步的，所述钡掺杂硫化钼材料的禁带宽度为0.7eV-1.3eV。Further, the forbidden band width of the barium-doped molybdenum sulfide material is 0.7eV-1.3eV.
进一步的，所述钡掺杂硫化钼MoS2半导体材料对红外光的响应范围为780-1550nm。Further, the response range of the barium-doped molybdenum sulfide MoS 2 semiconductor material to infrared light is 780-1550 nm.
进一步的，在温度为20-30℃的条件下，同时对主要由钡掺杂硫化钼材料和氨硼烷水溶液混合形成的制氢反应体系施加超声波和近红外光辐照，实现氢气的制备。Further, under the condition of temperature of 20-30°C, ultrasonic wave and near-infrared light irradiation are simultaneously applied to the hydrogen production reaction system mainly formed by mixing barium-doped molybdenum sulfide material and ammonia borane aqueous solution to realize the preparation of hydrogen gas.
更进一步的，所述超声波的功率为20-30KHz。Further, the power of the ultrasonic wave is 20-30KHz.
进一步的，所述钡掺杂硫化钼材料是采用水热法制备的，并且所述的制备方法包括以下步骤：Further, the barium-doped molybdenum sulfide material is prepared by a hydrothermal method, and the preparation method includes the following steps:
(1)将钼酸钠溶于去离子水中，并超声处理30-60mins至混合均匀制得溶液A；(1) dissolving sodium molybdate in deionized water, and ultrasonically treating it for 30-60mins to mix well to obtain solution A;
(2)将硫脲溶于去离子水中，并超声处理30-60mins至混合均匀制得溶液B；(2) dissolving thiourea in deionized water, and ultrasonically treating it for 30-60mins to mix uniformly to obtain solution B;
(3)将二水合氯化钡溶于去离子水中，并超声处理30-60mins至混合均匀制得溶液C；(3) dissolving barium chloride dihydrate in deionized water, and ultrasonically treating for 30-60mins to mixing to obtain solution C;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理30-60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 30-60mins to uniform mixing to obtain mixed solution D;
(5)将混合液D转至高压反应釜中，在温度为150-300℃的条件下反应20-30h，制得钡掺杂硫化钼材料。(5) Transfer the mixed solution D to an autoclave, and react at a temperature of 150-300° C. for 20-30 hours to obtain a barium-doped molybdenum sulfide material.
进一步的，所述溶液A的浓度为0.1mol/L～1.0mol/L。Further, the concentration of the solution A is 0.1 mol/L to 1.0 mol/L.
进一步的，所述溶液B的浓度为1.0mol/L～5.0mol/L。Further, the concentration of the solution B is 1.0 mol/L˜5.0 mol/L.
进一步的，所述溶液C的浓度为0.1mol/L～1.0mol/L。Further, the concentration of the solution C is 0.1 mol/L to 1.0 mol/L.
本发明实施例中还提供一种自供能压电增强光催化制氢方法，其包括：An embodiment of the present invention also provides a self-powered piezoelectric enhanced photocatalytic hydrogen production method, which includes:
对包含氨硼烷和钡掺杂硫化钼压电增强材料(Ba-MoS2半导体材料)的制氢反应体系同时施加机械能和近红外光照射所述制氢反应体系，使所述制氢反应体系内发生反应，并产生氢气。进一步的，所述机械能可以是施加于制氢反应体系的振动、噪声、超声波、搅拌等产生。The hydrogen production reaction system comprising ammonia borane and barium-doped molybdenum sulfide piezoelectric enhancement material (Ba - MoS semiconductor material) is simultaneously applied with mechanical energy and near-infrared light to irradiate the hydrogen production reaction system, so that the hydrogen production reaction system The reaction takes place and hydrogen gas is produced. Further, the mechanical energy may be generated by vibration, noise, ultrasonic waves, stirring, etc. applied to the hydrogen production reaction system.
