CN107185570A - A kind of method of the low temperature synthesis row transition metal of VIII first and the bimetallic carbide catalyst of molybdenum/tungsten - Google Patents
A kind of method of the low temperature synthesis row transition metal of VIII first and the bimetallic carbide catalyst of molybdenum/tungsten Download PDFInfo
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- CN107185570A CN107185570A CN201710314814.6A CN201710314814A CN107185570A CN 107185570 A CN107185570 A CN 107185570A CN 201710314814 A CN201710314814 A CN 201710314814A CN 107185570 A CN107185570 A CN 107185570A
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
Abstract
The invention provides a kind of low temperature synthesis row transition metal of VIII first and the method for the bimetallic carbide catalyst of molybdenum/tungsten, belong to material preparation technology and application field.It is characterized in that realizing the preparation of pure phase bimetallic carbide by obtaining the bimetallic oxide progress hot hydrogen reduction of carbon to hydro-thermal process.This method has the advantages that low temperature, simple to operate, energy-conservation and product particle is small, less surface carbon pollutes compared with traditional arc melting process and temperature-programmed reduction method.Prospects for commercial application is optimistic.The bimetallic carbide catalyst of preparation can be used to being hydrogenated with, dehydrogenation, hydrogenolysis, deoxidation, methane synthesis gas, isomerization, ammonolysis craft, evolving hydrogen reaction, hydroxide reaction, oxygen reduction reaction, Water gas shift/WGS and catalyst carrier etc..
Description
Technical field
The invention belongs to material preparation technology and application field, it is related to a kind of low temperature synthesis row transition metal of VIII first
With the bimetallic carbide catalyst of molybdenum tungsten and application.
Background technology
The bimetallic carbide catalyst of the row transition metal of VIII first and molybdenum tungsten is widely used, and is due to it
Available for being hydrogenated with, dehydrogenation, hydrogenolysis, deoxidation, methane synthesis gas, isomerization, ammonolysis craft, evolving hydrogen reaction, hydroxide reaction, hydrogen reduction
Reaction, Water gas shift/WGS and catalyst carrier etc..
At present, a variety of methods are used for the bimetallic carbide for synthesizing group VIII metal nickel, cobalt and iron and tungsten or molybdenum.
Earliest trial uses arc melting process, due to needing high temperature and needing long annealing time, so high energy is needed, and
And product generally has low surface area, so as to limit its application in terms of catalysis.Another common method is program liter
Warm reducing process, (is used as the CH of carbon source by appropriate hydrocarbon gas4,C2H6,C3H8And C4H10) reduce and the corresponding oxide of carburizing or nitridation
Thing prepares carbide.Compared with arc melting process, particle size can be greatly reduced, but phase purity, which is still one, chooses
War.Bimetallic carbide product prepared by this method usually contains monometallic carbide and metal phase.And it is difficult to conversion completely,
Because reaction occurs only on gas-solid interface.Meanwhile, the pyrolysis of excessive carbonaceous gas is easily caused bimetallic carbide
The polymer carbon pollution of particle surface, seriously reduces the avtive spot of catalyst.In addition, strict and complicated synthesis condition,
For example precise control of temperature increase rate (being generally no greater than 1 DEG C/min) and gas component and flow velocity, are seriously limited extensive
Ground manufactures carbide material.
In recent years, using bimetallic nitride bimetallic carbide is prepared as precursor with help size Control and
Phase purity (Wang, X.H.；Zhang,M.H.；Li,W.；Tao,K.Y.Catalysis Today 2008,131,(1-4),111-
117.Alconchel,S.；Sapina,F.；Martinez,E.Dalton Trans 2004,(16),2463-8).Ma, X.M are reported
Road is used for the synthetic method for preparing specific bimetallic carbide by introducing ion exchange resin as initial precursor
(Journal of the American Chemical Society 2012,134,(4),1954-1957.).These methods can
For preparing a kind of specific bimetallic carbide, but other bimetallic carbide can not be generally applicable to.Bimetallic is aoxidized
Carbothermic method (Regmi, the Y.N. of thing；Leonard,B.M.Chemistry of Materials 2014,26,(8),
2609-2616.) it has been used as synthesizing the pure phase bimetallic carbide of the row transition metal of VIII first and molybdenum/tungsten.But it is moved back
Fiery temperature is higher than 950 DEG C, and resulting bimetallic carbide particle size is almost in micron order, and it is observed that very great group
Cluster.This high temperature can also result in the carbon pollution on bimetallic carbide surface, and it will seriously stop its activity as catalyst
Site.
In order to prevent the phase separation in bimetallic carbide, it is important to produce the bimetallic oxide of nanostructured.Hydro-thermal
Processing has been used to prepare the nanometer rods of bimetallic oxide, such as NiMoO4(Peng,S.；Li,L.；Wu,H.B.；
Madhavi,S.；Lou, X.W.D.Advanced Energy Materials 2015,5, (2), 1401172) and CoWO4
(Zhen,L.；Wang,W.S.；Xu,C.Y.；Shao,W.Z.；Qin,L.C.Materials Letters 2008,62,(10),
1740-1742.).In this work, we establish the general way of the bimetallic carbide of synthesis pure phase, i.e., at hydro-thermal
The hot hydrogen reduction method of carbon of the bimetallic oxide of reason, it has low temperature, simple to operate, energy-conservation and the pollution of less surface carbon etc. excellent
Point.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of low temperature synthesis row transition metal of VIII first and molybdenum tungsten
Bimetallic carbide catalyst and application, and optimize preparation condition and catalytic applications.
Technical scheme：
A kind of low temperature synthesis row transition metal of VIII first and the method for the bimetallic carbide catalyst of molybdenum/tungsten, step
It is rapid as follows：
(1) formation of bimetallic oxide：By iron content, cobalt or nickel presoma metal salt and the presoma metal containing molybdenum or tungsten
Salt is dissolved in water respectively, is mixed after stirring, obtains precipitation mixture；
(2) bimetallic oxide of hydro-thermal method processing synthesis：The precipitation mixture that step (1) is obtained is transferred to autoclave
In, and hydro-thermal process is more than 1h at 110-260 DEG C, then naturally cools to room temperature；Yellow-green precipitate is collected, with water and ethanol
Fully dried after washing, it is the bimetallic oxide fine powder below 200 mesh to grind to form granularity；
(3) mixing of bimetallic oxide fine powder and carbonizable substance：Bimetallic oxide fine powder is mixed with carbonizable substance, the two
Mass ratio be 0.01-10, grinding particle diameter be less than 100 microns；
(4) the hot hydrogen reduction of the carbon of bimetallic oxide：The bimetallic oxide mixture that gained step (3) is obtained and work
Property carbon mixing, be transferred in the quartz boat for being placed on quartz tube reactor；At room temperature, by argon gas displaced air, in flowing
Hydrogen under be gradually heating to 500-1000 DEG C of target temperature, heating rate is 1-15 DEG C/min；Naturally cool to after room temperature, close
Hydrogen is closed to allow air slowly to diffuse back into be passivated bimetallic carbide surface in quartz boat, thus avoid vigorous oxidation and
Bulk oxidation.
The catalytic hydrogenation of naphthalene：Bimetallic carbide and naphthalene catalytic hydrogenation reaction, product are decahydronaphthalene and naphthane.
Carbonizable substance can be the materials such as activated carbon and carbon black.
The bimetallic carbide catalyst of the prepared row transition metal of VIII first and molybdenum tungsten can be used to be hydrogenated with, take off
Hydrogen, hydrogenolysis, deoxidation, methane synthesis gas, isomerization, ammonolysis craft, evolving hydrogen reaction, hydroxide reaction, oxygen reduction reaction, water-gas become
Change with catalyst carrier etc..
Beneficial effects of the present invention：This method is compared with traditional arc melting process and temperature-programmed reduction method, with low
Warm, simple to operate, energy-conservation and product particle it is small, the advantages of less surface carbon pollutes.
Brief description of the drawings
Fig. 1 is the XRD of NiMo bimetallic carbide catalysts.
Fig. 2 is the XRD of CoMo bimetallic carbide catalysts.
