CN109513442A - A kind of NaBH4Catalyst for preparing hydrogen Co-CoOx@C-rGO and preparation method thereof - Google Patents
A kind of NaBH4Catalyst for preparing hydrogen Co-CoOx@C-rGO and preparation method thereof Download PDFInfo
- Publication number
- CN109513442A CN109513442A CN201811138773.0A CN201811138773A CN109513442A CN 109513442 A CN109513442 A CN 109513442A CN 201811138773 A CN201811138773 A CN 201811138773A CN 109513442 A CN109513442 A CN 109513442A
- Authority
- CN
- China
- Prior art keywords
- coo
- catalyst
- rgo
- nabh
- preparation
- 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
- 229910002451 CoOx Inorganic materials 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000019441 ethanol Nutrition 0.000 claims abstract description 22
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000005253 cladding Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 7
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
- B01J23/75—Cobalt
-
- B01J35/393—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- 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 present invention discloses a kind of NaBH4Catalyst for preparing hydrogen Co-CoOx@C-rGO and preparation method thereof.The molecular formula of the catalyst is Co-CoOx@C-rGO, structure are the Co-CoO for being grown in the carbon shell cladding of rGO on piecexNano particle.Preparation step is as follows: GO is fully dispersed in ethyl alcohol；By metal salt C4H6CoO4Aqueous solution be added in the alcohol dispersion liquid of GO, then stirred in water bath；It is subsequently added into the aqueous solution of glucose, reaction kettle is moved into after stirring, hydro-thermal reaction is filtered, cleaned with water and ethyl alcohol；Then it is freeze-dried for 24 hours；Grinding obtained solid is put into tube furnace, in a nitrogen atmosphere, with 550-750 DEG C of roasting 1h, Co-CoOx@C-rGO is made.Catalyst prepared by the present invention is for being catalyzed NaBH4Producing hydrogen, catalyzing activity is very high.
Description
Technical field
The invention belongs to catalyzing manufacturing of hydrogen technical fields, and in particular to a kind of NaBH4Catalyst for preparing hydrogen Co-CoOx@C-rGO and
Preparation method.
Background technique
Growing energy demand promotes people to study efficient, low cost and environmentally friendly alternative energy source for industry
Production.Hydrogen Energy is the best alternative energy source of fossil fuel because its with energy density high, environmental-friendly, abundance and can
The advantages that regeneration.
NaBH4It is the good carrier of hydrogen energy source, is catalyzed NaBH4Hydrogen manufacturing has caused the extensive concern of people, is catalyzed NaBH4
The research of catalyst for preparing hydrogen has become research hotspot.The preparation cost and catalytic activity of catalyst are the key that influence its application
Problem.Although precious metals pt and Ru catalyst have high catalytic activity, reserves are low, at high cost, influence to use on a large scale.
Therefore, research high, cheap, the efficient non-precious metal catalyst of reserves is to realize NaBH4The key of inexpensive hydrogen manufacturing
Problem in science, and the research emphasis in the field at present.Transition metal is expected to the alternative catalysts as precious metals pt and Ru.Its
Middle metal Co has many advantages, such as that price is low, catalytic activity is high, nontoxic, stability is good, is catalysis NaBH4Produce the research of hydrogen catalyst
Emphasis.
Summary of the invention
For above-mentioned status, the purpose of the present invention is to provide a kind of NaBH4The catalyst Co-CoO of hydrogen manufacturingx@C-rGO and
Preparation method.
To achieve the above object, the technical solution adopted by the present invention is as follows: a kind of NaBH4Catalyst for preparing hydrogen, molecular formula are
Co-CoOx@C-rGO, structure are the Co-CoO for being grown in the carbon shell cladding of rGO on piecexNano particle.
A kind of NaBH4The preparation method of catalyst for preparing hydrogen, steps are as follows:
(1) it first disperses GO in ethanol solution, obtains the alcohol dispersion liquid of GO；
(2) by metal salt C4H6CoO4Aqueous solution be added in the alcohol dispersion liquid of GO, stirred in water bath reaction is abundant；
(3) aqueous solution that glucose is added continues to be stirred to react, then hydro-thermal reaction；
(4) it filters, is cleaned with water and ethyl alcohol, be then freeze-dried；
(5) after grinding, under nitrogen atmosphere, high-temperature roasting collects product and catalyst is made.
In step (1), the concentration of the alcohol dispersion liquid of GO is 0.95~1.05mgmL-1。
In step (2), by quality ratio, GO: C4H6CoO4=1: 3~4；Bath temperature is 75~85 DEG C, and water bath time is protected
Hold 9.5~10.5h.
In step (3), hydrothermal temperature is 170~180 DEG C, and the hydro-thermal time keeps 11.5~12.5h.
It is 24~26h with sublimation drying in step (4), temperature is -50~-40 DEG C, and vacuum degree is 25~45pa.
In step (5), when roasting, heating rate is 9~11 DEG C of min-1, maturing temperature is 550-750 DEG C, calcining time
For 0.9~1.1h.
The utility model has the advantages that
1. the present invention, which forms carbon-coated core-shell structure using metal Co, can prevent growing up, assembling for particle, be conducive to
The stability of catalysis；
2. graphene has been confirmed as the application advantage of base material, nano particle, which is supported on graphene, to be increased
The specific surface area of big catalyst, to be conducive to increase active site；
3. metal Co and metallic cobalt CoOxHetero-junctions is formed, Co and CoO can be playedxBetween synergistic effect, be conducive to improve
Catalytic activity reduces activation energy.Therefore, the present invention uses simple method base metal Co, glucose and rGO, forms carbon
The Co-CoO of shell claddingxHetero-junctions is simultaneously supported on graphene and obtains Co-CoOx@C-rGO catalyst, for being catalyzed NaBH4Water
It is very high to solve producing hydrogen, catalyzing activity.
Detailed description of the invention
Fig. 1: Co-CoOx@C-rGO-550(a)、Co-CoOx@C-rGO-650 (b) and Co-CoOx@C-rGO-750's (c)
Transmission electron microscope figure；
Fig. 2: Co-CoOx@C-rGO-550、Co-CoOx@C-rGO-650 and Co-CoOxThe x-ray powder of@C-rGO-750
Diffraction pattern；
Fig. 3: Co-CoOx@C-rGO-550, Co-CoOx@C-rGO-650 and Co-CoOxThe catalysis NaBH of@C-rGO-7504
Co-CoO under hydrogen manufacturing figure (a), different temperaturesx@C-rGO-550 is catalyzed NaBH4Hydrogen manufacturing figure (b) and Arrhenius corresponding with (b)
Curve graph (c).
Specific embodiment
To keep the present invention clearer, clear, the present invention is described in more detail below.It should be appreciated that this place is retouched
It states that specific examples are only used to explain the present invention, is not intended to limit the present invention.
The molecular formula of the catalyst is Co-CoOx@C-rGO, structure are to be grown in rGO (redox graphene) on piece
Carbon shell cladding Co-CoOxNano particle.
The NaBH4The preparation method of the catalyst of hydrogen manufacturing, steps are as follows:
(1), GO is put into ethyl alcohol, stirring alternately, obtains the alcohol dispersion liquid of GO with ultrasound；
(2), by metal salt C4H6CoO4Aqueous solution be added in the alcohol dispersion liquid of GO, the water-bath for being placed on 80 DEG C
Middle stirring 10h；
(3), the aqueous solution that glucose is added continues to stir 30min, then moves into 500mL reaction kettle, 170 DEG C of hydro-thermals 12
h；
(4), it filters, is cleaned, be then freeze-dried for 24 hours with water and ethyl alcohol；
(5), solid is put into tube furnace after grinding freeze-drying, in a nitrogen atmosphere with 10 DEG C of min-1Heating, in 550-
1h is roasted at 750 DEG C, collects product and catalyst is made.
Preferably, in step (1), the concentration of the alcohol dispersion liquid of GO is 0.95-1.05mgmL-1。
Preferably, in step (2), by quality ratio, GO: C4H6CoO4=1: 3-4, C4H6CoO4: water=1: 56-57；Water
Bath temperature is 80 DEG C, and water bath time keeps 10h.
Preferably, in step (3), by quality ratio, by quality ratio, glucose: water=1: 12-13；The reaction kettle
Volume is 500mL, and hydrothermal temperature is 170 DEG C, and the hydro-thermal time keeps 12h.
Preferably, dry with freeze drier in step (4), drying time is that for 24 hours, temperature is -45 DEG C, and vacuum degree is
35pa。
Preferably, in step (5), atmosphere is nitrogen, and heating rate is 10 DEG C of min-1, maturing temperature is 550-750 DEG C,
Calcining time is 1h.
Embodiment 1
Catalyst Co-CoOxThe preparation method of@C-rGO-550, steps are as follows:
(1), GO (300mg) is added in ethyl alcohol (300mL), stirs ultrasound alternately 2h, guarantee is evenly dispersed, obtains
The alcohol dispersion liquid of GO is transferred in there-necked flask (500mL)；
(2), by metal salt C4H6CoO4Aqueous solution (0.2M, 60mL) be added in the alcohol dispersion liquid of GO, be placed on
80 DEG C of stirred in water bath 10h；
(3), the aqueous solution (10mL) of glucose (800mg) is added in aforesaid liquid, continues to stir 30min, then moves
Enter 500mL reaction kettle, 170 DEG C of hydro-thermal 12h；
(4), it filters, is cleaned, be then freeze-dried for 24 hours with water and ethyl alcohol；
(5), solid is put into tube furnace after grinding freeze-drying, in a nitrogen atmosphere with 10 DEG C of min-1Heating, at 550 DEG C
Lower roasting 1h collects product and target product, number Co-CoO is madex@C-rGO-550。
Embodiment 2
Difference from example 1 is that: in step (5), maturing temperature is 650 DEG C, other with embodiment 1.
Gained target product number is Co-CoOx@C-rGO-650。
Embodiment 3
Difference from example 1 is that: in step (5), maturing temperature is 750 DEG C, other with embodiment 1.
Gained target product number is Co-CoOx@C-rGO-750。
Catalyst structure characterization
Fig. 1 is the catalyst Co-CoO of embodiment 1-3 preparationx@C-rGO-550(a)、Co-CoOx@C-rGO-650 (b) and
Co-CoOxThe transmission electron microscope figure of@C-rGO-750 (c).It can be seen that from Fig. 1 (a), (b) and in (c) what carbon shell coated
Co-CoOxIt is grown in large stretch of rGO on piece.It can be clearly seen in figure (a): lesser, carbon shell cladding Co-CoOxNano particle
Homoepitaxial is in rGO on piece；It can be seen that the raising due to reaction temperature, Co-CoO in figure (b)xNano particle becomes larger, uneven
It is grown in rGO on piece evenly；Scheme (c) it can be seen that due to reaction temperature further raising, Co-CoOxNano particle is into one
Step-length is big, and granular size is more inhomogenous, is more mussily grown in rGO on piece.
Fig. 2 is the catalyst Co-CoO of embodiment 1-3 preparationx@C-rGO-550(a)、Co-CoOx@C-rGO-650 (b) and
Co-CoOxThe X-ray powder diffraction figure of@C-rGO-750 (c).As can be seen from Figure 2: 2 θ angles 31.2 °, 36.5 °,
There is diffraction maximum at 42.4 °, 44.2 °, 61.5 ° and 73.7 °, has respectively corresponded Co3O4(220), (111) of CoO,
(200), (111) of Co, (220) of CoO, (311) crystal face, with Co3O4Standard diagram card (JCPDS No.43-1003),
The standard diagram card (JCPDS No.43-1004) of CoO and the standard diagram card (JCPDS No.15-0806) of Co are opposite
It answers.
Catalyst performance test
(1) the catalysis H2-producing capacity test of different catalysts: Co-CoO prepared by embodiment 1-3x@C-rGO-550、
Co-CoOx@C-rGO-650 and Co-CoOx@C-rGO-750 is respectively as catalyst for being catalyzed NaBH4Hydrogen manufacturing.Condition are as follows: temperature
25 DEG C of degree.By catalyst (10mg) and NaBH4(400mg) is set in a round bottom flask；NaOH solution (226 mg) is dissolved in 10mL water
It is placed in constant pressure funnel.Then hydrogen production bioreactor is put in intelligent magnetic force thermostat water bath, revolving speed 500rpm, temperature is set
25℃.NaOH solution is added in round-bottomed flask, collects gas with draining water gathering of gas law, and records volume and the time of hydrogen generation
Relationship.
(2)Co-CoOxCatalysis H2-producing capacity test under@C-rGO-550 different temperatures: by Co-CoOx@C-rGO-550
As catalyst, respectively for being catalyzed NaBH at 30 DEG C, 40 DEG C, 50 DEG C and 60 DEG C4Hydrogen manufacturing.Catalyst, NaBH4, NaOH and
The dosage of water and other operations are the same as (1).
Fig. 3 is that different catalysts are catalyzed NaBH4The figure (a) of hydrogen manufacturing, Co-CoOxCatalysis under@C-rGO-550 different temperatures
NaBH4Hydrogen manufacturing figure (b) and corresponding Arrhenius curve graph (c).From Fig. 3 (a) it can be seen that compared to other materials,
Co-CoO under identical conditionsx@C-rGO-550 has highest catalytic activity, and catalytic rate is 4184 mLmin-1·g-1.From
In Fig. 3 (b) it can be seen that with temperature raising, hydrolysis hydrogen-producing speed increased dramatically.At 30 DEG C, 40 DEG C, 50 DEG C and 60 DEG C,
Co-CoOx@C-rGO-550 is catalyzed NaBH4The rate of hydrogen manufacturing is respectively 5741,11741,19672 and 33149mLmin-1·
g.It can be seen that the relationship of lnk and 1/T is straight line from Fig. 3 (c), the activation energy for calculating reaction is 48.78kJmol-1, than
Other catalyst before reported in the literature it is low (1C.H.Liu, B.H.Chen, C.L.Hsueh, J.R.Ku, M.S.Jeng,
F.Tsau,Int.J.Hydrogen Energy,2009,34,2153–2163.2S.U.Jeong,R.K. Kim,E.A.Cho,
H.J.Kim,S.W.Nam,I.H.Oh,S.A.Hong,S.H.Kim,J.Power Sources,2005, 144,129–
134.3C.H.Liu,B.H.Chen,C.L.Hsueh,J.R.Ku,F.Tsau,K.J.Hwang,Appl.Catal.B, 2009,
91,368-379.), low activation energy may be because of Co and CoOxBetween the result that acts synergistically.
Claims (7)
1. a kind of NaBH4Catalyst for preparing hydrogen, it is characterised in that: molecular formula Co-CoOx@C-rGO, structure are to be grown in rGO on piece
Carbon shell cladding Co-CoOxNano particle.
2. NaBH described in a kind of claim 14The preparation method of catalyst for preparing hydrogen, which is characterized in that steps are as follows:
(1) it first disperses GO in ethanol solution, obtains the alcohol dispersion liquid of GO；
(2) by metal salt C4H6CoO4Aqueous solution be added in the alcohol dispersion liquid of GO, stirred in water bath reaction is abundant；
(3) aqueous solution that glucose is added continues to be stirred to react, then hydro-thermal reaction；
(4) it filters, is cleaned with water and ethyl alcohol, be then freeze-dried；
(5) after grinding, under nitrogen atmosphere, high-temperature roasting collects product and catalyst is made.
3. NaBH as claimed in claim 24The preparation method of catalyst for preparing hydrogen, it is characterised in that: in step (1), the ethyl alcohol of GO
The concentration of dispersion liquid is 0.95~1.05 mg mL-1。
4. NaBH as claimed in claim 24The preparation method of catalyst for preparing hydrogen, it is characterised in that: in step (2), with quality
Than counting, GO: C4H6CoO4=1: 3~4；Bath temperature is 75~85 °C, and water bath time keeps 9.5~10.5 h.
5. NaBH as claimed in claim 24The preparation method of catalyst for preparing hydrogen, it is characterised in that: in step (3), hydro-thermal reaction
Temperature is 170~180 °C, and the hydro-thermal time keeps 11.5~12.5 h.
6. NaBH as claimed in claim 24The preparation method of catalyst for preparing hydrogen, it is characterised in that: dry with freezing in step (4)
The dry time is 24~26 h, and temperature is -50~-40 °C, and vacuum degree is 25~45 pa.
7. NaBH as claimed in claim 24The preparation method of catalyst for preparing hydrogen, it is characterised in that: in step (5), when roasting,
Heating rate is 9~11 °C of min−1, maturing temperature is 550-750 °C, and calcining time is 0.9~1.1 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811138773.0A CN109513442B (en) | 2018-09-28 | 2018-09-28 | NaBH4Hydrogen production catalyst Co-CoOx@ C-rGO and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811138773.0A CN109513442B (en) | 2018-09-28 | 2018-09-28 | NaBH4Hydrogen production catalyst Co-CoOx@ C-rGO and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109513442A true CN109513442A (en) | 2019-03-26 |
| CN109513442B CN109513442B (en) | 2022-01-07 |
Family
ID=65772110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811138773.0A Active CN109513442B (en) | 2018-09-28 | 2018-09-28 | NaBH4Hydrogen production catalyst Co-CoOx@ C-rGO and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109513442B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110116003A (en) * | 2019-05-13 | 2019-08-13 | 太原理工大学 | Preparing hydrogen by sodium borohydride hydrolysis complex class coral pattern catalyst |
| CN114011412A (en) * | 2021-11-08 | 2022-02-08 | 燕山大学 | Cobalt oxide porous nanosheet and preparation method and application thereof |
| CN114904505A (en) * | 2022-05-11 | 2022-08-16 | 黑龙江哈船碳材料科技有限公司 | For KBH 4 Composite catalyst for hydrogen production and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11322301A (en) * | 1998-03-12 | 1999-11-24 | Nikon Corp | Production of hydrogen and/or oxygen and catalyst for production of hydrogen and/or oxygen |
| CN104056630A (en) * | 2014-06-30 | 2014-09-24 | 北京理工大学 | Preparation method of carbon-coated cobalt oxygen evolution reaction electro-catalyst |
-
2018
- 2018-09-28 CN CN201811138773.0A patent/CN109513442B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11322301A (en) * | 1998-03-12 | 1999-11-24 | Nikon Corp | Production of hydrogen and/or oxygen and catalyst for production of hydrogen and/or oxygen |
| CN104056630A (en) * | 2014-06-30 | 2014-09-24 | 北京理工大学 | Preparation method of carbon-coated cobalt oxygen evolution reaction electro-catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 省聪聪: "基于MOFs合成Co-空心/核壳结构@石墨烯复合材料、表征及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110116003A (en) * | 2019-05-13 | 2019-08-13 | 太原理工大学 | Preparing hydrogen by sodium borohydride hydrolysis complex class coral pattern catalyst |
| CN110116003B (en) * | 2019-05-13 | 2022-07-22 | 太原理工大学 | Sodium borohydride hydrolysis hydrogen production composite coral-like morphology catalyst |
| CN114011412A (en) * | 2021-11-08 | 2022-02-08 | 燕山大学 | Cobalt oxide porous nanosheet and preparation method and application thereof |
| CN114011412B (en) * | 2021-11-08 | 2023-08-22 | 燕山大学 | Cobalt oxide porous nano-sheet and preparation method and application thereof |
| CN114904505A (en) * | 2022-05-11 | 2022-08-16 | 黑龙江哈船碳材料科技有限公司 | For KBH 4 Composite catalyst for hydrogen production and preparation method thereof |
| CN114904505B (en) * | 2022-05-11 | 2024-02-09 | 黑龙江哈船碳材料科技有限公司 | Be used for KBH 4 Composite catalyst for hydrogen production and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109513442B (en) | 2022-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019109831A1 (en) | Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen | |
| CN107308977B (en) | Difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels and its preparation method and application | |
| CN108855159B (en) | Cobalt phosphide synthesized by prussian blue derivative and preparation method and application thereof | |
| CN109513442A (en) | A kind of NaBH4Catalyst for preparing hydrogen Co-CoOx@C-rGO and preparation method thereof | |
| CN109594101B (en) | Preparation method of porous carbon supported ruthenium catalyst | |
| CN108940328A (en) | Nanometer sheet-modified molybdenum carbide electro-catalysis catalyst for preparing hydrogen of nanometer rods coupling three-dimensional composite material Ni-Co and preparation method thereof | |
| CN107176598A (en) | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application | |
| CN111167495B (en) | Catalyst Ni for ammonia borane hydrogen production 2-x Fe x @ CN-G and preparation method thereof | |
| CN112264062A (en) | Preparation and application of monatomic platinum catalyst based on MXene quantum dots | |
| CN104209514A (en) | Method for preparing Ni@C or Co@C core-shell nanoparticles | |
| CN107597119B (en) | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof | |
| CN106252673A (en) | A kind of preparation method of Fe N/C oxygen reduction reaction catalyst based on natural plants tissue | |
| CN103223331A (en) | Preparation method of Ni (Co,Fe)-supported magnetic mesoporous carbon material with high adsorption performance on dyes | |
| CN109921040A (en) | The carbon-based elctro-catalyst of a kind of Ni, Fe doping and its preparation and application | |
| CN112604690A (en) | Method for preparing rare earth perovskite/biochar composite material by using agricultural and forestry wastes and application thereof | |
| CN113019376A (en) | Copper-based composite catalyst for growing graphene modified foam nickel substrate and preparation method thereof | |
| CN111604072A (en) | Nano particle-graphene-foam nickel composite material with bionic structure and preparation method thereof | |
| CN111686734B (en) | Preparation method and application of magnetic porous nickel nanosheets | |
| CN110496625A (en) | A kind of double transition metal oxide meso-porous nano pipes and its preparation method and application | |
| CN109499595B (en) | Oxygen Reduction Reaction (ORR) catalyst GPNCS and preparation method thereof | |
| CN104624191A (en) | CoO/C catalyst and preparation method thereof | |
| CN111203254B (en) | Co-N high-activity species modified vanadium sulfide hydrogen-producing electrocatalyst and preparation method and application thereof | |
| CN113215597B (en) | Preparation method of defective foam graphene loaded transition metal monatomic catalyst | |
| CN115193448A (en) | Synthesis method of zinc-cadmium-sulfur nano materials with different morphologies and application of zinc-cadmium-sulfur nano materials in photocatalytic hydrogen production | |
| CN110902672B (en) | Photothermal effect multi-stage structure microspherical graphene aerogel and preparation method thereof |
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 |