CN104857973A - Supported catalyst with kernel-shell structure, preparation method thereof and application - Google Patents
Supported catalyst with kernel-shell structure, preparation method thereof and application Download PDFInfo
- Publication number
- CN104857973A CN104857973A CN201510208693.8A CN201510208693A CN104857973A CN 104857973 A CN104857973 A CN 104857973A CN 201510208693 A CN201510208693 A CN 201510208693A CN 104857973 A CN104857973 A CN 104857973A
- Authority
- CN
- China
- Prior art keywords
- noble metal
- catalyst
- metal
- loaded catalyst
- nucleocapsid structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of catalyst materials, and discloses a supported catalyst with a kernel-shell structure, a preparation method thereof and an application. The preparation method of the catalyst includes: co-precipitating alcoholic solution of base metal soluble salt and carrier metal soluble salt under the function of precipitator; and then sintering and restoring sediment, and obtaining the precursor of the supported base metal; and then performing replacement reaction and sintering reaction twice on the supported base metal precursor and precious metal homogeneous solution, and obtaining the supported catalyst taking mesoporous metal oxide as a carrier, base metal as kernel, and alloy of the base metal and precious metal as a shell. The catalyst forms the supported kernel-shell structure, the shell is an alloy of the thin base metal and the precious metal; thus the dosage of the precious metal can be obviously reduced, the production cost of catalyst is decreased; during the catalyzing, decomposing and hydrogen-making processes of hydrazine hydrate, the supported catalyst has good catalyzing efficiency and hydrogen-making selectivity.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to a kind of loaded catalyst with nucleocapsid structure and preparation method thereof and application.
Background technology
Hydrazine hydrate (N
2h
4h
2o) catalytic decomposition hydrogen manufacturing is a storage/hydrogen manufacturing integration new technology having much vehicle-mounted/onboard hydrogen source application prospect, its advantage of storing up hydrogen (such as, sodium borohydride, ammonia borine and formic acid) technology compared to traditional chemical is: effectively hydrogen storage capability high (8wt%), without solid by-product, hydrogen manufacturing cost is low, materials handing is safe and simple.Effective storage hydrogen component of hydrazine hydrate is hydrazine (N
2h
4), its decomposition can be undertaken by two competitive paths: N
2h
4→ N
2+ 2H
2, 3N
2h
4→ 4NH
3+ N
2.From storage hydrogen application point, need selective promotion N
2h
4be decomposed into N
2and H
2, effectively suppress it to be decomposed into N simultaneously
2and NH
3reaction.
Hydrazine hydrate hydrogen manufacturing system is primarily of fuel fluid and catalyst composition, and fuel fluid is the alkaline aqueous solution containing hydrazine hydrate.The core topic that development has high catalytic activity concurrently, high hydrogen manufacturing catalyst that is selective, good durability is development hydrazine hydrate decomposing hydrogen-production technology.Research finds: most VIIIth group 4 transition metal can catalysis hydration hydrazine decomposition reaction, but catalytic activity at mild temperature and hydrogen manufacturing selective all lower.For this problem, usually adopt catalyst alloyization and introduce carrier two kinds of method of modifying.The former is the Electronic Structure of regulating catalyst and geometric configuration mainly, to improve intrinsic catalytic activity and reaction selectivity; Latter improves durability and the activity of catalyst by the nanoparticle structure of rugged catalyst and the strong interaction of carrier and catalyst.Consider catalytic performance and material cost, support type alloy catalyst is most with prospects.Alloy catalyst is primarily of base metal and noble metal composition, and base metal comprises Fe, Co, Ni, and noble metal comprises Ru, Rh, Pd, Ir, Pt.At present, the alloy catalyst of better catalytic activity, usual bullion content is higher, causes the preparation cost of catalyst high, limits the practical application of hydrazine hydrate catalytic decomposition hydrogen manufacturing.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of loaded catalyst with nucleocapsid structure.
Another object of the present invention is to provide the above-mentioned preparation method with the loaded catalyst of nucleocapsid structure.
Another object of the present invention is to provide the above-mentioned application of loaded catalyst in the hydrogen manufacturing of hydrazine hydrate catalytic decomposition with nucleocapsid structure.
The object of the invention is achieved through the following technical solutions:
Have a loaded catalyst for nucleocapsid structure, described catalyst is carrier with metal oxide, take base metal as core, with the alloy of base metal and noble metal for shell.
Described metal oxide preferably has the metal oxide of meso-hole structure, more preferably has magnesia (MgO), the lanthana (La of meso-hole structure
2o
3), cerium oxide (CeO
2) or europium oxide (Eu
2o
3).
The preferred iron of described base metal (Fe), cobalt (Co) or nickel (Ni); The preferred ruthenium of noble metal (Ru), rhodium (Rh), palladium (Pd), according to (Ir) or platinum (Pt).
The above-mentioned preparation method with the loaded catalyst of nucleocapsid structure, comprises following preparation process:
(1) coprecipitation prepares supported non-noble metal presoma:
By precipitating reagent at 30 ~ 60 DEG C with under stirring, dropwise add in the alcoholic solution containing base metal soluble-salt and carrier metal soluble-salt, reaction 1 ~ 2h, then reaction 8 ~ 12h under 80 ~ 100 DEG C and air-proof condition, centrifugation precipitates, under being deposited in 30 ~ 60 DEG C of conditions, dry 8 ~ 12h, then sinters 1 ~ 4h under air atmosphere and 400 ~ 600 DEG C of conditions, finally at flowing H
2under atmosphere and 300 ~ 600 DEG C of conditions, reduction 1.5 ~ 3h, obtains supported non-noble metal presoma;
(2) displacement method preparation has the loaded catalyst of nucleocapsid structure:
Under room temperature and stirring condition, the homogeneous phase solution that the supported non-noble metal presoma of step (1) is placed in noble metal is carried out first time displacement reaction, centrifugation precipitates, first sintering is carried out after precipitation being carried out washing drying, then the homogeneous phase solution being placed in noble metal carries out second time displacement reaction, after washing drying, carry out second time sintering, the loaded catalyst of nucleocapsid structure must be had.