Fig. 3 is the XRD of FeMo bimetallic carbide catalysts.
Fig. 4 is the XRD of NiW bimetallic carbide catalysts.
Fig. 5 is the XRD of CoW bimetallic carbide catalysts.
Fig. 6 is the XRD of FeW bimetallic carbide catalysts.
Fig. 7 a) it is Ni6Mo6Naphthalene hydrogenation reaction conversion results figure on C catalyst.
Fig. 7 b) it is Ni6Mo6Naphthalene hydrogenation reaction selectivity result figure on C catalyst.
Embodiment
Describe the embodiment of the present invention in detail below in conjunction with technical scheme.
Embodiment 1：By 0.005mol Na2MoO4·2H2O and 0.005mol Ni (NO3)2·6H2O is dissolved in respectively
In 20mL deionized waters, and mixing is stirred at room temperature.Greenish precipitate is obtained, after stirring 30 minutes, by mixture transfer simultaneously
In the stainless steel autoclave for being sealed in 60mL polytetrafluoroethyllining linings, and kept for 4 hours in 180 DEG C of electric dry oven.Then will
Autoclave takes out from baking oven and naturally cools to room temperature.By the way that yellow-green precipitate is collected by centrifugation, fully washed with water and ethanol,
And be dried overnight at 80 DEG C.Product finally is ground to form into fine powder is used to characterize.
Activated carbon (AC) is prepared by the chemical activation approach of cocoanut shell.Pass through the nitrogen adsorption under 77K and desorption etc.
Warm line measurement, the specific surface area for obtaining activated carbon is about 1000m2/ g, average pore size is about 1.87nm, and pore volume is about
0.62cm3/g.Synthesized bimetallic oxide is mixed with activated carbon so that the mol ratio of total metal and carbon is 1:25, and
Mixture is uniformly ground 30 minutes with mortar and pestle.Gained mixture (0.5g) is transferred to and is placed on quartz tube reactor
Quartz boat in.At room temperature by argon gas displaced air 1 hour after, in the H of flowing2Will with 5 DEG C/min under (60mL/min)
Temperature linearity increases to target temperature.After room temperature is naturally cooled to, close gas to allow air slowly to diffuse back into pipe
To be passivated carbide surface, so as to avoid vigorous oxidation and bulk oxidation.Obtain bimetallic carbide catalyst.XRD characterizes knot
Fruit is as shown in Figure 1.
Embodiment 2：By 0.005mol Na2MoO4·2H2O and 0.005mol Co (NO3)2·6H2O is dissolved in respectively
In 20mL deionized waters, and mixing is stirred at room temperature.Greenish precipitate is obtained, after stirring 30 minutes, by mixture transfer simultaneously
In the stainless steel autoclave for being sealed in 60mL polytetrafluoroethyllining linings, and kept for 4 hours in 180 DEG C of electric dry oven.Then will
Autoclave takes out from baking oven and naturally cools to room temperature.By the way that yellow-green precipitate is collected by centrifugation, fully washed with water and ethanol,
And be dried overnight at 80 DEG C.Product finally is ground to form into fine powder is used to characterize.
Synthesized bimetallic oxide is mixed with activated carbon so that the mol ratio of total metal and carbon is 1:25, it is used in combination
Mortar and pestle uniformly grind mixture 30 minutes.Gained mixture (0.5g) is transferred to and is placed on quartz tube reactor
In quartz boat.At room temperature by argon gas displaced air 1 hour after, in the H of flowing2With 2 DEG C/min by temperature under (60mL/min)
Degree is linearly increasing to target temperature.After room temperature is naturally cooled to, close gas with allow air slowly diffuse back into pipe with
Carbide surface is passivated, so as to avoid vigorous oxidation and bulk oxidation.Obtain bimetallic carbide catalyst.XRD characterization results
As shown in Figure 2.
Embodiment 3：By 0.005mol Na2MoO4·2H2O and 0.005mol FeCl2·6H2O is dissolved in 20mL respectively
In deionized water, and mixing is stirred at room temperature.Greenish precipitate is obtained, after stirring 30 minutes, mixture is shifted and sealed
Kept for 4 hours in the stainless steel autoclave of 60mL polytetrafluoroethyllining linings, and in 180 DEG C of electric dry oven.Then by high pressure
Kettle takes out from baking oven and naturally cools to room temperature.By the way that yellow-green precipitate is collected by centrifugation, fully washed with water and ethanol, and
It is dried overnight at 80 DEG C.Product finally is ground to form into fine powder is used to characterize.
Synthesized bimetallic oxide is mixed with activated carbon so that the mol ratio of total metal and carbon is 1:15, it is used in combination
Mortar and pestle uniformly grind mixture 30 minutes.Gained mixture (0.5g) is transferred to and is placed on quartz tube reactor
In quartz boat.At room temperature by argon gas displaced air 1 hour after, in the H of flowing2With 5 DEG C/min by temperature under (60mL/min)
Degree is linearly increasing to target temperature.After room temperature is naturally cooled to, close gas with allow air slowly diffuse back into pipe with
Carbide surface is passivated, so as to avoid vigorous oxidation and bulk oxidation.Obtain bimetallic carbide catalyst.XRD characterization results
As shown in Figure 3.
Embodiment 4：By 0.005mol Na2WO4·2H2O and 0.005mol Ni (NO3)2·6H2O is dissolved in respectively
In 20mL deionized waters, and mixing is stirred at room temperature.Greenish precipitate is obtained, after stirring 30 minutes, by mixture transfer simultaneously
In the stainless steel autoclave for being sealed in 60mL polytetrafluoroethyllining linings, and kept for 4 hours in 180 DEG C of electric dry oven.Then will
Autoclave takes out from baking oven and naturally cools to room temperature.By the way that yellow-green precipitate is collected by centrifugation, fully washed with water and ethanol,
And be dried overnight at 80 DEG C.Product finally is ground to form into fine powder is used to characterize.
Synthesized bimetallic oxide is mixed with activated carbon so that the mol ratio of total metal and carbon is 1:35, it is used in combination
Mortar and pestle uniformly grind mixture 30 minutes.Gained mixture (0.5g) is transferred to and is placed on quartz tube reactor
In quartz boat.At room temperature by argon gas displaced air 1 hour after, in the H of flowing2With 5 DEG C/min by temperature under (60mL/min)
Degree is linearly increasing to target temperature.After room temperature is naturally cooled to, close gas with allow air slowly diffuse back into pipe with
Carbide surface is passivated, so as to avoid vigorous oxidation and bulk oxidation.Obtain bimetallic carbide catalyst.XRD characterization results
As shown in Figure 4.
Embodiment 5：By 0.005mol Na2WO4·2H2O and 0.005mol Co (NO3)2·6H2O is dissolved in respectively
In 20mL deionized waters, and mixing is stirred at room temperature.Greenish precipitate is obtained, after stirring 30 minutes, by mixture transfer simultaneously
In the stainless steel autoclave for being sealed in 60mL polytetrafluoroethyllining linings, and kept for 4 hours in 180 DEG C of electric dry oven.Then will
Autoclave takes out from baking oven and naturally cools to room temperature.By the way that yellow-green precipitate is collected by centrifugation, fully washed with water and ethanol,
And be dried overnight at 80 DEG C.Product finally is ground to form into fine powder is used to characterize.
Synthesized bimetallic oxide is mixed with activated carbon so that the mol ratio of total metal and carbon is 1:35, it is used in combination
Mortar and pestle uniformly grind mixture 30 minutes.Gained mixture (0.5g) is transferred to and is placed on quartz tube reactor
In quartz boat.At room temperature by argon gas displaced air 1 hour after, in the H of flowing2With 5 DEG C/min by temperature under (60mL/min)
Degree is linearly increasing to target temperature.After room temperature is naturally cooled to, close gas with allow air slowly diffuse back into pipe with
Carbide surface is passivated, so as to avoid vigorous oxidation and bulk oxidation.Obtain bimetallic carbide catalyst.XRD characterization results
As shown in Figure 5.
Embodiment 6：By 0.005mol Na2WO4·2H2O and 0.005mol Fe (NO3)2·6H2O is dissolved in respectively
In 20mL deionized waters, and mixing is stirred at room temperature.Greenish precipitate is obtained, after stirring 30 minutes, by mixture transfer simultaneously
In the stainless steel autoclave for being sealed in 60mL polytetrafluoroethyllining linings, and kept for 4 hours in 180 DEG C of electric dry oven.Then will
Autoclave takes out from baking oven and naturally cools to room temperature.By the way that yellow-green precipitate is collected by centrifugation, fully washed with water and ethanol,
And be dried overnight at 80 DEG C.Product finally is ground to form into fine powder is used to characterize.
Synthesized bimetallic oxide is mixed with activated carbon so that the mol ratio of total metal and carbon is 1:15, it is used in combination
Mortar and pestle uniformly grind mixture 30 minutes.Gained mixture (0.5g) is transferred to and is placed on quartz tube reactor
In quartz boat.At room temperature by argon gas displaced air 1 hour after, in the H of flowing2With 5 DEG C/min by temperature under (60mL/min)
Degree is linearly increasing to target temperature.After room temperature is naturally cooled to, close gas with allow air slowly diffuse back into pipe with
Carbide surface is passivated, so as to avoid vigorous oxidation and bulk oxidation.Obtain bimetallic carbide catalyst.XRD characterization results
As shown in Figure 6.
Embodiment 7：The nickel molybdenum bimetallic carbide catalyst of preparation is used for naphthalene hydrogenation reaction, and the catalytic hydrogenation of naphthalene is in fixation
Carried out in bed stainless steel reactor (12 × 2 × 500mm).Therefore, after 0.2g catalyst is diluted with 2mL quartz sands, being loaded into
In the isothermal section of reactor, and in 4.0MPa H2In reductase 12 hour at 400 DEG C to remove transition in (50mL/min flow velocity)
The oxide on surface of metal carbides and bimetallic carbide.After reactor is cooled to 340 DEG C, introduce 5wt.% containing naphthalene with
The cyclohexane solution of 2wt.% n-decanes (internal standard).Condition is set as 4MP gross pressure and 500：1 H2/ oil standard volume ratio.
Fluid sample was collected with 2 hours intervals after the stationary phase of 2 hours.
When in Ni6Mo6When carrying out naphthalene hydrogenation on C, primary product is decahydronaphthalene (referring to Fig. 7).As shown in fig. 7, when WHSV is
7h-1When, conversion ratio is 98.5%, and the selectivity to decahydronaphthalenes is up to 97.8%.With WHSV increase, the conversion ratio of naphthalene and
Selectivity reduction to decahydronaphthalene.But when WHSV is up to 56h-1When, conversion ratio is 47.4%, and the selectivity of decahydronaphthalenes is maintained at
More than 53.9%.As can be seen that resulting Ni6Mo6C shows good performance in the reaction.
Claims (4)
1. a kind of method of low temperature synthesis row transition metal of VIII first and the bimetallic carbide catalyst of molybdenum/tungsten, it is special
Levy and be, step is as follows：
(1) formation of bimetallic oxide：By iron content, cobalt or nickel presoma metal salt and the presoma metal salinity containing molybdenum or tungsten
Water is not dissolved in, is mixed after stirring, is obtained precipitation mixture；
(2) bimetallic oxide of hydro-thermal method processing synthesis：The precipitation mixture that step (1) is obtained is transferred in autoclave,
And hydro-thermal process is more than 1h at 110-260 DEG C, then naturally cools to room temperature；Yellow-green precipitate is collected, is filled with water and ethanol
Divide after washing and dry, it is the bimetallic oxide fine powder below 200 mesh to grind to form granularity；
(3) mixing of bimetallic oxide fine powder and carbonizable substance：Bimetallic oxide fine powder is mixed with carbonizable substance, the matter of the two
Amount is than being 0.01-10, and grinding particle diameter is less than 100 microns；
(4) the hot hydrogen reduction of the carbon of bimetallic oxide：The bimetallic oxide mixture and activated carbon that gained step (3) is obtained
Mixing, is transferred in the quartz boat for being placed on quartz tube reactor；At room temperature, by argon gas displaced air, in the hydrogen of flowing
500-1000 DEG C of target temperature is gradually heating under gas, heating rate is 1-15 DEG C/min；Naturally cool to after room temperature, close hydrogen
Gas is to allow air slowly to diffuse back into quartz boat to be passivated bimetallic carbide surface, it is to avoid vigorous oxidation and body oxygen
Change.
2. the bimetallic carbide of low temperature the synthesis row transition metal of VIII first and molybdenum/tungsten according to claim 1 is urged
The method of agent, it is characterised in that described carbonizable substance is activated carbon or carbon black.
3. the application for the bimetallic carbide catalyst that claim 1 or 2 is prepared, it is characterised in that described bimetallic
Carbide catalyst be used for be hydrogenated with, dehydrogenation, hydrogenolysis, deoxidation, methane synthesis gas, isomerization, ammonolysis craft, evolving hydrogen reaction, hydroxide
Reaction, oxygen reduction reaction, Water gas shift/WGS and catalyst carrier.
4. described application according to claim 3, it is characterised in that described bimetallic carbide catalyst is urged with naphthalene
Change hydrogenation reaction, product is decahydronaphthalene and naphthane.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108425131A (en) * | 2018-01-30 | 2018-08-21 | 华东理工大学 | A kind of nickel-molybdenum based alloys being carried on nickel foam and amorphous carbon system and its preparation method and application |
| CN108588754A (en) * | 2018-05-11 | 2018-09-28 | 上海应用技术大学 | A kind of nickel molybdate/graphene composite material and preparation method for electrocatalytic hydrogen evolution |
| CN109351359A (en) * | 2018-10-18 | 2019-02-19 | 吉林师范大学 | It is a kind of using carbon nanotube as the preparation method of the more metal carbides of Material synthesis |
| CN109718821A (en) * | 2019-01-30 | 2019-05-07 | 中国矿业大学(北京) | A kind of coal tar and naphthalene catalytic hydrogenation transition metal carbide catalyst |
| CN113355687A (en) * | 2021-04-20 | 2021-09-07 | 广东石油化工学院 | Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof |
| CN113584520A (en) * | 2021-07-26 | 2021-11-02 | 中国科学院广州能源研究所 | Super-hydrophilic molybdenum-doped tungsten carbide nano array material and preparation method thereof |
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| CN102600877A (en) * | 2012-01-11 | 2012-07-25 | 大连理工大学 | High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof |
| CN106475113A (en) * | 2016-10-17 | 2017-03-08 | 武汉科技大学 | Multi-functional carbon-supported catalysts of a kind of cobalt sodium/molybdenum composite metal and its preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108425131A (en) * | 2018-01-30 | 2018-08-21 | 华东理工大学 | A kind of nickel-molybdenum based alloys being carried on nickel foam and amorphous carbon system and its preparation method and application |
| CN108588754A (en) * | 2018-05-11 | 2018-09-28 | 上海应用技术大学 | A kind of nickel molybdate/graphene composite material and preparation method for electrocatalytic hydrogen evolution |
| CN109351359A (en) * | 2018-10-18 | 2019-02-19 | 吉林师范大学 | It is a kind of using carbon nanotube as the preparation method of the more metal carbides of Material synthesis |
| CN109718821A (en) * | 2019-01-30 | 2019-05-07 | 中国矿业大学(北京) | A kind of coal tar and naphthalene catalytic hydrogenation transition metal carbide catalyst |
| CN113355687A (en) * | 2021-04-20 | 2021-09-07 | 广东石油化工学院 | Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof |
| CN113584520A (en) * | 2021-07-26 | 2021-11-02 | 中国科学院广州能源研究所 | Super-hydrophilic molybdenum-doped tungsten carbide nano array material and preparation method thereof |
| CN113584520B (en) * | 2021-07-26 | 2022-08-12 | 中国科学院广州能源研究所 | Super-hydrophilic molybdenum-doped tungsten carbide nano array material and preparation method thereof |
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