CN109718776A - Hydrogenation catalyst Co@C/ biomass and its preparation method and application - Google Patents
Hydrogenation catalyst Co@C/ biomass and its preparation method and application Download PDFInfo
- Publication number
- CN109718776A CN109718776A CN201910057275.1A CN201910057275A CN109718776A CN 109718776 A CN109718776 A CN 109718776A CN 201910057275 A CN201910057275 A CN 201910057275A CN 109718776 A CN109718776 A CN 109718776A
- Authority
- CN
- China
- Prior art keywords
- biomass
- hydrogenation catalyst
- preparation
- catalyst
- zif
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to catalyst preparation technical fields, especially a kind of hydrogenation catalyst Co C/ biomass and its preparation method and application, comprising: 1) take biomass and acid solution back flow reaction, biomass is washed with deionized water, air drying is sealed；2) cobalt salt is weighed respectively and 2-methylimidazole is dissolved in methanol, be uniformly mixing to obtain ZIF-67 precursor solution；3) the complete biomass of pre-treatment is immersed in ZIF-67 precursor solution and is aged, or the complete biomass of pre-treatment is placed in incubation water heating in hydrothermal reaction kettle together with ZIF-67 precursor solution and is reacted；Take out blocky biomass, air drying；4) precipitating in hydrothermal reaction kettle is collected by centrifugation, is repeatedly washed with methanol, dries and catalyst precursor ZIF-67 is made；5) biomass obtained by step (3) is placed in porcelain boat, leads to N2Hydrogenation catalyst Co@C/ biomass is made in lower calcining；Catalyst Co@C/ biomass obtained is used for hydrogenation catalyst synthetic reaction.
Description
Technical field
The present invention relates to catalyst preparation technical field, specific field be a kind of hydrogenation catalyst Co@C/ biomass and its
Preparation method.
Background technique
The energy is the important supporting substances of national development, is related to the various aspects such as politics, economic, society and military affairs.Many institutes
Known, world energy sources stock number is limited, and however as the continuous development of current world economy, energy consumption is growing day by day,
It rises one after another all over the world because disputing caused by energy problem, energy crisis is increasingly prominent, corresponding environmental pollution
It is also one of current major issue, countries in the world just actively take measures to be coped with.Therefore, reasonable, clean and efficient land productivity
With the current energy, it is of great significance to global economy and health, stabilization and the sustainable development of society.
Metal-organic framework material (Metal-Organic Frameworks, abbreviation MOFs) be it is a kind of by metal ion with
The novel porous mesh material that organic ligand is connected to form by coordination.It is to utilize organic ligand and metal ion or gold
Belong to cluster by having one-dimensional, two-dimentional or three-dimensional infinite network knot made of coordinate bond or intermolecular interaction self assembly
The crystalline material of structure.Metal ion in MOFs structure is coupled by organic ligand and high degree of dispersion is isolated, while these organic are matched
Body in thermal decomposition process height charing can barrier metal reunion, thus be hopeful be made high dispersive, partial size it is small and
Uniform metal or metal oxide nanoparticles, these nanoparticles can be used as active catalytic center.In addition, MOFs heat point
Solution prepares metal or metal oxide also has the advantage that, i.e. the porous carbon of the organic matter pyrolysis generation of ligand or filling,
Meeting portion envelops live metallic particles, to improve the stability of catalyst.
Hydrogenation synthesis catalyst will form stronger phase mainly using oxide as carrier between this kind of carrier and metallic particles
Interaction generates the cobalt species for being difficult to restore, reduces the utilization rate of cobalt.Usually, the catalytic performance of Fischer-Tropsch synthesis agent
It is highly relevant with the type of its carrier.The most common carrier of Co catalysts is various oxides and molecular sieve carrier, such as Al2O3、
SiO2、TiO2With Si-Al molecular sieve etc., for these conventional oxide carriers, active force between carrier and metal is strong, carrier
The factors such as the dropping place that unordered pore structure and cobalt is difficult to investigate in carrier surface allow researcher to be difficult to obtain carrier to urging
The influencing mechanism of agent catalyst performance.Active force is weaker between carbon carrier and metal, especially graphitized carbon material.
