CN110479290B - Low-temperature solid-phase interface doped CoB catalyst and preparation method and application thereof - Google Patents
Low-temperature solid-phase interface doped CoB catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000007790 solid phase Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 29
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 12
- 238000007710 freezing Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 230000005501 phase interface Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 150000004678 hydrides Chemical class 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004064 recycling 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
- 238000003860 storage Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 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
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011259 mixed solution 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
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
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- 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
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Abstract
A low-temperature solid-phase interface doped CoB catalyst is prepared by the following method: dissolving cobalt salt and doped metal salt in water, freezing the solution to form a solid, uniformly placing sodium borohydride powder on the surface of the solid obtained by freezing at the temperature of 1-5 ℃ for reduction reaction to obtain a black suspension, and performing suction filtration, washing and vacuum drying to obtain a doped CoB catalyst; according to the invention, a solid phase interface is adopted to react with a low-temperature environment at 1-5 ℃, so that the reduction rate of sodium borohydride is reduced, and the problem of low hydrogen production efficiency caused by easy agglomeration, degradation and even etching of a cobalt-based catalyst in the reaction process is solved; the metal salt is doped in the invention to prevent CoB agglomeration, make the particle distribution uniform and improve the specific surface area, thereby further improving the hydrogen production rate of sodium borohydride hydrolysis.
Description
(I) technical field
The invention belongs to the technical field of functional material preparation, and relates to a CoB catalyst, a preparation method and application thereof, in particular to a low-temperature solid-phase interface doped CoB catalyst, a preparation method thereof, and application thereof in catalyzing hydrolysis of sodium borohydride to produce hydrogen.
(II) background of the invention
In recent years, rapid consumption of natural fossil fuels is an important cause of global warming and environmental pollution, and the search for clean, sustainable energy sources is imminent. Hydrogen is considered as a new generation fuel with its advantages of high energy density, zero pollution and easy availability. In the current research on hydrogen production and storage methods, chemical hydrides are a research hotspot due to the advantages of mild hydrogen storage environment, safe and easily-controlled hydrogen production process and the like.
Although the hydrogen production by hydrolysis of chemical hydride is spontaneous at room temperature, the hydrogen production rate by hydrolysis is low. Therefore, the use of the catalyst is important to accelerate the hydrogen production rate of the chemical hydride hydrolysis. Among the catalysts for catalyzing the hydrolysis of chemical hydride to prepare hydrogen, cobalt-based nano-catalysts attract extensive attention of researchers due to the advantages of high catalytic activity, low price and the like.
The cobalt-based catalyst has high activity, is cheap and easy to obtain in all catalysts participating in hydrogen production by chemical hydride hydrolysis, but is easy to agglomerate, degrade and even be etched in the reaction process, so that the morphology and the structure of the material are changed, and the stability and the recycling rate of the catalyst are reduced. Therefore, the cobalt-based catalyst with a novel structure and a surface composition is developed, and the improvement of the hydrogen production efficiency of the chemical hydride and the recycling rate of the catalyst have very important significance in the current society.
Disclosure of the invention
In order to solve the problem that the existing cobalt-based catalyst is easy to agglomerate, is degraded and even is etched in the reaction process to cause low hydrogen production efficiency, the invention provides a low-temperature solid-phase interface doped CoB catalyst and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a low-temperature solid-phase interface doped CoB catalyst is prepared by the following method:
dissolving cobalt salt and doped metal salt in water, freezing the solution to obtain a solid, uniformly placing sodium borohydride powder on the surface of the solid obtained by freezing at the temperature of 1-5 ℃ for reduction reaction (the reaction time is usually 2 hours), obtaining a black suspension, performing suction filtration, washing (ethanol and distilled water are alternately washed for three times), and performing vacuum drying (the temperature is 60-100 ℃) to obtain a doped CoB catalyst;
the ratio of the amounts of the cobalt salt, the doped metal salt and the sodium borohydride is 1: 0.01-0.3: 1-20;
the volume usage of the water is 10mL/mmol based on the amount of the cobalt salt;
the cobalt salt is CoCl2·6H2O；
The doped metal salt is Ce (NO)3)3·6H2O、CuCl2·2H2O or FeCl3·6H2O。
The doped CoB catalyst prepared by the invention can be applied to the hydrolysis hydrogen production reaction.
Specifically, the application method comprises the following steps:
adding the doped CoB catalyst into a mixed aqueous solution of sodium borohydride and sodium hydroxide for hydrolysis to produce hydrogen under the condition of constant-temperature water bath at 25-30 ℃;
in the mixed aqueous solution of sodium borohydride and sodium hydroxide, the concentration of sodium borohydride is 1-10 wt%, and the concentration of sodium hydroxide is 1-10 wt%;
the dosage of the doped CoB catalyst is 1-5 mg/mL calculated by the volume of a mixed aqueous solution of sodium borohydride and sodium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a solid phase interface is adopted to react with a low-temperature environment at 1-5 ℃, so that the reduction rate of sodium borohydride is reduced, and the problem of low hydrogen production efficiency caused by easy agglomeration, degradation and even etching of the cobalt-based catalyst in the reaction process is solved.
The metal salt is doped in the invention to prevent CoB agglomeration, make the particle distribution uniform and improve the specific surface area, thereby further improving the hydrogen production rate of sodium borohydride hydrolysis.
(IV) description of the drawings
FIG. 1 is an SEM image of a CoB/Ce catalyst prepared according to the invention.
FIG. 2 is an XRD diffractogram of a CoB/Ce catalyst prepared according to the invention.
FIG. 3 is a BET powder plot of CoB/Ce catalyst prepared according to the present invention.
FIG. 4 is a graph of hydrogen production rates for various doped CoB catalysts prepared according to the present invention.
(V) detailed description of the preferred embodiments
The preparation method and hydrogen production application of the low-temperature solid phase interface doped type CoB catalyst of the present invention are further described in the following with reference to the accompanying drawings by specific embodiments, but the scope of the present invention is not limited thereto.
Example 1:
0.2379g (0.001mol) CoCl2·6H2O and 0.0217g (0.00005mol) Ce (NO)3)3·6H2Dissolving O in 10ml of distilled water under ultrasonic condition, placing in a flat dish with the diameter of 60mm, and freezing at low temperature to obtain a solid; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 60 ℃, and obtaining the CoB/Ce catalyst after 12 h.
Subjecting it to NaBH4An aqueous solution hydrogen production experiment is carried out, 10mg of CoB/Ce catalyst is added into 10ml of 1 wt% NaBH under the temperature of 30 ℃ of constant-temperature water bath4And a 1 wt% NaOH aqueous solution. The hydrogen production rate is 5.57L min-1gCatalyst and process for preparing same -1。
Example 2:
0.2379g (0.001mol) CoCl2·6H2O and 0.0434g (0.0001mol) Ce (NO)3)3·6H2Dissolving O in 10ml of distilled water under ultrasonic condition, placing in a flat dish with the diameter of 60mm, and freezing at low temperature to obtain a solid; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 60 ℃, and obtaining the CoB/Ce catalyst after 12 h.
Subjecting it to NaBH4Aqueous solution hydrogen production experiment, 10mg CoB/Ce catalyst is added into 10ml 1 wt% NaBH under the temperature of 30 ℃ in constant temperature water bath4And 1 wt% NaOH aqueous solution for hydrogen production rate measurementAnd (6) testing. The hydrogen production rate is 4.62L min- 1gCatalyst and process for preparing same -1。
Example 3:
0.2379g (0.001mol) CoCl2·6H2O and 0.0217g (0.0001mol) Ce (NO)3)3·6H2Dissolving O in 10ml of distilled water under ultrasonic condition, placing in a flat dish with the diameter of 60mm, and freezing at low temperature to obtain a solid; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 100 ℃, and obtaining the CoB/Ce catalyst after 12 h.
Subjecting it to NaBH4An aqueous solution hydrogen production experiment is carried out, 10mg of CoB/Ce catalyst is added into 10ml of 5 wt% NaBH under the temperature of 30 ℃ of constant-temperature water bath4And 5 wt% NaOH aqueous solution. The hydrogen production rate is 6.12L min- 1gCatalyst and process for preparing same -1。
Example 4:
0.2379g (0.001mol) CoCl2·6H2O and 0.0086g (0.00005) CuCl2·2H2Dissolving O in 10ml of distilled water under ultrasonic condition, placing in a flat dish with the diameter of 60mm, and freezing at low temperature to obtain a solid; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 60 ℃, and obtaining the CoB/Cu catalyst after 12 h.
Subjecting it to NaBH4An aqueous solution hydrogen production experiment is carried out, 10mg of CoB/Cu catalyst is added into 10ml of 1 wt% NaBH under the temperature of 30 ℃ of constant-temperature water bath4And a 1 wt% NaOH aqueous solution. The hydrogen production rate is 1.62L min- 1gCatalyst and process for preparing same -1。
Example 5:
0.2379g (0.001mol) CoCl2·6H2O and 0.0172g (0.0001) CuCl2·2H2Dissolving O in 10ml distilled water under ultrasonic condition, and placingFreezing the mixture into solid in a flat dish with the diameter of 60mm at low temperature; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 60 ℃, and obtaining the CoB/Cu catalyst after 12 h.
Subjecting it to NaBH4An aqueous solution hydrogen production experiment is carried out, 10mg of CoB/Cu catalyst is added into 10ml of 5 wt% NaBH under the temperature of 30 ℃ of constant-temperature water bath4And 5 wt% NaOH aqueous solution. The hydrogen production rate is 1.82L min- 1gCatalyst and process for preparing same -1。
Example 6:
0.2379g (0.001mol) CoCl2·6H2O and 0.0081g (0.00005mol) FeCl3·6H2Dissolving O in 10ml of distilled water under ultrasonic condition, placing in a flat dish with the diameter of 60mm, and freezing at low temperature to obtain a solid; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 60 ℃, and obtaining the CoB/Fe catalyst after 12 h.
Subjecting it to NaBH4Aqueous solution hydrogen production experiment, 10mg CoB/Fe catalyst is added into 10ml 1 wt% NaBH under the temperature of constant temperature water bath 25 DEG C4And a 1 wt% NaOH aqueous solution. The hydrogen production rate is 1.37L min- 1gCatalyst and process for preparing same -1。
Example 7:
0.2379g (0.001mol) CoCl2·6H2O and 0.0162g (0.0001mol) FeCl3·6H2Dissolving O in 10ml of distilled water under ultrasonic condition, placing in a flat dish with the diameter of 60mm, and freezing at low temperature to obtain a solid; 0.3783g (0.01mol) NaBH is added at 5 DEG C4Uniformly placing the solid powder on the ice surface to generate solid-solid interface reaction; obtaining black suspension after 2h, performing suction filtration, alternately washing with ethanol and water for three times, placing in a vacuum drying oven at 60 ℃, and obtaining the CoB/Fe catalyst after 12 h.
Subjecting it to NaBH4An aqueous solution hydrogen production experiment is carried out, 10mg of CoB/Fe catalyst is added into 10ml of 5 wt% NaBH under the temperature of 30 ℃ of constant-temperature water bath4And 5 wt% NaOH aqueous solution. The hydrogen production rate is 1.90L min- 1gCatalyst and process for preparing same -1。
Comparative example
Zhao et al (Zhao bin; Shenchen; Min Dynasty; Gaoying; Dingweiping.) A supported CoB catalyst for hydrogen production by sodium borohydride hydrolysis and its preparation method [ P]Chinese patent CN102950009A,2012-10-12.) TiO first2Sensitizing a carrier by using a mixed solution of silver nitrate, formaldehyde and sodium hydroxide, adopting cobalt acetate, borax and ammonium chloride as a chemical electroplating solution, slowly introducing a sodium borohydride solution after the pH value of the sodium hydroxide solution is adjusted to 11-12, and preparing the CoB/Ag-TiO by a chemical electroplating method2The hydrogen production rate of the catalyst and sodium borohydride is 4.69Lmin-1gCatalyst and process for preparing same -1。
The comparative example used an electroless plating process to prepare a supported CoB catalyst, which was expensive and complicated in steps. The method uses an interface synthesis method of solid-solid phase reaction, does not use an organic solvent and a template agent, and has simple and rapid preparation process and environmental protection; and the rare earth metal Ce is innovatively adopted to replace loading bodies such as noble metal and the like for doping, the cost is reduced, and the hydrogen production rate of sodium borohydride can reach 6.12Lmin-1gCatalyst and process for preparing same -1The rate is faster.
Claims (7)
1. A low-temperature solid-phase interface doped CoB catalyst is characterized by being prepared by the following method:
dissolving cobalt salt and doped metal salt in water, freezing the solution to form a solid, uniformly placing sodium borohydride powder on the surface of the solid obtained by freezing at the temperature of 1-5 ℃ for reduction reaction to obtain a black suspension, and performing suction filtration, washing and vacuum drying to obtain a doped CoB catalyst;
the doped metal salt is Ce (NO)3)3·6H2O、CuCl2·2H2O or FeCl3·6H2O。
2. The low-temperature solid-phase interface doped CoB catalyst according to claim 1, wherein the ratio of the amounts of the cobalt salt, the doping metal salt and the sodium borohydride is 1: 0.01-0.3: 1 to 20.
3. The low temperature solid phase interface doped CoB catalyst of claim 1, wherein the volume usage of water is 10mL/mmol based on the amount of cobalt salt species.
4. The low temperature solid phase interface doped CoB catalyst of claim 1, wherein the cobalt salt is CoCl2·6H2O。
5. The low-temperature solid-phase interface-doped CoB catalyst according to claim 1, wherein the time of the reduction reaction is 2 h.
6. The use of the low-temperature solid-phase interface doped CoB catalyst according to claim 1 in a hydrolysis hydrogen production reaction.
7. The application of claim 6, wherein the method of applying is:
adding the doped CoB catalyst into a mixed aqueous solution of sodium borohydride and sodium hydroxide for hydrolysis to produce hydrogen under the condition of constant-temperature water bath at 25-30 ℃;
in the mixed aqueous solution of sodium borohydride and sodium hydroxide, the concentration of sodium borohydride is 1-10 wt%, and the concentration of sodium hydroxide is 1-10 wt%;
the dosage of the doped CoB catalyst is 1-5 mg/mL calculated by the volume of a mixed aqueous solution of sodium borohydride and sodium hydroxide.
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