The ethanol of the preferred TMAH of precipitating reagent (TMAH) described in step (1) or methanol solution; Described alcoholic solution preferred alcohol solution or methanol solution.
Preferred Ni (the NO of base metal soluble-salt described in step (1)
3)
2, Fe (NO
3)
3or Co (NO
3)
2; Preferred La (the NO of described carrier metal soluble-salt
3)
3, Ce (NH
4)
2(NO
3)
6, Eu (NO
3)
3or Mg (NO
3)
2; The mol ratio of base metal soluble-salt and carrier metal soluble-salt is preferably 1:2.
The preferred H of homogeneous phase solution of the noble metal described in step (2)
2ptCl
6the aqueous solution, K
2ptCl
6the aqueous solution, RhCl
3the aqueous solution, K
2pdCl
4the aqueous solution or H
2irCl
6the aqueous solution.
First time described in step (2), the mol ratio of the precious metal element contained by homogeneous phase solution of noble metal and the non-noble metal j element contained by supported non-noble metal presoma in displacement reaction was 1:(10 ~ 80); Preferred mol ratio is 1:18; The mol ratio of non-noble metal j element contained in the precious metal element contained by homogeneous phase solution of noble metal and supported non-noble metal presoma in described second time displacement reaction is 1:(5 ~ 8); Preferred mol ratio is 1:8.
First sintering described in step (2) and second time sintering refer to the H in flowing
22 ~ 4h is sintered under atmosphere and 200 ~ 600 DEG C of temperature conditions; Preferably at the H of flowing
22h is sintered under atmosphere and 350 ~ 400 DEG C of temperature conditions.
The above-mentioned application of loaded catalyst in the hydrogen manufacturing of hydrazine hydrate catalytic decomposition with nucleocapsid structure, described application comprises the following steps: under the catalytic action of described loaded catalyst, containing N
2h
4h
2the fuel fluid decomposition of O obtains H
2.
The principle that the present invention is based on is:
First base metal soluble-salt and the co-precipitation under the effect of precipitating reagent of carrier metal soluble-salt, precipitation is through being sintered into non-noble metal oxide and carrier metal oxide, and then non-noble metal oxide is through H
2reduction becomes metal simple-substance, obtains supported non-noble metal presoma; Homogeneous phase solution supported non-noble metal presoma being placed in noble metal carries out displacement reaction, and the nucleocapsid structure load that to obtain take base metal as core, noble metal is shell, then at H
2sinter under atmosphere, base metal and noble metal are mutually diffused in base metal core surface and form alloy, and to obtain take base metal as core, be shell with the alloy of base metal and noble metal, take metal oxide as the loaded catalyst of carrier.
Product of the present invention and preparation method's tool have the following advantages and beneficial effect:
(1) the present invention being core by preparing with base metal, being shell with the alloy of base metal and noble metal, taking metal oxide as the loaded catalyst of carrier, due to the alloy that shell is thin layer base metal and noble metal, therefore, significantly can reduce the use amount of noble metal, reduce the production cost of catalyst;
(2) preparation method of the present invention selects suitable precipitating reagent and dicyandiamide solution, the metal oxide carrier generated is made to have good meso-hole structure, the contact of reactant and catalyst can be increased, simultaneously due to the confinement effect of meso-hole structure, the reunion of the catalyst nano-particles of load can be stoped, the catalytic performance of catalyst is not fully exerted;
(3) catalyst of the present invention has the selective and good durability of high catalytic activity, high hydrogen manufacturing.
Accompanying drawing explanation
Fig. 1 is the Ni/La that embodiment 1 obtains
2o
3, Ni@Ni – Pt/La
2o
3the Pt/La obtained with comparative example 1
2o
3the N of catalyst
2absorption/desorption isotherm figure;
Fig. 2 is the Ni/La that comparative example 2 obtains
2o
3with Ni@Ni – Pt/La
2o
3the N of catalyst
2absorption/desorption isotherm figure;
Fig. 3 is the Ni@Ni – Pt/La of the different Pt content that embodiment 1 obtains
2o
3, Ni/La
2o
3with the Pt/La that comparative example 1 obtains
2o
3reaction rate in the hydrogen manufacturing that catalyst decomposes at hydrazine hydrate and the selective comparison diagram of hydrogen manufacturing;
Fig. 4 is the loaded catalyst Ni@Ni – Pt/La of embodiment 2
2o
3durability experiment result figure;
Fig. 5 is the loading type catalyst Fe@Fe – Rh/CeO of embodiment 3
2durability experiment result figure;
Fig. 6 is the loaded catalyst Co@Co – Pd/Eu of embodiment 4
2o
3durability experiment result figure;
Fig. 7 is the durability experiment result figure of the loaded catalyst Ni@Ni – Ir/MgO of embodiment 5.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The hydrogen production process of the catalyst that following examples and comparative example obtain and hydrogen manufacturing performance are tested as follows:
The structure of hydrogen manufacturing system:
Fuel fluid: 4mL 0.5M N
2h
4h
2o+1.0M NaOH;
Catalyst: the catalyst that each embodiment and comparative example obtain.