Summary of the invention
The purpose of the present invention is to provide a kind of hydrogenation catalyst Co@C/ biomass and its preparation method and application, with one
Carrier of the cellular biomass of kind as hydrogenation synthesizing reaction agent, forms a kind of cellular hydrogenation catalyst -- biomass-based macropore
The derivative catalyst of interior growth ZIF-67.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of hydrogenation catalyst Co@C/ biomass, comprising the following steps:
(1) pre-treatment of catalyst carrier: take the acid solution of 1~5g bulk biomass and 30~150mL at 50~120 DEG C
At a temperature of back flow reaction 1~36 hour, then biomass is washed with deionized water, air drying, is sealed stand-by；
(2) it weighs molar ratio to be dissolved in methanol solution for the cobalt salt and 2-methylimidazole of 1:1~25, be uniformly mixing to obtain
ZIF-67 precursor solution；
(3) the complete biomass of pre-treatment is immersed in ZIF-67 precursor solution and is aged 3~48 hours, or by preceding place
The biomass managed is placed in 60~150 DEG C of incubation water heatings in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle together with ZIF-67 precursor solution
Reaction 3~48 hours；Take out blocky biomass, air drying；
(4) precipitating in reaction kettle is collected by centrifugation, is repeatedly washed with methanol, dries and catalyst precursor ZIF-67 is made；
(5) biomass obtained by step (3) is placed in porcelain boat, in logical N2Under conditions of calcine, be made hydrogenation catalyst Co@
C/ biomass.
The preparation method of hydrogenation catalyst Co@C/ biomass of the present invention, wherein the acid in the step (1) is molten
Liquid is nitric acid, hydrogen peroxide or liquor potassic permanganate.
The preparation method of hydrogenation catalyst Co@C/ biomass of the present invention, wherein biomass is in the step (1)
Biological material with natural macropore, preferably wooden unit, bamboo or falx straw.
The preparation method of hydrogenation catalyst Co@C/ biomass of the present invention, wherein washing times in the step (1)
It is 3~6 times.
The preparation method of hydrogenation catalyst Co@C/ biomass of the present invention, wherein cobalt salt is six in the step (2)
Nitric hydrate cobalt, four acetate hydrate cobalts or cobalt chloride.
The preparation method of hydrogenation catalyst Co@C/ biomass of the present invention, wherein calcination temperature in the step (5)
It is 300~900 DEG C.
The preparation method of hydrogenation catalyst Co@C/ biomass of the present invention, wherein calcining 0.5 in the step (5)~
6 hours.
Hydrogenation catalyst Co@C/ biomass made from any preparation method of the present invention.
Hydrogenation catalyst Co@C/ biomass of the present invention is used to carry out CO hydrogenation catalyst synthetic reaction and to CO2Into
Row hydrogenation catalyst synthetic reaction.
The combination of MOFs material derived metallic catalyst and blocky biomass catalyzing agent carrier, blocky biomass itself
With without curved duct, H2It is limited in duct with CO and passes through, is more advantageous to H2With the raising of the mass transfer effect of CO, make it
It is forced to come into full contact with and react with metallic catalyst derived from MOFs.Therefore the hydrogenation catalyst Co@C/ that the present invention synthesizes
Biomass can become the new catalyst of function admirable.
Compared with prior art, the beneficial effects of the present invention are:
Preparation method of the invention is auxiliary again through carbonizing with hydro-thermal method to impregnate, so that using charcoal duct as reaction vessel,
Reaction generates the derivative metallic catalyst of ZIF-67 in duct, efficiently generates active hydrogenation catalyst good, thermal stability is high
Co@C/ biomass.This Optimization of preparation technological reaction condition has significantly simplified synthesis technology and has reduced experimental cost.
Detailed description of the invention
Fig. 1 is the XRD diagram of ZIF-67 crystal made from embodiment 1；
Fig. 2 is the SEM shape appearance figure of ZIF-67 crystal made from embodiment 1；
Fig. 3 is the XRD spectrum of hydrogenation catalyst Co@C/ biomass made from embodiment 1；
Fig. 4 is the SEM shape appearance figure of hydrogenation catalyst Co@C/ biomass made from embodiment 1.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of hydrogenation catalyst Co@C/ biomass, comprising the following steps:
(1) 1.5g cube wooden unit is taken, by it with 50mL nitric acid solution back flow reaction 24 hours under conditions of 60 DEG C, then
Wooden unit is washed repeatedly 5 times under conditions of boiling with deionized water, dry under room temperature, sealing is stand-by；
(2) cabaltous nitrate hexahydrate for weighing 0.359g is dissolved in the methanol of 25ml, is uniformly mixing to obtain solution A, is weighed
The 2-methylimidazole of 0.811g is dissolved in 25ml methanol, is uniformly mixing to obtain solution B, and solution A is poured into solution B, at room temperature
1h is stirred, mixed solution C is obtained；
(3) by the complete cube wooden unit normal temperature dipping of pre-treatment in step (1) 24 hours in solution C, cube is taken out
Sample is collected by centrifugation in wooden unit air drying, remaining solution, is washed 3 times with methanol, dry obtained catalyst precursor ZIF-67；
(4) gained wooden unit in step (3) is placed in porcelain boat, in logical N2Under conditions of 600 DEG C of calcining 3h, obtained sample adds
Hydrogen catalyst Co@C/ biomass；
Fig. 1 is that step (3) obtain the XRD diagram of ZIF-67 crystalline material, and as shown in Figure 1, the present embodiment obtains ZIF-67's
The position of the diffraction maximum of crystal structure phasor is consistent, it was demonstrated that resulting sample is the ZIF-67 crystal of pure phase.
The present embodiment obtains the SEM appearance figure of ZIF-67 material as shown in Fig. 2, as can be seen from the figure according to the present embodiment
The ZIF-67 of preparation is dodecahedral shape.
Fig. 3 is that the present embodiment obtains the XRD diagram of hydrogenation catalyst Co@C/ biomass, obviously finds wooden unit by charcoal by Fig. 3
After change, metallic cobalt is highlighted, more conducively the raising of catalytic activity.
The present embodiment obtain hydrogenation catalyst Co@C/ biomass SEM appearance figure as shown in figure 4, as can be seen from the figure by
Porous material derived from ZIF-67 has obviously been grown in the charcoal duct prepared according to test method.
Hydrogenation catalyst Co@C/ biomass made from the above method is used for hydrogenation catalyst synthetic reaction.
Embodiment 2
A kind of preparation method of hydrogenation catalyst Co@C/ biomass, comprising the following steps:
(1) 2g bulk bamboo chip is taken, by it with 100mL hydrogen peroxide back flow reaction 36 hours under conditions of 80 DEG C, then is spent
Ionized water washs blocky bamboo chip 5 times under conditions of boiling repeatedly, dry under room temperature, and sealing is stand-by；
(2) the four acetate hydrate cobalts for weighing 0.83g are dissolved in the methanol of 25ml, are uniformly mixing to obtain solution A, are weighed
The 2-methylimidazole of 0.821g is dissolved in 25ml methanol, is uniformly mixing to obtain solution B, and solution A is poured into solution B, at room temperature
1h is stirred, mixed solution C is obtained；
(3) the complete blocky bamboo chip of pre-treatment in step (1) is placed in polytetrafluoroethylene (PTFE) together with mixed solution C is liner
In hydrothermal reaction kettle, 80 DEG C of hydro-thermal reaction 36h are cooled to room temperature, and take out bamboo chip air drying, and sample is collected by centrifugation in remaining solution
Product are washed 3 times with methanol, dry obtained catalyst precursor ZIF-67；
(4) gained bamboo chip in step (3) is placed in porcelain boat, in logical N2Under conditions of 800 DEG C of calcining 3h, obtained sample adds
Hydrogen catalyst Co@C/ biomass；
Hydrogenation catalyst Co@C/ biomass made from the above method is used for hydrogenation catalyst synthetic reaction.
