CN111111691B - Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof - Google Patents
Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof Download PDFInfo
- Publication number
- CN111111691B CN111111691B CN202010045006.6A CN202010045006A CN111111691B CN 111111691 B CN111111691 B CN 111111691B CN 202010045006 A CN202010045006 A CN 202010045006A CN 111111691 B CN111111691 B CN 111111691B
- Authority
- CN
- China
- Prior art keywords
- metal
- composite material
- graphene
- iron oxyhydroxide
- ternary composite
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 title claims abstract description 42
- 239000011206 ternary composite Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 229910002804 graphite Inorganic materials 0.000 claims description 38
- 239000010439 graphite Substances 0.000 claims description 38
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910001510 metal chloride Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 229910052763 palladium Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域technical field
本发明属于纳米复合材料的制备技术领域，具体涉及一种纳米羟基氧化铁/金属/石墨烯三元复合材料及其制备方法。The invention belongs to the technical field of preparation of nano-composite materials, in particular to a nano-iron oxyhydroxide/metal/graphene ternary composite material and a preparation method thereof.
背景技术Background technique
石墨烯材料具有比表面积大、物理性能优异和表面化学性质可调等特点，近年来备受关注。氧化石墨烯作为石墨烯家族的重要成员，由于含有丰富的含氧官能团而表现出较好的亲水性，而主片层的碳使其具有一定的疏水性，其性能接近于一个二维的表面活性剂，因此氧化石墨烯已表现出一定的界面活性。但是由于氧化石墨烯的酸碱稳定性和热稳定性较差，制约了其在界面催化有机化学反应方面的应用。亲疏水性固体粒子杂化协同作用能起到表面活性调控的作用，相对有机官能团，固体纳米粒子具有更优异的热稳定性及耐酸碱稳定性，为氧化石墨烯界面调控提供了新思路。Graphene materials have the characteristics of large specific surface area, excellent physical properties and adjustable surface chemical properties, which have attracted much attention in recent years. As an important member of the graphene family, graphene oxide exhibits good hydrophilicity due to its abundant oxygen-containing functional groups, and the carbon in the main sheet makes it hydrophobic to a certain extent, and its performance is close to that of a two-dimensional Surfactant, so graphene oxide has shown some interfacial activity. However, due to the poor acid-base stability and thermal stability of graphene oxide, its application in interfacial catalysis of organic chemical reactions is restricted. The hybrid synergistic effect of hydrophilic and hydrophobic solid particles can play a role in the regulation of surface activity. Compared with organic functional groups, solid nanoparticles have better thermal stability and acid and alkali resistance stability, which provides a new idea for graphene oxide interface regulation.
但目前关于石墨烯作为催化剂的载体材料，主要利用浸渍还原法、沉淀法、沉积沉淀法等实现金属纳米粒子的负载。这些方法的还原过程一般采用高毒性的联氨、水合肼等作为还原剂的液相化学还原法或氢气、一氧化碳等气体高温还原法。这些方法不仅不能有效控制负载金属纳米粒子的尺寸、分散性以及负载量，而且负载后的金属纳米粒子由于与基体结合力差，石墨烯表面的界面活性减弱，在催化过程中容易从基体脱落或发生团聚，导致催化活性降低。其实，在这些传统的方法中，面临的最大问题是在制备过程中石墨烯出现不可逆团聚，不易得到单分散的石墨烯；催化剂纳米粒子与载体之间的相互作用较弱，石墨烯难免团聚在一起，大部分报道的金属纳米粒子修饰的石墨烯片都处于聚集状态。这样石墨烯巨大的比表面积得不到充分利用，复合物的协同催化作用无法充分发挥。However, at present, regarding graphene as a support material for catalysts, metal nanoparticles are supported mainly by impregnation reduction method, precipitation method, and deposition precipitation method. The reduction process of these methods generally adopts a liquid-phase chemical reduction method with highly toxic hydrazine, hydrazine hydrate, etc. as reducing agents, or a high-temperature reduction method with gases such as hydrogen and carbon monoxide. These methods not only cannot effectively control the size, dispersion and loading of the supported metal nanoparticles, but also the loaded metal nanoparticles have poor binding force with the substrate, the interface activity of the graphene surface is weakened, and it is easy to fall off the substrate during the catalytic process or Agglomeration occurs, resulting in a decrease in catalytic activity. In fact, in these traditional methods, the biggest problem is the irreversible agglomeration of graphene during the preparation process, and it is not easy to obtain monodisperse graphene; the interaction between the catalyst nanoparticles and the carrier is weak, and the graphene is inevitably agglomerated in the Together, most of the reported metal nanoparticle-decorated graphene sheets are in the aggregated state. In this way, the huge specific surface area of graphene cannot be fully utilized, and the synergistic catalytic effect of the composite cannot be fully exerted.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种具有良好的两亲性和催化活性，且耐酸碱、耐高温的纳米羟基氧化铁/金属/石墨烯三元复合材料，并为该三元复合材料提供一种简单的制备方法，使带状羟基氧化铁颗粒和金属无表面活性剂包覆，以单分散状态分布在石墨烯表面，保持石墨烯表面的界面活性。The object of the present invention is to provide a nano-iron oxyhydroxide/metal/graphene ternary composite material with good amphiphilicity and catalytic activity, acid and alkali resistance and high temperature resistance, and provide a kind of ternary composite material for the ternary composite material. The simple preparation method enables the band-shaped iron oxyhydroxide particles and the metal to be coated with no surfactant, and distributed on the graphene surface in a monodispersed state to maintain the interfacial activity of the graphene surface.
针对上述目的，本发明采用的纳米羟基氧化铁/金属/石墨烯三元复合材料由下述方法制备得到：将氧化石墨超声分散于去离子水中，得到氧化石墨分散液；在搅拌条件下，向氧化石墨分散液中加入金属氯化物，并加入含五羰基铁的有机溶液，在密闭条件50～80℃反应1～3小时，反应完后过滤、洗涤、干燥，得到纳米羟基氧化铁/金属/石墨烯三元复合材料。For the above purpose, the nano iron oxyhydroxide/metal/graphene ternary composite material used in the present invention is prepared by the following method: ultrasonically dispersing graphite oxide in deionized water to obtain a graphite oxide dispersion; Metal chloride is added to the graphite oxide dispersion, and an organic solution containing iron pentacarbonyl is added, and the reaction is carried out at 50 to 80 ° C for 1 to 3 hours under airtight conditions. Graphene ternary composites.
上述制备方法中，优选所述氧化石墨分散液中氧化石墨的质量体积浓度为1～15mg/mL。In the above preparation method, preferably, the mass volume concentration of graphite oxide in the graphite oxide dispersion liquid is 1-15 mg/mL.
上述的金属氯化物为氯化钯、氯化镍、氯化钌中任意一种，优选氧化石墨与金属氯化物的质量比为5～1300:1，更优选氧化石墨与金属氯化物的质量比为5～150:1。Above-mentioned metal chloride is any one in palladium chloride, nickel chloride, ruthenium chloride, preferably the mass ratio of graphite oxide and metal chloride is 5～1300:1, more preferably the mass ratio of graphite oxide and metal chloride 5 to 150:1.
上述制备方法中，优选所述氧化石墨与五羰基铁的质量体积比为0.01～5g:1mL，更优选氧化石墨与五羰基铁的质量体积比为0.03～1g:1mL。In the above preparation method, preferably the mass volume ratio of the graphite oxide and pentacarbonyl iron is 0.01～5g:1mL, more preferably the mass volume ratio of graphite oxide and pentacarbonyl iron is 0.03～1g:1mL.
上述含五羰基铁的有机溶液中，优选五羰基铁的体积浓度1.5～135mL/L。In the above-mentioned organic solution containing iron pentacarbonyl, the volume concentration of iron pentacarbonyl is preferably 1.5-135 mL/L.
上述的有机溶液为乙腈、丙酮、苯甲醛中任意一种。The above-mentioned organic solution is any one in acetonitrile, acetone and benzaldehyde.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
本发明采用水和有机溶剂同时作为溶剂，用五羰基铁还原氧化石墨和金属氯化物，没有加入任何其它还原剂，一步法反应制得纳米羟基氧化铁/金属/石墨烯三元复合材料。羟基氧化铁和金属粒子以纳米级负载在石墨烯表面，粒径小且在石墨烯表面分布均匀，稳定性和分散性好。其中纳米羟基氧化铁形貌为纳米带状，在氧化石墨烯表面呈现单分散状态分布。该方法合成步骤少，生产成本低，易于实现工业化生产。The invention adopts water and organic solvent as solvent simultaneously, reduces graphite oxide and metal chloride with iron pentacarbonyl, does not add any other reducing agent, and prepares nano-iron oxyhydroxide/metal/graphene ternary composite material by one-step reaction. The iron oxyhydroxide and metal particles are supported on the graphene surface in nanoscale, with small particle size and uniform distribution on the graphene surface, with good stability and dispersion. Among them, the morphology of nano-iron oxyhydroxide is nano-ribbon, and it is distributed in a monodisperse state on the surface of graphene oxide. The method has few synthesis steps, low production cost, and is easy to realize industrialized production.
本发明制备的纳米羟基氧化铁/金属/石墨烯三元复合材料具有良好的两亲性，相对氧化石墨烯，耐酸碱、耐高温。而且通过羟基氧化铁比例的调节可实现复合材料表面润湿性的调控。同时该复合材料兼具高催化活性的金属物种，在乳液催化的两相有机反应中有着潜在的应用。The nanometer iron oxyhydroxide/metal/graphene ternary composite material prepared by the invention has good amphiphilicity, and is resistant to acid and alkali and high temperature relative to graphene oxide. Moreover, the wettability of the composite surface can be regulated by adjusting the ratio of iron oxyhydroxide. At the same time, the composite material has metal species with high catalytic activity, and has potential applications in emulsion-catalyzed two-phase organic reactions.
附图说明Description of drawings
图1是氧化石墨、实施例1制备的纳米羟基氧化铁/钯/石墨烯三元复合材料的XRD图及羟基氧化铁XRD标准卡片。Fig. 1 is the XRD pattern of graphite oxide, nano iron oxyhydroxide/palladium/graphene ternary composite material prepared in Example 1 and iron oxyhydroxide XRD standard card.
图2是实施例1制备的纳米羟基氧化铁/钯/石墨烯三元复合材料的透射电镜图。2 is a transmission electron microscope image of the nano-iron oxyhydroxide/palladium/graphene ternary composite material prepared in Example 1.
图3是实施例2(A)、实施例3(B)以及实施例4(C)制备的纳米羟基氧化铁/钯/石墨烯三元复合材料的接触角。3 is the contact angle of the nano-iron oxyhydroxide/palladium/graphene ternary composite materials prepared in Example 2(A), Example 3(B) and Example 4(C).
图4是实施例5制备的纳米羟基氧化铁/镍/石墨烯三元复合材料的扫描电镜图。4 is a scanning electron microscope image of the nano-iron oxyhydroxide/nickel/graphene ternary composite material prepared in Example 5.
图5是实施例5制备的纳米羟基氧化铁/镍/石墨烯三元复合材料的透射电镜图。5 is a transmission electron microscope image of the nano-iron oxyhydroxide/nickel/graphene ternary composite material prepared in Example 5.
图6是实施例6制备的纳米羟基氧化铁/钌/石墨烯三元复合材料的扫描电镜图。6 is a scanning electron microscope image of the nano-iron oxyhydroxide/ruthenium/graphene ternary composite material prepared in Example 6.
图7是实施例6制备的纳米羟基氧化铁/钌/石墨烯三元复合材料的透射电镜图。7 is a transmission electron microscope image of the nano-iron oxyhydroxide/ruthenium/graphene ternary composite material prepared in Example 6.
具体实施方式Detailed ways
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。The present invention is further described in detail below with reference to the accompanying drawings and embodiments, but the protection scope of the present invention is not limited to these embodiments.
实施例1Example 1
将150mg氧化石墨(GO)加入15mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入1mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度16.7mL/L五羰基铁的乙腈溶液，在密闭条件下60℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料(Pd/FeOOH@RGO)。150 mg of graphite oxide (GO) was added to 15 mL of deionized water, and ultrasonically dispersed to obtain a graphite oxide dispersion. Under stirring conditions, 1 mg of palladium chloride was added to the graphite oxide dispersion, then transferred to a 150 mL round-bottomed flask, 15 mL of acetonitrile solution with a volume concentration of 16.7 mL/L iron pentacarbonyl was added, and the reaction was carried out at 60 °C for 2 hours under airtight conditions. , filtered after the reaction, washed with deionized water, and freeze-dried to obtain nanometer iron oxyhydroxide/palladium/graphene ternary composite material (Pd/FeOOH@RGO).
由图1中XRD图谱可知，所得产物是纳米羟基氧化铁/钯/石墨烯三元复合材料，图2显示纳米羟基氧化铁呈带状，宽度在15nm左右，分散在石墨烯表面，纳米钯粒子尺寸为5nm左右。It can be seen from the XRD pattern in Figure 1 that the obtained product is a nano-iron oxyhydroxide/palladium/graphene ternary composite material. Figure 2 shows that the nano-iron oxyhydroxide is ribbon-shaped, with a width of about 15nm, dispersed on the surface of graphene, and nano-palladium particles. The size is about 5nm.
实施例2Example 2
将25mg氧化石墨加入5mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入5mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度5mL/L五羰基铁的乙腈溶液，在密闭条件下50℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料。25 mg of graphite oxide was added to 5 mL of deionized water, and ultrasonically dispersed to obtain a graphite oxide dispersion. Under stirring conditions, 5 mg of palladium chloride was added to the graphite oxide dispersion, then transferred to a 150 mL round-bottomed flask, 15 mL of an acetonitrile solution with a volume concentration of 5 mL/L iron pentacarbonyl was added, and the reaction was carried out at 50 °C for 2 hours under airtight conditions. After the reaction is completed, filter, wash with deionized water, and freeze-dry to obtain nanometer iron oxyhydroxide/palladium/graphene ternary composite material.
实施例3Example 3
将25mg氧化石墨加入5mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入5mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度20mL/L五羰基铁的乙腈溶液，在密闭条件下50℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料。25 mg of graphite oxide was added to 5 mL of deionized water, and ultrasonically dispersed to obtain a graphite oxide dispersion. Under stirring conditions, 5 mg of palladium chloride was added to the graphite oxide dispersion, then transferred to a 150 mL round-bottomed flask, 15 mL of an acetonitrile solution with a volume concentration of 20 mL/L iron pentacarbonyl was added, and the reaction was carried out at 50 °C for 2 hours under airtight conditions. After the reaction is completed, filter, wash with deionized water, and freeze-dry to obtain nanometer iron oxyhydroxide/palladium/graphene ternary composite material.
实施例4Example 4
将25mg氧化石墨加入5mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入5mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度50mL/L五羰基铁的乙腈溶液，在密闭条件下50℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料。25 mg of graphite oxide was added to 5 mL of deionized water, and ultrasonically dispersed to obtain a graphite oxide dispersion. Under stirring conditions, 5 mg of palladium chloride was added to the graphite oxide dispersion, then transferred to a 150 mL round-bottomed flask, and 15 mL of an acetonitrile solution with a volume concentration of 50 mL/L of iron pentacarbonyl was added, and the reaction was carried out at 50 °C for 2 hours under airtight conditions. After the reaction is completed, filter, wash with deionized water, and freeze-dry to obtain nanometer iron oxyhydroxide/palladium/graphene ternary composite material.
从图3可知，实施例2、3、4通过控制加入的五羰基铁的浓度，可以改变纳米羟基氧化铁/钯/石墨烯三元复合材料的接触角，进而改变复合材料的润湿性和表面活性。随着五羰基铁浓度的增大，复合材料的亲水性降低，亲油性增大。It can be seen from Figure 3 that in Examples 2, 3 and 4, the contact angle of the nano-iron oxyhydroxide/palladium/graphene ternary composite material can be changed by controlling the concentration of the added iron pentacarbonyl, thereby changing the wettability and the wettability of the composite material. Surface activity. With the increase of iron pentacarbonyl concentration, the hydrophilicity of the composites decreased and the lipophilicity increased.
实施例5Example 5
将125mg氧化石墨加入15mL去离子水中，超声分散得到氧化石墨分散液；在搅拌条件下，向氧化石墨分散液中加入1mg氯化镍，然后移至150mL圆底烧瓶中，加入15mL体积浓度16.7mL/L五羰基铁的乙腈溶液，在密闭条件下60℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/镍/石墨烯三元复合材料。由图4和图5可见，复合材料保持石墨烯的片状结构，且纳米羟基氧化铁呈带状，分散在石墨烯表面。Add 125 mg of graphite oxide to 15 mL of deionized water, and ultrasonically disperse to obtain a graphite oxide dispersion; under stirring, add 1 mg of nickel chloride to the graphite oxide dispersion, then move it to a 150 mL round-bottomed flask, and add 15 mL of 16.7 mL of volume concentration /L acetonitrile solution of iron pentacarbonyl, react at 60 °C for 2 hours under airtight conditions, filter after the reaction, wash with deionized water, freeze-dry, and obtain nano-iron oxyhydroxide/nickel/graphene ternary composite material. It can be seen from Figure 4 and Figure 5 that the composite material maintains the sheet-like structure of graphene, and the nano-iron oxyhydroxide is in the form of ribbons and is dispersed on the surface of graphene.
实施例6Example 6
将125mg氧化石墨加入15mL去离子水中，超声分散得到氧化石墨分散液；在搅拌条件下，向氧化石墨分散液中加入1mg氯化钌，然后移至150mL圆底烧瓶中，加入15mL体积浓度16.7mL/L五羰基铁的乙腈溶液，在密闭条件下60℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/钌/石墨烯三元复合材料。由图6和图7可见，复合材料保持石墨烯的片状结构，且纳米羟基氧化铁呈带状，分散在石墨烯表面。Add 125 mg of graphite oxide to 15 mL of deionized water, and ultrasonically disperse to obtain a graphite oxide dispersion; under stirring conditions, add 1 mg of ruthenium chloride to the graphite oxide dispersion, then move it to a 150 mL round-bottomed flask, and add 15 mL of 16.7 mL volume concentration /L acetonitrile solution of iron pentacarbonyl, react at 60°C for 2 hours under airtight conditions, filter after the reaction, wash with deionized water, freeze-dry, and obtain nano-iron oxyhydroxide/ruthenium/graphene ternary composite material. It can be seen from Fig. 6 and Fig. 7 that the composite material maintains the sheet-like structure of graphene, and the nano-iron oxyhydroxide is in the shape of a ribbon, which is dispersed on the surface of graphene.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010045006.6A CN111111691B (en) | 2020-01-16 | 2020-01-16 | Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010045006.6A CN111111691B (en) | 2020-01-16 | 2020-01-16 | Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111111691A CN111111691A (en) | 2020-05-08 |
| CN111111691B true CN111111691B (en) | 2022-10-21 |
Family
ID=70490302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010045006.6A Expired - Fee Related CN111111691B (en) | 2020-01-16 | 2020-01-16 | Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111111691B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5652192A (en) * | 1992-07-10 | 1997-07-29 | Battelle Memorial Institute | Catalyst material and method of making |
| US7829140B1 (en) * | 2006-03-29 | 2010-11-09 | The Research Foundation Of The State University Of New York | Method of forming iron oxide core metal shell nanoparticles |
| KR20150116489A (en) * | 2014-04-07 | 2015-10-16 | 인하대학교 산학협력단 | METHOD OF PREPARING IRON OXIDE-GRAPHENE COMPOSITES AND THE IRON OXIDE(β-FEOOH)-GRAPHENE COMPOSITES PREPARED BY THE SAME METHOD |
| CN106082351A (en) * | 2016-06-01 | 2016-11-09 | 浙江大学 | The preparation method of a kind of FeOOH nanometer sheet and product thereof |
| CN110152569A (en) * | 2018-04-28 | 2019-08-23 | 浙江大学 | A kind of nanometer FeO (OH) composite aerogel, its preparation method and use |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130099153A1 (en) * | 2011-10-23 | 2013-04-25 | Postech Academy-Industry Foundation | Hybrid material comprising graphene and iron oxide, method for manufacturing the same, and apparatus for treating waste water using the same |
-
2020
- 2020-01-16 CN CN202010045006.6A patent/CN111111691B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5652192A (en) * | 1992-07-10 | 1997-07-29 | Battelle Memorial Institute | Catalyst material and method of making |