Hydrogen production process:
0.2mmol catalyst is placed in the 4mL 0.5M N that temperature is 50 DEG C
2h
4h
2in O+1.0M NaOH fuel fluid, N can be started
2h
4h
2o cartalytic decomposition effect, catalyst/N
2h
4h
2o mol ratio=1/10.
Reaction equation involved by hydrogen production process is as follows:
N
2H
4→N
2+2H
2；
3N
2H
4→4NH
3+N
2。
Hydrogen manufacturing performance test (the catalytic performance test of catalyst) is adopted with the following method:
Gas (the N produced is measured with drainage
2+ H
2) volume, adopt The Ideal-Gas Equation to calculate mist amount of substance.Concrete operations are: the gas that reaction produces, and (decompose issuable NH for absorbing hydrazine through pickling
3), import the Meng Shi wash bottle of dress water, institute discharges the quality of water, the automatic recording quality of balance of employing precision 0.01g and the relation of time.Suppose that the hydrazine hydrate time of decomposing needed for 50% is used for calculating reaction rate or inversion frequency (TOF, h
– 1), and following formulae discovery is used in hydrogen manufacturing selective (X):
(Y is the gas (N produced
2+ H
2) and N
2h
4h
2the mol ratio of O).
Embodiment 1
A kind of loaded catalyst Ni@Ni – Pt/La with nucleocapsid structure of the present embodiment
2o
3, its preparation method is as follows:
(1) coprecipitation prepares supported non-noble metal presoma Ni/La
2o
3:
By 20mL 2.1M TMAH ethanolic solution, under 60 DEG C and magnetic agitation, dropwise add 60mL0.083M Ni (NO
3)
2with 0.17M La (NO
3)
3ethanolic solution in, reaction 1h, proceeds in the reactor of lining tetrafluoro, under 100 DEG C and air-proof condition, reaction 12h, is precipitated through centrifugation, is deposited in dry 12h at 60 DEG C of temperature, then precipitation is moved in tube furnace, under air atmosphere and 500 DEG C of temperature, sinter 2h, finally at flowing H
2reduce 1.5h at atmosphere and 500 DEG C of temperature, obtain supported non-noble metal presoma Ni/La
2o
3;
(2) displacement method preparation has the loaded catalyst Ni@Ni – Pt/La of nucleocapsid structure
2o
3:
Under room temperature and magnetic agitation, by the supported non-noble metal presoma Ni/La of 5 parts of steps (1)
2o
3be placed in the H of 20mL variable concentrations respectively
2ptCl
6(H of variable concentrations is regulated in the aqueous solution
2ptCl
6the aqueous solution makes the mol ratio of Pt element and Ni element in catalyst be respectively 1/78,1/58,1/38,1/18 and 1/8) carry out first time displacement reaction, reaction 1h, centrifugation precipitates, and precipitation carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2in tube furnace, at 350 DEG C of temperature, sinter 2h under atmosphere, obtain the loaded catalyst Ni@Ni – Pt/La with nucleocapsid structure through first time displacement reaction 5 batches of different Pt content
2o
3.
The chemical reaction occurred in the preparation process of the present embodiment is as follows:
Ni
2++2OH
–→Ni(OH)
2↓
La
3++3OH
–→La(OH)
3↓
Ni(OH)
2→NiO+H
2O
NiO+H
2→Ni+H
2O
2La(OH)
3→La
2O
3+3H
2O
2Ni+PtCl
6 2–→2Ni
2++Pt+6Cl
–。
Comparative example 1
Coprecipitation prepares Pt/La
2o
3catalyst:
By 20mL3.0M TMAH ethanolic solution, under 60 DEG C and magnetic agitation, dropwise add 60mL0.083M H
2ptCl
6with 0.17M La (NO
3)
3ethanolic solution in, reaction 1h, proceeds in the reactor of lining tetrafluoro, under 100 DEG C and air-proof condition, reaction 12h, is precipitated through centrifugation, is deposited in dry 12h at 60 DEG C of temperature, then precipitation is moved in tube furnace, under air atmosphere and 500 DEG C of temperature, sinter 2h, finally at flowing H
2reduce 1.5h at atmosphere and 500 DEG C of temperature, obtain Pt/La
2o
3catalyst.
The Ni/La that embodiment 1 obtains
2o
3, Ni@Ni – Pt/La
2o
3the Pt/La obtained with comparative example 1
2o
3the N of catalyst
2absorption/desorption isotherm as shown in Figure 1.As seen from Figure 1,3 kinds of materials all show IV type thermoisopleth, and adsorption line and desorption line are heavy and, there is hysteresis loop, show that 3 kinds of materials all have meso-hole structure.Can obtain through Brunauer-Emmett-Teller (BET) method and Barrett-Joyner-Halenda (BJH) model treatment absorption/desorption isotherm: Ni/La
2o
3, Ni@Ni – Pt/La
2o
3and Pt/La
2o
3specific area be respectively 34.4,73.2 and 55.4m
2/ g, average pore size is respectively 10.8,6.5 and 7.6nm.
Comparative example 2
Ni/La is prepared by the method for embodiment 1
2o
3with Ni@Ni – Pt/La
2o
3catalyst, difference is the NaOH aqueous solution TMAH ethanolic solution in step (1) being changed to comparable sodium; By Ni (NO
3)
2with La (NO
3)
3ethanolic solution be changed to the aqueous solution of equal material concentration, remainder is identical, obtains the Ni/La of this comparative example
2o
3with Ni@Ni – Pt/La
2o
3catalyst.
This comparative example gained Ni/La
2o
3with Ni@Ni – Pt/La
2o
3the N of catalyst
2absorption/desorption isotherm as shown in Figure 2.As seen from Figure 2,2 kinds of materials all show II type thermoisopleth, show that 2 kinds of materials all do not have meso-hole structure.This is because it is precipitating reagent that the supported non-noble metal presoma prepared according to the method for embodiment 1 step (1) adopts ethanol or methyl alcohol to be solvent and organic base TMAH, the organic solvent adsorbed in sintering process sloughs with the remaining relative organic base TMAH with long-chain the meso-hole structure defining metal oxide carrier, and organic base TMAH is replaced with NaOH and after solvent is changed to water by alcoholic solution, gained metal oxide carrier will not have meso-hole structure.
The loaded catalyst Ni@Ni – Pt/La with nucleocapsid structure of 5 batches of different Pt content of embodiment 1
2o
3(not carrying out second time displacement reaction), Ni/La
2o
3and the Pt/La of comparative example 1 (Pt/Ni=0)
2o
3the hydrogen production reaction speed that catalyst decomposes at hydrazine hydrate and the selective contrast of hydrogen manufacturing are as shown in Figure 3.As can be seen from Figure 3: Pt/La
2o
3catalyst does not have activity to hydrazine hydrate, and Ni/La
2o
3illustrate lower activity and hydrogen manufacturing selective.And forming Ni – Pt alloy when Ni and Pt passes through displacement reaction and sintering processes for the first time, the activity and selectivity of catalyst increases substantially, such as, compared to Ni/La
2o
3, when Pt/Ni mol ratio is 1/78, gained Ni@Ni – Pt/La
2o
3catalytic activity add 3 times, hydrogen manufacturing is selective is increased to 92% from 72%; When Pt/Ni mol ratio is 1/18, the activity of the catalyst of preparation is best, and at 50 DEG C, hydrazine hydrate decomposes needs 7 minutes, and its hydrogen manufacturing is selective is increased to 97%, but, continue to increase Pt/Ni mol ratio, the hydraulic performance decline of catalyst.
Embodiment 2
A kind of loaded catalyst Ni@Ni – Pt/La with nucleocapsid structure of the present embodiment
2o
3, its preparation method is as follows:
(1) coprecipitation prepares supported non-noble metal presoma Ni/La
2o
3: identical with embodiment 1;
(2) twice replaced legal system is got everything ready the loaded catalyst Ni@Ni – Pt/La of nucleocapsid structure
2o
3:
Under room temperature and magnetic agitation, by the supported non-noble metal presoma Ni/La of step (1)
2o
3be placed in 20mL K
2ptCl
6(K is regulated in the aqueous solution
2ptCl
6the concentration of the aqueous solution makes the mol ratio of Pt element and Ni element in catalyst be 1:18) carry out first time displacement reaction, reaction 1h, centrifugation precipitates, and precipitation carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2in tube furnace, at 350 DEG C of temperature, sinter 2h under atmosphere, then the product after sintering is placed in 20mLK
2ptCl
6(K is regulated in the aqueous solution
2ptCl
6the concentration of the aqueous solution makes the mol ratio of Pt element and Ni element in catalyst be 1:8) carry out second time displacement reaction, product carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2under atmosphere, 4 parts of products after above-mentioned process are sintered 2h at 250 DEG C, 350 DEG C, 450 DEG C and 600 DEG C, obtains the loaded catalyst Ni@Ni – Pt/La that 4 batches have nucleocapsid structure
2o
3.
4 batches of the present embodiment have the loaded catalyst Ni@Ni – Pt/La of nucleocapsid structure
2o
3be 1/18 with Pt/Ni mol ratio in embodiment 1, do not carry out the catalyst of second time displacement reaction and carry out the contrast that the unsintered catalyst of second time displacement reaction carries out hydrogen manufacturing performance, result is as shown in table 1.
Table 1
As can be seen from Table 1, by a displacement reaction, the hydrogen manufacturing of catalyst is selective reaches as high as 97%, but this means to create a certain amount of NH simultaneously
3, NH
3the operation of acidic proton exchange membrane fuel cell is harmful to, fuel cell can be made poisoning.And the present invention is by twice replaced reaction, namely " secondary alloyed " process is carried out to the catalyst of " alloying ", then at flowing H
22h is sintered, the Ni@Ni – Pt/La of preparation at atmosphere and 350 DEG C
2o
3catalyst performance is best, and through chemical analysis, it consists of 48.4mol%Ni
88.4pt
11.6/ 51.6mol%La
2o
3, its hydrogen manufacturing is selective reaches 100%, and at 50 DEG C, hydrazine hydrate decomposes needs 2.6 minutes, and reaction rate can reach 312h
– 1.Sintering temperature is too high or too low, all has adverse effect to the performance of catalyst, and inappropriate heat treatment can affect the diffusion of Ni and Pt on Ni core surface, thus have impact on the performance of catalyst.
Get the loaded catalyst Ni@Ni – Pt/La of the present embodiment
2o
3(after second time displacement reaction, sintering temperature is 350 DEG C) carries out the durability experiment (recycling by hydrogen production process) of catalyst, and result as shown in Figure 4.As seen from Figure 4: at 50 DEG C, Ni@Ni – Pt/La
2o
3catalyst recycles through 10 times, and catalyst still can keep 82% of its initial activity, but the selective almost no change of 100% hydrogen manufacturing.