Embodiment 3
A kind of preparation method of hydrogenation catalyst Co@C/ biomass, comprising the following steps:
(1) 1g bulk falx straw is taken, the back flow reaction 12 under conditions of 100 DEG C is small with 80mL liquor potassic permanganate by it
When, then blocky falx straw is washed 5 times repeatedly under conditions of boiling with deionized water, dry under room temperature, sealing is stand-by；
(2) cobalt chloride for weighing 0.2425g is dissolved in the methanol of 30ml, is uniformly mixing to obtain solution A, weighs 0.821g's
2-methylimidazole is dissolved in 30ml methanol, is uniformly mixing to obtain solution B, and solution A is poured into solution B, stirs 0.5h at room temperature,
Obtain mixed solution C；
(3) the complete blocky falx straw of pre-treatment in step (1) is placed in polytetrafluoroethylene (PTFE) together with mixed solution C is liner
Hydrothermal reaction kettle in, 100 DEG C of hydro-thermal reaction 18h are cooled to room temperature, take out falx straw air drying, remaining solution centrifugation receive
Collect sample, is washed 3 times with methanol, dry obtained catalyst precursor ZIF-67；
(4) gained falx straw in step (3) is placed in porcelain boat, in logical N2Under conditions of 700 DEG C of calcining 4h, be made sample
Hydrogenation catalyst Co@C/ biomass；
(5) hydrogenation catalyst Co@C/ biomass obtained is used for hydrogenation catalyst synthetic reaction.
Hydrogenation catalyst Co@C/ biomass is obtained by embodiment 1, and it is living to carry out Fischer-Tropsch synthesis at different temperatures
Property test, it is as shown in table 1 from test result.It can be seen that the hydrogenation catalyst Co@C/ biology prepared according to above-mentioned implementation method
Matter has higher catalytic activity.Show derivative catalyst --- the hydrogenation catalyst Co@C/ of growth ZIF-67 in biomass-based macropore
Biomass is successfully prepared, significant effect.
Table 1
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of preparation method of hydrogenation catalyst Co@C/ biomass, which comprises the following steps:
(1) pre-treatment of catalyst carrier: take the acid solution of 1~5g bulk biomass and 30~150mL in 50~120 DEG C of temperature
Lower back flow reaction 1~36 hour, then biomass is washed with deionized water, air drying, it is sealed stand-by；
(2) it weighs molar ratio to be dissolved in methanol solution for the cobalt salt and 2-methylimidazole of 1:1~25, is uniformly mixing to obtain ZIF-67
Precursor solution；
(3) the complete biomass of pre-treatment is immersed in ZIF-67 precursor solution and is aged 3~48 hours, or pre-treatment is complete
Biomass 60~150 DEG C of incubation water heatings reactions are placed in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle together with ZIF-67 precursor solution
3~48 hours；Take out blocky biomass, air drying；
(4) precipitating in reaction kettle is collected by centrifugation, is repeatedly washed with methanol, dries and catalyst precursor ZIF-67 is made；
(5) biomass obtained by step (3) is placed in porcelain boat, in logical N2Under conditions of calcine, it is raw that hydrogenation catalyst Co@C/ is made
Substance.
2. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step
(1) acid solution in is nitric acid, hydrogen peroxide or liquor potassic permanganate.
3. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step (1)
Middle biomass is the biological material with natural macropore.
4. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step (1)
Middle biomass includes wooden unit, bamboo and falx straw.
5. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step (1)
Middle washing times are 3~6 times.
6. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step (2)
Middle cobalt salt is cabaltous nitrate hexahydrate, four acetate hydrate cobalts or cobalt chloride.
7. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step (5)
Middle calcination temperature is 300~900 DEG C.
8. the preparation method of hydrogenation catalyst Co@C/ biomass according to claim 1, it is characterised in that: the step (5)
Middle calcining 0.5~6 hour.
9. hydrogenation catalyst Co@C/ biomass made from any preparation method of claim 1-8.
10. the application of hydrogenation catalyst Co@C/ biomass described in claim 9, it is characterised in that: add hydrogen to urge for carrying out to CO
It is combined to reaction and to CO2Carry out hydrogenation catalyst synthetic reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910057275.1A CN109718776B (en) | 2019-01-22 | 2019-01-22 | Hydrogenation catalyst Co @ C/biomass and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910057275.1A CN109718776B (en) | 2019-01-22 | 2019-01-22 | Hydrogenation catalyst Co @ C/biomass and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109718776A true CN109718776A (en) | 2019-05-07 |
| CN109718776B CN109718776B (en) | 2021-02-09 |
Family
ID=66299195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910057275.1A Active CN109718776B (en) | 2019-01-22 | 2019-01-22 | Hydrogenation catalyst Co @ C/biomass and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109718776B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280246A (en) * | 2019-06-28 | 2019-09-27 | 中南民族大学 | The preparation method of a kind of Co/C-N catalyst and its in CO2Application in synthesizing methanol by hydrogenating reaction |
| CN110492065A (en) * | 2019-07-26 | 2019-11-22 | 江苏理工学院 | It is a kind of based on the S/Co/CNF composite material and preparation method of discarded cigarette butt and application |
| CN112774682A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院城市环境研究所 | Aluminum-cobalt composite catalyst and preparation method and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN113289666A (en) * | 2021-06-25 | 2021-08-24 | 南京工业大学 | Simple preparation method of Co/CM ceramic catalytic membrane |
| CN113351207A (en) * | 2021-04-09 | 2021-09-07 | 临涣焦化股份有限公司 | Multi-wall catalyst for preparing liquid fuel by carbon dioxide hydrogenation and preparation method and application thereof |
| CN114797927A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院大连化学物理研究所 | Composite carrier material loaded cobalt-based catalyst, preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096542A (en) * | 2014-06-23 | 2014-10-15 | 广西师范大学 | Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN107394214A (en) * | 2017-07-13 | 2017-11-24 | 北京化工大学常州先进材料研究院 | The preparation and application of the nitrogen co-doped porous carbon microsphere material of cobalt |
| CN107970893A (en) * | 2017-11-29 | 2018-05-01 | 广西大学 | A kind of Jasmine base porous charcoal MOFs composite materials and preparation method thereof |
| CN108339525A (en) * | 2018-02-11 | 2018-07-31 | 华南理工大学 | A kind of sorbing material and preparation method and application |
| CN108993411A (en) * | 2018-07-14 | 2018-12-14 | 启东创绿绿化工程有限公司 | A kind of preparation method of Copper-cladding Aluminum Bar ZIF-8 nano-complex |
-
2019
- 2019-01-22 CN CN201910057275.1A patent/CN109718776B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096542A (en) * | 2014-06-23 | 2014-10-15 | 广西师范大学 | Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN107394214A (en) * | 2017-07-13 | 2017-11-24 | 北京化工大学常州先进材料研究院 | The preparation and application of the nitrogen co-doped porous carbon microsphere material of cobalt |
| CN107970893A (en) * | 2017-11-29 | 2018-05-01 | 广西大学 | A kind of Jasmine base porous charcoal MOFs composite materials and preparation method thereof |
| CN108339525A (en) * | 2018-02-11 | 2018-07-31 | 华南理工大学 | A kind of sorbing material and preparation method and application |
| CN108993411A (en) * | 2018-07-14 | 2018-12-14 | 启东创绿绿化工程有限公司 | A kind of preparation method of Copper-cladding Aluminum Bar ZIF-8 nano-complex |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280246A (en) * | 2019-06-28 | 2019-09-27 | 中南民族大学 | The preparation method of a kind of Co/C-N catalyst and its in CO2Application in synthesizing methanol by hydrogenating reaction |
| CN110492065A (en) * | 2019-07-26 | 2019-11-22 | 江苏理工学院 | It is a kind of based on the S/Co/CNF composite material and preparation method of discarded cigarette butt and application |
| CN110492065B (en) * | 2019-07-26 | 2022-02-08 | 江苏理工学院 | S/Co/CNF composite material based on waste cigarette ends and preparation method and application thereof |
| CN112774682A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院城市环境研究所 | Aluminum-cobalt composite catalyst and preparation method and application thereof |
| CN112774682B (en) * | 2019-11-11 | 2023-04-07 | 中国科学院城市环境研究所 | Aluminum-cobalt composite catalyst and preparation method and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN114797927A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院大连化学物理研究所 | Composite carrier material loaded cobalt-based catalyst, preparation and application thereof |
| CN114797927B (en) * | 2021-01-27 | 2024-06-28 | 中国科学院大连化学物理研究所 | Composite carrier material supported cobalt-based catalyst and preparation and application thereof |
| CN113351207A (en) * | 2021-04-09 | 2021-09-07 | 临涣焦化股份有限公司 | Multi-wall catalyst for preparing liquid fuel by carbon dioxide hydrogenation and preparation method and application thereof |
| CN113351207B (en) * | 2021-04-09 | 2023-02-28 | 临涣焦化股份有限公司 | Multi-wall catalyst for preparing liquid fuel by carbon dioxide hydrogenation and preparation method and application thereof |
| CN113289666A (en) * | 2021-06-25 | 2021-08-24 | 南京工业大学 | Simple preparation method of Co/CM ceramic catalytic membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109718776B (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109718776A (en) | Hydrogenation catalyst Co@C/ biomass and its preparation method and application | |
| CN107855128B (en) | Preparation method of cobalt manganese sulfide electrocatalyst and product | |
| CN109516505B (en) | Preparation method of cobalt sulfide, product and application thereof | |
| CN106925314B (en) | A kind of method of nickel assisted cryogenic synthesis molybdenum carbide elctro-catalyst | |
| CN111545208A (en) | Cobalt-nickel bimetallic catalyst and preparation method thereof | |
| CN110197909B (en) | Nickel-iron catalytic material, preparation method thereof and application thereof in hydrogen production by electrolyzing water and preparation of liquid solar fuel | |
| CN107737597B (en) | A kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application | |
| CN109794246A (en) | A kind of monolithic devices honeycomb Ni@C/C catalyst and its preparation method and application | |
| CN108097255A (en) | It is a kind of for porous carbon frame nickel-base catalyst of CO 2 reforming reaction and preparation method thereof and application method | |
| CN112076738B (en) | Boron-doped defective zinc oxide and preparation method and application thereof | |
| CN109569609A (en) | A kind of preparation method of novel nickel-base composite material | |
| CN114588912B (en) | Preparation method and application of alkali metal doped perovskite catalyst suitable for methane dry reforming | |
| CN109569607A (en) | A kind of preparation method of novel cobalt-based composite material | |
| CN109647459A (en) | A kind of preparation method for the Ni-based phosphide that composition is controllable | |
| CN110013855B (en) | High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof | |
| CN109046394B (en) | Hollow tubular CoSe2Nano material and preparation method and application thereof | |
| CN112553643B (en) | Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application | |
| CN108273560B (en) | Fe3S4Preparation method of @ MIL-53(Fe) composite material and application thereof in electrocatalytic hydrogen evolution | |
| CN117845256A (en) | Phosphorus doped cobalt molybdate HER/SOR dual-function catalyst, preparation method and application | |
| CN110116003B (en) | Sodium borohydride hydrolysis hydrogen production composite coral-like morphology catalyst | |
| CN109926095B (en) | Cobalt-based oxygen evolution catalyst based on eutectic solvent, preparation method and electrocatalytic oxygen evolution application thereof | |
| CN109999839B (en) | Preparation method of inorganic non-noble metal Ni-doped Cu-based bifunctional electrocatalyst | |
| CN109908884A (en) | Complete type honeycomb Zinc-base compounded material ((ZnO@C)/C) and its preparation method and application | |
| CN110732328B (en) | Multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof | |
| CN107159294B (en) | A method of preparing carbonitride modification cobalt-based oxygen-separating catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |