CN114797920A - Cu-Mo双金属纳米复合材料及其应用 - Google Patents
Cu-Mo双金属纳米复合材料及其应用 Download PDFInfo
- Publication number
- CN114797920A CN114797920A CN202210464448.3A CN202210464448A CN114797920A CN 114797920 A CN114797920 A CN 114797920A CN 202210464448 A CN202210464448 A CN 202210464448A CN 114797920 A CN114797920 A CN 114797920A
- Authority
- CN
- China
- Prior art keywords
- reaction
- composite material
- nano composite
- bimetal nano
- nitrophenol
- 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.)
- Granted
Links
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- -1 benzyl bromide compound Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000007333 cyanation reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 4
- 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 2
- 239000007788 liquid Substances 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000002474 experimental method Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical class BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- NVNPLEPBDPJYRZ-UHFFFAOYSA-N 1-(bromomethyl)-4-fluorobenzene Chemical compound FC1=CC=C(CBr)C=C1 NVNPLEPBDPJYRZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- WZRKSPFYXUXINF-UHFFFAOYSA-N 1-(bromomethyl)-4-methylbenzene Chemical compound CC1=CC=C(CBr)C=C1 WZRKSPFYXUXINF-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- LZIYAIRGDHSVED-UHFFFAOYSA-N 1-(bromomethyl)-3-chlorobenzene Chemical compound ClC1=CC=CC(CBr)=C1 LZIYAIRGDHSVED-UHFFFAOYSA-N 0.000 description 2
- KQNBRMUBPRGXSL-UHFFFAOYSA-N 1-(bromomethyl)-4-chlorobenzene Chemical compound ClC1=CC=C(CBr)C=C1 KQNBRMUBPRGXSL-UHFFFAOYSA-N 0.000 description 2
- BQTRMYJYYNQQGK-UHFFFAOYSA-N 1-(bromomethyl)-4-iodobenzene Chemical compound BrCC1=CC=C(I)C=C1 BQTRMYJYYNQQGK-UHFFFAOYSA-N 0.000 description 2
- GIGRWGTZFONRKA-UHFFFAOYSA-N 1-(bromomethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CBr)C=C1 GIGRWGTZFONRKA-UHFFFAOYSA-N 0.000 description 2
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 description 2
- VOLRSQPSJGXRNJ-UHFFFAOYSA-N 4-nitrobenzyl bromide Chemical compound [O-][N+](=O)C1=CC=C(CBr)C=C1 VOLRSQPSJGXRNJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了Cu‑Mo双金属纳米复合材料,它是由下述方法制备的:将Cu(NO3)2·3H2O与H3PMo12O40溶于水;将2‑甲基咪唑溶解于水;混合,搅拌,加热反应1h~5h,得到褐色沉淀;将褐色沉淀离心收集,清洗,得褐色固体;干燥,得到Cu‑Mo双金属纳米复合材料;Cu‑Mo双金属纳米复合材料在催化有机物方面的应用;结果表明催化对硝基苯酚过程中始终漂浮在溶液表面,反应结束后,可直接方便回收,成功进行至少18次催化循环实验后,转化率依旧可以达到97%;催化溴化苄化合物的氰化反应的产物收率高,转率可以达到98%;优点在于:催化降解效果好,易于回收、可循环反应,产物收率高、底物范围广。
Description
技术领域
本发明属于纳米材料技术领域,具体涉及Cu-Mo双金属纳米复合材料及其应用。
背景技术
有机合成中的氰化反应是指在反应分子中引入一个氰基,生成各种氰化物。例如,芳基乙腈是一种重要的氰化物,它是化学研究中常见的结构基序,应用范围相当广泛,是合成羧酸、酰胺、醛和含氮杂环化合物的重要单元,或用于合成的中间体以及各种杂化侧键取代芳烃的官能团的转化等。在过去的几十年里,有机化学家通常使用贵金属作为各种氰化反应的催化剂。由于贵金属催化剂价格昂贵、经常需要额外的配体,并且部分贵金属对氰化物有很高的亲和力,易使催化剂中毒,使反应催化成本更高。因此寻找一种具有易获得、价格低廉和反应条件温和等优点的催化剂,更有利于研究的发展及应用的需要。
对硝基苯酚,是农业和工业制造过程中大量产生的有毒有机污染物之一,其在水介质中具有高溶解度和高稳定性,会对环境和人体健康造成危害。因此,迫切需要将对硝基苯酚转化为更良性的产品。目前,去除环境中硝基苯酚的方法很多,如超声波增强氧化、电化学氧化、催化臭氧氧化、光催化降解等。然而,繁琐的加工步骤和高昂的成本极大地限制了这些方法的实际应用。另一方面,将硝基苯酚催化还原为氨基衍生物是去除环境中有毒硝基化合物的替代和新兴工艺。 还原产物氨基苯酚是一种对环境无毒的化合物,且广泛用作合成解热剂、缓蚀剂、染料和颜料的中间体。 因此,催化还原在还原硝基苯酚方面越来越受到重视。研究表明,硝基苯酚不能在没有催化剂的情况下被还原,因此有必要开发一种合适的、低成本、高效的催化剂。
发明内容
本发明目的是为解决有毒有机污染物的催化剂成本高的问题,而提供一种合适的、低成本、高效的催化剂——Cu-Mo双金属纳米复合材料及其应用。
Cu-Mo双金属纳米复合材料,它是由下述方法制备的:
1)将硝酸铜与H3PMo12O40的物质的量比为10~100:1溶于10 mL~100 mL水,形成A溶液;
2)将0.01 mol~0.1 mol 2-甲基咪唑溶解于10 mL~100 mL水,形成B溶液;
3)A溶液与B溶液混合,在20℃~200℃下搅拌15 min~30 min,加热反应1~5h,得到褐色沉淀;
4)将步骤3)所述的褐色沉淀离心收集,清洗,得褐色固体;
5)将褐色固体干燥,得到Cu-Mo双金属纳米复合材料;
步骤1)所述的Cu(NO3)2·3H2O与H3PMo12O40的物质的量比为60~100 :1;步骤2)所述的2-甲基咪唑添加量为0.03~0.1 mol;
步骤3)所述的搅拌,温度为50℃,时间15min,加热反应1h;
步骤5)所述的干燥,是在50~80℃下干燥20~30 h;
所述Cu-Mo双金属纳米复合材料呈梭形片层状形貌,厚度为15-25nm;
所述梭形片层状的结构使其密度小于水,在反应过程中漂浮在液面上,使催化剂易于循环回收。
Cu-Mo双金属纳米复合材料在催化有机物方面的应用;
所述的催化,是催化降解硝基酚类化合物转化为氨基酚化合物;即催化苄基卤代烃的氰基化反应;
所述的有机物为苄基卤代烃或对硝基苯酚。
Cu-Mo双金属纳米复合材料作为催化剂,可催化降解硝基酚类化合物转化为氨基酚化合物,可催化苄基卤代烃的氰基化反应,苄基卤代烃包括:氯化苄化合物,溴化苄化合物如溴化苄、4-甲基溴化苄、4-甲氧基溴化苄、4-氟溴化苄、4-氯溴化苄、对溴溴化苄、4-碘溴化苄、对硝基溴化苄、3-氯苄化溴、二苯基溴甲烷等。
本发明提供了Cu-Mo双金属纳米复合材料,它是由下述方法制备的:1)将Cu(NO3)2·3H2O与H3PMo12O40溶于水;2)将2-甲基咪唑溶解于水;3)混合,在20℃~200℃下搅拌15min~30min,加热反应1h~5h,得到褐色沉淀;4)将步骤3)所述的褐色沉淀离心收集,清洗,得褐色固体;5)将褐色固体干燥,得到Cu-Mo双金属纳米复合材料;Cu-Mo双金属纳米复合材料在催化有机物方面的应用;结果表明催化对硝基苯酚过程中始终漂浮在溶液表面,并能高效催化底物得到高转化率,反应结束后,可直接方便回收,成功进行至少18次催化循环实验;催化循环实验后转化率依旧可以达到97%;催化苄基卤代烃化合物的氰化反应的产物收率高,苄溴到苄腈、4-氟溴化苄到4-氟苄腈的转率可以达到98%;
本发明的显著优点在于:
1)避免使用重金属、成本低、原料廉价,制备方法简单、耗时短,易实现产业化生产;
2)所得到的Cu-Mo双金属纳米复合材料新颖,对有机污染物-对硝基苯酚的催化降解效果很明显、具有漂浮在溶液表面、易回收等特点,非常有利于进行催化循环实验;
3)所得到的Cu-Mo双金属纳米复合材料对4-硝基苯酚(4-NP)的催化降解效果明显,这种成本低廉,简单方便的方法可以制备其他多功能纳米多孔金属氧化物,用作催化剂降解有机污染物;
4)由催化苄基卤代烃的氰基化反应结果得知,所得到的Cu-Mo双金属纳米复合材料可以实现产物收率高、底物范围广,产物收率最高可达到98%,因此该复合材料在苄基卤代烃的氰基化方面具有巨大潜力。
附图说明
图1 本发明实例所得Cu-Mo双金属纳米复合材料的XRD图谱;
图2 本发明实例所得Cu-Mo双金属纳米复合材料的红外光谱图;
图3 本发明实例所得Cu-Mo双金属纳米复合材料的SEM图像;
图4 本发明实例所得Cu-Mo双金属纳米复合材料作为催化剂使用过量NaBH4还原4-NP的紫外可见光谱;
图5 本发明实例所得Cu-Mo双金属纳米复合材料催化剂在NaBH4存在的条件下循环催化还原对硝基苯酚:ln(Ct/C0)与还原反应时间的线性关系(图a-q为第2-18次);
图6 本发明实例所得Cu-Mo双金属纳米复合材料催化剂在催化反应过程中漂浮在反应溶液表面的图像;
图7 Cu-Mo双金属纳米复合材料作为催化剂可催化不同苄基卤代烃底物反应式。
具体实施方式
实施例1 Cu-Mo双金属纳米复合材料的制备
Cu-Mo 双金属纳米复合材料的合成:Cu-Mo双金属纳米复合材料的制备采用了一步化学合成法。
制备方法如下:
1)将Cu(NO3)2·3H2O(0.749g)和 H3PMo12O40(0.064g)溶解于蒸馏水(20 mL)中;
2)将2-甲基咪唑(2.75g)溶解于蒸馏水中(50mL);
3)将步骤1)和2)的两种溶液混合,在50℃下搅拌15min,加热1h,产生褐色沉淀;
4)褐色沉淀经离心收集,用甲醇溶液和水反复交替清洗;
5)将制备好的褐色固体在60℃的烘箱中干燥24小时,得到最终产品Cu-Mo双金属纳米复合材料。
Cu-Mo 双金属纳米复合材料的各种表征:图1. Cu-Mo 双金属纳米复合材料的XRD,图2. Cu-Mo 双金属纳米复合材料的红外光谱,图3. Cu-Mo 双金属纳米复合材料的扫描电镜图像。
实施例2 Cu-Mo双金属纳米复合材料的制备
Cu-Mo双金属纳米复合材料的合成:Cu-Mo双金属纳米复合材料的制备采用了一步化学合成法。
制备方法如下:
1)将Cu(NO3)2·3H2O(0.749 g)和 H3PMo12O40(0.064 g)溶解于蒸馏水(20 mL)中;
2)将2-甲基咪唑(2.75 g)溶解于蒸馏水中(50 mL);
3)将步骤1)和2)的两种溶液混合,在(100)℃下搅拌(15)min,加热(1)h,产生褐色沉淀;
4)褐色沉淀经离心收集,用甲醇溶液和水反复交替清洗;
5)将制备好的褐色固体在(60)℃的烘箱中干燥(24)小时,得到最终产品Cu-Mo双金属纳米复合材料。
实施例3 Cu-Mo双金属纳米复合材料的制备
Cu-Mo双金属纳米复合材料的合成:Cu-Mo双金属纳米复合材料的制备采用了一步化学合成法。
制备方法如下:
1)将Cu(NO3)2·3H2O(0.8 g)和 H3PMo12O40(0.064 g)溶解于蒸馏水(20 mL)中;
2)将2-甲基咪唑(3 g)溶解于蒸馏水中(50 mL);
3)将步骤1)和2)的两种溶液混合,在(200)℃下搅拌(15)min,加热(1)h,产生褐色沉淀;
4)褐色沉淀经离心收集,用甲醇溶液和水反复交替清洗;
5)将制备好的褐色固体在(60)℃的烘箱中干燥(24)小时,得到最终产品Cu-Mo双金属纳米复合材料。
实施例4 Cu-Mo双金属纳米复合材料催化对硝基苯酚
将对硝基苯酚4-NP的水溶液(0.01 M,0.03 mL)与新制备的NaBH4溶液(0.5 M,0.2mL)混合,加入到干净的比色皿中,然后加入实施例1制备的Cu-Mo双金属纳米复合材料(2mg·mL-1,0.03 mL)到混合溶液中;通过紫外-可见光谱以30秒的间隔实时监测反应(图4)。
结果:对于本发明所得到的Cu-Mo双金属纳米复合材料,在催化对硝基苯酚过程中始终漂浮在溶液表面,并能高效催化底物得到高转化率,反应结束后,可直接方便回收,成功进行至少18次催化循环实验;催化循环实验后转化率依旧可以达到97%。表明Cu-Mo双金属纳米复合材料具有催化性能好、易回收和能循环使用的优点。
实施例5 Cu-Mo 双金属纳米复合材料催化苄基卤代烃的氰基化反应
Cu-Mo双金属纳米复合材料催化剂催化苄基卤代烃氰基化的方法:在干净的25毫升反应管中称取Cu-Mo双金属纳米复合材料(0.01 g)和碳酸钾(0.138g),加入乙腈(2.0mL)并充分搅拌,再加入1.0 mmol溴化苄化合物(溴化苄、4-甲基溴化苄、4-甲氧基溴化苄、4-氟溴化苄、4-氯溴化苄、对溴溴化苄、4-碘溴化苄、对硝基溴化苄、3-氯苄化溴、二苯基溴甲烷)和三甲基氰硅烷(2.0 mmol),并套上一个氮气气球密封。在80℃的条件下充分搅拌24h。图7所示,为Cu-Mo双金属纳米复合材料作为催化剂可催化不同苄基卤代烃底物;其中R1代表-CH3、-CH3O、-F、-Cl、-Br、-I、-NO2,R2代表C6H5;
反应结束后,向溶液中加入少量乙酸乙酯进行萃取,重复萃取3次。有机相蒸发干燥得粗产品,粗产品经柱层析分离提纯(展开剂:乙酸乙酯:石油醚=1:10)分离纯化。
结果表明,以Cu-Mo双金属纳米复合材料作为催化剂用于在苄基卤代烃的氰基化中制取苄腈,氰化反应的产物收率很高,例如:苄溴到苄腈、4-氟溴化苄到4-氟苄腈的转率可以达到98%,并且在苄基卤代烃的氰基化反应中具有广阔的底物范围(可将C-Br键转化为C-CN键)。该催化剂具有优异的稳定性和可重复使用性,并将在未来的应用中发挥其优势,这为有机污染物降解、苄基卤代烃的氰基化提供了高效、低成本的催化剂。
Claims (9)
1.Cu-Mo双金属纳米复合材料,它是由下述方法制备的:
1)将硝酸铜与H3PMo12O40的物质的量比为10~100:1溶于10 mL~100 mL水,形成A溶液;
2)将0.01 mol~0.1 mol 2-甲基咪唑溶解于10 mL~100 mL水,形成B溶液;
3)A溶液与B溶液混合,在20℃~200℃下搅拌15 min~30 min,加热反应1~5h,得到褐色沉淀;
4)将步骤3)所述的褐色沉淀离心收集,清洗,得褐色固体;
5)将褐色固体干燥,得到Cu-Mo双金属纳米复合材料。
2.根据权利要求1所述的Cu-Mo双金属纳米复合材料,其特征在于:步骤1)所述的Cu(NO3)2·3H2O与H3PMo12O40的物质的量比为60~100 :1;步骤2)所述的2-甲基咪唑添加量为0.03~0.1 mol。
3.根据权利要求2所述的Cu-Mo双金属纳米复合材料,其特征在于:步骤3)所述的搅拌,温度为50℃,时间15min,加热反应1h。
4.根据权利要求3所述的Cu-Mo双金属纳米复合材料,其特征在于:步骤5)所述的干燥,是在50~80℃下干燥20~30 h。
5.根据权利要求4所述的Cu-Mo双金属纳米复合材料,其特征在于:所述Cu-Mo双金属纳米复合材料呈梭形片层状形貌,厚度为15-25nm。
6.根据权利要求5所述的Cu-Mo双金属纳米复合材料,其特征在于:所述梭形片层状的结构使其密度小于水,在反应过程中漂浮在液面上,使催化剂易于循环回收。
7.Cu-Mo双金属纳米复合材料在催化有机物方面的应用。
8.根据权利要求7所述的应用,其特征在于:所述的催化,是催化降解硝基酚类化合物转化为氨基酚化合物。
9.根据权利要求8所述的应用,其特征在于:所述的催化反应为苄基卤代烃的氰基化反应。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210464448.3A CN114797920B (zh) | 2022-04-29 | 2022-04-29 | Cu-Mo双金属纳米复合材料及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210464448.3A CN114797920B (zh) | 2022-04-29 | 2022-04-29 | Cu-Mo双金属纳米复合材料及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114797920A true CN114797920A (zh) | 2022-07-29 |
CN114797920B CN114797920B (zh) | 2023-09-29 |
Family
ID=82508902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210464448.3A Active CN114797920B (zh) | 2022-04-29 | 2022-04-29 | Cu-Mo双金属纳米复合材料及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114797920B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1915504A (zh) * | 2006-08-28 | 2007-02-21 | 中国科学院成都有机化学有限公司 | 一种用于酯交换合成碳酸二苯酯的钼-铜双金属复合氧化物催化剂 |
CN103880894A (zh) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | 一种直接合成双活性中心杂多酸类材料的方法 |
CN109569665A (zh) * | 2018-11-28 | 2019-04-05 | 东莞理工学院 | 一种硫化铜/硫化钼复合材料的制备方法和应用 |
-
2022
- 2022-04-29 CN CN202210464448.3A patent/CN114797920B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1915504A (zh) * | 2006-08-28 | 2007-02-21 | 中国科学院成都有机化学有限公司 | 一种用于酯交换合成碳酸二苯酯的钼-铜双金属复合氧化物催化剂 |
CN103880894A (zh) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | 一种直接合成双活性中心杂多酸类材料的方法 |
CN109569665A (zh) * | 2018-11-28 | 2019-04-05 | 东莞理工学院 | 一种硫化铜/硫化钼复合材料的制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
B. AGHABARARI ET AL.,: ""Non-precious Melamine/Chitosan Composites for the Oxygen Reduction Reaction: Effect of the Transition Metal"", 《FRONTIERS IN MATERIALS》, vol. 7, pages 578518 * |
Also Published As
Publication number | Publication date |
---|---|
CN114797920B (zh) | 2023-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Riente et al. | Application of metal oxide semiconductors in light-driven organic transformations | |
Shang et al. | Photocatalytic materials for sustainable chemistry via cooperative photoredox catalysis | |
Hao et al. | Modification of heterogeneous photocatalysts for selective organic synthesis | |
CN106925349B (zh) | 一种固载型金属卟啉催化剂及其在制备马来酸方面的应用 | |
CN107056649A (zh) | 一种负载席夫碱配合物的金属有机骨架材料的制备方法及其应用 | |
Zolfigol et al. | Application of silica vanadic acid as a heterogeneous, selective and highly reusable catalyst for oxidation of sulfides at room temperature | |
Jiang et al. | Photocatalytic aldehydes/alcohols/toluenes oxidative amidation over bifunctional Pd/MOFs: Effect of Fe-O clusters and Lewis acid sites | |
CN115069298B (zh) | 活性炭固载的催化剂、制备方法和制备醛酮类物质的方法 | |
Ishida et al. | Aerobic oxidation of glucose and 1-phenylethanol over gold nanoparticles directly deposited on ion-exchange resins | |
Shi et al. | Synthesis Cu (I)–CN-based MOF with in-situ generated cyanogroup by cleavage of acetonitrile: Highly efficient for catalytic cyclization of propargylic alcohols with CO2 | |
Sun et al. | Covalently immobilized Mn (III) deuteroporphyrin on chitosan: An efficient and recyclable catalyst for aerobic oxidation of cyclohexane | |
Yadav et al. | Selective liquid phase oxidation of secondary alcohols into ketones by tert-butyl hydroperoxide on nano-fibrous Ag-OMS-2 catalyst | |
CN101032697A (zh) | 苯羟基化合成苯酚的催化剂及其应用方法 | |
CN112076776B (zh) | 用于选择性光催化氧化醇生成酯的质子化氮化碳及其应用 | |
CN114797920B (zh) | Cu-Mo双金属纳米复合材料及其应用 | |
Gholinejad et al. | Palladium supported on hydrophilic magnetic nanoparticles as a new efficient catalyst in aqueous media✰ | |
US20060167313A1 (en) | Process for preparing encapsulated metalloporphyrin catalyst and process for oxidation of alcohols | |
Choudhary et al. | Solvent-free oxidation of aldehydes to acids by TBHP using environmental-friendly-exchanged Mg-Al hydrotalcite catalyst | |
Kano et al. | Direct asymmetric aminoxylation reaction catalyzed by axially chiral amino acids | |
CN101450324A (zh) | 高分子担载三元氨基酸席夫碱金属铜配合物催化剂及其合成方法 | |
CN109529938B (zh) | 一种超分子金属催化剂的制备和应用 | |
CN101157677A (zh) | 一种用负载型纳米金催化剂制备δ-戊内酯的方法 | |
CN101463016B (zh) | 2,6-二甲基哌嗪的合成方法 | |
CN100551899C (zh) | 一种由甲苯一步直接氨基化合成甲苯胺的方法 | |
Zhang et al. | Conversion of nitrogenous small molecules into value-added chemicals by building N–C bonds |
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 |