Embodiment 3
A kind of loading type catalyst Fe@Fe – Rh/CeO with nucleocapsid structure of the present embodiment
2, its preparation method is as follows:
(1) coprecipitation prepares supported non-noble metal presoma Fe/CeO
2:
By 20mL 1.6M TMAH ethanolic solution, under 30 DEG C and magnetic agitation, dropwise add 60mL0.067M Fe (NO
3)
3with 0.067M Ce (NH
4)
2(NO
3)
6ethanolic solution in, reaction 2h, proceeds in the reactor of lining tetrafluoro, under 80 DEG C and air-proof condition, reaction 12h, is precipitated through centrifugation, is deposited in dry 12h at 30 DEG C of temperature, then precipitation is moved in tube furnace, under air atmosphere and 400 DEG C of temperature, sinter 4h, finally at flowing H
2reduce 3h at atmosphere and 450 DEG C of temperature, obtain supported non-noble metal presoma Fe/CeO
2;
(2) displacement method preparation has the loading type catalyst Fe@Fe – Rh/CeO of nucleocapsid structure
2:
Under room temperature and magnetic agitation, by the supported non-noble metal presoma Fe/CeO of step (1)
2be placed in 20mL RhCl
3(RhCl is regulated in the aqueous solution
3the concentration of the aqueous solution makes the mol ratio of Rh element and Fe element in catalyst be 1/10) carry out first time displacement reaction, reaction 1h, centrifugation precipitates, and precipitation carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2in tube furnace, at 400 DEG C of temperature, sinter 2h under atmosphere, then the product after sintering is placed in 20mL RhCl
3(RhCl is regulated in the aqueous solution
3the concentration of the aqueous solution makes the mol ratio of Rh element and Fe element in catalyst be 1/5) carry out second time displacement reaction, product carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2sinter 2h at atmosphere and 400 DEG C, the loading type catalyst Fe@Fe – Rh/CeO of nucleocapsid structure must be had
2.Gained catalyst has meso-hole structure after tested, chemical analysis its consist of 32.4mol%Fe
82.8rh
17.2/ 67.6mol%CeO
2.
The loading type catalyst Fe@Fe – Rh/CeO of the present embodiment
2carry out the durability experiment (recycling by hydrogen production process) of catalyst, result as shown in Figure 5, as seen from Figure 5: at 50 DEG C, Fe@Fe – Rh/CeO
2the initial activity of catalyst and hydrogen manufacturing is selective is respectively 508h
– 1with 100%, recycle through 20 times, it is active and hydrogen manufacturing is selective almost constant.
Embodiment 4
A kind of loaded catalyst Co@Co – Pd/Eu with nucleocapsid structure of the present embodiment
2o
3, its preparation method is as follows:
(1) coprecipitation prepares supported non-noble metal presoma Co/Eu
2o
3:
By 20mL 2.1M TMAH methanol solution, under 50 DEG C and magnetic agitation, dropwise add 60mL0.083M Co (NO
3)
2with 0.17M Eu (NO
3)
3methanol solution in, reaction 1h, proceeds in the reactor of lining tetrafluoro, under 80 DEG C and air-proof condition, reaction 12h, is precipitated through centrifugation, is deposited in dry 8h at 60 DEG C of temperature, then precipitation is moved in tube furnace, under air atmosphere and 600 DEG C of temperature, sinter 1h, finally at flowing H
2reduce 1.5h at atmosphere and 600 DEG C of temperature, obtain supported non-noble metal presoma Co/Eu
2o
3;
(2) displacement method preparation has the loaded catalyst Co@Co – Pd/Eu of nucleocapsid structure
2o
3:
Under room temperature and magnetic agitation, by the supported non-noble metal presoma Co/Eu of step (1)
2o
3be placed in 20mL K
2pdCl
4(K is regulated in the aqueous solution
2pdCl
4the concentration of the aqueous solution makes the mol ratio of Pd element and Co element in catalyst be 1/18) carry out first time displacement reaction, reaction 1h, centrifugation precipitates, and precipitation carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2in tube furnace, at 400 DEG C of temperature, sinter 2h under atmosphere, then the product after sintering is placed in 20mLK
2pdCl
4(K is regulated in the aqueous solution
2pdCl
4the concentration of the aqueous solution makes the mol ratio of Pd element and Co element in catalyst be 1/8) carry out second time displacement reaction, product carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2sinter 2h at atmosphere and 400 DEG C, the loaded catalyst Co@Co – Pd/Eu of nucleocapsid structure must be had
2o
3.Gained catalyst has meso-hole structure after tested, chemical analysis its consist of 47.8%Co
87.3pd
12.7/ 53.2mol%Eu
2o
3.
The loaded catalyst Co@Co – Pd/Eu of the present embodiment
2o
3carry out the durability experiment (recycling by hydrogen production process) of catalyst, result as shown in Figure 6, as seen from Figure 6: at 50 DEG C, Co@Co – Pd/Eu
2o
3the initial activity of catalyst and hydrogen manufacturing is selective is respectively 286h
– 1with 100%, recycle through 15 times, its activity decrease 13%, but hydrogen manufacturing is selective almost constant.
Embodiment 5
A kind of loaded catalyst Ni@Ni – Ir/MgO with nucleocapsid structure of the present embodiment, its preparation method is as follows:
(1) coprecipitation prepares supported non-noble metal presoma Ni/MgO:
By 20mL 2.1M TMAH ethanolic solution, under 50 DEG C and magnetic agitation, dropwise add 60mL0.083M Ni (NO
3)
2with 0.17M Mg (NO
3)
2ethanolic solution in, reaction 1h, proceeds in the reactor of lining tetrafluoro, under 100 DEG C and air-proof condition, reaction 12h, is precipitated through centrifugation, is deposited in dry 12h at 50 DEG C of temperature, then precipitation is moved in tube furnace, under air atmosphere and 500 DEG C of temperature, sinter 2h, finally at flowing H
2reduce 1.5h at atmosphere and 300 DEG C of temperature, obtain supported non-noble metal presoma Ni/MgO;
(2) displacement method preparation has the loaded catalyst Ni@Ni – Ir/MgO of nucleocapsid structure:
Under room temperature and magnetic agitation, the supported non-noble metal presoma Ni/MgO of step (1) is placed in 20mL H
2irCl
6(H is regulated in the aqueous solution
2irCl
6the concentration of the aqueous solution makes the mol ratio of Ir element and Ni element in catalyst be 1/18) carry out first time displacement reaction, reaction 1h, centrifugation precipitates, and precipitation carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2in tube furnace, at 350 DEG C of temperature, sinter 2h under atmosphere, then the product after sintering is placed in 20mL H
2irCl
6(H is regulated in the aqueous solution
2irCl
6the concentration of the aqueous solution makes the mol ratio of Ir element and Ni element in catalyst be 1/8) carry out second time displacement reaction, product carries out washing successively, alcohol wash, the dry 12h of dynamic vacuum at 30 DEG C of temperature, then at flowing H
2sinter 2h at atmosphere and 350 DEG C, the loaded catalyst Ni@Ni – Ir/MgO of nucleocapsid structure must be had.Gained catalyst has meso-hole structure after tested, chemical analysis its consist of 47.8%Ni
87.3ir
12.7/ 53.2mol%MgO.
The loaded catalyst Ni@Ni – Ir/MgO of the present embodiment carries out the durability experiment (recycling by hydrogen production process) of catalyst, result as shown in Figure 7, as seen from Figure 7: at 50 DEG C, Ni@Ni – Ir/MgO catalyst initial activity and hydrogen manufacturing is selective is respectively 240h
– 1with 100%, recycle through 15 times, its activity decrease 20%, but hydrogen manufacturing is selective almost constant.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. having a loaded catalyst for nucleocapsid structure, it is characterized in that: described catalyst is carrier with metal oxide, take base metal as core, with the alloy of base metal and noble metal for shell.
2. a kind of loaded catalyst with nucleocapsid structure according to claim 1, is characterized in that: described metal oxide refers to the metal oxide with meso-hole structure.
3. a kind of loaded catalyst with nucleocapsid structure according to claim 1 and 2, is characterized in that: described metal oxide refers to magnesia, lanthana, cerium oxide or europium oxide; Described base metal refers to iron, cobalt or nickel; Described noble metal refers to ruthenium, rhodium, palladium, complies with or platinum.
4. a kind of preparation method with the loaded catalyst of nucleocapsid structure described in any one of claims 1 to 3, is characterized in that comprising following preparation process:
(1) coprecipitation prepares supported non-noble metal presoma:
By precipitating reagent at 30 ~ 60 DEG C with under stirring, dropwise add in the alcoholic solution containing base metal soluble-salt and carrier metal soluble-salt, reaction 1 ~ 2h, then reaction 8 ~ 12h under 80 ~ 100 DEG C and air-proof condition, centrifugation precipitates, under being deposited in 30 ~ 60 DEG C of conditions, dry 8 ~ 12h, then sinters 1 ~ 4h under air atmosphere and 400 ~ 600 DEG C of conditions, finally at flowing H
2under atmosphere and 300 ~ 600 DEG C of conditions, reduction 1.5 ~ 3h, obtains supported non-noble metal presoma;
(2) displacement method preparation has the loaded catalyst of nucleocapsid structure:
Under room temperature and stirring condition, the homogeneous phase solution that the supported non-noble metal presoma of step (1) is placed in noble metal is carried out first time displacement reaction, centrifugation precipitates, first sintering is carried out after precipitation being carried out washing drying, then the homogeneous phase solution being placed in noble metal carries out second time displacement reaction, after washing drying, carry out second time sintering, the loaded catalyst of nucleocapsid structure must be had.
5. a kind of preparation method with the loaded catalyst of nucleocapsid structure according to claim 4, is characterized in that: the precipitating reagent described in step (1) refers to ethanol or the methanol solution of TMAH; Described alcoholic solution refers to ethanolic solution or methanol solution; Described base metal soluble-salt refers to Ni (NO
3)
2, Fe (NO
3)
3or Co (NO
3)
2; Described carrier metal soluble-salt refers to La (NO
3)
3, Ce (NH
4)
2(NO
3)
6, Eu (NO
3)
3or Mg (NO
3)
2; The homogeneous phase solution of the noble metal described in step (2) refers to H
2ptCl
6the aqueous solution, K
2ptCl
6the aqueous solution, RhCl
3the aqueous solution, K
2pdCl
4the aqueous solution or H
2irCl
6the aqueous solution.
6. a kind of preparation method with the loaded catalyst of nucleocapsid structure according to claim 4, is characterized in that: the first time described in step (2) mol ratio of the precious metal element contained by homogeneous phase solution of noble metal and the non-noble metal j element contained by supported non-noble metal presoma in displacement reaction be 1:(10 ~ 80); The mol ratio of non-noble metal j element contained in the precious metal element contained by homogeneous phase solution of noble metal and supported non-noble metal presoma in described second time displacement reaction is 1:(5 ~ 8).
7. a kind of preparation method with the loaded catalyst of nucleocapsid structure according to claim 6, is characterized in that: the first time described in step (2) mol ratio of the precious metal element contained by homogeneous phase solution of noble metal and the non-noble metal j element contained by supported non-noble metal presoma in displacement reaction be 1:18; The mol ratio of non-noble metal j element contained in the precious metal element contained by homogeneous phase solution of noble metal and supported non-noble metal presoma in described second time displacement reaction is 1:8.
8. a kind of preparation method with the loaded catalyst of nucleocapsid structure according to claim 4, is characterized in that: the first sintering described in step (2) and second time sintering refer to the H in flowing
22 ~ 4h is sintered under atmosphere and 200 ~ 600 DEG C of temperature conditions.
9. a kind of preparation method with the loaded catalyst of nucleocapsid structure according to claim 8, is characterized in that: the first sintering described in step (2) and second time sintering refer to the H in flowing
22 ~ 4h is sintered under atmosphere and 350 ~ 400 DEG C of temperature conditions.
10. a kind of application of loaded catalyst in the hydrogen manufacturing of hydrazine hydrate catalytic decomposition with nucleocapsid structure described in any one of claims 1 to 3, is characterized in that: under the catalytic action of described loaded catalyst, containing N
2h
4h
2the fuel fluid decomposition of O obtains H
2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510208693.8A CN104857973B (en) | 2015-04-28 | 2015-04-28 | A kind of loaded catalyst with core shell structure and preparation method and application |
| PCT/CN2015/098906 WO2016173285A1 (en) | 2015-04-28 | 2015-12-25 | Supported catalyst having core-shell structure, preparation method therefor, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510208693.8A CN104857973B (en) | 2015-04-28 | 2015-04-28 | A kind of loaded catalyst with core shell structure and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104857973A true CN104857973A (en) | 2015-08-26 |
| CN104857973B CN104857973B (en) | 2017-04-05 |
Family
ID=53904397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510208693.8A Expired - Fee Related CN104857973B (en) | 2015-04-28 | 2015-04-28 | A kind of loaded catalyst with core shell structure and preparation method and application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN104857973B (en) |
| WO (1) | WO2016173285A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195159A (en) * | 2015-10-13 | 2015-12-30 | 天津工业大学 | Catalyst for decomposing hydrazine hydrate to prepare hydrogen and preparation method of catalyst |
| CN105839150A (en) * | 2016-04-25 | 2016-08-10 | 广西大学 | Preparation method of platinum modified material |
| WO2016173285A1 (en) * | 2015-04-28 | 2016-11-03 | 华南理工大学 | Supported catalyst having core-shell structure, preparation method therefor, and application thereof |
| CN106732548A (en) * | 2016-11-24 | 2017-05-31 | 中国石油大学(华东) | A kind of surface modification method of loaded platinum catalyst |
| CN109065893A (en) * | 2018-06-21 | 2018-12-21 | 华南理工大学 | A kind of composite electro catalytic material and its preparation method and application |
| CN114931950A (en) * | 2022-05-27 | 2022-08-23 | 中国科学院大连化学物理研究所 | Carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN115064711A (en) * | 2022-07-13 | 2022-09-16 | 清科(深圳)氢能科技有限公司 | Preparation method and application of high-activity in-situ nitrogen-doped carbon carrier loaded platinum-based alloy catalyst |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433130B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | Embedded copper oxide nanotube catalyst and preparation method and application thereof |
| CN114643069A (en) * | 2022-03-25 | 2022-06-21 | 桂林电子科技大学 | CoP-NiCoP/NC composite material and preparation method and application thereof |
| CN114792817B (en) * | 2022-05-14 | 2023-06-23 | 北京亿华通科技股份有限公司 | Co@Pt core-shell fuel cell catalyst with Au doped subsurface layer and preparation method thereof |
| CN114752963A (en) * | 2022-05-17 | 2022-07-15 | 陕西科技大学 | Preparation method of two-dimensional layered hexagonal nanoscale fullerene sheet/hydrotalcite oxygen evolution electrocatalyst |
| CN115584511A (en) * | 2022-09-21 | 2023-01-10 | 中国船舶重工集团公司第七一八研究所 | Preparation method of copper-iron oxygen evolution catalyst |
| CN115970680A (en) * | 2022-12-28 | 2023-04-18 | 厦门大学 | Wet oxidation catalyst and preparation method and application thereof |
| CN116371404B (en) * | 2023-04-18 | 2023-11-07 | 中国科学院兰州化学物理研究所 | Catalytic wet oxidation catalyst and preparation method and application thereof |
| CN117187870A (en) * | 2023-09-21 | 2023-12-08 | 北京未来氢能科技有限公司 | Preparation method of low iridium catalyst for hydrogen production by water electrolysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
| CN102903939A (en) * | 2012-10-17 | 2013-01-30 | 厦门大学 | Fuel-cell catalyst with non-platinum core-shell structure and preparation method of fuel-cell catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9005331B2 (en) * | 2004-12-22 | 2015-04-14 | Brookhaven Science Associates, Llc | Platinum-coated non-noble metal-noble metal core-shell electrocatalysts |
| CN101664685B (en) * | 2009-09-27 | 2012-05-02 | 西北师范大学 | Low-platinum high active core-shell structure catalyst and preparation method thereof |
| CN102500365A (en) * | 2011-10-19 | 2012-06-20 | 华南理工大学 | Preparation method of catalyst with core-shell structure for low-temperature fuel cell |
| CN104857973B (en) * | 2015-04-28 | 2017-04-05 | 华南理工大学 | A kind of loaded catalyst with core shell structure and preparation method and application |
-
2015
- 2015-04-28 CN CN201510208693.8A patent/CN104857973B/en not_active Expired - Fee Related
- 2015-12-25 WO PCT/CN2015/098906 patent/WO2016173285A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
| CN102903939A (en) * | 2012-10-17 | 2013-01-30 | 厦门大学 | Fuel-cell catalyst with non-platinum core-shell structure and preparation method of fuel-cell catalyst |
Non-Patent Citations (3)
| Title |
|---|
| CHANGMING LI等: "Synthesis of supported Ni@(RhNi-alloy) nanocomposites as an efficient catalyst towards hydrogen generation from N2H4BH3", 《CHEM. COMM.》 * |
| D. CLÉMENÇON等: "Nickel- and platinum-containing core@shell catalysts for hydrogen generation of aqueous hydrazine borane", 《JOURNAL OF POWER SOURCES》 * |
| YUANYUAN JIANG等: "High-performance nickeleplatinum nanocatalyst supported on mesoporous alumina for hydrogen generation from hydrous hydrazine", 《JOURNAL OF POWER SOURCES》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016173285A1 (en) * | 2015-04-28 | 2016-11-03 | 华南理工大学 | Supported catalyst having core-shell structure, preparation method therefor, and application thereof |
| CN105195159A (en) * | 2015-10-13 | 2015-12-30 | 天津工业大学 | Catalyst for decomposing hydrazine hydrate to prepare hydrogen and preparation method of catalyst |
| CN105839150A (en) * | 2016-04-25 | 2016-08-10 | 广西大学 | Preparation method of platinum modified material |
| CN105839150B (en) * | 2016-04-25 | 2017-12-12 | 广西大学 | A kind of material modified preparation method of platinum |
| CN106732548A (en) * | 2016-11-24 | 2017-05-31 | 中国石油大学(华东) | A kind of surface modification method of loaded platinum catalyst |
| CN106732548B (en) * | 2016-11-24 | 2019-02-15 | 中国石油大学(华东) | A kind of surface modification method of loaded platinum catalyst |
| CN109065893A (en) * | 2018-06-21 | 2018-12-21 | 华南理工大学 | A kind of composite electro catalytic material and its preparation method and application |
| CN114931950A (en) * | 2022-05-27 | 2022-08-23 | 中国科学院大连化学物理研究所 | Carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN115064711A (en) * | 2022-07-13 | 2022-09-16 | 清科(深圳)氢能科技有限公司 | Preparation method and application of high-activity in-situ nitrogen-doped carbon carrier loaded platinum-based alloy catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104857973B (en) | 2017-04-05 |
| WO2016173285A1 (en) | 2016-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104857973A (en) | Supported catalyst with kernel-shell structure, preparation method thereof and application | |
| Wei et al. | Boosting the removal of diesel soot particles by the optimal exposed crystal facet of CeO2 in Au/CeO2 catalysts | |
| Xie et al. | Oxygen vacancies of Cr-doped CeO2 nanorods that efficiently enhance the performance of electrocatalytic N2 fixation to NH3 under ambient conditions | |
| Zhou et al. | Available hydrogen from formic acid decomposed by rare earth elements promoted Pd-Au/C catalysts at low temperature | |
| CN104923225B (en) | A kind of loaded noble metal catalyst and its preparation and application | |
| CN103240088B (en) | Catalyst for macro-porous oxide supported core-shell structure nanoparticles and preparation method of catalyst | |
| US20190326607A1 (en) | Method for forming noble metal nanoparticles on a support | |
| CN100445207C (en) | Flower structure nano cerium oxide base composite material and its preparing method and use | |
| CN101940925B (en) | Catalyst of three-dimensional ordered macroporous cerium-based oxide supported gold for purifying diesel soot | |
| CN107552054A (en) | A kind of methane dry gas reforms core shell structure nickel-base catalyst and preparation method | |
| CN104261347B (en) | Method for producing hydrogen by hydrolyzing ammonia borane | |
| CN102631932A (en) | Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof | |
| CN1994563A (en) | Carbon supported noble metal catalyst and method for preparing same | |
| CN104258864A (en) | Nanocomposite catalyst and preparation method and application thereof | |
| CN103977792B (en) | Composite oxide catalyst for catalytic combustion of soot in diesel engine exhaust, and preparation method of catalyst | |
| CN101632929B (en) | Hydrogen production catalyst with high-temperature methyl alcohol water vapour and preparation method thereof | |
| CN104645981A (en) | Pyrolysis gasoline hydrogenation catalyst and preparation method thereof | |
| CN104815635A (en) | Catalyst for combustion of carbon smoke particles, preparation method and application thereof | |
| CN104600327A (en) | Preparation method of carbon-supported nano platinum alloy catalyst | |
| CN108144608A (en) | Carbon monoxide water-gas shift platinum based catalyst and preparation method | |
| CN113941325A (en) | Noble metal catalyst with specific valence state, preparation method and application thereof | |
| CN105618065A (en) | Applications of catalyst in hydrogen production through hydrazine decomposition | |
| CN100588461C (en) | Process for preparation of catalysts for making synthesis gas through tri-reforming of methane | |
| CN105148930A (en) | Modified Co-Ce core-shell structure catalyst for carbon monoxide (CO) low-temperature oxidation | |
| CN107442117A (en) | A kind of exhaust gas catalytic conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate 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: 20170405 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |