CN106334561A - Non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride and preparation method of non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride - Google Patents
Non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride and preparation method of non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride Download PDFInfo
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- CN106334561A CN106334561A CN201610807168.2A CN201610807168A CN106334561A CN 106334561 A CN106334561 A CN 106334561A CN 201610807168 A CN201610807168 A CN 201610807168A CN 106334561 A CN106334561 A CN 106334561A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 60
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 35
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 35
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 175
- 239000006260 foam Substances 0.000 claims abstract description 88
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 88
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 53
- 239000010941 cobalt Substances 0.000 claims abstract description 53
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000007747 plating Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 22
- 239000012498 ultrapure water Substances 0.000 claims description 22
- 239000010970 precious metal Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- VWFLTHZUCYHIEC-UHFFFAOYSA-N cobalt sulfamic acid Chemical compound [Co].S(N)(O)(=O)=O VWFLTHZUCYHIEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 238000009713 electroplating Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 4
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PYZLRNMGUBDIHK-UHFFFAOYSA-N molecular hydrogen;nickel Chemical compound [Ni].[H][H] PYZLRNMGUBDIHK-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride and a preparation method of the non-noble metal catalyst for the alcoholysis hydrogen production of sodium borohydride. The non-noble metal catalyst for the alcoholysis hydrogen production of sodium borohydride comprises carrier nickel foam and loaded non-noble metal cobalt, and the cobalt is loaded on the surface of the nickel foam through an electroplating method to form a cobalt metal plating layer. Experiments show: under the conditions that the plating time is 1.5h, the temperature of a plating solution is 40 DEG C, the current density is 5mA/cm2 and the concentration of cobalt sulfamate is 50g/L, the catalyst prepared with the method has a best hydrogen production effect in a sodium borohydride alcoholysis solution. Moreover, the catalyst has dense distribution and stable performance, and has the characteristics of high efficiency, stability, low cost and practicality in the hydrogen production while being used in the alcoholysis hydrogen production of sodium borohydride.
Description
Technical field
The present invention relates to a kind of non-precious metal catalyst and preparation method thereof, be particularly suited for sodium borohydride as raw material,
By the chemical reaction of its alcoholysis reaction hydrogen making, belong to catalyst technical field.
Background technology
Hydrogen is a kind of clean energy resource, is also one of major way of hydrogen utilization simultaneously.At present, the method for hydrogen making
Mainly have following several: petrochemical industry, the comprehensive utilization of coal, electrolysis water, solar energy hydrolysis, chemical method, bioanalysis etc..Wherein,
Raw material is easy to storage, easy to carry, hydrogen purity is high etc. is had as the method for chemical fuel hydrogen making by sodium borohydride
Feature, and sodium borohydride alcoholysis hydrogen production reaction then has reaction with respect to hydrolysis and starts that fast, accessory substance is soluble, catalysis
The advantages of agent antidamping ability is strong, thus have a good application prospect.
In the presence of a catalyst, nabh4And ch3Oh reaction generates h2With nab (och3)4, reaction equation is as follows:.This reaction is exothermic reaction, in the situation that there is no catalyst
Under can slowly carry out, but after adding catalyst its reaction rate can increase substantially such that it is able to realize more efficient should
With the structural stability requirement only for catalyst is higher.
The species of sodium borohydride alcoholysis catalyst for hydrogen is a lot, is broadly divided into support type and non-loading type, due to load
Type catalyst is easily recycled and controls product hydrogen process, therefore suffers from more attention rates.Supported catalyst agent carrier typically adopts
There is the light material of high-ratio surface, and active component is then to have transition metal or some non-noble gold of high catalytic activity
Metal catalyst and co-catalysis component, at present based on viii race element, such as fe, co, ni, ru, rh, pd, pt etc., cr, mn, cu,
The elements such as zn also have a small amount of research.Wherein, best with the catalytic effect of noble metal catalyst rhodium and ruthenium, but the catalyst circulation longevity
Life not ideal enough, and relatively costly it is difficult to commercialization promote.
Due to sodium borohydride alcoholysis hydrogen manufacturing prospect preferably, so researching and developing a kind of efficient, stable, cheap practical urging
Agent is this technical field technical barrier urgently to be resolved hurrily.
Content of the invention
For above-mentioned existing technical problem, the present invention provides a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst
And preparation method thereof, to realize efficient, stable, cheap practical purpose.
For achieving the above object, the present invention provides a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst, including load
Body nickel foam and load base metal cobalt, and cobalt is carried on foam nickel surface by galvanoplastic, forms the coat of metal of one layer of cobalt.
And, described nickel foam is many pore size distributions, surface density is 300-500g/m2.
Because nickel foam has high-specific surface area, volume density is little, technical maturity, the advantages of with low cost, is preferably to urge
Agent carrier, and nearest metal co catalyst is considered as progressively can to replace noble metal catalyst and to sodium borohydride water
The solution the most promising class catalyst of hydrogen manufacturing, catalyst therefore of the present invention to be made with foam nickel carrier ni from metallic element co
Standby.Both components make the catalysis activity of this catalyst more preferable not only through shared electronics, and its H2-producing capacity reaches or even super
Get over noble metal catalyst；And make the activity of this catalyst be more difficult to inactivate, it is the head of current sodium borohydride catalyst for preparing hydrogen
Choosing.Additionally, this nickel foam carries Co catalysts can be effectively improved gas-liquid two in sodium borohydride reaction hydrogen production process for the catalyst
Phase properties of flow, is conducive to hydrogen production reaction to be smoothly rapidly performed by.
The present invention provides a kind of preparation method of above-mentioned sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst again, concrete step
Suddenly as follows:
A, nickel foam pretreatment: first nickel foam is immersed in successively absolute ethyl alcohol, ultra-pure water, hydrochloric acid, carries out respectively in ultra-pure water
Sonic oscillation cleans, then drying for standby.
Further, nickel foam is immersed in absolute ethyl alcohol, swings cleaning 30 minutes with ultrasound cleaner vibrator at 25 DEG C.
Further, nickel foam is immersed in the hydrochloric acid of 0.01mol/l, swings cleaning 20 with ultrasound cleaner vibrator under normal temperature
Minute.
B, plating: standby nickel foam is put in the cobalt plating solution that temperature is 40-60 DEG C, with platinum electrode as anode, bubble
Foam nickel is negative electrode, is 1-500ma/cm in current density2Under conditions of electroplate 5-200 minute, make the cobalt ions in cobalt plating solution
In the surface of nickel foam deposition, form the coating of one layer of cobalt；
Further, cobalt plating solution is containing sulfamic acid cobalt 10-100g/l, boric acid 10-20g/l, trisodium citrate 10-20g/l
Mixed solution, and instill the sulfuric acid that concentration is 30%, adjust ph value to 1-4.
Preferably plating conditions are as follows: cobalt plating solution temperature is 40 DEG C, and current density is 5ma/cm2, electroplating time is
1.5h, sulfamic acid cobalt concentration is 50g/l.
C, post processing: the nickel foam after cobalt plating is taken out, with ultrapure water, and kept dry.
The present invention passes through galvanoplastic and will have the cobalt appendix of high catalytic activity in foam nickel surface, and prepared nickel foam carries cobalt
Catalyst distribution is fine and close, stable performance.And during dedicated for sodium borohydride alcoholysis hydrogen production reaction, there is product hydrogen efficient, stable, low
The features such as Lian Shiyong.Can also be compact power and outdoor hydrogen balloon offer Hydrogen Generation with Chemical Methods.
Brief description
Fig. 1-1 is nickel foam pictorial diagram after pretreated for the present invention；
Fig. 1-2 is the pictorial diagram that the nickel foam that the present invention makes after direct current electrode position carries Co catalysts；
Fig. 2-1 is the sem photo of 200 times of amplification before foam nickel carrier cobalt plating in the present invention；
Fig. 2-2 is the sem photo of 10000 times of amplification before foam nickel carrier cobalt plating in the present invention；
Fig. 3-1 is the sem photo of 200 times of amplification after foam nickel carrier cobalt plating in the present invention；
Fig. 3-2 is the sem photo of 10000 times of amplification after foam nickel carrier cobalt plating in the present invention；
Fig. 4 is hydrogen-producing speed under different electroplating times for the catalyst of the present invention；
Fig. 5 is hydrogen-producing speed under different electroplating temperatures for the catalyst of the present invention；
Fig. 6 is hydrogen-producing speed under different current densities for the catalyst of the present invention；
Fig. 7 is hydrogen-producing speed under different bath concentrations for the catalyst of the present invention；
Fig. 8 is sodium borohydride alcoholysis hydrogen production reaction under using optimum plating conditions during this catalyst of preparation, produce hydrogen volume with
The graph of relation in reaction time.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
The active component of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst of the present invention includes carrier foam nickel and load
Base metal cobalt.Wherein: nickel foam is many pore size distributions, surface density is 300-500g/m2, before cobalt plating as shown in Fig. 2-1 and Fig. 2-1
Foam nickel carrier sem photo, and from Fig. 1-1, the nickel foam material object after pretreated presents in itself
Color is silver gray.Cobalt is carried on foam nickel surface by electric plating method, forms the coat of metal of one layer of cobalt, can from Fig. 1-2
Know, the surface in kind that the nickel foam made after direct current electrode position carries Co catalysts presents pale red, the as face of cobalt
Color.The sem photo of the nickel foam load cobalt after plating cobalt as shown in Fig. 3-1 and Fig. 3-2, i.e. the sem photo of this finished catalyst,
It can be seen that metallic cobalt is evenly distributed on foam nickel surface and combines fine and close.Prepare the method for above-mentioned catalyst and optimum plating conditions
Can be drawn by following groups experiment.
Embodiment 1:
A, nickel foam pretreatment.
A-1, by surface density 300g/m2Nickel foam be immersed in absolute ethyl alcohol, shaken with ultrasonic cleaner at 25 DEG C
Swing cleaning 30 minutes, with the abundant spot removing foam nickel surface.
A-2, nickel foam is taken out from absolute ethyl alcohol after, use ultra-pure water cleaned by ultrasonic vibration.
A-3, nickel foam is taken out from ultra-pure water after, be immersed in the hydrochloric acid of 0.01mol/l concentration, with super under normal temperature
Sound wave washer sonic oscillation 15 minutes.
A-4, nickel foam is taken out from hydrochloric acid after, use ultra-pure water cleaned by ultrasonic vibration.
A-5, the nickel foam after cleaning is placed in air dry oven and is dried, weigh and save backup.
B, plating.
B-1, the sulfamic acid cobalt preparing 30g/l, 15g/l boric acid, the mixed solution of 15g/l trisodium citrate, instill suitable
Amount concentration is 30% sulfuric acid, adjusts ph value to 1 about, as cobalt plating solution.
B-2, positive source connect platinum electrode, and power cathode connects nickel foam, are 40 DEG C in cobalt plating solution temperature, electric current is close
Spend for 5ma/cm2Under conditions of, electroplating time is respectively and is electroplated for 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours,
So that cobalt ions in plating solution is deposited on the surface of nickel foam, form the coat of metal of one layer of cobalt.
C, post processing: 5 parts of nickel foam electroplated after cobalts are taken out respectively, with ultrapure water 5 to 10 times, puts into air blast and do
Dry case is dried, and is respectively used to sodium borohydride alcoholysis hydrogen manufacturing, observes its catalytic effect.Figure 4, it is seen that this different catalysis
Agent sample, electroplating time increased to 3 hours from 1 hour, and time interval is half an hour, when electroplating time is 1.5 hours,
Catalytic effect is optimal.
Embodiment 2:
A, nickel foam pretreatment.
A-1, by surface density 400g/m2Nickel foam be immersed in absolute ethyl alcohol, shaken with ultrasonic cleaner at 25 DEG C
Swing cleaning 30 minutes, with the abundant spot removing foam nickel surface.
A-2, nickel foam is taken out from absolute ethyl alcohol after, use ultra-pure water cleaned by ultrasonic vibration.
A-3, nickel foam is taken out from ultra-pure water after, be immersed in the hydrochloric acid of 0.01mol/l concentration, with super under normal temperature
Sound wave washer sonic oscillation 15 minutes.
A-4, nickel foam is taken out from hydrochloric acid after, use ultra-pure water cleaned by ultrasonic vibration.
A-5, the nickel foam after cleaning is placed in air dry oven and is dried, weigh and save backup.
B, plating.
B-1, the sulfamic acid cobalt preparing 30g/l, 15g/l boric acid, the mixed solution of 15g/l trisodium citrate, instill suitable
Amount concentration is 30% sulfuric acid, adjusts ph value to 2 about, as cobalt plating solution.
B-2, positive source connect platinum electrode, and power cathode connects nickel foam, is 5ma/cm in current density2, plating when
Between under the conditions of 1.5 hours, the water bath with thermostatic control temperature adjusting cobalt plating solution respectively is entered for 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C
Row plating, makes cobalt ions in plating solution deposit on the surface of nickel foam, forms the coat of metal of one layer of cobalt.
C, post processing: 5 parts of nickel foam electroplated after cobalts are taken out respectively, with ultrapure water 5 to 10 times, puts into air blast and do
Dry case is dried, and is respectively used to sodium borohydride alcoholysis hydrogen manufacturing, observes its catalytic effect.
When on probation, being controlled using the method for water bath with thermostatic control makes bath temperature be maintained at a certain particular value.As shown in Figure 5, exist
When bath temperature is 40 DEG C, the catalytic effect of catalyst is optimal.In the case that other conditions are constant, raise solution temperature, can
To increase current density, thus increasing cathodic polarization effect.Meanwhile, temperature rising can make cathode reaction accelerate, and accelerates electrolysis
The diffusion of liquid intermediate ion, leads to cathodic polarization effect to reduce so that coated metal is roughening.
Embodiment 3:
A, nickel foam pretreatment.
A-1, by surface density 500g/m2Nickel foam be immersed in absolute ethyl alcohol, shaken with ultrasonic cleaner at 25 DEG C
Swing cleaning 30 minutes, with the abundant spot removing foam nickel surface.
A-2, nickel foam is taken out from absolute ethyl alcohol after, use ultra-pure water cleaned by ultrasonic vibration.
A-3, nickel foam is taken out from ultra-pure water after, be immersed in the hydrochloric acid of 0.01mol/l concentration, with super under normal temperature
Sound wave washer sonic oscillation 15 minutes.
A-4, nickel foam is taken out from hydrochloric acid after, use ultra-pure water cleaned by ultrasonic vibration.
A-5, the nickel foam after cleaning is placed in air dry oven and is dried, weigh and save backup.
B, plating.
B-1, the sulfamic acid cobalt preparing 30g/l, 15g/l boric acid, the mixed solution of 15g/l trisodium citrate, instill suitable
Amount concentration is 30% sulfuric acid, adjusts ph value to 3 about, as cobalt plating solution.
B-2, positive source connect platinum electrode, and power cathode connects nickel foam, when cobalt plating solution temperature is 40 DEG C, electroplates
Between make current density to 3 under the conditions of 1.5 hours, adjusting direct current electrode position power supply respectively, 5,8,10,15ma/cm2, to nickel foam
Electroplated, so that cobalt ions in plating solution is deposited on the surface of nickel foam, form the coat of metal of one layer of cobalt.
C, post processing: the nickel foam after plating cobalt is taken out, with ultrapure water 5 to 10 times, puts into air dry oven and do
Dry.
The hydrogen-producing speed that Fig. 6 is shown under different current densities by this catalyst.As can be seen that current density is big
Little, on catalyst impact less, optimum current density is 5ma.In electroplating process, due to the effect of electric current, make in electrolyte
Cobalt ions is reduced into metal, and forms layer of metal coating in foam nickel surface.So allow for being free near negative electrode
Concentration of cobalt ions reduce, slow down electrodepositing speed.Therefore, in this experiment, after electric current reaches 8ma, on negative electrode, hydrogen separates out
Amount increases so that current efficiency reduces, and quality of coating is deteriorated.
Embodiment 4:
A, nickel foam pretreatment.
A-1, by surface density 400g/m2Nickel foam be immersed in absolute ethyl alcohol, shaken with ultrasonic cleaner at 25 DEG C
Swing cleaning 30 minutes, with the abundant spot removing foam nickel surface.
A-2, nickel foam is taken out from absolute ethyl alcohol after, use ultra-pure water cleaned by ultrasonic vibration.
A-3, nickel foam is taken out from ultra-pure water after, be immersed in the hydrochloric acid of 0.01mol/l concentration, with super under normal temperature
Sound wave washer sonic oscillation 15 minutes.
A-4, nickel foam is taken out from hydrochloric acid after, use ultra-pure water cleaned by ultrasonic vibration.
A-5, the nickel foam after cleaning is placed in air dry oven and is dried, weigh and save backup.
B, plating.
B-1, preparation sulfamic acid cobalt, 15g/l boric acid, some groups of the mixed solution of 15g/l trisodium citrate, wherein amino
The concentration of sulfonic acid cobalt is respectively 10g/l, 20g/l, 30g/l, 40g/l, 50g/l, instills the sulfuric acid that appropriate concentration is 30%, adjusts
Ph value to 4 about, as cobalt plating solution.
B-2, positive source connect platinum electrode, and power cathode connects nickel foam, when cobalt plating solution temperature is 40 DEG C, electroplates
Between be 1.5 hours, current density 5ma/cm2Under the conditions of, nickel foam is electroplated, makes in plating solution cobalt ions in the table of nickel foam
Face deposits, and forms the coat of metal of one layer of cobalt.
C, post processing: 5 parts of nickel foam electroplated after cobalts are taken out respectively, with ultrapure water 5 to 10 times, puts into air blast and do
Dry case is dried, and is respectively used to sodium borohydride alcoholysis hydrogen manufacturing, observes its catalytic effect.
Fig. 7 be in the plating solution cobalt content when 10g/l increases to 50g/l, the hydrogen-producing speed that this catalyst is measured.Display bubble
Foam Raney nickel hydrogen-producing speed when bath concentration is for 50g/l is the fastest.
This catalyst of above-mentioned four groups experiment gained are respectively applied in sodium borohydride alcoholysis hydrogen production reaction it is known that hydrogen manufacturing
The catalyst of best results, its plating conditions is as follows: electroplating time is 1.5h, and bath temperature is 40 DEG C, and current density is 5ma,
In plating solution, the concentration of sulfamic acid cobalt is 50g/l.And, carry out sodium borohydride using the catalyst prepared under this optimum condition
During alcoholysis hydrogen production reaction, produce hydrogen volume as shown in Figure 8 with the relation curve in reaction time: catalyst product hydrogen rate when at the beginning relatively
Height, when being because just starting hydrogen production reaction, catalyst surface is entirely cobalt, and the growth with the reaction time, catalyst
Surface deposited nab (och3)4, partially catalyzed activated centre is capped, thus causing catalytic efficiency to decline.
In sum, the present invention, by cobalt galvanoplastic are carried on foam nickel surface, forms the monometallic plating of one layer of cobalt
Layer, prepared nickel foam carries the specific system mainly for sodium borohydride alcoholysis hydrogen manufacturing for the Co catalysts, have hydrogen-producing speed fast,
The features such as stable performance, cheap practicality, it is easy to reclaiming and controlling product hydrogen process, can be widely applied to Hydrogen Generation with Chemical Methods.
Claims (7)
1. a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst is it is characterised in that including carrier foam nickel and loading non-
Noble metal cobalt, and cobalt is carried on foam nickel surface by galvanoplastic, forms one layer of fine and close cobalt coat of metal.
2. a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst according to claim 1 is it is characterised in that described
Nickel foam be many pore size distributions, surface density be 300-500g/m2.
3. a kind of a kind of as claimed in claim 1 or 2 preparation method of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst,
It is characterized in that, specifically comprise the following steps that
A, nickel foam pretreatment: first nickel foam is immersed in successively absolute ethyl alcohol, ultra-pure water, hydrochloric acid, carries out respectively in ultra-pure water
Sonic oscillation cleans certain time, then drying for standby；
B, plating: standby nickel foam is put in the cobalt plating solution that temperature is 40-60 DEG C, with platinum electrode as anode, nickel foam
For negative electrode, it is 1-500ma/cm in current density2Under conditions of electroplate 5-200 minute, make cobalt ions in cobalt plating solution in bubble
The surface deposition of foam nickel, forms the coating of one layer of cobalt；
C, post processing: the nickel foam after cobalt plating is taken out, with ultrapure water, and kept dry.
4. the preparation method of a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst according to claim 3, it is special
Levy and be, in described step a, nickel foam is immersed in absolute ethyl alcohol, at 25 DEG C, swing 30 points of cleaning with ultrasound cleaner vibrator
Clock.
5. the preparation method of a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst according to claim 3 or 4, its
It is characterised by, in described step a, nickel foam is immersed in the hydrochloric acid of 0.01mol/l, swung with ultrasound cleaner vibrator under normal temperature
Cleaning 20 minutes.
6. the preparation method of a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst according to claim 3, it is special
Levy and be, the cobalt plating solution in described step b is containing sulfamic acid cobalt 10-100g/l, boric acid 10-20g/l, trisodium citrate
The mixed solution of 10-20g/l, and instill the sulfuric acid that concentration is 30%, adjusts ph value to 1-4.
7. the preparation method of a kind of sodium borohydride alcoholysis hydrogen manufacturing non-precious metal catalyst according to claim 6, it is special
Levy and be, the preferred plating conditions of described step b are as follows: cobalt plating solution temperature is 40 DEG C, current density is 5ma/cm2, plating
Time is 1.5h, and sulfamic acid cobalt concentration is 50g/l.
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