CN107855130A - A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method - Google Patents

A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method Download PDF

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CN107855130A
CN107855130A CN201711177885.2A CN201711177885A CN107855130A CN 107855130 A CN107855130 A CN 107855130A CN 201711177885 A CN201711177885 A CN 201711177885A CN 107855130 A CN107855130 A CN 107855130A
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董晓丽
毕元清
王宇
马红超
张秀芳
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Abstract

本发明公开了一种太阳能固氮光催化剂，为氢化溴氧化铋，分子式H‑BiOBr，用于太阳能固氮光催化，用于以水作为还原剂的太阳能固氮光催化反应。催化剂的制备方法，包括步骤：1、取乙二醇、异丙醇或丙三醇溶液；2、将含铋化合物和含溴化合物加入醇溶液，混合并充分搅拌；3、搅拌至澄清溶液后加入中性溶液，搅拌后装入反应釜中，进行恒温反应；4、冷却至室温进行离心分离并用水和乙醇溶液多次洗涤，干燥后，研磨至粉末；5、在氢气氛围下煅烧，得到氢化溴氧化铋。本发明方法得到的氢化溴氧化铋光催化剂为绿色无毒、价格低廉、原材料简单、来源广泛、方法易操作并且可以短时间内大量制备，具有良好的太阳能固氮光催化性能。

The invention discloses a solar nitrogen fixation photocatalyst, which is bismuth oxybromide hydrochloride and has the molecular formula H-BiOBr, which is used for solar nitrogen fixation photocatalysis and is used for the solar nitrogen fixation photocatalysis reaction using water as a reducing agent. The preparation method of the catalyst comprises the steps of: 1. taking ethylene glycol, isopropanol or glycerol solution; 2. adding a bismuth-containing compound and a bromine-containing compound into the alcohol solution, mixing and fully stirring; 3. stirring until the solution becomes clear Add a neutral solution, stir and put it into a reaction kettle for constant temperature reaction; 4. Cool to room temperature, perform centrifugation and wash with water and ethanol solution for several times, after drying, grind to powder; 5. Calcinate in a hydrogen atmosphere to obtain Bismuth oxybromide. The bismuth oxybromide photocatalyst obtained by the method of the invention is green, non-toxic, low in price, simple in raw materials, wide in sources, easy to operate and can be prepared in large quantities in a short time, and has good solar nitrogen fixation photocatalytic performance.

Description

一种太阳能固氮光催化剂及其用途和制备方法A kind of solar nitrogen fixation photocatalyst and its application and preparation method

技术领域technical field

本发明涉及一种光催化材料技术领域，更具体地说，涉及涉及一种氢化溴氧化铋(H-BiOBr)太阳能固氮光催化剂的制备及应用。The invention relates to the technical field of photocatalytic materials, in particular to the preparation and application of a hydrogenated bismuth oxybromide (H-BiOBr) solar nitrogen-fixing photocatalyst.

背景技术Background technique

众所周知，钼基固氮酶能固定大气中60％的氮气，在生物领域中它是一种较有效的基质将氮气还原成氨气。相对于生物固氮，光催化技术还原大气中的氮气制备氨气引起了人们广泛的关注。光催化技术为固氮提供了一种有效途径。半导体光催化剂可以将太阳能转化为化学能，相比于工业固氮大量的化石燃料燃烧危害环境(传统哈柏法在25MPa，723-773K条件下)，这一反应过程更加绿色，反应条件更加温和，反应可以在水中进行。但是在过去的几十年，光催化技术固氮很难令人们满意，可能归于以下原因：(1)氮分子由于存在N≡N形成高度稳定状态，将氮分子分解成原子需要吸收大约941.69kJ mol-1，在太阳能驱动下，依靠半导体光催化剂中的光生载流子作用去断开N≡N是一个极大的挑战；(2)大多数半导体拥有更高的导带最小值，导致了在水中固氮时，通过光催化剂作用水优先分解产生氢气，这种竞争反应降低了固氮的效果。As we all know, molybdenum-based nitrogenase can fix 60% nitrogen in the atmosphere, and it is a more effective substrate in the biological field to reduce nitrogen to ammonia. Compared with biological nitrogen fixation, photocatalytic reduction of nitrogen in the atmosphere to produce ammonia has attracted widespread attention. Photocatalytic technology provides an effective way for nitrogen fixation. Semiconductor photocatalysts can convert solar energy into chemical energy. Compared with industrial nitrogen fixation, a large amount of fossil fuel combustion is harmful to the environment (traditional Haber method at 25MPa, 723-773K), this reaction process is greener and the reaction conditions are milder. The reaction can be carried out in water. However, in the past few decades, photocatalytic nitrogen fixation has been unsatisfactory, which may be attributed to the following reasons: (1) Nitrogen molecules form a highly stable state due to the existence of N≡N, and the decomposition of nitrogen molecules into atoms needs to absorb about 941.69kJ mol -1 , it is a great challenge to disconnect N≡N by photogenerated carriers in semiconductor photocatalysts driven by solar energy; (2) most semiconductors have higher conduction band minima, leading to When nitrogen is fixed in water, water is preferentially decomposed to generate hydrogen through the action of photocatalyst, and this competitive reaction reduces the effect of nitrogen fixation.

现在，越来越多的光催化剂被利用去固定氮气。例如：二氧化钛、石墨相氮化碳、二硫化钼、钨酸等等。然而，溴氧化铋(BiOBr)是由[Bi2O2]2+层和两个Br离子层组成的且具有独特层状结构的半导体晶体。此外，它还具有生产工艺简单、廉价、无毒等优点。BiOBr吸引人们广泛注意最主要的是它拥有合适的带隙、更低的导带最小值、较宽的光吸收范围和一致的表面结构。尽管如此，传统的BiOBr仍表现出与氮气较弱的结合能力。Nowadays, more and more photocatalysts are utilized to fix nitrogen. For example: titanium dioxide, graphite phase carbon nitride, molybdenum disulfide, tungstic acid, etc. However, bismuth oxybromide (BiOBr) is a semiconductor crystal composed of a [Bi 2 O 2 ] 2+ layer and two Br ion layers and has a unique layered structure. In addition, it also has the advantages of simple production process, cheap, non-toxic and so on. BiOBr has attracted widespread attention mainly because of its suitable bandgap, lower conduction band minimum, wider light absorption range, and consistent surface structure. Nevertheless, conventional BiOBr still exhibits a weak binding ability to nitrogen.

发明内容Contents of the invention

本发明目的在于提供一种高效光催化固氮催化剂及其合成方法、用途及应用。The purpose of the present invention is to provide a high-efficiency photocatalytic nitrogen fixation catalyst and its synthesis method, use and application.

为了实现上述目的，本发明的技术方案为：In order to achieve the above object, the technical solution of the present invention is:

本发明一种太阳能固氮光催化剂，催化剂为氢化溴氧化铋，分子式H-BiOBr。呈具有氧空位的花球状空腔微球结构。The invention discloses a solar nitrogen fixation photocatalyst, the catalyst is bismuth oxybromide, and the molecular formula is H-BiOBr. It is a curd-like hollow microsphere structure with oxygen vacancies.

本发明提供的催化剂，用于太阳能固氮光催化。具体应用，应用于以水作为还原剂的太阳能固氮光催化反应。The catalyst provided by the invention is used for solar nitrogen fixation and photocatalysis. The specific application is applied to the photocatalytic reaction of solar nitrogen fixation using water as a reducing agent.

本发明还提供了一种太阳能固氮光催化剂的制备方法，包括如下步骤：The present invention also provides a preparation method of a solar nitrogen fixation photocatalyst, comprising the following steps:

S1、取60～120℃的乙二醇、异丙醇或丙三醇溶液；S1. Take ethylene glycol, isopropanol or glycerin solution at 60-120°C;

S2、将含铋化合物和含溴化合物加入所述醇溶液，混合并充分搅拌；S2, adding bismuth-containing compound and bromine-containing compound to the alcohol solution, mixing and fully stirring;

S3、搅拌至澄清溶液后加入中性溶液，搅拌后装入压力为1～2Mpa的高压反应釜中，进行100～180℃恒温反应；S3. After stirring until the solution becomes clear, add a neutral solution, and after stirring, put it into a high-pressure reactor with a pressure of 1-2Mpa, and perform a constant temperature reaction at 100-180°C;

S4、冷却至室温进行离心分离并用水和乙醇溶液多次洗涤，在50～80℃干燥后，研磨至粉末；S4. Cool to room temperature, perform centrifugation, wash with water and ethanol solution several times, dry at 50-80°C, and grind to powder;

S5、在100～300℃、300～380ml/min氢气氛围下煅烧2～6h，得到氢化溴氧化铋。S5. Calcining at 100-300° C. and 300-380 ml/min hydrogen atmosphere for 2-6 hours to obtain hydrogenated bismuth oxybromide.

其中，步骤S2中，所述含铋化合物为五水合硝酸铋、氯化铋或铋离子络合物；所述含溴化合物为溴化纳、溴化钾或CTAB。步骤S3中，所述中性溶液为水、乙醇或异丙醇。Wherein, in step S2, the bismuth-containing compound is bismuth nitrate pentahydrate, bismuth chloride or bismuth ion complex; the bromine-containing compound is sodium bromide, potassium bromide or CTAB. In step S3, the neutral solution is water, ethanol or isopropanol.

本发明一种太阳能固氮光催化剂的制备方法，具体包括以下步骤：The preparation method of a kind of solar nitrogen fixation photocatalyst of the present invention specifically comprises the following steps:

S1、将20ml～40ml乙二醇、异丙醇或丙三醇溶液加热至120℃～200℃，降温至60℃～120℃；S1. Heat 20ml to 40ml of ethylene glycol, isopropanol or glycerol solution to 120°C to 200°C, then cool down to 60°C to 120°C;

S2、将0.2g～2.0g含铋化合物和0.05g～0.5g含溴化合物加入热的醇溶液，混合并充分搅拌；S2. Add 0.2g-2.0g bismuth-containing compound and 0.05g-0.5g bromine-containing compound into the hot alcohol solution, mix and fully stir;

S3、搅拌至澄清溶液后加入60ml～120ml中性溶液，所得溶液搅拌后装入高压反应釜，进行100℃～180℃恒温反应8h以上；S3. After stirring until the solution becomes clear, add 60ml-120ml neutral solution, stir the obtained solution, put it into a high-pressure reactor, and carry out constant temperature reaction at 100°C-180°C for more than 8 hours;

S4、冷却至室温进行离心分离并用水和乙醇溶液洗3～5次，在50～80℃干燥后，研磨至粉末；S4. Cool to room temperature for centrifugation, wash with water and ethanol solution for 3 to 5 times, dry at 50 to 80°C, and grind to powder;

S5、在100～300℃、300～380ml/min氢气氛围下煅烧2～6h，得到氢化溴氧化铋。S5. Calcining at 100-300° C. and 300-380 ml/min hydrogen atmosphere for 2-6 hours to obtain hydrogenated bismuth oxybromide.

优选方式下，步骤S2至S3中所述搅拌时间为10～35min。此外，步骤S3所述恒温反应时，填充溶液的体积占高压釜内衬体积的比例为50％～90％，反应时间为8～24h。In a preferred manner, the stirring time in steps S2 to S3 is 10-35 minutes. In addition, during the constant temperature reaction described in step S3, the volume of the filling solution accounts for 50% to 90% of the volume of the inner lining of the autoclave, and the reaction time is 8 to 24 hours.

本发明具有如下优点：The present invention has the following advantages:

本发明的光催化剂为H-BiOBr，本发明的光催化剂不仅具有卓越的光催化固氮性能，而且拥有极高的量子效率。在太阳光下以水作为反应剂，每小时每克催化剂可产生180～400μmol氨气，是传统BiOBr产量的2.6倍。相应的在380nm单色光下量子效率达到3.5～4.5％。不仅在自然条件下展现了有效的固氮性能，而且在染料降解方面也有显著效果。在环境污染与治理方向具有很大的应用潜力，为该类型催化剂提供了有力的理论基础和更广阔的发展空间。The photocatalyst of the present invention is H-BiOBr, and the photocatalyst of the present invention not only has excellent photocatalytic nitrogen fixation performance, but also has extremely high quantum efficiency. Using water as a reactant under sunlight, 180-400 μmol of ammonia gas can be produced per gram of catalyst per hour, which is 2.6 times that of traditional BiOBr. Correspondingly, the quantum efficiency reaches 3.5-4.5% under 380nm monochromatic light. Not only exhibits effective nitrogen fixation performance under natural conditions, but also has remarkable effect on dye degradation. It has great application potential in the direction of environmental pollution and governance, providing a strong theoretical basis and broader development space for this type of catalyst.

附图说明Description of drawings

图1为实施例1催化剂的XRD衍射图。Fig. 1 is the XRD diffractogram of embodiment 1 catalyst.

图2为实施例1催化剂的扫描电镜图。Fig. 2 is the scanning electron micrograph of embodiment 1 catalyst.

图3为实施例1催化剂的UV-vis吸收光谱图。Fig. 3 is the UV-vis absorption spectrogram of embodiment 1 catalyst.

图4为实施例1催化剂的电流-时间曲线图。Fig. 4 is the current-time graph of the catalyst of Example 1.

图5为实施例1催化剂的交流阻抗图。Fig. 5 is the AC impedance diagram of the catalyst of Example 1.

图6为实施例1～4催化剂的光催化固氮效果图。Fig. 6 is a photocatalytic nitrogen fixation effect diagram of the catalysts of Examples 1-4.

具体实施方式Detailed ways

本发明一种氢化溴氧化铋高效太阳能固氮光催化剂的制备方法，属于光催化材料技术领域。该方法包括如下步骤：将溴源与铋源溶解在醇溶液中；进行水热反应；用水和醇洗涤并且离心分离；干燥研磨得到固体粉末；在管式炉中通入氢气煅烧；冷却到室温得到产品。本发明方法得到的氢化溴氧化铋光催化剂为绿色无毒、价格低廉、原材料简单、来源广泛、方法易操作并且可以短时间内大量制备，具有良好的太阳能固氮光催化性能。The invention discloses a preparation method of a bismuth oxybromide high-efficiency solar nitrogen fixation photocatalyst, belonging to the technical field of photocatalytic materials. The method comprises the following steps: dissolving a bromine source and a bismuth source in an alcohol solution; performing a hydrothermal reaction; washing with water and alcohol and centrifuging; drying and grinding to obtain a solid powder; passing hydrogen into a tube furnace for calcination; cooling to room temperature get the product. The bismuth oxybromide photocatalyst obtained by the method of the invention is green, non-toxic, low in price, simple in raw materials, wide in sources, easy to operate and can be prepared in large quantities in a short time, and has good solar nitrogen fixation photocatalytic performance.

以下将结合本发明实施例中的附图，来对本发明实施例中的技术方案做出清楚、完整的表述。以下所描述的实施例仅仅是本发明的一部分，并不是全部的实施例。本领域的技术人员根据本发明的上述内容做出一些非本质的改进均属于本发明的保护范围。The technical solution in the embodiment of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiment of the present invention. The embodiments described below are only part of the present invention, not all of them. Some non-essential improvements made by those skilled in the art according to the above contents of the present invention belong to the protection scope of the present invention.

本发明的目的是，提供一种高效太阳能固氮光催化剂，同时提供一种制备所述光催化剂的方法。The object of the present invention is to provide a high-efficiency solar nitrogen fixation photocatalyst and a method for preparing the photocatalyst.

本发明中将20ml～40ml醇溶液加热至120℃～200℃，降温至60℃～120℃。所述醇溶液包括但不限于乙二醇或丙三醇。In the present invention, 20ml to 40ml of alcohol solution is heated to 120°C to 200°C, and cooled to 60°C to 120°C. The alcohol solution includes but is not limited to ethylene glycol or glycerol.

将0.2g～2.0g含铋化合物和0.05g～0.5g含溴化合物加入热的醇溶液，混合并充分搅拌，搅拌时间为10～35min。含铋化合物包括但不限于五水合硝酸铋、氯化铋或铋离子络合物。含溴化合物包括但不限于溴化纳、溴化钾或CTAB。Add 0.2g-2.0g bismuth-containing compound and 0.05g-0.5g bromine-containing compound into the hot alcohol solution, mix and fully stir for 10-35min. Bismuth-containing compounds include, but are not limited to, bismuth nitrate pentahydrate, bismuth chloride, or bismuth ion complexes. Bromine-containing compounds include, but are not limited to, sodium bromide, potassium bromide, or CTAB.

本发明中将上述溶液搅拌至澄清溶液后加入60ml～120ml中性溶液，所得溶液搅拌后装入高压反应釜，进行100℃～180℃恒温水热反应8h以上。所述中性溶液包括但不限于水、乙醇或异丙醇。产品冷却至室温进行离心分离并用水和乙醇溶液洗3次～5次，干燥在50℃～80℃后研磨至粉末。其中，合成反应时，填充溶液的体积占高压釜内衬体积的比例为50％～90％；反应时间为8～24h。In the present invention, the above solution is stirred to a clear solution, then 60ml-120ml of neutral solution is added, and the obtained solution is stirred and put into an autoclave, and subjected to constant temperature hydrothermal reaction at 100°C-180°C for more than 8 hours. The neutral solution includes but is not limited to water, ethanol or isopropanol. The product is cooled to room temperature, centrifuged, washed with water and ethanol solution for 3 to 5 times, dried at 50°C to 80°C, and ground to powder. Wherein, during the synthesis reaction, the volume of the filling solution accounts for 50% to 90% of the volume of the inner lining of the autoclave; the reaction time is 8 to 24 hours.

在100℃～300℃、300～380ml/min氢气氛围下煅烧2h～6h，得到最终产品H-BiOBr。Calcining at 100°C-300°C and 300-380ml/min hydrogen atmosphere for 2h-6h to obtain the final product H-BiOBr.

与现有光催化技术相比，本发明具有如下优势：Compared with the existing photocatalytic technology, the present invention has the following advantages:

(1)本发明获得的H-BiOBr光催化材料，不仅具有卓越的光催化固氮性能，而且拥有极高的量子效率。在太阳光下以水作为反应剂，每小时每克催化剂可产生180～400μmol氨气，是传统BiOBr产量的2.6倍。相应的在380nm单色光下量子效率达到3.5～4.5％。在自然条件下显示了极好的固氮效果，具有应用前景。(1) The H-BiOBr photocatalytic material obtained in the present invention not only has excellent photocatalytic nitrogen fixation performance, but also has extremely high quantum efficiency. Using water as a reactant under sunlight, 180-400 μmol of ammonia gas can be produced per gram of catalyst per hour, which is 2.6 times that of traditional BiOBr. Correspondingly, the quantum efficiency reaches 3.5-4.5% under 380nm monochromatic light. It shows excellent nitrogen fixation effect under natural conditions and has application prospects.

(2)H-BiOBr光催化材料的制备方法绿色、无毒、便捷、廉价，无需特殊设备，可控性强，具有实用性。(2) The preparation method of H-BiOBr photocatalytic material is green, non-toxic, convenient and cheap, without special equipment, strong controllability and practicality.

实施例1Example 1

将40ml乙二醇溶液加热至160℃，降温至120℃。1.92g五水合硝酸铋和0.416g溴化钠加入上述溶液，混合并充分搅拌35min至澄清溶液后加入120ml异丙醇溶液，所得溶液搅拌30min后装入1～2Mpa高压反应釜，进行160℃恒温水热反应12h。产品冷却至室温进行离心分离并用水和乙醇溶液洗5次，干燥在60℃后研磨至粉末。在200℃、360ml/min氢气氛围下煅烧4h，得到最终产品H-BiOBr。Heat 40ml of ethylene glycol solution to 160°C and cool down to 120°C. 1.92g of bismuth nitrate pentahydrate and 0.416g of sodium bromide were added to the above solution, mixed and fully stirred for 35 minutes to a clear solution, then 120ml of isopropanol solution was added, the resulting solution was stirred for 30 minutes, then put into a 1-2Mpa high-pressure reactor, and kept at a constant temperature of 160°C Hydrothermal reaction 12h. The product was cooled to room temperature, centrifuged and washed 5 times with water and ethanol solution, dried at 60°C and ground to powder. Calcined at 200°C and 360ml/min hydrogen atmosphere for 4h to obtain the final product H-BiOBr.

图1是本实施例获得的H-BiOBr光催化剂XRD衍射图谱，经与PDF标准卡片对比得知，所获得的为四角形相的BiOBr。Figure 1 is the XRD diffraction pattern of the H-BiOBr photocatalyst obtained in this example, and compared with the PDF standard card, it can be seen that the obtained BiOBr is a tetragonal phase.

图2是本实施例获得的H-BiOBr光催化剂扫描电镜图，所获的为片聚合而成的2.5μm中空花球。Fig. 2 is a scanning electron microscope image of the H-BiOBr photocatalyst obtained in this example, and the obtained one is a 2.5 μm hollow curd formed by sheet polymerization.

图3是本实施例获得的H-BiOBr光催化剂UV-vis吸收光谱，相比于纯相BiOBr吸收边红移，在可见光范围内吸光度显著提升，有较强的光吸收范围，同时带隙也相对较窄，加快了电子传输速度，从而提升光催化活性。Figure 3 is the UV-vis absorption spectrum of the H-BiOBr photocatalyst obtained in this example. Compared with the red shift of the absorption edge of the pure phase BiOBr, the absorbance in the visible light range is significantly improved, and there is a stronger light absorption range, and the band gap is also large. Relatively narrow, speeding up the electron transport speed, thereby enhancing the photocatalytic activity.

图4是本实施例获得的H-BiOBr光催化剂光电流-时间曲线图，相比于纯相BiOBr，展现了较强的光电流，说明有效分离了光生电子和空穴。Figure 4 is the photocurrent-time graph of the H-BiOBr photocatalyst obtained in this example. Compared with the pure phase BiOBr, it shows a stronger photocurrent, indicating that the photogenerated electrons and holes are effectively separated.

图5是本实施例获得的H-BiOBr光催化剂交流阻抗图，相比于纯相BiOBr，展现了较小的电阻，同时说明对于光生载流子的复合率低，较好的促进电荷转换与有效分离。Figure 5 is the AC impedance diagram of the H-BiOBr photocatalyst obtained in this example. Compared with the pure phase BiOBr, it shows a smaller resistance, and at the same time shows that the recombination rate of photogenerated carriers is low, and it is better to promote charge conversion and effective separation.

实施例2Example 2

将20ml乙二醇溶液加热至200℃，降温至60℃。0.24g五水合硝酸铋和0.052g溴化钠加入上述溶液，混合并充分搅拌30min至澄清溶液后加入60ml异丙醇溶液，所得溶液搅拌30min后装入高压反应釜，进行160℃恒温水热反应20h。产品冷却至室温进行离心分离并用水和乙醇溶液洗5次，干燥在60℃后研磨至粉末。在150℃、360ml/min氢气氛围下煅烧4h，得到最终产品H-BiOBr。Heat 20ml of ethylene glycol solution to 200°C and cool down to 60°C. Add 0.24g of bismuth nitrate pentahydrate and 0.052g of sodium bromide to the above solution, mix and stir thoroughly for 30 minutes until the solution becomes clear, then add 60ml of isopropanol solution, stir the resulting solution for 30 minutes, put it into a high-pressure reactor, and perform a constant temperature hydrothermal reaction at 160°C 20h. The product was cooled to room temperature, centrifuged and washed 5 times with water and ethanol solution, dried at 60°C and ground to powder. Calcined at 150°C and 360ml/min hydrogen atmosphere for 4h to obtain the final product H-BiOBr.

实施例3Example 3

将20ml乙二醇溶液加热至200℃，降温至60℃。0.24g五水合硝酸铋和0.052g溴化钠加入上述溶液，混合并充分搅拌30min至澄清溶液后加入60ml异丙醇溶液，所得溶液搅拌30min后装入高压反应釜，进行160℃恒温水热反应20h。产品冷却至室温进行离心分离并用水和乙醇溶液洗5次，干燥在60℃后研磨至粉末。在150℃、360ml/min氢气氛围下煅烧2h，得到最终产品H-BiOBr。Heat 20ml of ethylene glycol solution to 200°C and cool down to 60°C. Add 0.24g of bismuth nitrate pentahydrate and 0.052g of sodium bromide to the above solution, mix and stir thoroughly for 30 minutes until the solution becomes clear, then add 60ml of isopropanol solution, stir the resulting solution for 30 minutes, then put it into an autoclave, and conduct a constant temperature hydrothermal reaction at 160°C 20h. The product was cooled to room temperature, centrifuged and washed 5 times with water and ethanol solution, dried at 60°C and ground to powder. Calcined at 150°C and 360ml/min hydrogen atmosphere for 2h to obtain the final product H-BiOBr.

实施例4Example 4

将1.92g五水合硝酸铋和0.416g溴化钠在室温下加入乙二醇溶液，混合并充分搅拌35min至澄清溶液后加入120ml异丙醇溶液，所得溶液搅拌30min后装入高压反应釜，进行160℃恒温水热反应12h。产品冷却至室温进行离心分离并用水和乙醇溶液洗5次，干燥在60℃后研磨至粉末。得到最终产品为纯相BiOBr。Add 1.92g of bismuth nitrate pentahydrate and 0.416g of sodium bromide to the ethylene glycol solution at room temperature, mix and fully stir for 35 minutes to a clear solution, then add 120ml of isopropanol solution, stir the resulting solution for 30 minutes, then put it into a high-pressure reactor, and carry out 160°C constant temperature hydrothermal reaction for 12h. The product was cooled to room temperature, centrifuged and washed 5 times with water and ethanol solution, dried at 60°C and ground to powder. The final product is pure phase BiOBr.

对于实施例1～4样品进行光催化固氮测试。The photocatalytic nitrogen fixation test was carried out for the samples of Examples 1-4.

所有的光催化实验在室温下用300W氙灯模拟太阳光执行。对于光催化固氮过程：在玻璃固氮反应器中加入0.02g催化剂和100ml去离子水，并通入循环水以维持室温。混合溶液通入氮气65ml/min在黑暗下搅拌30min，在光照下每30min抽出5ml溶液。进一步用0.22μm滤头过滤，并滴入纳氏试剂在紫外分光光度计420nm下测定吸光度。All photocatalytic experiments were performed at room temperature with a 300 W xenon lamp simulating sunlight. For the photocatalytic nitrogen fixation process: add 0.02g catalyst and 100ml deionized water into the glass nitrogen fixation reactor, and pass circulating water to maintain room temperature. The mixed solution was passed through nitrogen gas at 65ml/min and stirred for 30min in the dark, and 5ml of the solution was extracted every 30min under the light. It was further filtered with a 0.22 μm filter head, and Nessler's reagent was added dropwise to measure the absorbance at 420 nm with a UV spectrophotometer.

图6展示了实施例1～4催化剂的3小时光催化固氮效果。很明显，实施例1催化剂显示了最佳的光催化固氮效果，3小时达到了216.5μmol/L。实施例2催化剂为123μmol/L，实施例3催化剂为105.75μmol/L，而未经氢化处理的实施例4催化剂为85.75μmol/L。从而看出，本发明的H-BiOBr光催化剂拥有卓越的光催化固氮效果。Figure 6 shows the 3-hour photocatalytic nitrogen fixation effect of the catalysts of Examples 1-4. Obviously, the catalyst of Example 1 showed the best photocatalytic nitrogen fixation effect, reaching 216.5 μmol/L in 3 hours. The catalyst in Example 2 is 123 μmol/L, the catalyst in Example 3 is 105.75 μmol/L, and the catalyst in Example 4 without hydrotreatment is 85.75 μmol/L. Thus it can be seen that the H-BiOBr photocatalyst of the present invention has an excellent photocatalytic nitrogen fixation effect.

为了更好的利用BiOBr进行固氮光催化反应，本发明采用了低温氢气煅烧的方法，成功制备了具有大量氧空位的花球状的BiOBr空腔微球。以水作为还原剂下，呈现了极好的光催化固氮性能。由于氢气的还原性质，氢化过程会使纳米颗粒表面混乱从而移除氧原子。这是一种简易的方法去制造氧空位并控制氧空位的量。同时，空腔微球结构拥有一个高的氢气存储能力，利用这种方法在太阳光照射下展现了卓越的吸收能力。另外，在光催化体系中，激子、光子、氮分子有效的能量耦合，使光催化太阳能驱动氮气固定展现了意想不到的性能。In order to better utilize BiOBr for nitrogen fixation photocatalytic reaction, the present invention adopts the method of low-temperature hydrogen calcination, and successfully prepares flower-shaped BiOBr cavity microspheres with a large number of oxygen vacancies. With water as the reducing agent, it exhibits excellent photocatalytic nitrogen fixation performance. Due to the reducing nature of hydrogen, the hydrogenation process clutters the surface of the nanoparticles and removes oxygen atoms. This is an easy way to create oxygen vacancies and control the amount of oxygen vacancies. At the same time, the cavity microsphere structure possesses a high hydrogen storage capacity, and exhibits excellent absorption capacity under sunlight irradiation by this method. In addition, in the photocatalytic system, the effective energy coupling of excitons, photons, and nitrogen molecules makes the photocatalytic solar-driven nitrogen fixation exhibit unexpected performance.

以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Anyone familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (10)

1.一种太阳能固氮光催化剂，其特征在于，催化剂为氢化溴氧化铋，分子式H-BiOBr。1. A solar nitrogen fixation photocatalyst is characterized in that the catalyst is bismuth oxybromide, molecular formula H-BiOBr. 2.根据权利要求1所述太阳能固氮光催化剂，其特征在于，呈具有氧空位的花球状空腔微球结构。2 . The solar nitrogen fixation photocatalyst according to claim 1 , characterized in that, it has a flower-shaped hollow microsphere structure with oxygen vacancies. 3 . 3.一种催化剂的用途，其特征在于，用于太阳能固氮光催化。3. A use of a catalyst, characterized in that it is used for solar nitrogen fixation photocatalysis. 4.一种催化剂的应用，其特征在于，应用于以水作为还原剂的太阳能固氮光催化反应。4. The application of a catalyst, characterized in that it is applied to the solar nitrogen fixation photocatalytic reaction using water as a reducing agent. 5.一种太阳能固氮光催化剂的制备方法，其特征在于，包括如下步骤：5. A preparation method of solar nitrogen fixation photocatalyst, is characterized in that, comprises the steps: S1、取60～120℃的乙二醇、异丙醇或丙三醇溶液；S1. Take ethylene glycol, isopropanol or glycerin solution at 60-120°C; S2、将含铋化合物和含溴化合物加入所述醇溶液，混合并充分搅拌；S2, adding bismuth-containing compound and bromine-containing compound to the alcohol solution, mixing and fully stirring; S3、搅拌至澄清溶液后加入中性溶液，搅拌后装入压力为1～2Mpa的高压反应釜中，进行100～180℃恒温反应；S3. After stirring until the solution becomes clear, add a neutral solution, and after stirring, put it into a high-pressure reactor with a pressure of 1-2Mpa, and perform a constant temperature reaction at 100-180°C; S4、冷却至室温进行离心分离并用水和乙醇溶液多次洗涤，在50～80℃干燥后，研磨至粉末；S4. Cool to room temperature, perform centrifugation, wash with water and ethanol solution several times, dry at 50-80°C, and grind to powder; S5、在100～300℃、300～380ml/min氢气氛围下煅烧2～6h，得到氢化溴氧化铋。S5. Calcining at 100-300° C. and 300-380 ml/min hydrogen atmosphere for 2-6 hours to obtain hydrogenated bismuth oxybromide. 6.根据权利要求5所述太阳能固氮光催化剂的制备方法，其特征在于，步骤S2中，所述含铋化合物为五水合硝酸铋、氯化铋或铋离子络合物；所述含溴化合物为溴化纳、溴化钾或CTAB。6. according to the preparation method of the described solar nitrogen fixation photocatalyst of claim 5, it is characterized in that, in step S2, described bismuth-containing compound is bismuth nitrate pentahydrate, bismuth chloride or bismuth ion complex; Described bromine-containing compound It is sodium bromide, potassium bromide or CTAB. 7.根据权利要求5所述太阳能固氮光催化剂的制备方法，其特征在于，步骤S3中，所述中性溶液为水、乙醇或异丙醇。7. The preparation method of solar nitrogen fixation photocatalyst according to claim 5, characterized in that, in step S3, the neutral solution is water, ethanol or isopropanol. 8.根据权利要求5～7任一所述太阳能固氮光催化剂的制备方法，其特征在于，包括以下步骤：8. According to the preparation method of the solar nitrogen fixation photocatalyst described in any one of claims 5 to 7, it is characterized in that, comprising the following steps: S1、将20ml～40ml乙二醇、异丙醇或丙三醇溶液加热至120℃～200℃，降温至60℃～120℃；S1. Heat 20ml to 40ml of ethylene glycol, isopropanol or glycerol solution to 120°C to 200°C, then cool down to 60°C to 120°C; S2、将0.2g～2.0g含铋化合物和0.05g～0.5g含溴化合物加入热的醇溶液，混合并充分搅拌；S2. Add 0.2g-2.0g bismuth-containing compound and 0.05g-0.5g bromine-containing compound into the hot alcohol solution, mix and fully stir; S3、搅拌至澄清溶液后加入60ml～120ml中性溶液，所得溶液搅拌后装入高压反应釜，进行100℃～180℃恒温反应8h以上；S3. After stirring until the solution becomes clear, add 60ml-120ml neutral solution, stir the obtained solution, put it into a high-pressure reactor, and carry out constant temperature reaction at 100°C-180°C for more than 8 hours; S4、冷却至室温进行离心分离并用水和乙醇溶液洗3～5次，在50～80℃干燥后，研磨至粉末；S4. Cool to room temperature for centrifugation, wash with water and ethanol solution for 3 to 5 times, dry at 50 to 80°C, and grind to powder; S5、在100～300℃、300～380ml/min氢气氛围下煅烧2～6h，得到氢化溴氧化铋。S5. Calcining at 100-300° C. and 300-380 ml/min hydrogen atmosphere for 2-6 hours to obtain hydrogenated bismuth oxybromide. 9.根据权利要求8所述太阳能固氮光催化剂的制备方法，其特征在于，9. according to the preparation method of the described solar energy nitrogen fixation photocatalyst of claim 8, it is characterized in that, 步骤S2至S3中所述搅拌时间为10～35min。The stirring time in steps S2 to S3 is 10 to 35 minutes. 10.根据权利要求8所述太阳能固氮光催化剂的制备方法，其特征在于，步骤S3所述恒温反应时，填充溶液的体积占高压釜内衬体积的比例为50％～90％，反应时间为8～24h。10. according to the preparation method of the described solar nitrogen fixation photocatalyst of claim 8, it is characterized in that, during the constant temperature reaction described in step S3, the volume of filling solution accounts for the ratio of autoclave lining volume to be 50%～90%, and reaction time is 8～24h.
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CN109248695A (en) * 2018-09-07 2019-01-22 同济大学 A kind of Bi base shape fixed nitrogen photochemical catalyst and preparation method thereof that Lacking oxygen mediates
CN109261173A (en) * 2018-11-21 2019-01-25 大连工业大学 A kind of the solar energy fixed nitrogen method and application of hydrotreated bismuth deposit bismuth oxybromide
CN113649040A (en) * 2021-06-16 2021-11-16 华东理工大学 Preparation method and application of carbon nitride-titanium dioxide heterojunction material for efficiently synthesizing ammonia by visible light
CN114749115A (en) * 2022-03-24 2022-07-15 福州大学 Gas-phase photocatalytic nitrogen fixation reaction method
CN114956118A (en) * 2022-04-08 2022-08-30 大连理工大学 Method for reducing nitrogen into ammonia by visible light photocatalysis
CN115779936A (en) * 2022-10-26 2023-03-14 江苏科技大学 Spherical BiOBr/BiOCl composite material and preparation method and application thereof
CN116586083A (en) * 2023-07-03 2023-08-15 辽宁大学 A kind of Mo-doped BiOBr photocatalyst rich in oxygen vacancies and its preparation method and application
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CN108906085A (en) * 2018-07-17 2018-11-30 河南师范大学 A kind of Bi2S3The preparation method and applications of/BiOBr composite photocatalyst material
CN108993548A (en) * 2018-07-19 2018-12-14 大连工业大学 A kind of visible light responsive photocatalyst and application thereof, preparation method and application method
CN108993550B (en) * 2018-08-06 2021-01-29 宁夏大学 A kind of surface oxygen vacancy modified bismuth oxybromide photocatalyst and preparation method thereof
CN108993550A (en) * 2018-08-06 2018-12-14 宁夏大学 A kind of bromine oxygen bismuth photochemical catalyst and preparation method thereof that surface Lacking oxygen is modified
CN109248695B (en) * 2018-09-07 2021-09-03 同济大学 Oxygen vacancy mediated Bi-based layered nitrogen fixation photocatalyst and preparation method thereof
CN109248695A (en) * 2018-09-07 2019-01-22 同济大学 A kind of Bi base shape fixed nitrogen photochemical catalyst and preparation method thereof that Lacking oxygen mediates
CN109261173A (en) * 2018-11-21 2019-01-25 大连工业大学 A kind of the solar energy fixed nitrogen method and application of hydrotreated bismuth deposit bismuth oxybromide
CN113649040A (en) * 2021-06-16 2021-11-16 华东理工大学 Preparation method and application of carbon nitride-titanium dioxide heterojunction material for efficiently synthesizing ammonia by visible light
CN114749115A (en) * 2022-03-24 2022-07-15 福州大学 Gas-phase photocatalytic nitrogen fixation reaction method
CN114956118A (en) * 2022-04-08 2022-08-30 大连理工大学 Method for reducing nitrogen into ammonia by visible light photocatalysis
CN115779936A (en) * 2022-10-26 2023-03-14 江苏科技大学 Spherical BiOBr/BiOCl composite material and preparation method and application thereof
WO2023246306A1 (en) * 2023-02-15 2023-12-28 安徽科技学院 Preparation method for cd0.5zn0.5s and experimental method for nitrogen fixation under photocatalysis thereof
CN116586083A (en) * 2023-07-03 2023-08-15 辽宁大学 A kind of Mo-doped BiOBr photocatalyst rich in oxygen vacancies and its preparation method and application

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