CN110479290A - A kind of Low Temperature Solid-Phase interface doping type CoB catalyst and the preparation method and application thereof - Google Patents
A kind of Low Temperature Solid-Phase interface doping type CoB catalyst and the preparation method and application thereof Download PDFInfo
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- CN110479290A CN110479290A CN201910601796.9A CN201910601796A CN110479290A CN 110479290 A CN110479290 A CN 110479290A CN 201910601796 A CN201910601796 A CN 201910601796A CN 110479290 A CN110479290 A CN 110479290A
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- catalyst
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- sodium borohydride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000007790 solid phase Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 37
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000005501 phase interface Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 238000007710 freezing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010792 warming Methods 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
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/50—
-
- B01J35/61—
-
- 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
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
A kind of Low Temperature Solid-Phase interface doping type CoB catalyst, it is prepared as follows to obtain: cobalt salt, doped metal salt is dissolved in water, frost is solid, sodium borohydride powder is then homogeneously disposed in frost obtained solid surface at 1~5 DEG C and carries out reduction reaction, black suspension is obtained, is filtered, washing, vacuum drying, obtains doping type CoB catalyst；The present invention is reacted using solid phase interface and 1~5 DEG C of low temperature environment, reduces sodium borohydride reduction rate, and then overcome the problems, such as that cobalt-base catalyst is easy to reunite during the reaction, being degraded or even being etched causes hydrogen generation efficiency low；The purpose that the present invention is doped metal salt is to prevent CoB from reuniting, and keeps its distribution of particles uniform, increasing specific surface area, to further increase sodium borohydride hydrolysis hydrogen-producing speed.
Description
(1) technical field
The invention belongs to functional material preparation technical field, it is related to a kind of CoB catalyst and the preparation method and application thereof, especially
It is a kind of Low Temperature Solid-Phase interface doping type CoB catalyst and preparation method thereof, and is produced in hydrogen in catalysis sodium borohydride hydrolysis
Application.
(2) background technique
In recent years, rapidly depleting for natural calculus-dissolving fuel is the major reason for causing global warming and environmental pollution,
Seek cleaning, the energy of sustainable development it is extremely urgent.Hydrogen is many excellent with its high-energy density, no pollution and easily acquisition etc.
Point is counted as the fuel of a new generation.In the method for current research hydrogen manufacturing and hydrogen storage, chemical hydride is due to hydrogen storage environment temperature
The advantages that easily-controllable safely with hydrogen production process and become research hotspot.
Although chemical hydride hydrolyze at room temperature produce hydrogen be it is spontaneous, hydrolysis hydrogen-producing speed it is lower.Therefore, in order to add
Fast chemistry hydride hydrolyzes hydrogen-producing speed, and the use of catalyst is particularly important.In catalytic chemistry hydride hydrolytic hydrogen production
In numerous catalyst, cobalt-based nanocatalyst with its high catalytic activity and it is cheap the advantages that cause the extensive concern of researcher.
Although cobalt-base catalyst activity in participating in all catalyst that chemical hydride hydrolysis produces hydrogen is high and cheap and easy to get,
But it is easy to reunite during the reaction, be degraded or even be etched, change so as to cause the pattern and structure of material, into
And reduce the stability and recycling rate of catalyst.Therefore the cobalt-base catalyst for developing new structure and surface composition, is improved
Chemical hydride hydrogen generation efficiency and catalyst circulation utilization rate have a very important significance in current social.
(3) summary of the invention
In order to overcome, existing cobalt-base catalyst is easy to reunite during the reaction, being degraded or even being etched leads to hydrogen generation efficiency
Low problem, the present invention provides a kind of Low Temperature Solid-Phase interface doping type CoB catalyst and the preparation method and application thereof, the present invention
Preparation method is simple, and the hydrogen-producing speed that gained catalyst is applied in sodium borohydride hydrolysis is very fast.
Technical scheme is as follows:
A kind of Low Temperature Solid-Phase interface doping type CoB catalyst, is prepared as follows to obtain:
Cobalt salt, doped metal salt are dissolved in water, freezes as solid, then uniformly sets sodium borohydride powder at 1~5 DEG C
Reduction reaction (reaction time is usually in 2h) is carried out in frost obtained solid surface, black suspension is obtained, filters, wash (second
Alcohol replaces washing with distilled water three times), vacuum drying (temperature is 60~100 DEG C) obtains doping type CoB catalyst；
The ratio between the cobalt salt, doped metal salt, amount of substance of sodium borohydride are 1:0.01~0.3:1~20；
The volumetric usage of the water is calculated as 10mL/mmol with the amount of the substance of cobalt salt；
The cobalt salt is CoCl2·6H2O；
The doped metal salt is Ce (NO3)3·6H2O、CuCl2·2H2O or FeCl3·6H2O。
Doping type CoB catalyst produced by the present invention can be applied to hydrolysis and produce in hydrogen reaction.
Specifically, the method for the application are as follows:
Under the conditions of 25~30 DEG C of waters bath with thermostatic control, the doping type CoB catalyst is added to sodium borohydride and sodium hydroxide
Production hydrogen is hydrolyzed in mixed aqueous solution；
In the mixed aqueous solution of the sodium borohydride and sodium hydroxide, the concentration of sodium borohydride is 1~10wt%, hydroxide
The concentration of sodium is 1~10wt%；
The dosage of the doping type CoB catalyst is calculated as 1 with the volume of sodium borohydride and the mixed aqueous solution of sodium hydroxide
~5 mg/mL.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is reacted using solid phase interface and 1~5 DEG C of low temperature environment, reduces sodium borohydride reduction rate, into
And overcome the problems, such as that cobalt-base catalyst is easy to reunite during the reaction, being degraded or even being etched causes hydrogen generation efficiency low.
The purpose that the present invention is doped metal salt is to prevent CoB from reuniting, and keeps its distribution of particles uniform, improves specific surface
Product, to further increase sodium borohydride hydrolysis hydrogen-producing speed.
(4) Detailed description of the invention
Fig. 1 is that the SEM of CoB/Ce catalyst prepared by the present invention schemes.
Fig. 2 is the XRD diffraction pattern of CoB/Ce catalyst prepared by the present invention.
Fig. 3 is the BET coatings of CoB/Ce catalyst prepared by the present invention.
Fig. 4 is the hydrogen-producing speed figure of various doping type CoB catalyst prepared by the present invention.
(5) specific embodiment
With reference to the accompanying drawing, by specific embodiment to a kind of Low Temperature Solid-Phase interface doping type CoB catalyst of the present invention
Preparation method and produce hydrogen application and be described further, but protection scope of the present invention is not limited to that.
Embodiment 1:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0217g (0.00005mol) Ce (NO3)3·6H2O is in ultrasound
Under the conditions of be dissolved in 10ml distilled water after, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；It will under the conditions of 5 DEG C
0.3783 g(0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；It is suspended that black is obtained after 2h
Liquid, through filtering, ethyl alcohol replaces washing with water and is put in afterwards in 60 DEG C of vacuum ovens three times, and CoB/Ce catalysis can be obtained after 12h
Agent.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 30 DEG C of water bath with thermostatic control, 10mg CoB/Ce catalyst is added
10ml 1wt%NaBH4With progress hydrogen-producing speed test in 1wt%NaOH aqueous solution.Hydrogen-producing speed is 5.57L min-1gCatalyst -1。
Embodiment 2:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0434g (0.0001mol) Ce (NO3)3·6H2O is in ultrasound
Under the conditions of be dissolved in 10ml distilled water after, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；It will under the conditions of 5 DEG C
0.3783 g(0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；It is suspended that black is obtained after 2h
Liquid, through filtering, ethyl alcohol replaces washing with water and is put in afterwards in 60 DEG C of vacuum ovens three times, and CoB/Ce catalysis can be obtained after 12h
Agent.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 30 DEG C of water bath with thermostatic control, 10mg CoB/Ce catalyst is added
To 10ml 1wt%NaBH4With progress hydrogen-producing speed test in 1wt%NaOH aqueous solution.Hydrogen-producing speed is 4.62L min- 1gCatalyst -1。
Embodiment 3:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0217g (0.0001mol) Ce (NO3)3·6H2O is in ultrasound
Under the conditions of be dissolved in 10ml distilled water after, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；It will under the conditions of 5 DEG C
0.3783g (0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；It is suspended that black is obtained after 2h
Liquid, through filtering, ethyl alcohol replaces washing with water and is put in afterwards in 100 DEG C of vacuum ovens three times, and CoB/Ce catalysis can be obtained after 12h
Agent.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 30 DEG C of water bath with thermostatic control, 10mg CoB/Ce catalyst is added
To 10ml 5wt%NaBH4With progress hydrogen-producing speed test in 5wt%NaOH aqueous solution.Hydrogen-producing speed is 6.12L min- 1gCatalyst -1。
Embodiment 4:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0086g (0.00005) CuCl2·2H2O is in ultrasound condition
Under be dissolved in 10ml distilled water after, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；By 0.3783g under the conditions of 5 DEG C
(0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；Black suspension is obtained after 2h, through taking out
Filter, ethyl alcohol replace washing with water and are put in afterwards in 60 DEG C of vacuum ovens three times, and CoB/Cu catalyst can be obtained after 12h.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 30 DEG C of water bath with thermostatic control, 10mg CoB/Cu catalyst is added
To 10ml 1wt%NaBH4With progress hydrogen-producing speed test in 1wt%NaOH aqueous solution.Hydrogen-producing speed is 1.62L min- 1gCatalyst -1。
Embodiment 5:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0172g (0.0001) CuCl2·2H2O is under ultrasound condition
After being dissolved in 10ml distilled water, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；By 0.3783g under the conditions of 5 DEG C
(0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；Black suspension is obtained after 2h, through taking out
Filter, ethyl alcohol replace washing with water and are put in afterwards in 60 DEG C of vacuum ovens three times, and CoB/Cu catalyst can be obtained after 12h.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 30 DEG C of water bath with thermostatic control, 10mg CoB/Cu catalyst is added
To 10ml 5wt%NaBH4With progress hydrogen-producing speed test in 5wt%NaOH aqueous solution.Hydrogen-producing speed is 1.82L min- 1gCatalyst -1。
Embodiment 6:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0081g (0.00005mol) FeCl3·6H2O is in ultrasonic item
After being dissolved in 10ml distilled water under part, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；It will under the conditions of 5 DEG C
0.3783g (0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；It is suspended that black is obtained after 2h
Liquid, through filtering, ethyl alcohol replaces washing with water and is put in afterwards in 60 DEG C of vacuum ovens three times, and CoB/Fe catalysis can be obtained after 12h
Agent.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 25 DEG C of water bath with thermostatic control, 10mg CoB/Fe catalyst is added
To 10ml 1wt%NaBH4With progress hydrogen-producing speed test in 1wt%NaOH aqueous solution.Hydrogen-producing speed is 1.37L min- 1gCatalyst -1。
Embodiment 7:
By 0.2379g (0.001mol) CoCl2·6H2O and 0.0162g (0.0001mol) FeCl3·6H2O is in ultrasonic item
After being dissolved in 10ml distilled water under part, being placed in the plane ware cryogenic freezing that diameter is 60mm is solid；It will under the conditions of 5 DEG C
0.3783g (0.01mol)NaBH4Solid powder is homogeneously disposed in ice surface and solid solid interface reaction occurs；It is suspended that black is obtained after 2h
Liquid, through filtering, ethyl alcohol replaces washing with water and is put in afterwards in 60 DEG C of vacuum ovens three times, and CoB/Fe catalysis can be obtained after 12h
Agent.
NaBH is carried out to it4Aqueous solution produces hydrogen experiment, and at 30 DEG C of water bath with thermostatic control, 10mg CoB/Fe catalyst is added
To 10ml 5wt%NaBH4With progress hydrogen-producing speed test in 5wt%NaOH aqueous solution.Hydrogen-producing speed is 1.90L min- 1gCatalyst -1。
Comparative example
Zhao et al. (Zhao Bin；Shen Xiaochen；Dai Min；Shriek；A kind of load type Co B of preparing hydrogen by sodium borohydride hydrolysis of Ding Weiping is urged
Agent and preparation method thereof [P] Chinese patent: CN102950009A, 2012-10-12.) first by TiO2Carrier silver nitrate,
Formaldehyde and sodium hydroxide mixed solution carry out sensitized treatment, using cobalt acetate, borax and ammonium chloride as chemical-electrical plating solution, hydrogen-oxygen
Change after sodium adjusts pH value of solution=11~12 and be slowly introducing sodium borohydride solution, CoB/Ag- has been made by electroless plating method
TiO2Catalyst, sodium borohydride hydrogen-producing speed are 4.69Lmin-1gCatalyst -1。
Comparative example carries out preparing load type Co B catalyst using chemical-electrical plating method, and expensive and step is complicated.And this Shen
The interfacial synthesis method that please use solid solid phase reaction, does not use organic solvent and template, and preparation process is simple and quick, green ring
It protects；And innovation is substituted the loads such as noble metal using rare earth metal Ce and is doped, and cost, sodium borohydride hydrogen-producing speed are reduced
Up to 6.12Lmin-1gCatalyst -1, rate is very fast.
Claims (7)
1. a kind of Low Temperature Solid-Phase interface doping type CoB catalyst, which is characterized in that be prepared as follows to obtain:
Cobalt salt, doped metal salt are dissolved in water, freezes as solid, sodium borohydride powder is then homogeneously disposed in ice at 1~5 DEG C
Freeze obtained solid surface and carry out reduction reaction, obtain black suspension, filter, wash, vacuum drying obtains doping type CoB and urges
Agent；
The doped metal salt is Ce (NO3)3·6H2O、CuCl2·2H2O or FeCl3·6H2O。
2. doping type CoB catalyst in Low Temperature Solid-Phase interface as described in claim 1, which is characterized in that the cobalt salt, doping gold
Belonging to the ratio between amount of substance of salt, sodium borohydride is 1:0.01~0.3:1~20.
3. doping type CoB catalyst in Low Temperature Solid-Phase interface as described in claim 1, which is characterized in that the volume of the water is used
Amount is calculated as 10mL/mmol with the amount of the substance of cobalt salt.
4. doping type CoB catalyst in Low Temperature Solid-Phase interface as described in claim 1, which is characterized in that the cobalt salt is
CoCl2·6H2O。
5. doping type CoB catalyst in Low Temperature Solid-Phase interface as described in claim 1, which is characterized in that the reduction reaction
Time is in 2h.
6. Low Temperature Solid-Phase interface doping type CoB catalyst as described in claim 1 produces the application in hydrogen reaction in hydrolysis.
7. application as claimed in claim 6, which is characterized in that the method for the application are as follows:
Under the conditions of 25~30 DEG C of waters bath with thermostatic control, the doping type CoB catalyst is added to the mixing of sodium borohydride and sodium hydroxide
Production hydrogen is hydrolyzed in aqueous solution；
In the mixed aqueous solution of the sodium borohydride and sodium hydroxide, the concentration of sodium borohydride is 1~10wt%, sodium hydroxide
Concentration is 1~10wt%；
The dosage of the doping type CoB catalyst is calculated as 1 with the volume of sodium borohydride and the mixed aqueous solution of sodium hydroxide~
5mg/mL。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910601796.9A CN110479290B (en) | 2019-07-05 | 2019-07-05 | Low-temperature solid-phase interface doped CoB catalyst and preparation method and application thereof |
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| CN201910601796.9A CN110479290B (en) | 2019-07-05 | 2019-07-05 | Low-temperature solid-phase interface doped CoB catalyst and preparation method and application thereof |
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