CN106179422B - A kind of oxygen doping MOS of carried metal nickel2The preparation method of graphen catalyst - Google Patents
A kind of oxygen doping MOS of carried metal nickel2The preparation method of graphen catalyst Download PDFInfo
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- CN106179422B CN106179422B CN201610599680.2A CN201610599680A CN106179422B CN 106179422 B CN106179422 B CN 106179422B CN 201610599680 A CN201610599680 A CN 201610599680A CN 106179422 B CN106179422 B CN 106179422B
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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Abstract
The invention discloses a kind of oxygen doping MOS of carried metal nickel2The preparation method of graphen catalyst；It is intended to provide one kind to be uniformly dispersed, stability is good, the catalyst with excellent hydrodesulfurization catalytic effect；Technical points: in nanoscale MOS2Oxygen atom is adulterated on the basis of graphene film, is added reducing agent and is made；Belong to catalyst technical field.
Description
Technical field
The present invention relates to a kind of catalyst, specifically, being related to a kind of oxygen doping MOS of carried metal nickel2Graphene is urged
The preparation method of agent；Belong to catalyst technical field.
Background technique
Ni nanoparticle-Mo catalyst is a kind of catalyst for hydrogenation deoxidation desulfurization, can be applied to diesel hydrogenation for removal sulphur, washes
Oil plus hydrogen, the hydrogenation deoxidation, bio oil model compound hydrogenation deoxidation, the macromolecular bio-oil hydrogenation deoxidation that are catalyzed acetic acid etc.
Deng.
Graphene oxide is a kind of carbon nanomaterial with unique hexagon carbon web frame, because it has excellent electronics
The advantages that performance, water dispersion, surface functional group abundant and high specific surface area, the application in terms of catalyst will become
One research emphasis.
Patent (application number 201510747086.9) discloses a kind of Ni nanoparticle-Mo/ graphene oxide catalyst and its system
Preparation Method adds sulfide and nickel, molybdenum precursor, uses after stirring by graphene oxide ultrasonic disperse into deionized water
Excellent Ni nanoparticle-Mo the catalyst of large specific surface area, catalytic performance is made in reducing agent hydrazine hydrate reduction.
Based on above example, although the preparation method in relation to Ni nanoparticle-Mo/ graphene oxide catalyst it has been reported that
So far, there is not yet using lauryl sodium sulfate or cetyl trimethylammonium bromide as surfactant, in carried metal
The MOS of nickel2The related domestic and foreign literature of oxygen and the report of patent are adulterated on the basis of graphen catalyst.The application patent system
The oxygen doping MOS of standby carried metal nickel2Graphen catalyst has higher catalytic activity, has well in catalytic field
Application prospect.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of oxygen doping MOS of carried metal nickel2Graphene catalysis
Agent and preparation method thereof；The graphene carrier large specific surface area of the catalyst, the active component nickel and molybdenum particle size of load are small
And be uniformly dispersed, stability is good, has excellent hydrodesulfurization catalytic effect, and preparation process is simple.
To solve the above problems, previous technical solution provided by the invention is such that
A kind of oxygen doping MOS of carried metal nickel2Graphen catalyst, the catalyst are the oxidation stone after activation
Black alkene area load nanometer nickel particles and nanometer MoS2。
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2Graphen catalyst, using lauryl sodium sulfate or
After the active group of cetyl trimethylammonium bromide surfactant active oxidation graphene surface, load nanometer nickel particles and
After adulterating upper oxygen while nanometer molybdenum particle, adds reducing agent reduction and be made.
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2Graphen catalyst, reducing agent used are hydroboration
Sodium.
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2Graphen catalyst, the nano nickel and nanometer molybdenum
The molar ratio of particle are as follows: 2~6:1~2.5.
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2Graphen catalyst, the nanometer nickel particles are received
The partial size of rice molybdenum particle is 5~100nm.
Latter technique scheme provided by the invention is such that
1) appropriate graphene oxide ultrasonic disperse is weighed into water, is added surfactant, is obtained mixed liquor A；
2) sulfide is soluble in water, nickel, molybdenum presoma that molar ratio is 2~6:1~2.5 are added, 10- is stirred
50min obtains mixed liquid B；
3) mixed liquid B is added in mixed liquor A, adds reducing agent sodium borohydride, and be mixed liquid and go to 100mL
In reaction kettle, 12~36h is reacted at 200~260 DEG C；
4) it is centrifuged after cooling, after ethanol washing 3 times, is dried in vacuo 12h at 60 DEG C.