本发明实施例中还提供一种自供能压电增强光催化制氢方法，其包括以下步骤：An embodiment of the present invention also provides a self-powered piezoelectric enhanced photocatalytic hydrogen production method, which includes the following steps:
(1)将氨硼烷水溶液置于光催化制氢反应器中，再向该氨硼烷水溶液中加入钡掺杂硫化钼压电增强材料(Ba-MoS2半导体材料)，形成制氢反应体系，之后密封所述反应器；(1) The ammonia borane aqueous solution is placed in a photocatalytic hydrogen production reactor, and then a barium-doped molybdenum sulfide piezoelectric reinforcing material (Ba - MoS semiconductor material) is added to the ammonia borane aqueous solution to form a hydrogen production reaction system , then sealing the reactor;
(2)将所述反应器的温度调节至1-5℃后将系统抽至真空，待所述反应器内达到真空状态后再将所述反应器内的温度调至20-30℃；；(2) after the temperature of the reactor is adjusted to 1-5 ℃, the system is evacuated to a vacuum, and the temperature in the reactor is adjusted to 20-30 ℃ after the vacuum state is reached in the reactor;
(3)对所述反应器内的制氢反应体系施加超声波，同时以近红外光照射所述制氢反应体系，使所述制氢反应体系内发生反应，并产生氢气。(3) ultrasonic waves are applied to the hydrogen production reaction system in the reactor, and at the same time, the hydrogen production reaction system is irradiated with near-infrared light, so that a reaction occurs in the hydrogen production reaction system and hydrogen gas is generated.
进一步的，对所述光催化制氢反应器进行遮光处理，以避免紫外光和可见光进入制氢反应体系。Further, shading treatment is performed on the photocatalytic hydrogen production reactor to prevent ultraviolet light and visible light from entering the hydrogen production reaction system.
进一步的，所述近红外光的波长为850nm。Further, the wavelength of the near-infrared light is 850 nm.
进一步的，采用真空树脂进行密封处理。Further, vacuum resin is used for sealing treatment.
与现有技术相比，本发明的优点包括：本发明提供的钡掺杂硫化钼材料具有增强的压电效应，可有效利用自然界的机械能(如振动、噪声、超声波和搅拌等方式制得的能量)产生氢能，为制备氢能源提供一个新的渠道，扩展了制氢技术的实际应用，而且制得的氢随制随用，解决了氢气不易储存的难题。采用硼烷作为储氢材料，实现了自供能压电增强制氢，且本发明的钡掺杂硫化钼材料的制备方法简单易行，绿色环保。Compared with the prior art, the advantages of the present invention include: the barium-doped molybdenum sulfide material provided by the present invention has enhanced piezoelectric effect, and can effectively utilize the mechanical energy of nature (such as vibration, noise, ultrasonic wave and stirring etc.) energy) to generate hydrogen energy, providing a new channel for the preparation of hydrogen energy, expanding the practical application of hydrogen production technology, and the produced hydrogen can be used as it is produced, which solves the problem that hydrogen is not easy to store. By using borane as the hydrogen storage material, self-powered piezoelectric enhanced hydrogen production is realized, and the preparation method of the barium-doped molybdenum sulfide material of the present invention is simple, easy, and environmentally friendly.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments described in the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.
图1为本发明提供的MoS2和Ba-MoS2样品的XRD图；Fig. 1 is the XRD pattern of MoS 2 and Ba-MoS 2 samples provided by the present invention;
图2a为本发明提供的MoS2样品的透射电镜表征图，图2b为本发明提供的Ba-MoS2样品的透射电镜表征图；Figure 2a is a TEM characterization diagram of the MoS 2 sample provided by the present invention, and Figure 2b is a TEM characterization diagram of the Ba-MoS 2 sample provided by the present invention;
图3为本发明提供的MoS2和Ba-MoS2样品的固体荧光图；Fig. 3 is the solid fluorescence image of MoS 2 and Ba-MoS 2 samples provided by the present invention;
图4为本发明提供的Ba-MoS2样品制氢时氢的产量曲线图；Fig. 4 is the curve diagram of the yield of hydrogen when the Ba - MoS sample provided by the present invention produces hydrogen;
图5为本发明提供的光催化制氢反应的反应机理图。FIG. 5 is a reaction mechanism diagram of the photocatalytic hydrogen production reaction provided by the present invention.
具体实施方式Detailed ways
鉴于现有技术中的不足，本案发明人经长期研究和大量实践，得以提出本发明的技术方案。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。In view of the deficiencies in the prior art, the inventor of the present application was able to propose the technical solution of the present invention after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows.
本发明实施例中提供一种钡掺杂硫化钼压电增强材料(Ba-MoS2)在红外光照射下自供能压电增强制氢中的用途。The embodiments of the present invention provide the use of a barium-doped molybdenum sulfide piezoelectric enhancement material (Ba-MoS 2 ) in self-powered piezoelectric enhanced hydrogen production under infrared light irradiation.
进一步的，所述钡掺杂硫化钼材料包括对近红外光具有响应的硫化钼MoS2材料以及掺杂在硫化钼内部及表面的二价钡离子。Further, the barium-doped molybdenum sulfide material includes a molybdenum sulfide MoS 2 material that is responsive to near-infrared light and divalent barium ions doped inside and on the surface of the molybdenum sulfide.
进一步的，所述二价钡离子的质量为所述硫化钼材料质量的10.0wt％-35.0wt％。Further, the mass of the divalent barium ions is 10.0wt%-35.0wt% of the mass of the molybdenum sulfide material.
进一步的，所述钡掺杂硫化钼材料的禁带宽度为0.7eV-1.3eV。Further, the forbidden band width of the barium-doped molybdenum sulfide material is 0.7eV-1.3eV.
进一步的，所述钡掺杂硫化钼MoS2半导体材料对红外光的响应范围为780-1550nm。Further, the response range of the barium-doped molybdenum sulfide MoS 2 semiconductor material to infrared light is 780-1550 nm.
进一步的，在温度为20-30℃的条件下，同时对主要由钡掺杂硫化钼材料和氨硼烷水溶液混合形成的制氢反应体系施加超声波和近红外光辐照，实现氢气的制备。Further, under the condition of temperature of 20-30°C, ultrasonic wave and near-infrared light irradiation are simultaneously applied to the hydrogen production reaction system mainly formed by mixing barium-doped molybdenum sulfide material and ammonia borane aqueous solution to realize the preparation of hydrogen gas.
更进一步的，所述超声波的功率为20-30KHz。Further, the power of the ultrasonic wave is 20-30KHz.
进一步的，所述钡掺杂硫化钼材料是采用水热法制备的，并且所述的制备方法包括以下步骤：Further, the barium-doped molybdenum sulfide material is prepared by a hydrothermal method, and the preparation method includes the following steps:
(1)将钼酸钠溶于去离子水中，并超声处理30-60mins至混合均匀制得溶液A；(1) dissolving sodium molybdate in deionized water, and ultrasonically treating it for 30-60mins to mix well to obtain solution A;
(2)将硫脲溶于去离子水中，并超声处理30-60mins至混合均匀制得溶液B；(2) dissolving thiourea in deionized water, and ultrasonically treating it for 30-60mins to mix uniformly to obtain solution B;
(3)将二水合氯化钡溶于去离子水中，并超声处理30-60mins至混合均匀制得溶液C；(3) dissolving barium chloride dihydrate in deionized water, and ultrasonically treating for 30-60mins to mixing to obtain solution C;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理30-60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 30-60mins to uniform mixing to obtain mixed solution D;
(5)将混合液D转至高压反应釜中，在温度为150-300℃的条件下反应20-30h，制得钡掺杂硫化钼材料。(5) Transfer the mixed solution D to an autoclave, and react at a temperature of 150-300° C. for 20-30 hours to obtain a barium-doped molybdenum sulfide material.
进一步的，所述溶液A的浓度为0.1mol/L～1.0mol/L。Further, the concentration of the solution A is 0.1 mol/L to 1.0 mol/L.
所述溶液B的浓度为1.0mol/L～5.0mol/L。The concentration of the solution B is 1.0 mol/L to 5.0 mol/L.
所述溶液C的浓度为0.1mol/L～1.0mol/L。The concentration of the solution C is 0.1 mol/L to 1.0 mol/L.
本发明实施例中还提供一种自供能压电增强光催化制氢方法，其包括以下步骤：An embodiment of the present invention also provides a self-powered piezoelectric enhanced photocatalytic hydrogen production method, which includes the following steps:
(1)将氨硼烷水溶液置于光催化制氢反应器中，再向该氨硼烷水溶液中加入钡掺杂硫化钼压电增强材料(Ba-MoS2半导体材料)，形成制氢反应体系，之后密封所述反应器；(1) The ammonia borane aqueous solution is placed in a photocatalytic hydrogen production reactor, and then a barium-doped molybdenum sulfide piezoelectric reinforcing material (Ba - MoS semiconductor material) is added to the ammonia borane aqueous solution to form a hydrogen production reaction system , then sealing the reactor;
(2)将所述反应器的温度调节至1-5℃后将系统抽至真空，待所述反应器内达到真空状态后再将所述反应器内的温度调至20-30℃；；(2) after the temperature of the reactor is adjusted to 1-5 ℃, the system is evacuated to a vacuum, and the temperature in the reactor is adjusted to 20-30 ℃ after the vacuum state is reached in the reactor;
(3)对所述反应器内的制氢反应体系施加超声波，同时以近红外光照射所述制氢反应体系，使所述制氢反应体系内发生反应，并产生氢气。(3) ultrasonic waves are applied to the hydrogen production reaction system in the reactor, and at the same time, the hydrogen production reaction system is irradiated with near-infrared light, so that a reaction occurs in the hydrogen production reaction system and hydrogen gas is generated.
进一步的，对所述光催化制氢反应器进行遮光处理，以避免紫外光和可见光进入制氢反应体系。Further, shading treatment is performed on the photocatalytic hydrogen production reactor to prevent ultraviolet light and visible light from entering the hydrogen production reaction system.
进一步的，所述近红外光的波长为850nm。Further, the wavelength of the near-infrared light is 850 nm.
进一步的，采用真空树脂进行密封处理。Further, vacuum resin is used for sealing treatment.
本发明提供的光催化制氢的反应机理为:在合适的催化剂存在下，NH3BH3可以通过溶剂分解或热分解释放氢，如下所示：The reaction mechanism of photocatalytic hydrogen production provided by the present invention is: in the presence of a suitable catalyst, NH 3 BH 3 can release hydrogen through solvolysis or thermal decomposition, as shown below:
NH3BH3(aq)+2H2O(l)＝NH4 +(aq)+BO2 -(aq)+3H2(g)(如图5所示) NH3BH3 (aq) + 2H2O(l)= NH4 + (aq)+ BO2- ( aq ) + 3H2 (g) (as shown in Figure 5)
在本发明中，硫化钼本身是一种可以响应近红外光且具有压电效应的半导体材料。催化剂有三种催化途径，第一种是催化剂自身的热催化，其降低了氨硼烷和水的反应势能，使反应速率加快。第二种是响应850nm近红外光的光催化，材料因受到850nm近红外光辐射发生电子跃迁，光生电子与水中质子h+发生反应产生氢气。而因体系中H的电负性高于B的电负性，所以H会吸引自由电子形成氢负离子H-。光生空穴再与氢负离子H-结合产生氢气。第三种是催化剂在超声波震荡中产生压电效应，材料内部形成自建电场，使电子定向移动，产生的电子与水中质子H+发生反应产生氢气，产生的空穴与氢负离子H-结合产生氢气。当钡掺入硫化钼中后，从光催化角度来说，材料的禁带宽度变窄，拓宽了材料的理论吸收边界，提高了光的利用效率。也因为掺杂之后使材料的缺陷增加，减少了电子与空穴的复合，提高了材料的光催化效率。从压电催化角度来说，材料的表面缺陷增多，导致材料的熵和混乱度增加，材料的体缺陷增多，都导致了材料的对称性变差。对称性的下降使材料的压电效应增强，有效的抑制了电子与空穴的复合，提高了材料的压电催化效率。综上，钡的掺入提高了硫化钼的光催化制氢活性。In the present invention, molybdenum sulfide itself is a semiconductor material that can respond to near-infrared light and has piezoelectric effect. The catalyst has three catalytic pathways, the first one is the thermal catalysis of the catalyst itself, which reduces the reaction potential energy of ammonia borane and water and accelerates the reaction rate. The second is photocatalysis in response to 850nm near-infrared light. The material undergoes electron transition due to the radiation of 850nm near-infrared light, and the photogenerated electrons react with proton h+ in water to generate hydrogen. Since the electronegativity of H in the system is higher than that of B, H will attract free electrons to form hydride ions H - . The photogenerated holes combine with the hydride ions H- to generate hydrogen gas. The third is that the catalyst produces a piezoelectric effect in the ultrasonic vibration. A self-built electric field is formed inside the material, which makes the electrons move directionally. The generated electrons react with the proton H + in the water to generate hydrogen, and the generated holes combine with the negative hydrogen ions H - to generate hydrogen. When barium is doped into molybdenum sulfide, from the perspective of photocatalysis, the forbidden band width of the material is narrowed, the theoretical absorption boundary of the material is broadened, and the utilization efficiency of light is improved. Also, because the defects of the material are increased after doping, the recombination of electrons and holes is reduced, and the photocatalytic efficiency of the material is improved. From the perspective of piezoelectric catalysis, the increase of surface defects of materials leads to the increase of entropy and disorder of materials, and the increase of bulk defects of materials, which leads to the deterioration of material symmetry. The decrease of symmetry enhances the piezoelectric effect of the material, effectively suppresses the recombination of electrons and holes, and improves the piezoelectric catalytic efficiency of the material. In conclusion, the incorporation of barium improves the photocatalytic hydrogen production activity of molybdenum sulfide.
在一具体实施例中，可以将本发明制得的钡掺杂硫化钼材料Ba-MoS2半导体材料应用于汽车中，将汽车行驶过程中的振动能转化为电能，再经光催化反应制得氢气，作为汽车燃料，实现自供能制氢。In a specific embodiment, the barium-doped molybdenum sulfide material Ba-MoS 2 semiconductor material prepared by the present invention can be applied to automobiles, and the vibration energy during the driving process of the automobile is converted into electric energy, and then obtained by photocatalytic reaction. Hydrogen, as a vehicle fuel, realizes self-supply hydrogen production.
以下结合若干实施例对本发明的技术方案作进一步的解释说明。The technical solutions of the present invention will be further explained below with reference to several embodiments.
实施例1Example 1
压电增强材料钡掺杂硫化钼材料Ba-MoS2半导体材料的制备，其中Ba的质量为MoS2的质量的10％。The piezoelectric enhancement material barium-doped molybdenum sulfide material Ba - MoS2 semiconductor material is prepared, wherein the mass of Ba is 10 % of the mass of MoS2.
(1)将2.42g(0.01mol)钼酸钠(NaMoO4.2H2O)溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液A；(1) Dissolve 2.42 g (0.01 mol) of sodium molybdate (NaMoO 4 .2H 2 O) in 30 mL of deionized water, and ultrasonically treat it for 30 mins to uniformly mix to obtain solution A;
(2)将3.05g(0.04mol)硫脲[(NH2)2CS]溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液B；(2) Dissolve 3.05 g (0.04 mol) of thiourea [(NH 2 ) 2 CS] in 30 mL of deionized water, and perform ultrasonic treatment for 30 mins until the mixture is uniform to obtain solution B;
(3)将0.366g(0.0015mol)二水合氯化钡溶于去离子水中，并超声处理60mins至混合均匀制得溶液C；(3) Dissolve 0.366g (0.0015mol) barium chloride dihydrate in deionized water, and ultrasonically treat for 60mins to mixing to obtain solution C;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 60mins to mixing to obtain mixed solution D;
(5)将混合液D定容至100mL处理后转至高压反应釜中，控制温度为200℃条件下反应24h，待反应结束后经冷却、抽滤和置于真空干燥箱中60℃条件下干燥6h后制得所述自供能压电增强材料Ba-MoS2半导体材料。(5) Dilute the mixture D to 100mL and transfer it to an autoclave, control the temperature to react at 200°C for 24h, and after the reaction is completed, cool, filter with suction and place it in a vacuum drying oven at 60°C The self-powered piezoelectric enhancement material Ba-MoS 2 semiconductor material was prepared after drying for 6 hours.
将实施例1制得的钡掺杂硫化钼材料Ba-MoS2半导体材料和硫化钼MoS2材料进行XRD检测，检测结果如图1所示。The barium-doped molybdenum sulfide material Ba-MoS 2 semiconductor material and the molybdenum sulfide MoS 2 material prepared in Example 1 were subjected to XRD detection, and the detection results are shown in FIG. 1 .
制氢反应如下：The hydrogen production reaction is as follows:
(1)提供浓度为0.05mol/L的100mL的NH3BH3溶液中，并置于光催化制氢反应器中，再向溶液中加入自供能压电增强材料(0.01gBa-MoS2半导体材料)，盖上石英玻璃板并密封反应器；(1) Provide 100 mL of NH 3 BH 3 solution with a concentration of 0.05 mol/L, and place it in a photocatalytic hydrogen production reactor, and then add self-powered piezoelectric enhancement material (0.01 g Ba-MoS 2 semiconductor material to the solution) ), cover the quartz glass plate and seal the reactor;
(2)将步骤(1)中的反应器光解水制氢系统和低温恒温槽连接好后密封处理，控制低温恒温槽温度为1℃后将系统内抽至真空，待系统内到达真空状态后再通过低温恒温槽将控制系统温度为25℃；(2) after the reactor photo-splitting water hydrogen production system in step (1) is connected with the low temperature constant temperature tank, the temperature of the low temperature constant temperature tank is controlled to be 1 ℃ and then the system is evacuated to a vacuum, and the system reaches a vacuum state Then, the temperature of the control system is controlled to 25 ℃ through a low temperature constant temperature tank;
(3)将反应器置于28KHz超声波清洗器中，打开超声，将850nm的近红外光光源置于反应器上方10cm处，光源通过石英玻璃板进入反应器内进行光催化反应，将光解水制氢系统调整至系统循环状态后进行实验，每隔一个小时通过气相色谱仪检测每个小时的氢气产量。(3) place the reactor in a 28KHz ultrasonic cleaner, turn on the ultrasound, place a near-infrared light source of 850 nm at 10 cm above the reactor, and the light source enters the reactor through a quartz glass plate for photocatalytic reaction, and the photolysis water After the hydrogen production system was adjusted to the system circulation state, the experiment was carried out, and the hydrogen production per hour was detected by gas chromatograph every hour.
实施例2Example 2
压电增强材料钡掺杂硫化钼材料Ba-MoS2半导体材料的制备，其中Ba的质量为MoS2的质量的15％。Piezoelectric enhancement material barium-doped molybdenum sulfide material Ba - MoS2 semiconductor material preparation, wherein the mass of Ba is 15 % of the mass of MoS2.
(1)将2.42g(0.01mol)钼酸钠(NaMoO4.2H2O)溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液A；(1) Dissolve 2.42 g (0.01 mol) of sodium molybdate (NaMoO 4 .2H 2 O) in 30 mL of deionized water, and ultrasonically treat it for 30 mins to uniformly mix to obtain solution A;
(2)将3.05g(0.04mol)硫脲[(NH2)2CS]溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液B；(2) Dissolve 3.05 g (0.04 mol) of thiourea [(NH 2 ) 2 CS] in 30 mL of deionized water, and perform ultrasonic treatment for 30 mins until the mixture is uniform to obtain solution B;
(3)将0.549g(0.0022mol)二水合氯化钡溶于去离子水中，并超声处理60mins至混合均匀制得溶液C；(3) 0.549g (0.0022mol) of barium chloride dihydrate is dissolved in deionized water, and ultrasonically treated for 60mins to uniformly mixed to obtain solution C;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 60mins to mixing to obtain mixed solution D;
(5)将混合液D定容至100mL处理后转至高压反应釜中，控制温度为200℃条件下反应24h，待反应结束后经冷却、抽滤和置于真空干燥箱中60℃条件下干燥6h后制得所述自供能压电增强材料Ba-MoS2半导体材料。(5) Dilute the mixture D to 100mL and transfer it to an autoclave, control the temperature to react at 200°C for 24h, and after the reaction is completed, cool, filter with suction and place it in a vacuum drying oven at 60°C The self-powered piezoelectric enhancement material Ba-MoS 2 semiconductor material was prepared after drying for 6 hours.
将实施例2制得的压电增强材料钡掺杂硫化钼Ba-MoS2半导体材料和硫化钼MoS2材料进行透射电镜表征，检测结果如图2所示。The piezoelectric enhancement material barium-doped molybdenum sulfide Ba-MoS 2 semiconductor material and molybdenum sulfide MoS 2 material prepared in Example 2 were characterized by transmission electron microscopy, and the detection results are shown in FIG. 2 .
其中，图2a为本发明提供的MoS2样品的透射电镜表征图，图2b为本发明提供的Ba-MoS2样品的透射电镜表征图；Wherein, Fig. 2a is a TEM characterization diagram of the MoS 2 sample provided by the present invention, and Fig. 2b is a TEM characterization diagram of the Ba-MoS 2 sample provided by the present invention;
制氢反应与实施例1中的光催化反应步骤相同。The hydrogen production reaction is the same as that of the photocatalytic reaction in Example 1.
实施例3Example 3
压电增强材料钡掺杂硫化钼材料Ba-MoS2半导体材料的制备，其中Ba的质量为MoS2的质量的20％。Piezoelectric enhancement material barium-doped molybdenum sulfide material Ba - MoS2 semiconductor material preparation, wherein the mass of Ba is 20 % of the mass of MoS2.
(1)将2.42g(0.01mol)钼酸钠(NaMoO4.2H2O)溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液A；(1) Dissolve 2.42 g (0.01 mol) of sodium molybdate (NaMoO 4 .2H 2 O) in 30 mL of deionized water, and ultrasonically treat it for 30 mins to uniformly mix to obtain solution A;
(2)将3.05g(0.04mol)硫脲[(NH2)2CS]溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液B；(2) Dissolve 3.05 g (0.04 mol) of thiourea [(NH 2 ) 2 CS] in 30 mL of deionized water, and perform ultrasonic treatment for 30 mins until the mixture is uniform to obtain solution B;
(3)将0.672g(0.0027mol)二水合氯化钡溶于去离子水中，并超声处理60mins至混合均匀制得溶液C；(3) 0.672g (0.0027mol) of barium chloride dihydrate was dissolved in deionized water, and the solution C was obtained by ultrasonic treatment for 60mins to uniform mixing;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 60mins to mixing to obtain mixed solution D;
(5)将混合液D定容至100mL处理后转至高压反应釜中，控制温度为200℃条件下反应24h，待反应结束后经冷却、抽滤和置于真空干燥箱中60℃条件下干燥6h后制得所述自供能压电增强材料Ba-MoS2半导体材料。(5) Dilute the mixture D to 100mL and transfer it to an autoclave, control the temperature to react at 200°C for 24h, and after the reaction is completed, cool, filter with suction and place it in a vacuum drying oven at 60°C The self-powered piezoelectric enhancement material Ba-MoS 2 semiconductor material was prepared after drying for 6 hours.
将实施例3将制得的压电增强材料钡掺杂硫化钼Ba-MoS2半导体材料和硫化钼MoS2材料进行紫外可见近红外漫反射检测，检测出MoS2和Ba-MoS2样品的固体荧光图如图3所示。The piezoelectric enhancement material barium-doped molybdenum sulfide Ba-MoS 2 semiconductor material and molybdenum sulfide MoS 2 material prepared in Example 3 were subjected to ultraviolet-visible-near-infrared diffuse reflection detection, and the solid samples of MoS 2 and Ba-MoS 2 were detected. The fluorescence map is shown in Figure 3.
制氢反应与实施例1中的光催化反应步骤相同。The hydrogen production reaction is the same as that of the photocatalytic reaction in Example 1.
实施例4Example 4
压电增强材料钡掺杂硫化钼材料Ba-MoS2半导体材料的制备，其中Ba的质量为MoS2的质量的25％。Piezoelectric enhancement material barium-doped molybdenum sulfide material Ba - MoS2 semiconductor material preparation, wherein the mass of Ba is 25 % of the mass of MoS2.
(1)将2.42g(0.01mol)钼酸钠(NaMoO4.2H2O)溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液A；(1) Dissolve 2.42 g (0.01 mol) of sodium molybdate (NaMoO 4 .2H 2 O) in 30 mL of deionized water, and ultrasonically treat it for 30 mins to uniformly mix to obtain solution A;
(2)将3.05g(0.04mol)硫脲[(NH2)2CS]溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液B；(2) Dissolve 3.05 g (0.04 mol) of thiourea [(NH 2 ) 2 CS] in 30 mL of deionized water, and perform ultrasonic treatment for 30 mins until the mixture is uniform to obtain solution B;
(3)将0.915g(0.0037mol)二水合氯化钡溶于去离子水中，并超声处理60mins至混合均匀制得溶液C；(3) 0.915g (0.0037mol) of barium chloride dihydrate was dissolved in deionized water, and the solution C was obtained by ultrasonic treatment for 60mins to uniform mixing;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 60mins to mixing to obtain mixed solution D;
(5)将混合液D定容至100mL处理后转至高压反应釜中，控制温度为200℃条件下反应24h，待反应结束后经冷却、抽滤和置于真空干燥箱中60℃条件下干燥6h后制得所述自供能压电增强材料Ba-MoS2半导体材料。(5) Dilute the mixture D to 100mL and transfer it to an autoclave, control the temperature to react at 200°C for 24h, and after the reaction is completed, cool, filter with suction and place it in a vacuum drying oven at 60°C The self-powered piezoelectric enhancement material Ba-MoS 2 semiconductor material was prepared after drying for 6 hours.
制氢反应与实施例1中的光催化反应步骤相同。The hydrogen production reaction is the same as that of the photocatalytic reaction in Example 1.
实施例5Example 5
压电增强材料钡掺杂硫化钼材料Ba-MoS2半导体材料的制备，其中Ba的质量为MoS2的质量的30％。The piezoelectric enhancement material barium- doped molybdenum sulfide material Ba - MoS2 semiconductor material is prepared, wherein the mass of Ba is 30% of the mass of MoS2.
(1)将2.42g(0.01mol)钼酸钠(NaMoO4.2H2O)溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液A；(1) Dissolve 2.42 g (0.01 mol) of sodium molybdate (NaMoO 4 .2H 2 O) in 30 mL of deionized water, and ultrasonically treat it for 30 mins to uniformly mix to obtain solution A;
(2)将3.05g(0.04mol)硫脲[(NH2)2CS]溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液B；(2) Dissolve 3.05 g (0.04 mol) of thiourea [(NH 2 ) 2 CS] in 30 mL of deionized water, and perform ultrasonic treatment for 30 mins until the mixture is uniform to obtain solution B;
(3)将1.098g(0.0045mol)二水合氯化钡溶于去离子水中，并超声处理60mins至混合均匀制得溶液C；(3) 1.098g (0.0045mol) of barium chloride dihydrate was dissolved in deionized water, and the solution C was obtained by ultrasonic treatment for 60mins to uniform mixing;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 60mins to mixing to obtain mixed solution D;
(5)将混合液D定容至100mL处理后转至高压反应釜中，控制温度为200℃条件下反应24h，待反应结束后经冷却、抽滤和置于真空干燥箱中60℃条件下干燥6h后制得所述自供能压电增强材料Ba-MoS2半导体材料。(5) Dilute the mixture D to 100mL and transfer it to an autoclave, control the temperature to react at 200°C for 24h, and after the reaction is completed, cool, filter with suction and place it in a vacuum drying oven at 60°C The self-powered piezoelectric enhancement material Ba-MoS 2 semiconductor material was prepared after drying for 6 hours.
制氢反应与实施例1中的光催化反应步骤相同。The hydrogen production reaction is the same as that of the photocatalytic reaction in Example 1.
实施例6Example 6
压电增强材料钡掺杂硫化钼材料Ba-MoS2半导体材料的制备，其中Ba的质量为MoS2的质量的35％。Piezoelectric enhancement material barium- doped molybdenum sulfide material Ba - MoS2 semiconductor material preparation, wherein the mass of Ba is 35% of the mass of MoS2.
(1)将2.42g(0.01mol)钼酸钠(NaMoO4.2H2O)溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液A；(1) Dissolve 2.42 g (0.01 mol) of sodium molybdate (NaMoO 4 .2H 2 O) in 30 mL of deionized water, and ultrasonically treat it for 30 mins to uniformly mix to obtain solution A;
(2)将3.05g(0.04mol)硫脲[(NH2)2CS]溶于30mL去离子水中，并超声处理30mins至混合均匀制得溶液B；(2) Dissolve 3.05 g (0.04 mol) of thiourea [(NH 2 ) 2 CS] in 30 mL of deionized water, and perform ultrasonic treatment for 30 mins until the mixture is uniform to obtain solution B;
(3)将1.281g(0.0052mol)二水合氯化钡溶于去离子水中，并超声处理60mins至混合均匀制得溶液C；(3) 1.281g (0.0052mol) of barium chloride dihydrate was dissolved in deionized water, and the solution C was obtained by ultrasonic treatment for 60mins to uniform mixing;
(4)将溶液B和溶液C逐滴加入到溶液A中，并超声处理60mins至混合均匀制得混合液D；(4) adding solution B and solution C dropwise to solution A, and ultrasonically treating for 60mins to mixing to obtain mixed solution D;
(5)将混合液D定容至100mL处理后转至高压反应釜中，控制温度为200℃条件下反应24h，待反应结束后经冷却、抽滤和置于真空干燥箱中60℃条件下干燥6h后制得所述自供能压电增强材料Ba-MoS2半导体材料。(5) Dilute the mixture D to 100mL and transfer it to an autoclave, control the temperature to react at 200°C for 24h, and after the reaction is completed, cool, filter with suction and place it in a vacuum drying oven at 60°C The self-powered piezoelectric enhancement material Ba-MoS 2 semiconductor material was prepared after drying for 6 hours.
制氢反应与实施例1中的光催化反应步骤相同。The hydrogen production reaction is the same as that of the photocatalytic reaction in Example 1.
如图4为本发明实施例1、实施例2、实施例3、实施例4、实施例5和实施例6制得的Ba-MoS2样品制氢时氢的产量随曲线图。FIG. 4 is a graph showing the hydrogen yield of the Ba-MoS 2 samples prepared in Example 1, Example 2, Example 3, Example 4, Example 5 and Example 6 of the present invention during hydrogen production.
应当理解，上述实施例仅为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。It should be understood that the above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and the purpose thereof is to enable those who are familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.
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