CN107138165B - A preparation method of supported Bi2MoO6/Cu(OH)2/graphene photocatalyst - Google Patents
A preparation method of supported Bi2MoO6/Cu(OH)2/graphene photocatalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910002900 Bi2MoO6 Inorganic materials 0.000 title claims description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 title claims 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 title claims 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 18
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000011858 nanopowder Substances 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000120 microwave digestion Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 239000003426 co-catalyst Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002800 charge carrier Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000005622 photoelectricity Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的制备方法，属于无机环保光催化材料的合成技术领域。本发明的技术方案要点为：将廉价Cu(OH)2和石墨烯负载到Bi2MoO6的表面，Cu(OH)2作为助催化剂促进电荷载流子从Bi2MoO6迁移到Cu(OH)2上，抑制了电子和空穴的复合；而具有高电子传导性的石墨烯有助于电子的传输，使更多的电子参与到制氢的反应过程中，从而提高Bi2MoO6光解水制氢的催化活性，具有巨大的潜在工业应用前景。
The invention discloses a preparation method of a loaded Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst, which belongs to the technical field of synthesis of inorganic environment-friendly photocatalytic materials. The key points of the technical solution of the present invention are: loading cheap Cu(OH) 2 and graphene on the surface of Bi 2 MoO 6 , and Cu(OH) 2 acts as a co-catalyst to promote the transfer of charge carriers from Bi 2 MoO 6 to Cu(OH) ) 2 , the recombination of electrons and holes is suppressed; while graphene with high electron conductivity facilitates the transport of electrons, so that more electrons participate in the reaction process of hydrogen production, thereby improving the photoelectricity of Bi 2 MoO 6 The catalytic activity of water splitting and hydrogen production has huge potential industrial application prospects.
Description
技术领域technical field
本发明属于无机环保光催化材料的合成技术领域，具体涉及一种负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的制备方法。The invention belongs to the technical field of synthesis of inorganic environment-friendly photocatalytic materials, and in particular relates to a preparation method of a supported Bi2MoO6 /Cu(OH )2 / graphene photocatalyst.
背景技术Background technique
近几十年来，环境污染和能源危机已成为一个直接威胁人类生存，亟需解决的焦点问题。基于无机半导体材料的光催化技术是从20世纪70年代逐步发展起来的绿色化工技术，在环境治理和能源转化等领域显示出广阔的应用前景。光催化技术的枋心是半导体材料，在众多的半导体材料中，稳定的TiO2、ZnO等常见的半导体光催化剂带隙宽，对光的吸收仅限于在紫外区，极大地限制了对太阳能的利用效率；而对可见光响应较好的光催化剂如CdS、CdSe等又存在光腐蚀现象严重等问题。此外。由于半导体光催化剂在催化反应过程中具有较高的光生载流子高复合率，导致其光催化效率和量子效率低。因此，开发和研制新型可见光响应的高效光催化剂已成为近年来半导体光催化的研究热点之一，并取得了一定的进展。In recent decades, environmental pollution and energy crisis have become a focal issue that directly threatens human existence and needs to be resolved urgently. The photocatalytic technology based on inorganic semiconductor materials is a green chemical technology gradually developed in the 1970s, showing broad application prospects in the fields of environmental governance and energy conversion. The core of photocatalytic technology is semiconductor materials. Among many semiconductor materials, common semiconductor photocatalysts such as stable TiO 2 and ZnO have wide band gaps, and their absorption of light is limited to the ultraviolet region, which greatly limits the ability to absorb solar energy. Utilization efficiency; and photocatalysts such as CdS and CdSe that respond well to visible light have problems such as serious photocorrosion. also. Due to the high recombination rate of photogenerated carriers in the catalytic reaction process of semiconductor photocatalysts, their photocatalytic efficiency and quantum efficiency are low. Therefore, the development and manufacture of new visible light-responsive high-efficiency photocatalysts has become one of the research hotspots of semiconductor photocatalysis in recent years, and some progress has been made.
在目前已开发的各类新型光催化剂中，Bi2MoO6因具有较高的可见光催化响应性能和潜在的制氢性能，而受到广泛的关注。但纯Bi2MoO6在光催化分解水的过程中存在光生电子和空穴容易复合，量子效率低的缺点，限制了其在工业上的应用。为了提高Bi2MoO6的量子效率及光解水制氢的效率，通常将金属铂作为助催剂负载在Bi2MoO6表面，从而有效降低光生电子的复合效率，进而提高Bi2MoO6光解水制氢的效率。然而，助催化剂金属铂的价格昂贵，从而限制其在工业中的应用。Among the various new photocatalysts that have been developed so far, Bi 2 MoO 6 has attracted extensive attention due to its high catalytic response performance to visible light and potential hydrogen production performance. However, pure Bi 2 MoO 6 has the disadvantages of easy recombination of photogenerated electrons and holes and low quantum efficiency in the process of photocatalytic water splitting, which limits its industrial application. In order to improve the quantum efficiency of Bi 2 MoO 6 and the efficiency of photolysis of water to produce hydrogen, metal platinum is usually loaded on the surface of Bi 2 MoO 6 as a co-catalyst, so as to effectively reduce the recombination efficiency of photogenerated electrons, thereby improving the photoluminescence of Bi 2 MoO 6 . Efficiency of splitting water to produce hydrogen. However, the high price of Pt as the cocatalyst metal limits its industrial application.
石墨烯作为结构特殊的碳材料，具有比碳纳米管更优异的导电性和化学稳定性，这使得其可以成为比碳纳米管更好的电子或空穴传递的多功能材料。近年来，利用石墨烯独特的电学性质对一些半导体材料进行修饰以制备量子效率高、催化性能好的复合半导体材料成为当前的研究热点。本发明将廉价Cu(OH)2和石墨烯负载到Bi2MoO6的表面，Cu(OH)2作为助催化剂促进电荷载流子从Bi2MoO6迁移到Cu(OH)2上，抑制了电子和空穴的复合；而具有高电子传导性的石墨烯有助于电子的传输，使更多的电子参与到制氢的反应过程中，从而提高Bi2MoO6光解水制氢的催化活性，具有巨大的潜在工业应用前景。Graphene, as a carbon material with a special structure, has better electrical conductivity and chemical stability than carbon nanotubes, which makes it a multifunctional material that can transport electrons or holes better than carbon nanotubes. In recent years, using the unique electrical properties of graphene to modify some semiconductor materials to prepare compound semiconductor materials with high quantum efficiency and good catalytic performance has become a current research hotspot. In the present invention, cheap Cu(OH) 2 and graphene are supported on the surface of Bi 2 MoO 6 , and Cu(OH) 2 acts as a co-catalyst to promote the transfer of charge carriers from Bi 2 MoO 6 to Cu(OH) 2 , suppressing the The recombination of electrons and holes; and graphene with high electron conductivity helps the transport of electrons, so that more electrons participate in the reaction process of hydrogen production, thereby improving the catalysis of Bi 2 MoO 6 photolysis of water to produce hydrogen activity and has great potential industrial application prospects.
发明内容Contents of the invention
本发明解决的技术问题是提供了一种操作简单且易于实现的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的制备方法，该方法制得的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂可见光利用率高、光量子效率高且光催化制氢活性好。The technical problem solved by the present invention is to provide a simple and easy-to-implement preparation method of supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst, the prepared supported Bi 2 MoO 6 / Cu(OH) 2 /graphene photocatalyst has high utilization rate of visible light, high photon quantum efficiency and good photocatalytic hydrogen production activity.
本发明为解决上述技术问题采用如下技术方案，一种负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的制备方法，其特征在于具体步骤为：The present invention adopts following technical scheme for solving above-mentioned technical problem, a kind of preparation method of loaded Bi2MoO6 /Cu(OH )2 / graphene photocatalyst, it is characterized in that concrete steps are:
（1）在搅拌条件下将五水合硝酸铋和二水合钼酸钠按摩尔比2:1溶于去离子水中形成硝酸铋与钼酸钠的混合溶液，在室温条件下将硝酸铋与钼酸钠的混合溶液搅拌2h后转移至水热反应釜中，然后将水热反应釜放入微波消解仪中于120℃微波反应5-30min，待反应结束后冷却、洗涤、干燥得到Bi2MoO6纳米粉体；(1) Dissolve bismuth nitrate pentahydrate and sodium molybdate dihydrate in a molar ratio of 2:1 in deionized water under stirring conditions to form a mixed solution of bismuth nitrate and sodium molybdate, and mix bismuth nitrate and molybdate at room temperature The mixed solution of sodium was stirred for 2 hours, then transferred to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus, and reacted with microwaves at 120°C for 5-30min, after the reaction was completed, cooled, washed, and dried to obtain Bi 2 MoO 6 Nano powder;
（2）配制硝酸铜溶液，在搅拌状态下向硝酸铜溶液中加入氢氧化钠、石墨烯和步骤（1）得到的Bi2MoO6纳米粉体得到混合溶液，其中氢氧化钠与硝酸铜的摩尔比为1:0.5，Bi2MoO6纳米粉体与硝酸铜的摩尔比为1:0.005-0.015，石墨烯与Bi2MoO6纳米粉体的质量比为0.03-0.15:1；(2) Prepare copper nitrate solution, add sodium hydroxide, graphene and the Bi2MoO 6 nanometer powder obtained in step (1) to the copper nitrate solution under stirring to obtain a mixed solution, wherein the sodium hydroxide and copper nitrate The molar ratio is 1:0.5, the molar ratio of Bi 2 MoO 6 nano powder to copper nitrate is 1:0.005-0.015, and the mass ratio of graphene to Bi 2 MoO 6 nano powder is 0.03-0.15:1;
（3）将步骤（2）得到的混合溶液在室温下搅拌反应6h，反应结束后过滤、干燥得到具有高催化活性的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂。(3) The mixed solution obtained in step (2) was stirred and reacted at room temperature for 6 hours, filtered and dried after the reaction to obtain a supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst with high catalytic activity.
进一步优选，所述硝酸铋与钼酸钠的混合溶液中硝酸铋的摩尔浓度为0.01-0.05mol/L。Further preferably, the molar concentration of bismuth nitrate in the mixed solution of bismuth nitrate and sodium molybdate is 0.01-0.05 mol/L.
进一步优选，所述硝酸铜溶液中硝酸铜的摩尔浓度为0.001-0.006mol/L。Further preferably, the molar concentration of copper nitrate in the copper nitrate solution is 0.001-0.006 mol/L.
本发明与现有技术相比具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、采用适宜的合成工艺制备出能带结构相匹配的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂，利用两种半导体之间的能级差能使光生载流子由一种半导体微粒的能级注入到另一种半导体微粒的能级上，从而提高光生电荷的分离效率，进而提高负载型光催化剂的制氢性能；1. Prepare a supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst with a matching energy band structure by using a suitable synthesis process, and use the energy level difference between the two semiconductors to make the photogenerated carriers from one The energy level of one semiconductor particle is injected into the energy level of another semiconductor particle, thereby improving the separation efficiency of photogenerated charges, thereby improving the hydrogen production performance of the supported photocatalyst;
2、根据微波水热法加热速率快和溶液受热均匀等特点，采用微波水热法制备出的晶粒粒度小且团聚程度低的高活性Bi2MoO6纳米粉体，有效提高了负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的活性；2. According to the characteristics of fast heating rate and uniform heating of the solution by the microwave hydrothermal method, the highly active Bi 2 MoO 6 nanopowder with small grain size and low degree of agglomeration was prepared by the microwave hydrothermal method, which effectively improved the loading Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst activity;
3、采用廉价的Cu(OH)2助催化剂代替昂贵的金属铂，从而有效降低了负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的生产成本，提升其工业应用前景。3. The use of cheap Cu(OH) 2 co-catalysts to replace expensive metal platinum effectively reduces the production cost of supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalysts and enhances its industrial application prospects.
附图说明Description of drawings
图1为300W氙灯照射下，本发明实施例1所制备的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂和纯Bi2MoO6光催化剂的光催化分解水制氢效率柱形图（操作条件：催化剂的量：0.05g；牺牲剂三乙醇胺的量：10mL）。从图中可以看出，在模拟可见光的照射下，光照6h后，负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂的产氢效率明显高于纯Bi2MoO6光催化剂的产氢效率，表现出明显增强的光催化活性。Fig. 1 is a 300W xenon lamp irradiation, the photocatalytic water splitting hydrogen production efficiency column of the supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst and pure Bi 2 MoO 6 photocatalyst prepared in Example 1 of the present invention Diagram (operating conditions: amount of catalyst: 0.05g; amount of sacrificial agent triethanolamine: 10mL). It can be seen from the figure that under the irradiation of simulated visible light, the hydrogen production efficiency of the supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst is significantly higher than that of the pure Bi 2 MoO 6 photocatalyst after 6 hours of illumination. Hydrogen production efficiency, showing significantly enhanced photocatalytic activity.
具体实施方式Detailed ways
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。The above content of the present invention will be described in further detail below through the embodiments, but this should not be interpreted as the scope of the above subject of the present invention is limited to the following embodiments, all technologies realized based on the above content of the present invention all belong to the scope of the present invention.
实施例1Example 1
（1）在搅拌条件下将0.01mol五水合硝酸铋和0.005mol二水合钼酸钠溶于1000mL去离子水中形成硝酸铋与钼酸钠的混合溶液，在室温条件下将硝酸铋与钼酸钠的混合溶液搅拌2h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于120℃微波反应5min，待反应结束后冷却、洗涤、干燥得到Bi2MoO6纳米粉体；(1) Dissolve 0.01mol bismuth nitrate pentahydrate and 0.005mol sodium molybdate dihydrate in 1000mL deionized water under stirring conditions to form a mixed solution of bismuth nitrate and sodium molybdate, and mix bismuth nitrate and sodium molybdate at room temperature After the mixed solution was stirred for 2 hours, it was transferred to a hydrothermal reaction kettle, and then the hydrothermal reaction kettle was put into a microwave digestion apparatus for microwave reaction at 120°C for 5 minutes. After the reaction was completed, it was cooled, washed, and dried to obtain Bi 2 MoO 6 nanometer powder;
（2）配制0.001mol/L的硝酸铜溶液25mL，在搅拌状态下向硝酸铜溶液中加入0.002g氢氧化钠、0.673g石墨烯和5mmol步骤（1）得到的Bi2MoO6纳米粉体得到混合溶液；(2) Prepare 25mL of 0.001mol/L copper nitrate solution, add 0.002g sodium hydroxide, 0.673g graphene and 5mmol of Bi 2 MoO 6 nanopowder obtained in step (1) to the copper nitrate solution under stirring to obtain mixture;
（3）将步骤（2）得到的混合溶液在室温下搅拌反应6h，反应结束后过滤、干燥得到具有高催化活性的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂。(3) The mixed solution obtained in step (2) was stirred and reacted at room temperature for 6 hours, filtered and dried after the reaction to obtain a supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst with high catalytic activity.
实施例2Example 2
（1）在搅拌条件下将0.02mol五水合硝酸铋和0.01mol二水合钼酸钠溶于1000mL去离子水中形成硝酸铋与钼酸钠的混合溶液，在室温条件下将硝酸铋与钼酸钠的混合溶液搅拌2h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于120℃微波反应10min，待反应结束后冷却、洗涤、干燥得到Bi2MoO6纳米粉体；(1) Dissolve 0.02mol bismuth nitrate pentahydrate and 0.01mol sodium molybdate dihydrate in 1000mL deionized water under stirring conditions to form a mixed solution of bismuth nitrate and sodium molybdate, and mix bismuth nitrate and sodium molybdate at room temperature After the mixed solution was stirred for 2 hours, it was transferred to a hydrothermal reaction kettle, and then the hydrothermal reaction kettle was put into a microwave digestion apparatus for microwave reaction at 120°C for 10 minutes. After the reaction was completed, it was cooled, washed, and dried to obtain Bi 2 MoO 6 nanometer powder;
（2）配制0.002mol/L的硝酸铜溶液75mL，在搅拌状态下向硝酸铜溶液中加入0.012g氢氧化钠、0.673g石墨烯和10mmol步骤（1）得到的Bi2MoO6纳米粉体得到混合溶液；(2) Prepare 75mL of 0.002mol/L copper nitrate solution, add 0.012g sodium hydroxide, 0.673g graphene and 10mmol Bi 2 MoO 6 nanopowder obtained in step (1) to the copper nitrate solution under stirring to obtain mixture;
（3）将步骤（2）得到的混合溶液在室温下搅拌反应6h，反应结束后过滤、干燥得到具有高催化活性的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂。(3) The mixed solution obtained in step (2) was stirred and reacted at room temperature for 6 hours, filtered and dried after the reaction to obtain a supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst with high catalytic activity.
实施例3Example 3
（1）在搅拌条件下将0.05mol五水合硝酸铋和0.025mol二水合钼酸钠溶于1000mL去离子水中形成硝酸铋与钼酸钠的混合溶液，在室温条件下将硝酸铋与钼酸钠的混合溶液搅拌2h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于120℃微波反应30min，待反应结束后冷却、洗涤、干燥即可得到Bi2MoO6纳米粉体；(1) Dissolve 0.05mol bismuth nitrate pentahydrate and 0.025mol sodium molybdate dihydrate in 1000mL deionized water under stirring conditions to form a mixed solution of bismuth nitrate and sodium molybdate, and mix bismuth nitrate and sodium molybdate at room temperature After the mixed solution was stirred for 2 hours, it was transferred to a hydrothermal reaction kettle, and then the hydrothermal reaction kettle was put into a microwave digestion apparatus for microwave reaction at 120°C for 30 minutes. After the reaction was completed, Bi 2 MoO 6 nanometer powder could be obtained by cooling, washing and drying. body;
（2）配制0.006mol/L的硝酸铜溶液50mL，在搅拌状态下向硝酸铜溶液中加入0.024g氢氧化钠、0.673g石墨烯和25mmol步骤（1）得到的Bi2MoO6纳米粉体得到混合溶液；(2) Prepare 50mL of 0.006mol/L copper nitrate solution, add 0.024g sodium hydroxide, 0.673g graphene and 25mmol of Bi 2 MoO 6 nanopowder obtained in step (1) to the copper nitrate solution under stirring to obtain mixture;
（3）将步骤（2）得到的混合溶液在室温下搅拌反应6h，反应结束后过滤、干燥得到具有高催化活性的负载型Bi2MoO6/Cu(OH)2/石墨烯光催化剂。(3) The mixed solution obtained in step (2) was stirred and reacted at room temperature for 6 hours, filtered and dried after the reaction to obtain a supported Bi 2 MoO 6 /Cu(OH) 2 /graphene photocatalyst with high catalytic activity.
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What are described in the above embodiments and description are only to illustrate the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the protection scope of the present invention.
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| CN103721713A (en) * | 2014-01-07 | 2014-04-16 | 福州大学 | Three-phase composite visible-light-driven photocatalyst capable of efficiently degrading dyes |
| CN104607200A (en) * | 2015-01-05 | 2015-05-13 | 延安大学 | Copper/bismuth tungstate composite photocatalytic material and preparation method thereof |
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