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2The preparation method of graphen catalyst, before the nickel
Drive body, molybdenum presoma, sulfide molar ratio be 2~6:1~2.5:2~8.
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2The preparation method of graphen catalyst, before the molybdenum
Drive body is (NH4)2MoS4Or K2MoO4。
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2The preparation method of graphen catalyst, before the nickel
Drive body is NiCl2·6H2O or Ni (NO3)2·6H2O。
Preferably, the oxygen doping MOS of above-mentioned carried metal nickel2The preparation method of graphen catalyst, the vulcanization
Object is vulcanized sodium or one of thiocarbamide or four thio ammonium molybdate.
Compared with prior art, technical solution provided by the invention has following technological merit:
Technical solution provided by the invention uses hydrothermal synthesis method, the oxygen doping MOS of the carried metal nickel of preparation2Graphite
Alkene catalyst has higher catalytic activity, has good application prospect in catalytic field.
Detailed description of the invention
Fig. 1 is the oxygen doping MOS of carried metal nickel provided by the invention2Graphen catalyst electron-microscope scanning figure.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not constitute any limitation of the invention, is appointed
The modification for the limited times that who is made in scope of the presently claimed invention is still in scope of the presently claimed invention.
Embodiment 1
1) the oxygen doping MOS of carried metal nickel2The preparation of graphen catalyst: by 12mg graphene oxide ultrasonic disperse
Into 35mL deionized water, it is separately added into 240mg lauryl sodium sulfate, 383mg Ni (NO3)2·6H2O、114mg(NH4)2MoS4(Ni:Mo:S=3:1:4), 30min is stirred, the sodium borohydride solution of 20mL 0.4mol/L is added.Mixed liquor is gone to
In 100mL ptfe autoclave, it is heated to reacting for 24 hours at 220 DEG C.It is centrifuged after cooling, after ethanol washing 3 times, 60
12h is dried in vacuo at DEG C.According to the oxygen doping MOS of the carried metal nickel of above-mentioned steps preparation2Graphen catalyst, partial size
About 20-60nm.
2) hydrodesulfurization catalytic reacts: 2.8g naphthalene and 0.224g dibenzothiophenes being dissolved in 28g normal heptane, are placed in
In 250mL pyroreaction kettle.Weigh the oxygen doping MOS of 1g carried metal nickel2Graphen catalyst is added in mixed solution,
In logical H2Under the conditions of, pressure regulation power is 5MPa, is heated to 230 DEG C of reaction 4h, is calculated through detection, model compound hydrogenation conversion
Up to 66.2%, desulfurization degree is up to 71.4%.
Embodiment 2
1) the oxygen doping MOS of carried metal nickel2The preparation of graphen catalyst: by 24mg graphene oxide ultrasonic disperse
Into 35mL deionized water, it is separately added into 120mg cetyl trimethylammonium bromide, 400mg NiCl2·6H2O、200mg
K2MoO4, 524mg vulcanized sodium (Ni:Mo:S=2:1:8) stir 30min, add the sodium borohydride solution of 20mL 0.4mol/L.
Mixed liquor is gone in 100mL ptfe autoclave, is heated to reacting 12h at 200 DEG C.It is centrifuged after cooling, uses ethyl alcohol
After washing 3 times, 12h is dried in vacuo at 60 DEG C.According to the oxygen doping MOS of the carried metal nickel of above-mentioned steps preparation2Graphene is urged
Agent, partial size are about 30-70nm.
2) hydrodesulfurization catalytic reacts: 2.8g naphthalene and 0.224g dibenzothiophenes being dissolved in 28g normal heptane, are placed in
In 250mL pyroreaction kettle.Weigh the oxygen doping MOS of carried metal nickel2Graphen catalyst is added in mixed solution,
Logical H2Under the conditions of, pressure regulation power is 5MPa, is heated to 230 DEG C of reaction 4h, is calculated through detection, and model compound hydrogenation conversion reaches
82.4%, desulfurization degree is up to 76.6%.
Embodiment 3
1) the oxygen doping MOS of carried metal nickel2The preparation of graphen catalyst: by 36mg graphene oxide ultrasonic disperse
Into 35mL deionized water, it is separately added into 240mg lauryl sodium sulfate, 179mg Ni (NO3)2·6H2O、100mg K2MoO4、
77mg thiocarbamide (Ni:Mo:S=4:2.5:6) stirs 30min, adds the sodium borohydride solution of 20mL 0.4mol/L.It will mixing
Liquid is gone in 100mL ptfe autoclave, is heated to reacting 12h at 240 DEG C.It is centrifuged after cooling, with ethanol washing 3 times
Afterwards, 12h is dried in vacuo at 60 DEG C.According to the oxygen doping MOS of the carried metal nickel of above-mentioned steps preparation2Graphen catalyst,
Partial size is about 20-60nm.
2) hydrodesulfurization catalytic reacts: 2.8g naphthalene and 0.224g dibenzothiophenes being dissolved in 28g normal heptane, are placed in
In 250mL pyroreaction kettle.Weigh the oxygen doping MOS of 1g carried metal nickel2Graphen catalyst is added in mixed solution,
In logical H2Under the conditions of, pressure regulation power is 5MPa, is heated to 230 DEG C of reaction 4h, is calculated through detection, model compound hydrogenation conversion
Up to 93.4%, desulfurization degree is up to 88.2%.
By above-mentioned example it is found that the additive amount of surfactant is to the oxygen doping MOS of carried metal nickel2Graphene catalysis
The hydrodesulfurization effect of agent is affected.
Claims (4)
1. a kind of oxygen doping MoS of carried metal nickel2The preparation method of graphen catalyst, which is characterized in that under successively including
State step:
1) appropriate graphene oxide and surfactant mixing are weighed, mixed liquor A is obtained；
2) sulfide is soluble in water, nickel, molybdenum presoma that molar ratio is 2~6:1~2.5 are added, 10-50min is stirred, obtains
Mixed liquid B；
3) mixed liquid B is added in mixed liquor A, adds reducing agent sodium borohydride, and be mixed liquid and go to 100mL reaction
In kettle, 12~36h is reacted at 200~260 DEG C；
4) it is centrifuged after cooling, after ethanol washing 3 times, is dried in vacuo 12h at 60 DEG C, obtains the oxygen doping of carried metal nickel
MoS2Graphen catalyst；
The nickel presoma, molybdenum presoma, sulfide molar ratio be 2~6:1~2.5:2~8；
The sulfide is vulcanized sodium or one of thiocarbamide or four thio ammonium molybdate；
Surfactant used is lauryl sodium sulfate or cetyl trimethylammonium bromide.
2. the oxygen doping MoS of carried metal nickel according to claim 12The preparation method of graphen catalyst, feature
It is, the molybdenum presoma is (NH4)2MoS4Or K2MoO4。
3. the oxygen doping MoS of carried metal nickel according to claim 12The preparation method of graphen catalyst, feature
It is, the nickel presoma is NiCl2·6H2O or Ni (NO3)2·6H2O。
4. a kind of oxygen doping MoS for the carried metal nickel that preparation method according to claim 1 is prepared2Graphene is urged
Agent.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107694579B (en) * | 2017-03-14 | 2021-03-02 | 中国石油大学(北京) | Vulcanization type hydrodesulfurization catalyst and preparation method and application thereof |
| CN108441879B (en) * | 2018-03-21 | 2019-08-30 | 吉林大学 | Nanoporous nickel-molybdenum disulfide/graphene composite material preparation method and application |
| CN108607582B (en) * | 2018-05-29 | 2020-11-24 | 潍坊学院 | Molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, and preparation method and application thereof |
| CN111403658A (en) * | 2020-03-04 | 2020-07-10 | 南昌大学 | Preparation method of diaphragm with electrocatalysis function and application of diaphragm in lithium-sulfur battery |
| CN112010291B (en) * | 2020-09-03 | 2022-03-29 | 郑州工程技术学院 | Preparation method and application of nickel-doped molybdenum disulfide/graphene three-dimensional composite material |
| CN113713833B (en) * | 2021-09-15 | 2022-10-28 | 北京师范大学 | Molybdenum oxysulfide/nickel sulfide/foamed nickel complex and preparation method and application thereof |
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| CN105214676A (en) * | 2015-11-03 | 2016-01-06 | 广东工业大学 | A kind of Ni nanoparticle-Mo/ graphene oxide Catalysts and its preparation method |
| CN105289636A (en) * | 2015-11-03 | 2016-02-03 | 广东工业大学 | Nanometer Ni-Mo/graphene oxide catalyst and preparation method thereof |
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| CN105214676A (en) * | 2015-11-03 | 2016-01-06 | 广东工业大学 | A kind of Ni nanoparticle-Mo/ graphene oxide Catalysts and its preparation method |
| CN105289636A (en) * | 2015-11-03 | 2016-02-03 | 广东工业大学 | Nanometer Ni-Mo/graphene oxide catalyst and preparation method thereof |
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