CN104437572A - Preparation method of graphene-loaded nano nickel phosphate hydrogenation catalyst - Google Patents
Preparation method of graphene-loaded nano nickel phosphate hydrogenation catalyst Download PDFInfo
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- CN104437572A CN104437572A CN201410607150.9A CN201410607150A CN104437572A CN 104437572 A CN104437572 A CN 104437572A CN 201410607150 A CN201410607150 A CN 201410607150A CN 104437572 A CN104437572 A CN 104437572A
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Abstract
The invention relates to a preparation method of a graphene-loaded nano nickel phosphate hydrogenation catalyst. According to the method, graphene oxide capable of being stably dispersed in water is used as a carrier precursor and loaded nano nickel phosphate is prepared by a static hydrothermal synthesis method. The graphene oxide can be uniformly and stably dispersed into a water solution due to a unique two-dimensional structure and abundant oxyl radicals of the graphene oxide; and furthermore, the graphene oxide has a strong adsorption capability on metal cations, and a nickel source can be highly dispersed. The catalyst provided by the invention is used for hydrogenation of olefin and has relatively high catalytic activity and good reusability. According to the catalyst, preparation conditions are moderate, the process is simple and the cost is low; and industrial production is easy to realize.
Description
Technical field
The present invention relates to non-noble metal hydrogenation catalyst and preparing technical field thereof, particularly a kind of preparation method of graphene-supported nano nickel phosphide hydrogenation catalyst.
Background technology
To be a large class enter by phosphorus atoms the compound that metal lattice formed to transition metal phosphide, and this compounds Heat stability is good, hardness are large, anti-oxidant and corrosion resistance strong, and show very high surface-active bit density.Research finds, transition metal phosphide has excellent hydroprocessing activity, and hydrogen-consuming volume is few, to a certain extent alternative precious metals pt, arouses great concern in new catalytic material field.In current studied transition metal phosphide, nickel phosphide shows more superior hydrogenation activity, and being expected to becomes a new generation's oil refining hydrotreating catalyst.
Many scholars start the research being devoted to transition metal phosphide, find that the size of its particle diameter directly restricts the height of catalytic activity, and the phosphide of high dispersive is the activated centre of reaction.And traditional temperature-programmed reduction method is due to temperature required higher (600-800 DEG C), the phosphide particle of preparation is easily reunited, and its specific area is less than 10m usually
2/ g.In recent years, people attempt developing multiple method and prepare high activity phosphide.Wherein solvent-thermal method [A " user-friendly " chemical approach towards paramagnetic cobaltphosphide hollow structures:preparation, characterization, and formationmechanism of Co
2p hollow spheres and tubes, Eur.J.Inorg.Chem., 2005,13:2625-2630.] mild condition, obtained phosphide particle is less, has larger specific area; In addition, be the approach easily and effectively reducing phosphide particle diameter further, increase its active sites quantity by the porous material of high-ratio surface as carrier.But solvent-thermal method is generally static treatment in crystallizing kettle, and conventional carrier can not long-time stable be scattered in solvent, therefore cannot prepare support type phosphide by solvent-thermal method.The carrier studied at present is as γ-Al
2o
3, SiO
2, active carbon, MCM-41, SBA-15 etc. mainly through physical action dispersion phosphide, active force is more weak, easily makes phosphide reunite; And the load capacity of phosphide is comparatively large (>15wt.%) usually, and easily blocking carrier duct, makes its specific area degradation, hinders the contact in reactant and activated centre.Industrial conventional carrier γ-Al
2o
3also can with active mutually between produce strong interaction and generate AlPO
4, cause the loss even catalyst surface structural damage of active component.Therefore, more suitable carrier and easy method is necessary to find to prepare high dispersive, high activity phosphide catalyst.
Summary of the invention
The technical problem to be solved in the present invention is complicated, harsh for current transition metal phosphide preparation condition, cost is high, particle agglomeration is serious, conventional carrier and its active force more weak, the problems such as catalytic activity can not give full play to, provide that a kind of synthetic method is simple, the method for mild condition, Graphene high degree of dispersion nickel phosphide nano particle hydrogenation catalyst with low cost.
The technical solution adopted for the present invention to solve the technical problems is:
It can the graphene oxide of stable dispersion be support precursor that the present invention selects in water, by static hydrothermal synthesis legal system for loaded nano nickel phosphide.Specifically carry out according to following steps:
(1) taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h obtains the graphene oxide water solution of stable dispersion;
(2) in above-mentioned solution, phosphorus source and nickel source is added, wherein the mol ratio of phosphorus and nickel is 2:1-3:1, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 150-190 DEG C of crystallization 5-20h, crystallization terminates rear centrifugation, namely washing, 80 DEG C of oven dry obtain described catalyst.
As limitation of the invention, phosphorus source of the present invention is sodium dihydric hypophosphite, phosphorous acid or red phosphorus; Described nickel source is nickel chloride, nickel acetate or nickelous sulfate.
In the present invention, adopt graphene oxide as carrier, on the one hand the two-dimensional structure of graphene oxide uniqueness and abundant oxygen base group can often time stable dispersion in the aqueous solution, can be used as the carrier of water (solvent) hot legal system for nickel phosphide, overcome the bottleneck problem of static hydrothermal legal system for support type phosphide; Graphene oxide has strong adsorption capacity to metal cation on the other hand, can realize the high degree of dispersion in nickel source; And the nano nickel phosphide of high dispersive is obtained by the defective bit of surface of graphene oxide and the high forces of nickel phosphide.
The support type nickel phosphide that the present invention synthesizes comprises NiP, Ni
2p, Ni
3p and Ni
12p
5mixture, mainly with Ni
2p is main.In addition, also have the existence of a small amount of simple substance Ni in this catalyst, this makes catalyst have certain magnetic, the separation of very convenient subsequent catalyst in catalyst system and catalyzing.
In addition, Graphene also has many advantages as the carrier of heterogeneous catalyst nickel phosphide:
(1) unique two-dimentional lamellar structure, compared with conventional porous materials, this structure can avoid high capacity amount active component to the blocking in duct, simultaneously also can eliminative reaction thing and product in duct in diffusion, thus improve reaction rate.
(2) excellent thermal conductivity makes it in the catalytic reaction of Process of absorption or liberation of heat, have obvious heat conduction advantage.
(3) relative to the dissatisfactory hydrothermal stability of traditional porous material, the stability of Graphene excellence and corrosion resistance make it in actual production, have better application prospect.
And this synthetic method is simple to operate, mild condition and with low cost, is easy to suitability for industrialized production.Catalyst of the present invention shows good catalytic activity and durability in the hydrogenation reaction of alkene.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, catalyst of the present invention is described.
Fig. 1 is the TEM collection of illustrative plates of the graphene-supported catalyst of phosphatizing nickel (figure below) that the catalyst of phosphatizing nickel (upper figure) of non-load and the embodiment of the present invention 7 obtain.
TEM adopts JEOLJEM-2100 transmissioning electric mirror test, method for making sample: sample dispersion, in ethanol, drips to after ultrasonic process and carries on the net, then dries and removes ethanol.As can be seen from Figure 1, the catalyst of phosphatizing nickel particle of non-load in upper figure is very large, reunites comparatively severe; Adopt Graphene to be that nickel phosphide particle prepared by carrier is very little in figure below and be only about 7nm, and dispersion is comparatively even.
Detailed description of the invention
The present invention is further illustrated with the following Examples more below, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
Embodiment 1
Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 1mmol sodium dihydric hypophosphite and 0.5mmol nickel chloride, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 150 DEG C of crystallization 20h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst A.
Embodiment 2
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 6mmol sodium dihydric hypophosphite and 2mmol nickel chloride, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 170 DEG C of crystallization 15h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst B.
Embodiment 3
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 6mmol sodium dihydric hypophosphite and 2mmol nickel chloride, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 190 DEG C of crystallization 5h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst C.
Embodiment 4
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 6mmol phosphorous acid and 2mmol nickel chloride, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 170 DEG C of crystallization 15h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst D.
Embodiment 5
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 6mmol red phosphorus and 2mmol nickel chloride, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 170 DEG C of crystallization 15h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst E.
Embodiment 6
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 6mmol phosphorus sodium dihydric hypophosphite and 2mmol nickelous sulfate, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 170 DEG C of crystallization 15h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst F.
Embodiment 7
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 6mmol phosphorus sodium dihydric hypophosphite and 2mmol nickel acetate, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 170 DEG C of crystallization 15h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst G.
Embodiment 8
Employing Graphene is carrier, prepares high dispersive nickel phosphide/graphen catalyst by hydro-thermal method.Taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process 3 times, each 0.5h, obtains the graphene oxide water solution of stable dispersion; In above-mentioned solution, add 12mmol phosphorus sodium dihydric hypophosphite and 4mmol nickel acetate, mixed liquor is loaded in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 170 DEG C of crystallization 15h, crystallization terminates rear centrifugation, sample deionized water is fully washed, and 80 DEG C of oven dry, obtain described catalyst H.
By the catalyst application in above-described embodiment in cyclohexene hydrogenation process, reaction condition is as follows:
Solvent: ethanol; Catalyst: 20mg; Cyclohexene: 1mL; Hydrogen Vapor Pressure: 1.0MPa; Reaction temperature: 80 DEG C; Reaction time: 1h, prior to H before catalyst uses
2in, activate 2h at 300 DEG C, its catalytic performance is as shown in table 1:
The catalytic performance of table 1 catalyst
| Catalyst | Cyclohexene conversion rate (%) | Cyclohexane selective (%) |
| Nickel phosphide | 12.0 | 100 |
| A | 60.3 | 100 |
| B | 99.6 | 100 |
| C | 92.1 | 100 |
| D | 96.5 | 100 |
| E | 91.4 | 100 |
| F | 97.7 | 100 |
| G | 99.8 | 100 |
| H | 81.0 | 100 |
As can be seen from Table 1, catalyst of the present invention is used for the hydrogenation of cyclohexene, compared with the nickel phosphide of non-load, activity is all improved largely.At 80 DEG C, maximum conversion can reach 99.8%.
Carry out multiplexing performance investigation to the catalyst G that above-described embodiment 7 obtains, be left intact after the centrifugal recovery of this catalyst directly multiplexing, performance is as shown in table 2:
The multiplexing performance of table 2 catalyst G
| Multiplexing number | Cyclohexene conversion rate (%) | Cyclohexane selective (%) |
| 1 | 99.8 | 100 |
| 2 | 100 | 100 |
| 3 | 99.6 | 100 |
| 4 | 98.9 | 100 |
| 5 | 99.7 | 100 |
| 6 | 99.3 | 100 |
Table 2 show catalyst use 6 times after activity almost do not decline, multiplexing performance is very good.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.
Claims (4)
1. a preparation method for graphene-supported nano nickel phosphide hydrogenation catalyst, it is characterized in that the method is selected can the graphene oxide of stable dispersion be support precursor in water, by static hydrothermal synthesis legal system for loaded nano nickel phosphide.
2. the preparation method of a kind of graphene-supported nano nickel phosphide hydrogenation catalyst according to claim 1, is characterized in that the method is carried out according to following step:
(1) taking a certain amount of graphite oxide joins in deionized water, and make the concentration of graphite oxide be 2mg/mL, ultrasonic process obtains the graphene oxide water solution of stable dispersion;
(2) in above-mentioned solution, phosphorus source and nickel source is added, wherein the mol ratio of phosphorus and nickel is 2:1-3:1, loaded by mixed liquor in polytetrafluoroethylene (PTFE) crystallizing kettle after stirring at room temperature 1h, 150-190 DEG C of crystallization 5-20h, crystallization terminates rear centrifugation, washing, oven dry and namely obtains described catalyst.
3. the preparation method of a kind of graphene-supported nano nickel phosphide hydrogenation catalyst according to claim 2, is characterized in that the phosphorus source described in step (2) is sodium dihydric hypophosphite, phosphorous acid or red phosphorus.
4. the preparation method of a kind of graphene-supported nano nickel phosphide hydrogenation catalyst according to claim 2, is characterized in that the nickel source described in step (2) is nickel chloride, nickel acetate or nickelous sulfate.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810165A (en) * | 2015-04-29 | 2015-07-29 | 华东理工大学 | Nickel phosphide / graphene composite film preparing method |
| CN105195208A (en) * | 2015-09-24 | 2015-12-30 | 神华集团有限责任公司 | Monolithic catalyst, preparation method thereof and desulphurization method utilizing monolithic catalyst |
| CN105642321A (en) * | 2015-12-31 | 2016-06-08 | 青岛科技大学 | Nano red phosphorus/graphene composite photocatalyst and preparation method thereof |
| CN105964288A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Method for preparing mesoporous carbon nitride loaded nano nickel phosphide |
| CN107256950A (en) * | 2017-06-07 | 2017-10-17 | 安徽师范大学 | Magnetic metal phosphide/the preparation method of graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery |
| CN108786868A (en) * | 2018-05-18 | 2018-11-13 | 燕山大学 | A kind of preparation method of nickel phosphorus/fluorine doped reduction-oxidation graphite liberation of hydrogen composite material |
| CN109395753A (en) * | 2018-09-26 | 2019-03-01 | 昆明理工大学 | A kind of preparation method and application of catalyst for hydrogenation |
| CN109647459A (en) * | 2019-01-17 | 2019-04-19 | 淮北师范大学 | A kind of preparation method for the Ni-based phosphide that composition is controllable |
| CN110983360A (en) * | 2019-12-13 | 2020-04-10 | 中国人民大学 | Porous nitrogen-doped graphene composite cobalt phosphide nanosheet and preparation method and application thereof |
| CN111111731A (en) * | 2019-12-20 | 2020-05-08 | 济南大学 | Preparation method of graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst |
| CN112090434A (en) * | 2020-09-16 | 2020-12-18 | 常州大学 | Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol |
| CN112931531A (en) * | 2021-02-08 | 2021-06-11 | 泉州师范学院 | Carbon-doped nickel phosphide composite antibacterial material and preparation method and application thereof |
| CN113004969A (en) * | 2021-02-27 | 2021-06-22 | 新疆佳宇恒能源科技有限公司 | Hydrogenation method for regeneration of waste lubricating oil |
| CN114164448A (en) * | 2021-10-31 | 2022-03-11 | 吉林大学 | Heterogeneous nickel phosphide material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354614A (en) * | 2011-09-15 | 2012-02-15 | 南开大学 | Phosphide counter electrode for dye sensitized solar cell and preparation method for phosphide counter electrode |
| WO2013062951A1 (en) * | 2011-10-27 | 2013-05-02 | Garmor, Inc. | Composite graphene structures |
-
2014
- 2014-10-31 CN CN201410607150.9A patent/CN104437572B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354614A (en) * | 2011-09-15 | 2012-02-15 | 南开大学 | Phosphide counter electrode for dye sensitized solar cell and preparation method for phosphide counter electrode |
| WO2013062951A1 (en) * | 2011-10-27 | 2013-05-02 | Garmor, Inc. | Composite graphene structures |
Non-Patent Citations (1)
| Title |
|---|
| Y. Y. DOU，ET AL: ""Nickel phosphide-embedded graphene as counter electrode for dye-sensitized solar cells"", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
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| CN104810165B (en) * | 2015-04-29 | 2017-06-23 | 华东理工大学 | A kind of method for preparing nickel phosphide/Graphene composite thin film material |
| CN104810165A (en) * | 2015-04-29 | 2015-07-29 | 华东理工大学 | Nickel phosphide / graphene composite film preparing method |
| CN105195208A (en) * | 2015-09-24 | 2015-12-30 | 神华集团有限责任公司 | Monolithic catalyst, preparation method thereof and desulphurization method utilizing monolithic catalyst |
| CN105642321A (en) * | 2015-12-31 | 2016-06-08 | 青岛科技大学 | Nano red phosphorus/graphene composite photocatalyst and preparation method thereof |
| CN105642321B (en) * | 2015-12-31 | 2019-05-31 | 青岛科技大学 | A kind of nanometer of red phosphorus/graphene composite photocatalyst and preparation method thereof |
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| CN109395753B (en) * | 2018-09-26 | 2021-07-16 | 昆明理工大学 | Preparation method and application of hydrogenation reaction catalyst |
| CN109395753A (en) * | 2018-09-26 | 2019-03-01 | 昆明理工大学 | A kind of preparation method and application of catalyst for hydrogenation |
| CN109647459A (en) * | 2019-01-17 | 2019-04-19 | 淮北师范大学 | A kind of preparation method for the Ni-based phosphide that composition is controllable |
| CN109647459B (en) * | 2019-01-17 | 2021-07-30 | 淮北师范大学 | Preparation method of nickel-based phosphide with controllable composition |
| CN110983360A (en) * | 2019-12-13 | 2020-04-10 | 中国人民大学 | Porous nitrogen-doped graphene composite cobalt phosphide nanosheet and preparation method and application thereof |
| CN110983360B (en) * | 2019-12-13 | 2021-06-08 | 中国人民大学 | Porous nitrogen-doped graphene composite cobalt phosphide nanosheet and preparation method and application thereof |
| CN111111731A (en) * | 2019-12-20 | 2020-05-08 | 济南大学 | Preparation method of graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst |
| CN112090434A (en) * | 2020-09-16 | 2020-12-18 | 常州大学 | Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol |
| CN112090434B (en) * | 2020-09-16 | 2023-05-23 | 常州大学 | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural |
| CN112931531A (en) * | 2021-02-08 | 2021-06-11 | 泉州师范学院 | Carbon-doped nickel phosphide composite antibacterial material and preparation method and application thereof |
| CN112931531B (en) * | 2021-02-08 | 2021-11-30 | 泉州师范学院 | Carbon-doped nickel phosphide composite antibacterial material and preparation method and application thereof |
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| CN114164448B (en) * | 2021-10-31 | 2022-12-16 | 吉林大学 | Heterogeneous nickel phosphide material and preparation method thereof |
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