CN106984312B - 一种复合型光催化剂及其制备方法 - Google Patents
一种复合型光催化剂及其制备方法 Download PDFInfo
- Publication number
- CN106984312B CN106984312B CN201710271195.7A CN201710271195A CN106984312B CN 106984312 B CN106984312 B CN 106984312B CN 201710271195 A CN201710271195 A CN 201710271195A CN 106984312 B CN106984312 B CN 106984312B
- Authority
- CN
- China
- Prior art keywords
- tio
- nanometer sheet
- preparation
- catalyst
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- -1 substituted-nitrobenzene Chemical class 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract 4
- 239000010931 gold Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical class [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明属于光催化剂的制备领域,具体涉及一种简单合成的Au‑TiO2‑Bi2WO6光催化剂及其制备方法。以TiO2纳米片作为材料核心,通过简单的静电自组装的方法将其与Bi2WO6纳米片和Au纳米粒子复合得到Au纳米粒子负载的TiO2‑Bi2WO6二维‑二维复合型光催化剂。本发明首次将Au‑TiO2‑Bi2WO6复合光催化剂用于水相光催化选择性还原取代硝基苯。合成的Au‑TiO2‑Bi2WO6光催化剂具有高催化效率和高选择性。该催化剂制备方法简单,方便回收重复利用,该复合型光催化材料在材料制备技术领域和选择性有机合成领域具有广泛地实用价值和应用前景。
Description
技术领域
本发明属于催化剂制备以及环境和能源的可持续发展领域,具体涉及一种复合型光催化剂及其制备方法。
背景技术
通过人工光合作用直接将太阳能转化为化学能为解决能源和环境危机提供了一种绿色环保的途径。这一先进技术的核心问题是设计高效的催化剂以期最大限度地吸收太阳光来产生大量的光生载流子从而驱动氧化还原反应。然而,大多数传统的半导体催化剂由于电子空穴对的复合率高而很难达到理想的太阳能利用率。半导体与半导体的复合以及半导体上的金属负载为提高电子空穴的分离效率提供了良好途径。但是单一的载流子分离途径并不能最大化的提高其分离效率,而将多种通道的载流子转移有效的结合起来则为分离效率最大化提供了新的可能。
半导体异质结是提高电子空穴分离效率的常用策略之一,其中二维-二维异质结复合光催化剂由于其良好的界面接触被认为可以实现更好的载流子分离效率。另一方面,金属粒子在半导体表面的负载可以通过转移半导体导带上的电子来促进载流子的分离;并且,对于有表面等离子共振效应(SPR)的金属粒子,比如Au和Ag,它们可以通过SPR增强效应来进一步提高光催化活性。于是,我们用两步静电自组装的方法设计合成了一个Au纳米颗粒负载的TiO2-Bi2WO6二维-二维复合光催化剂,并考察了其在光催化选择性还原芳香硝基化合物方面的应用。
发明内容
本发明的目的在于提供一种Au-TiO2-Bi2WO6复合型光催化剂及其制备方法,该催化剂易于制备,对环境友好;该Au-TiO2-Bi2WO6催化剂通过有效结合多种电子转移途径实现了高的电子空穴分离效率和光催化还原取代硝基苯到相应胺的活性。
所述的取代硝基苯及相应胺具有如下结构:
、、、、、、、、、
为实现上述目的,本发明采用如下技术方案:
一种Au-TiO2-Bi2WO6光催化剂的制备方法,包括以下步骤:
(1)TiO2纳米片的制备:将5 ml钛酸正四丁酯(Ti(OBu)4)和1 ml氢氟酸(HF)混合搅拌均匀后转移到50 ml反应釜中,在180 ℃下水热24 h,然后离心、洗涤、干燥得到TiO2纳米片;
(2)TiO2纳米片的修饰:将步骤(1)制得的TiO2纳米片用3-氨丙基三乙氧基硅烷(APTES)修饰,得到表面带正电的TiO2纳米片;
(3)Bi2WO6纳米片的制备:将1 mmol钨酸钠(Na2WO4·2H2O),2 mmol硝酸铋Bi(NO3)3·5H2O和0.05 g十六烷基三甲基溴化铵(CTAB)加入80 ml蒸馏水中,混合搅拌均匀后转移到100 mL反应釜中,在120 ℃下水热24 h,然后离心、洗涤、干燥得到Bi2WO6纳米片;
(4)Au纳米粒子的制备:将26 ml 2.8 mM柠檬酸钠(Na3C6H5O7·2H2O)溶液加入到50ml 0.4 mM氯金酸(H2AuCl4)溶液中,混合搅拌均匀,然后将5 ml 12 mM硼氢化钠(NaBH4)滴加进去,在室温条件下搅拌2 h后得到Au纳米粒子胶体溶液(Au NPs);
(5)Au-TiO2-Bi2WO6复合物的制备:将修饰后的TiO2纳米片与Bi2WO6纳米片以及Au纳米粒子按照比例混合搅拌均匀,然后离心、洗涤、干燥得到Au-TiO2-Bi2WO6复合光催化剂。
上述的步骤(4)中:所制备出的金纳米粒子胶体溶液的浓度为0.05 mg/ml。
上述的步骤(5)中复合物的制备方法为:先将TiO2纳米片与Bi2WO6纳米片复合,再将TiO2-Bi2WO6复合物与Au纳米粒子复合。
上述的Au-TiO2-Bi2WO6光催化剂中,Bi2WO6纳米片与TiO2纳米片的质量比为1:10,Au纳米粒子与TiO2-Bi2WO6复合光催化剂的质量比为1:1000,所述的Au-TiO2-Bi2WO6光催化剂在紫外-可见全波段光照射下,表现出优异的光催化还原取代对硝基苯的活性和较高的选择性;以选择性还原4-硝基苯胺为例,在紫外-可见光下照射16 min,对硝基苯胺的转化率为99%,选择性达到97%。
光催化选择性还原具体步骤如下:
(1)取10 mg Au-TiO2-Bi2WO6光催化剂、60 mg空穴捕获剂甲酸铵以及40 ml 10mg/l的取代硝基苯溶液于反应瓶中,搅拌均匀,并通入氮气(80 ml/min),在黑暗状态下吸附1.5 h,使取代硝基苯在光催化剂表面达到吸附平衡;
(2)在氮气保护下,对上述体系进行光照,每隔4 min取2 ml反应液体,反应结束后,离心,回收催化剂,溶液通过紫外-可见分光光度计和液相色谱进行分析。
本发明的显著优点在于:
(1)本发明将Au-TiO2-Bi2WO6复合型光催化剂用于光催化选择性还原取代硝基苯,具有高催化效率,对相应一种产物具有高选择性。
(2)Au-TiO2-Bi2WO6光催化剂的制备方法简单,成本低廉,便于放大生产且对环境友好。
附图说明
图1分别是空白TiO2(图1中的A图),空白Bi2WO6(图1中的B图),TiO2-Bi2WO6(图1中的C图)和Au-TiO2-Bi2WO6(图1中的D图)复合材料的透射电子显微镜(TEM)图。
图2是空白TiO2,TiO2-Bi2WO6和Au-TiO2-Bi2WO6复合材料在紫外-可见光下选择性还原对硝基苯胺活性图。
图3是空白TiO2,TiO2-Bi2WO6和Au-TiO2-Bi2WO6光电流测试图。
具体实施方式
下面将结合具体实施例进一步阐明本发明的内容,但这些实施例并不限制本发明的保护范围。
实施例1
空白TiO2的制备:
将5 ml钛酸正四丁酯(Ti(OBu)4)和1 ml氢氟酸(HF)混合搅拌均匀后转移到50 ml反应釜中,在180 ℃下水热24 h,然后离心、洗涤、干燥得到TiO2纳米片。
将10 mg TiO2纳米片光催化剂和60 mg甲酸铵加入40 ml 10 mg/l的对硝基苯胺溶液中,在黑暗条件下搅拌1 h,同时通入氮气(80 ml/min)将溶液中的空气排掉,达到吸附平衡后将其置于紫外-可见光下照射。每隔4 min从反应液中取出2 ml溶液,通过紫外-可见分光光度计和液相色谱进行分析。
实施例2
TiO2-Bi2WO6的制备:
将5 ml钛酸正四丁酯(Ti(OBu)4)和1 ml氢氟酸(HF)混合搅拌均匀后转移到50 ml反应釜中,在180 ℃下水热24 h,然后离心、洗涤、干燥得到TiO2纳米片。将所制得的TiO2纳米片(40 mg)与2 ml 3-氨丙基三乙氧基硅烷(APTES)分散到200 ml乙醇中,在60 ℃下回流4 h,然后离心、洗涤、干燥得到表面带正电的TiO2纳米片。将1 mmol钨酸钠(Na2WO4·2H2O),2 mmol硝酸铋Bi(NO3)3·5H2O和0.05 g十六烷基三甲基溴化铵(CTAB)加入80 ml蒸馏水中,混合搅拌均匀后转移到100 mL反应釜中,在120 ℃下水热24 h,然后离心、洗涤、干燥得到Bi2WO6纳米片。将超声分散均匀的Bi2WO6纳米片的水溶液(4 ml 0.5 mg/ml)缓慢滴加到超声分散均匀的正电修饰后的TiO2纳米片的水溶液(20 ml 1mg/ml),搅拌30 min,离心,洗涤和干燥得到TiO2-10%Bi2WO6样品(10%为质量分数)。
将10 mg TiO2-10%Bi2WO6复合光催化剂和60 mg甲酸铵加入40 ml 10 mg/l的对硝基苯胺溶液中,在黑暗条件下搅拌1 h,同时通入氮气(80 ml/min)将溶液中的空气排掉,达到吸附平衡后将其置于紫外-可见光下照射。每隔4 min从反应液中取出2 ml溶液,通过紫外-可见分光光度计和液相色谱进行分析。
实施例3
Au-TiO2-Bi2WO6的制备:
将5 ml钛酸正四丁酯(Ti(OBu)4)和1 ml氢氟酸(HF)混合搅拌均匀后转移到50 ml反应釜中,在180 ℃下水热24 h,然后离心、洗涤、干燥得到TiO2纳米片。将所制得的TiO2纳米片(40 mg)与2 ml 3-氨丙基三乙氧基硅烷(APTES)分散到200 ml乙醇中,在60 ℃下回流4 h,然后离心、洗涤、干燥得到表面带正电的TiO2纳米片。将1 mmol钨酸钠(Na2WO4·2H2O),2 mmol硝酸铋Bi(NO3)3·5H2O和0.05 g十六烷基三甲基溴化铵(CTAB)加入80 ml蒸馏水中,混合搅拌均匀后转移到100 mL反应釜中,在120 ℃下水热24 h,然后离心、洗涤、干燥得到Bi2WO6纳米片。将26 ml 2.8 mM柠檬酸钠(Na3C6H5O7·2H2O)溶液加入到50 ml 0.4 mM氯金酸(H2AuCl4)溶液中,混合搅拌均匀,然后将5 ml 12 mM硼氢化钠(NaBH4)滴加进去,在室温条件下搅拌2 h后得到Au纳米粒子胶体溶液(Au NPs)。将超声分散均匀的Bi2WO6纳米片的水溶液(4 ml 0.5 mg/ml)缓慢滴加到超声分散均匀的正电修饰后的TiO2纳米片的水溶液(20ml 1 mg/ml),搅拌30 min,离心,洗涤和干燥得到TiO2-10%Bi2WO6样品。将Au纳米粒子胶体溶液(1ml 0.05 mg/ml)缓慢滴加到超声分散均匀的TiO2-10%Bi2WO6的水溶液(50 ml 1 mg/ml),搅拌30 min,离心,洗涤和干燥得到0.1%Au-TiO2-10%Bi2WO6样品(0.1%和10%为质量分数)。
将10 mg 0.1%Au-TiO2-10%Bi2WO6复合光催化剂和60 mg甲酸铵加入40 ml 10 mg/l的对硝基苯胺溶液中,在黑暗条件下搅拌1 h,同时通入氮气(80 ml/min)将溶液中的空气排掉,达到吸附平衡后将其置于紫外-可见光下照射。每隔4 min从反应液中取出2 ml溶液,通过紫外-可见分光光度计和液相色谱进行分析。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (3)
1.一种复合型光催化剂的制备方法,其特征在于:所述光催化剂为Au-TiO2-Bi2WO6复合型光催化剂,其是通过TiO2纳米片与Bi2WO6纳米片复合的二维-二维异质结构材料并负载Au纳米粒子得到的;所述的催化剂中,Bi2WO6纳米片与TiO2纳米片的质量比为1:10,Au纳米粒子与TiO2-Bi2WO6复合的二维-二维异质结构材料的质量比为1:1000;包括以下步骤:
(1)TiO2纳米片的制备:将5 ml钛酸正四丁酯和1 ml氢氟酸混合搅拌均匀后转移到50ml反应釜中,在180℃下水热24 h,然后离心、洗涤、干燥得到TiO2纳米片;
(2)TiO2纳米片的修饰:将步骤(1)制得的TiO2纳米片用3-氨丙基三乙氧基硅烷修饰,得到表面带正电的TiO2纳米片;
(3)Bi2WO6纳米片的制备:将1 mmol钨酸钠,2 mmol硝酸铋和0.05 g十六烷基三甲基溴化铵加入80 ml蒸馏水中,混合搅拌均匀后转移到100 mL反应釜中,在120 ℃下水热24 h,然后离心、洗涤、干燥得到Bi2WO6纳米片;
(4)Au纳米粒子的制备:将26 ml 2.8 mM柠檬酸钠溶液加入到50 ml 0.4 mM氯金酸溶液中,混合搅拌均匀,然后将5 ml 12 mM硼氢化钠滴加进去,在室温条件下搅拌2 h后得到Au纳米粒子胶体溶液;
(5)Au-TiO2-Bi2WO6复合物的制备:将修饰后的TiO2纳米片与Bi2WO6纳米片混合,然后再与Au纳米粒子混合搅拌均匀,然后离心、洗涤、干燥得到Au-TiO2-Bi2WO6复合光催化剂。
2.根据权利要求1所述的复合型光催化剂的制备方法,其特征在于:所述的步骤(4)中制备出的Au纳米粒子胶体溶液的浓度为0.05 mg/ml。
3.一种如权利要求1所述方法制备的复合型光催化剂的应用,其特征在于:所制备的光催化剂用于光催化选择性还原取代硝基苯到相应的胺。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710271195.7A CN106984312B (zh) | 2017-04-24 | 2017-04-24 | 一种复合型光催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710271195.7A CN106984312B (zh) | 2017-04-24 | 2017-04-24 | 一种复合型光催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106984312A CN106984312A (zh) | 2017-07-28 |
CN106984312B true CN106984312B (zh) | 2019-05-10 |
Family
ID=59417044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710271195.7A Expired - Fee Related CN106984312B (zh) | 2017-04-24 | 2017-04-24 | 一种复合型光催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106984312B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107790159B (zh) * | 2017-09-28 | 2020-05-01 | 浙江理工大学 | 一种高选择性催化氧化醇成醛的光催化剂及其制备与应用 |
CN108043400B (zh) * | 2017-12-08 | 2019-10-18 | 浙江工业大学 | 一种Au-Bi2MoO6/硅藻土复合材料及其制备方法与应用 |
CN109894149B (zh) * | 2017-12-11 | 2021-11-16 | 中国科学院大连化学物理研究所 | 一种复合纳米结构催化剂及其制备和应用 |
CN112091232A (zh) * | 2020-09-11 | 2020-12-18 | 合肥工业大学 | 一种在酸性条件下快速制备Au-TiO2复合结构的方法 |
CN113289610A (zh) * | 2021-03-18 | 2021-08-24 | 合肥工业大学 | 一种Bi2WO6/Si复合光电催化阳极材料及其制备方法 |
CN114405526A (zh) * | 2021-12-29 | 2022-04-29 | 天津工业大学 | 一种二维MXene纳米片修饰多孔Au@Ag@Pd核壳结构光催化剂的制备及其应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1775351A (zh) * | 2005-10-10 | 2006-05-24 | 大连理工大学 | 一种用于硝基苯类化合物催化加氢制备芳胺的催化剂及使用方法 |
CN101623630A (zh) * | 2009-07-24 | 2010-01-13 | 中国科学院上海硅酸盐研究所 | 具有多级异质结构的Bi2WO6/氧化物纤维布、方法及应用 |
CN101658788A (zh) * | 2009-09-24 | 2010-03-03 | 西华师范大学 | 一种用于卤代芳香硝基化合物高效催化加氢绿色合成卤代芳胺的催化剂及其制备方法 |
CN102335602A (zh) * | 2010-07-21 | 2012-02-01 | 中国科学院上海硅酸盐研究所 | 一种钨酸铋复合光催化剂及其制备和应用 |
CN102824917A (zh) * | 2012-09-12 | 2012-12-19 | 天津师范大学 | 一种氧化铁/钨酸铋复合光催化剂及其制备方法与应用 |
CN103272584A (zh) * | 2013-06-18 | 2013-09-04 | 山东大学 | 一种全谱光催化剂及其制备方法 |
CN104607178A (zh) * | 2015-01-30 | 2015-05-13 | 延安大学 | 一种钨酸铋-二氧化钛异质结复合光催化材料的制备方法 |
CN105214648A (zh) * | 2015-11-09 | 2016-01-06 | 安徽理工大学 | 一种暴露面{001}TiO2/Bi2WO6的光催化材料的制备方法 |
-
2017
- 2017-04-24 CN CN201710271195.7A patent/CN106984312B/zh not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1775351A (zh) * | 2005-10-10 | 2006-05-24 | 大连理工大学 | 一种用于硝基苯类化合物催化加氢制备芳胺的催化剂及使用方法 |
CN101623630A (zh) * | 2009-07-24 | 2010-01-13 | 中国科学院上海硅酸盐研究所 | 具有多级异质结构的Bi2WO6/氧化物纤维布、方法及应用 |
CN101658788A (zh) * | 2009-09-24 | 2010-03-03 | 西华师范大学 | 一种用于卤代芳香硝基化合物高效催化加氢绿色合成卤代芳胺的催化剂及其制备方法 |
CN102335602A (zh) * | 2010-07-21 | 2012-02-01 | 中国科学院上海硅酸盐研究所 | 一种钨酸铋复合光催化剂及其制备和应用 |
CN102824917A (zh) * | 2012-09-12 | 2012-12-19 | 天津师范大学 | 一种氧化铁/钨酸铋复合光催化剂及其制备方法与应用 |
CN103272584A (zh) * | 2013-06-18 | 2013-09-04 | 山东大学 | 一种全谱光催化剂及其制备方法 |
CN104607178A (zh) * | 2015-01-30 | 2015-05-13 | 延安大学 | 一种钨酸铋-二氧化钛异质结复合光催化材料的制备方法 |
CN105214648A (zh) * | 2015-11-09 | 2016-01-06 | 安徽理工大学 | 一种暴露面{001}TiO2/Bi2WO6的光催化材料的制备方法 |
Non-Patent Citations (2)
Title |
---|
Enhanced photocatalytic activities of visible-light driven green synthesis in water and environmental remediation on Au/Bi2WO6 hybrid nanostructures;Juan Yang等;《RSC Advances》;20150107;第5卷;摘要 |
Fabrication of TiO2−Bi2WO6 Binanosheet for Enhanced Solar Photocatalytic Disinfection of E. coli: Insights on the Mechanism;Yanan Jia等;《ACS Applied Materials Interfaces》;20160224;第8卷;摘要,第6844页3.1节 |
Also Published As
Publication number | Publication date |
---|---|
CN106984312A (zh) | 2017-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106984312B (zh) | 一种复合型光催化剂及其制备方法 | |
CN105413712B (zh) | 金纳米棒‑CdS‑金纳米粒子复合光催化剂和应用 | |
CN107233924B (zh) | 巯基修饰的金属有机骨架化合物催化剂的制备及应用 | |
CN107233906A (zh) | 一种还原氧化石墨烯/钒酸铋/氮化碳复合材料的制备方法及用途 | |
CN105935594B (zh) | 一种碘氧化铋/氮掺石墨烯复合光催化剂及其制备方法 | |
CN101653732B (zh) | 一种分子筛负载卤氧化铋光催化剂、制备方法及其应用 | |
CN106238085A (zh) | 一种氧掺杂碳化氮‑贵金属复合光催化剂、制备方法及应用 | |
CN108786792B (zh) | 一种金属/半导体复合光催化剂及其制备与应用 | |
CN109201065A (zh) | 一种泡沫镍复合材料及其制备方法与在光电催化去除水体污染物中的应用 | |
CN107020143A (zh) | 一种可见光响应三元复合光催化剂的制备方法和用途 | |
CN106890654A (zh) | 一种溴化氧铋/钼酸铋异质结光催化剂及制备与应用 | |
Deng et al. | The facile boosting sunlight-driven photocatalytic performance of a metal–organic-framework through coupling with Ag 2 S nanoparticles | |
CN109126784B (zh) | 一种可见光-近红外光响应的金属纳米粒子/二氧化硅复合光催化剂 | |
CN107469804A (zh) | 一种纳米颗粒铋负载的二氧化钛基复合光催化材料及其制备方法和应用 | |
CN105056973B (zh) | 化学腐蚀法原位生长制备高效的硫化铋‑铁酸铋复合可见光催化剂及其应用 | |
CN110102312A (zh) | 一种一维氧化亚铜/银/氧化锌纳米棒光催化复合材料及其制备方法与应用 | |
CN106268881B (zh) | 一种方块状Ag2MoO4@Ag@AgBr三元复合物及其制备方法和应用 | |
CN106902852A (zh) | 一种ZnFe2O4/AgBr/Ag复合光催化剂及其制备方法 | |
CN109847780A (zh) | 一种AgBr/BiOI/g-C3N4三元复合催化材料的制备方法及其应用 | |
CN108636436A (zh) | 有效构筑z型三元异质结光催化剂的制备方法 | |
CN108031475A (zh) | 一种金负载氧化铁纳米光催化剂的制备方法 | |
CN107008259A (zh) | 核壳结构纳米金团簇‑二氧化钛复合型催化剂 | |
CN107790129A (zh) | 氧化亚铜/石墨烯可见光光催化剂的制备方法及其产品和应用 | |
CN104492464B (zh) | 一种碘化银/β型氧化铋复合材料的制备方法 | |
CN106693996A (zh) | 硫化铋‑铁酸铋复合可见光催化剂的制备方法及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190510 |
|
CF01 | Termination of patent right due to non-payment of annual fee |