CN108855137A - A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen - Google Patents
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen Download PDFInfo
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- CN108855137A CN108855137A CN201810494150.0A CN201810494150A CN108855137A CN 108855137 A CN108855137 A CN 108855137A CN 201810494150 A CN201810494150 A CN 201810494150A CN 108855137 A CN108855137 A CN 108855137A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000446 fuel Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000008213 purified water Substances 0.000 claims abstract description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017586 La2S3 Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000001338 self-assembly Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- 150000002603 lanthanum Chemical class 0.000 claims description 33
- 150000003751 zinc Chemical class 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000005864 Sulphur Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 230000003213 activating effect Effects 0.000 claims description 17
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 238000010790 dilution Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 11
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 description 53
- 238000004519 manufacturing process Methods 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulphur Compound Chemical class 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- YTYSNXOWNOTGMY-UHFFFAOYSA-N lanthanum(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[La+3].[La+3] YTYSNXOWNOTGMY-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/33—
-
- B01J35/39—
Abstract
The present invention relates to a kind of preparation methods of film catalyst for being used to prepare fuel cell hydrogen, include the following steps：S1 raw material preparation；S2 prepares film solution；The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated, it is dry in nitrogen atmosphere after combining base material and silane coupling agent sufficiently, it is stand-by to obtain pretreated base material；S4 prepares complex sulfide film catalyst：Base material immerses in film solution, and 2-3h is heated and is stirred to react in water bath with thermostatic control, is cleaned 2-3 times to film surface using purified water after reaction, base material is removed, the ZnS of self assembly is obtained2/La2S3Film is to get complex sulfide film catalyst.It is the efficient film catalyst for being exclusively used in preparing fuel cell hydrogen.
Description
Technical field
The present invention relates to the Hydrogen Energy preparation fields of fuel cell industry, and in particular to one kind is used to prepare fuel cell hydrogen
Film catalyst preparation method.
Background technique
The contradictory aggravation between energy demand that increases severely with limited fossil fuel and the mankind and environmental problem
It becomes increasingly conspicuous, so that exploitation cleaning, efficient new energy have been very urgent.Hydrogen Energy fuel value is high, odorless nontoxic, combustion product
It is pollution-free, it is renewable energy.And Hydrogen Energy can provide power directly as the raw material of the fuel of fuel cell for electric vehicle, solution
Certainly current tail gas pollution problem.And solar energy photocatalytic hydrogen production by water decomposition is utilized, energy density is low, the dispersed strong sun
It can be converted into Hydrogen Energy, then be electrochemically reacted the hydrogen of generation and oxygen by fuel cell, produced electricl energy, product water
Any pollution will not be generated but also as the raw material of solar hydrogen making, and to environment, the energy system of benign cycle can be formed.Cause
This, is referred to as " technology of 21st century dream " using solar energy photocatalytic hydrogen production by water decomposition, receives deep extensively grind
Study carefully.The catalyst material ternary indium base sulfide of photocatalysis hydrogen production is good with its stability at present, and photoelectricity and catalytic performance are high, forbidden band
Width is narrow, has in visible region and absorbs the features such as strong, has broad development space.
Multi-element metal sulfide photocatalyst can regulate and control band structure by adjusting its composition, make its ABSORPTION EDGE red shift,
It realizes visible light-responded, effectively improves light-catalyzed reaction performance, realize the controllable preparation of photochemical catalyst, become photochemical catalyst and set
The hot spot of meter and research,.Ternary metal sulfide has unique photoelectricity and catalytic performance, and forbidden bandwidth is relatively narrow, visible
There is stronger absorption in light area, by researcher concern and further investigate, be that there is the novel light of broad development space to urge
Change material.New century, energy problem had become the significant problem of facing mankind with environmental problem, and developing cleaning new energy is to solve
One important channel of the problem.Semiconductor material is applied to light-catalyzed reaction, is one using solar energy abundant as the energy
Kind reasonable energy utilization and the effective ways to reduce environmental pollution, developing efficient, stable photochemical catalyst becomes numerous scholars'
Research hotspot.Multi-element metal sulfide is a kind of photochemical catalyst with high catalytic activity and high stability, being capable of effective benefit
With sunlight, its catalytic activity can be significantly improved by the approach such as doping, load, compound.
Photocatalysis hydrogen production becomes the major concern of next-generation hydrogen manufacturing means due to the advantage of its environmental protection, energy conservation.But by
It is low in its catalytic efficiency, it is temporarily popularized not in industrial application the features such as poor catalyst activity.The core of photocatalysis hydrogen production is to inhale
Electronics is generated after receiving optical radiation energy, to participate in water decomposition reaction.In water splitting processes, hydrogen-evolution overpotential and oxygen evolution potential point
Not Wei 0ev and 1.23ev need the forbidden bandwidth of catalyst much larger than 1.23ev and due to miscellaneous phase and side reaction.Metal sulphur
Compound is since it is with excellent liberation of hydrogen and oxygen evolution potential, by a large number of scientific researchers research and concern.But monometallic sulfide is such as
Zinc sulphide is easily oxidized, and lanthanum sulfide hydrogen-evolution overpotential is excessively high, it is difficult to which single application is in photocatalysis hydrogen production field.Therefore for compound
Type metal sulfide has highly important practical significance for photocatalysis hydrogen production field.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of films for being used to prepare fuel cell hydrogen
The preparation method of catalyst solves the problems, such as that catalytic efficiency is low and poor catalytic activity.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：Zinc salt, lanthanum salt, sulphur source, activating agent and purified water are prepared according to mol ratio；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise and adjusts pH, stands, it is molten to obtain film
Liquid is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated, substrate is made
It is dry in nitrogen atmosphere after material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 2-3h is heated and is stirred to react in water bath with thermostatic control, is cleaned 2-3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
La2S3Hydrogen-evolution overpotential it is higher（-1.25ev）, oxygen evolution potential is lower（1.66ev）, and ZnS2It is then opposite to that（Analysis
Hydrogen potential -0.21ev, oxygen evolution potential 2.41ev）, and the two forbidden bandwidth is closer to.It is compound by the two, it enables with curved
Song forms class pn-junction structure, selective in ZnS2Chromatograph hydrogen and in La2S3Oxygen is chromatographed, electronics and hole are efficiently separated, thus
Its catalytic activity, while simple process are improved, large-scale industrial production is suitable for.
The special structure of complex sulfide film catalyst, enables light induced electron to transmit rapidly, is conducive to react
The transmission of object and product promotes the progress of light-catalyzed reaction.
Metal sulfide is considered as excellent visible-light photocatalyst, and suitable valence band conduction band positions make metal sulphur
Compound has good catalytic effect in photochemical catalytic oxidation and photodegradation water hydrogen manufacturing.
Further, the mol ratio of zinc salt in the S1 step, lanthanum salt, sulphur source, activating agent and purified water is 1：（1.2-
1.5）：（6-8）：（0.5-0.8）：（25-30）.
Further, zinc salt is zinc chloride, zinc nitrate or zinc sulfate in the S1 step.The selectable range of zinc salt is wide,
And it is at low cost, the performance of film in preparation process is influenced small.
Further, lanthanum salt is lanthanum chloride, lanthanum nitrate or lanthanum sulfate in the S1 step.The selectable range of lanthanum salt is wide,
The performance of film in preparation process is influenced small.
Further, sulphur source is thioacetamide in the S1 step；Activating agent is triethanolamine in the S1 step.Sulphur
For acetamide for producing catalyst, stabilizer, polymerization inhibitor, electroplating additive, photographic chemical, pesticide, dyeing assistant and ore dressing
Agent etc. also serves as vulcanizing agent, crosslinking agent, rubber chemicals and the medical material of polymer.The alkalinity of triethanolamine is weaker than ammonia
(pKa7.82), with the property of tertiary amine and alcohol, it can be used as sulfide active agent.
Further, stirring rate is 80-100r/min in the S2 step；Dilute sulfuric acid is mole dense in the S2 step
Degree is 0.1mol/L；PH is adjusted to 2-3 in the S2 step；Time of repose is 2-3h in the S2 step.
Further, additive amount of the silane coupling agent in anhydrous methanol is 200-300g/L in the S3 step；It is described
Sonication treatment time is 2.5-3.5h in S3 step.Silane coupling agent wiring solution-forming is conducive to silane coupling agent on the surface of the material
Dispersion, solvent is the solution that water and alcohol are configured to, and solution is generally silane (20%), alcohol (72%), water (8%), and alcohol is generally second
Alcohol (to Ethoxysilane) methanol (to methoxy silane) and isopropanol (to the silane for being not readily dissolved in ethyl alcohol, methanol) are because of silane water
It is related with pH value to solve speed, neutral most slow, meta-acid, meta-alkali are all very fast, therefore need to generally adjust the pH value of solution, remove amino silane
Outside, a small amount of acetic acid can be added in other silane, adjust pH value to 4-5, amino silane is because of tool alkalinity, it is not necessary to adjust.
Further, the temperature of water bath with thermostatic control is 75-85 DEG C in the S4 step；Stirring rate is in the S4 step
40-50r/min.Stirring rate is low to facilitate film forming, and stirring is conducive to uniformly molding.
The beneficial effects of the invention are as follows：La2S3Hydrogen-evolution overpotential it is higher（-1.25ev）, oxygen evolution potential is lower（1.66ev）,
And ZnS2It is then opposite to that（Hydrogen-evolution overpotential -0.21ev, oxygen evolution potential 2.41ev）, and the two forbidden bandwidth is closer to, and is led to
It is compound to cross the two, makes band curvature, forms class pn-junction structure, it is selective in ZnS2Chromatograph hydrogen and in La2S3Oxygen is chromatographed, effectively
It separates electronics and hole and is suitable for large-scale industrial production to improve its catalytic activity, while simple process.Composite sulfur
The special structure of compound film catalyst, enables light induced electron to transmit rapidly, is conducive to the transmission of reactants and products,
Promote the progress of light-catalyzed reaction.Hydrogen manufacturing is with high purity, high-efficient, prepares fuel cell hydrogen suitable for batch stabilization.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.2：6：
0.5：25；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 2, stands 2h, obtains thin
Coating solution is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 2.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 2h is heated and is stirred to react in 75 DEG C of waters bath with thermostatic control, is cleaned 2 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc chloride in the S1 step；Lanthanum salt is lanthanum chloride in the S1 step；In the S2 step
Stirring rate is 80r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step；It is silane coupled in the S3 step
Additive amount of the agent in anhydrous methanol is 200g/L；, stirring rate is 40r/min in the S4 step.Base material is ceramics
Plate, film catalyst with a thickness of 0.015mm.
The catalyst hydrogen production rate of embodiment 1 is 650 μm of ol/h.
Embodiment 2
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.5：8：
0.8：30；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtains thin
Coating solution is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc nitrate in the S1 step；Lanthanum salt is lanthanum nitrate in the S1 step；In the S2 step
Stirring rate is 100r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step；Silane is even in the S3 step
Joining additive amount of the agent in anhydrous methanol is 300g/L；, stirring rate is 50r/min in the S4 step.Base material is pottery
Porcelain plate, film catalyst with a thickness of 0.017mm.
The catalyst hydrogen production rate of embodiment 2 is 700 μm of ol/h.
Embodiment 3
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.3：7：
0.7：28；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 2.5h, obtains
Film solution is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.0h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 2.5h is heated and is stirred to react in 80 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by base
Bottom material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc sulfate in the S1 step；Lanthanum salt is lanthanum sulfate in the S1 step；In the S2 step
Stirring rate is 90r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step；It is silane coupled in the S3 step
Additive amount of the agent in anhydrous methanol is 250g/L；, stirring rate is 45r/min in the S4 step.Base material is ceramics
Plate, film catalyst with a thickness of 0.016mm.
The catalyst hydrogen production rate of embodiment 3 is 720 μm of ol/h.
Embodiment 4
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.4：7：
0.6:28；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtains thin
Coating solution is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc sulfate in the S1 step；Lanthanum salt is lanthanum sulfate in the S1 step；In the S2 step
Stirring rate is 95r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step；It is silane coupled in the S3 step
Additive amount of the agent in anhydrous methanol is 280g/L；, stirring rate is 45r/min in the S4 step.Base material is ceramics
Plate, film catalyst with a thickness of 0.018mm.
The catalyst hydrogen production rate of embodiment 4 is 750 μm of ol/h.
Embodiment 5
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.5：8：
0.6：30；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtains thin
Coating solution is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc sulfate in the S1 step；Lanthanum salt is lanthanum sulfate in the S1 step；In the S2 step
Stirring rate is 95r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step；It is silane coupled in the S3 step
Additive amount of the agent in anhydrous methanol is 280g/L；, stirring rate is 45r/min in the S4 step.Base material is ceramics
Plate, film catalyst with a thickness of 0.019mm.
The catalyst hydrogen production rate of embodiment 5 is 750 μm of ol/h.
Embodiment 6
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.5：8：
0.8：30；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtains thin
Coating solution is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc sulfate in the S1 step；Lanthanum salt is lanthanum sulfate in the S1 step；In the S2 step
Stirring rate is 90r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step；It is silane coupled in the S3 step
Additive amount of the agent in anhydrous methanol is 250g/L；, stirring rate is 45r/min in the S4 step.Base material is ceramics
Plate, film catalyst with a thickness of 0.020mm.
The catalyst hydrogen production rate of embodiment 6 is 700 μm of ol/h.
Comparative example 1
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, thioacetamide, triethanolamine and purified water：7：0.6:28；
S2 prepares film solution：The zinc salt prepared in S1 step is added into purified water, stirring at normal temperature to being completely dissolved, then plus
Enter sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtain film solution
For use；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2Film is to get complex sulfide film catalyst.
Specifically, zinc salt is zinc sulfate in the S1 step；Stirring rate is 95r/min in the S2 step；The S2
The molar concentration of dilute sulfuric acid is 0.1mol/L in step；Additive amount of the silane coupling agent in anhydrous methanol is in the S3 step
280g/L；, stirring rate is 45r/min in the S4 step.Base material is ceramic wafer, film catalyst with a thickness of
0.015mm。
The catalyst hydrogen production rate of comparative example 1 is 500 μm of ol/h.
Comparative example 2
A kind of preparation method for the film catalyst being used to prepare fuel cell hydrogen, includes the following steps：
S1 raw material preparation：It is 1.4 by the mol ratio of lanthanum salt, thioacetamide, triethanolamine and purified water：7：0.6:28；
S2 prepares film solution：The lanthanum salt prepared in S1 step is added into purified water, stirring at normal temperature to being completely dissolved, then plus
Enter sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtain film solution
For use；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated 3.5h, is made
It is dry in nitrogen atmosphere after base material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, is cleaned 3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the La of self assembly2S3Film is to get complex sulfide film catalyst.
Specifically, lanthanum salt is lanthanum sulfate in the S1 step；Stirring rate is 95r/min in the S2 step；The S2
The molar concentration of dilute sulfuric acid is 0.1mol/L in step；Additive amount of the silane coupling agent in anhydrous methanol is in the S3 step
280g/L；, stirring rate is 45r/min in the S4 step.
The catalyst hydrogen production rate of comparative example 2 is 490 μm of ol/h.
Comparative example 3
S1 raw material preparation：It is 1 by the mol ratio of zinc salt, lanthanum salt, thioacetamide, triethanolamine and purified water：1.5：8：
0.8：30；
S2 prepares solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to being completely dissolved, then
Sulphur source is added and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise, pH is adjusted 3, stands 3h, obtains solution and wait for
With；
The preparation of S3 catalyst：By in S3 step, 3h is heated and is stirred to react in 85 DEG C of waters bath with thermostatic control, using purified water cleaning 3
It is secondary, obtain the ZnS of self assembly2/La2S3Powder is to get catalyst.
Specifically, zinc salt is zinc sulfate in the S1 step；Lanthanum salt is lanthanum sulfate in the S1 step；In the S2 step
Stirring rate is 90r/min；The molar concentration of dilute sulfuric acid is 0.1mol/L in the S2 step.
3 catalyst hydrogen production rate of comparative example is 175 μm of ol/h.
It is selective by the pn-junction structure that under equal conditions hydrogen manufacturing is compared to obtained film catalyst, and the present invention obtains
In ZnS2Chromatograph hydrogen and in La2S3Oxygen is chromatographed, electronics and hole are efficiently separated, to improve its catalytic activity, while technique letter
It is single, it is suitable for large-scale industrial production.The special construction of filming, enables light induced electron to transmit rapidly, is conducive to
The transmission of reactants and products promotes the progress of light-catalyzed reaction.
Claims (8)
1. a kind of preparation method for the film catalyst for being used to prepare fuel cell hydrogen, which is characterized in that include the following steps：
S1 raw material preparation：Zinc salt, lanthanum salt, sulphur source, activating agent and purified water are prepared according to mol ratio；
S2 prepares film solution：The zinc salt and lanthanum salt that prepare in S1 step are added into purified water, stirring at normal temperature to completely it is molten
Solution, adds sulphur source and activating agent stirring at normal temperature is uniformly mixed, then dilution heat of sulfuric acid is added dropwise and adjusts pH, stands, it is molten to obtain film
Liquid is stand-by；
The pretreatment of S3 base material：Base material is placed in the anhydrous methanol containing silane coupling agent and is ultrasonically treated, substrate is made
It is dry in nitrogen atmosphere after material and silane coupling agent sufficiently combine, it is stand-by to obtain pretreated base material；
S4 prepares complex sulfide film catalyst：Base material pretreated in S3 step is immersed to the film solution of S2 step
In, 2-3h is heated and is stirred to react in water bath with thermostatic control, is cleaned 2-3 times to film surface using purified water after reaction, by substrate
Material removal, obtains the ZnS of self assembly2/La2S3Film is to get complex sulfide film catalyst.
2. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is, zinc salt in the S1 step, lanthanum salt, sulphur source, the mol ratio of activating agent and purified water are 1：（1.2-1.5）：（6-
8）：（0.5-0.8）：（25-30）.
3. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is that zinc salt is zinc chloride, zinc nitrate or zinc sulfate in S1 step.
4. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is that lanthanum salt is lanthanum chloride, lanthanum nitrate or lanthanum sulfate in S1 step.
5. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is that sulphur source is thioacetamide in S1 step；Activating agent is triethanolamine in S1 step.
6. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is that stirring rate is 80-100r/min in S2 step；The molar concentration of dilute sulfuric acid is 0.1mol/L；PH is adjusted to 2-3；
Time of repose is 2-3h.
7. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is that additive amount of the silane coupling agent in anhydrous methanol is 200-300g/L in S3 step；Sonication treatment time is 2.5-
3.5h。
8. a kind of preparation method of film catalyst for being used to prepare fuel cell hydrogen according to claim 1, special
Sign is that the temperature of water bath with thermostatic control is 75-85 DEG C in S4 step；Stirring rate is 40-50r/min.
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| CN110548522A (en) * | 2019-07-19 | 2019-12-10 | 华南师范大学 | recyclable photocatalytic material for degrading tetracycline A ring and preparation method thereof |
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Cited By (2)
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| CN110548522A (en) * | 2019-07-19 | 2019-12-10 | 华南师范大学 | recyclable photocatalytic material for degrading tetracycline A ring and preparation method thereof |
| CN110548522B (en) * | 2019-07-19 | 2021-09-07 | 华南师范大学 | Recyclable photocatalytic material for degrading tetracycline A ring and preparation method thereof |
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