| US7829140B1 (en) * | 2006-03-29 | 2010-11-09 | The Research Foundation Of The State University Of New York | Method of forming iron oxide core metal shell nanoparticles |
| KR20150116489A (en) * | 2014-04-07 | 2015-10-16 | 인하대학교 산학협력단 | METHOD OF PREPARING IRON OXIDE-GRAPHENE COMPOSITES AND THE IRON OXIDE(β-FEOOH)-GRAPHENE COMPOSITES PREPARED BY THE SAME METHOD |
| CN106082351A (en) * | 2016-06-01 | 2016-11-09 | 浙江大学 | The preparation method of a kind of FeOOH nanometer sheet and product thereof |
| CN110152569A (en) * | 2018-04-28 | 2019-08-23 | 浙江大学 | A kind of nanometer FeO (OH) composite aerogel, its preparation method and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111111691A (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108516528B (en) | A 3D composite structure based on 3D MXene and its general synthesis method | |
| CN107754793B (en) | Porous carbon loaded Fischer-Tropsch synthesis catalyst and preparation method and application thereof | |
| CN105251484B (en) | Three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method | |
| CN104722777B (en) | Quick preparation method for starch-stabilizing nanometer zero-valent iron | |
| CN107335403A (en) | Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle | |
| CN107096529B (en) | A kind of graphene aerogel supported by nanometer silver with extremely small particle size and its preparation method and application | |
| CN110385126B (en) | High-dispersity ultra-small carbon-supported noble metal catalyst and preparation method thereof | |
| CN103263921A (en) | Metal/graphene catalyst and preparation method thereof | |
| CN103007963A (en) | Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier | |
| WO2008036743A2 (en) | Supported nickel catalysts having high nickel loading and high metal dispersion and methods of making same | |
| CN104971759A (en) | Preparation method of supported palladium-carbon catalyst | |
| CN1762590A (en) | A transition metal-γ-Fe2O3 nanomaterial and its preparation method and application | |
| CN107073458A (en) | Carrier nano-particle compound, the preparation method of the compound and the catalyst comprising the compound | |
| CN107537517A (en) | A kind of alloy colloid and its preparation method and application | |
| Li et al. | Platinum clusters anchored on sulfur-doped ordered mesoporous carbon for chemoselective hydrogenation of halogenated nitroarenes | |
| CN111349245B (en) | Overlapped structure nanosheet layer material and preparation method and application thereof | |
| CN108927154A (en) | A kind of preparation method of intermetallic compound nanocatalyst | |
| CN112705193A (en) | Porous carbon self-reduction preparation method of porous carbon loaded small-size noble metal nanoparticle composite material | |
| CN104069855A (en) | Method for preparing monodisperse graphene-supported nano-palladium particles by using solvothermal process | |
| CN106881089B (en) | A kind of preparation method of controllable graphene-supported cheap IB-VIIIB race duplex metal nano granule composite material | |
| CN103521750B (en) | Carbon nanometer tube metal particle composite and comprise the catalyst material of this compound | |
| CN107851807B (en) | Carrier-nanoparticle composite, method of preparing the same, and membrane electrode assembly comprising the same | |
| CN111111691B (en) | Nano-iron oxyhydroxide/metal/graphene ternary composite material and preparation method thereof | |
| CN105720273A (en) | One-step controllable preparation method and application of high-capacity and high-dispersity supported nano-gold catalyst | |
| CN103521265B (en) | The preparation method of carbon nanometer tube metal particle composite |
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: 20221021 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |