CN107020139A - Photocatalysis prepares the method that the catalyst of hydrogen and photocatalysis prepare hydrogen - Google Patents
Photocatalysis prepares the method that the catalyst of hydrogen and photocatalysis prepare hydrogen Download PDFInfo
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- CN107020139A CN107020139A CN201710282840.5A CN201710282840A CN107020139A CN 107020139 A CN107020139 A CN 107020139A CN 201710282840 A CN201710282840 A CN 201710282840A CN 107020139 A CN107020139 A CN 107020139A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 76
- 239000001257 hydrogen Substances 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 62
- 239000003426 co-catalyst Substances 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052946 acanthite Inorganic materials 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical group [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 24
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000005864 Sulphur Substances 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- -1 octadecylene Chemical group 0.000 claims description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 11
- FRGKKTITADJNOE-UHFFFAOYSA-N sulfanyloxyethane Chemical compound CCOS FRGKKTITADJNOE-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 230000005476 size effect Effects 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 150000002431 hydrogen Chemical class 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000013078 crystal Substances 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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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
-
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to photocatalysis hydrogen production technical field, specifically disclose a kind of photocatalysis and prepare the method that the catalyst of hydrogen and photocatalysis prepare hydrogen, the catalyst is Ag2X nano is brilliant, PbX is nanocrystalline or InY it is nanocrystalline in one or more, wherein, X=S, Se or Te；Y=P, As or Sb；Ag2The brilliant average grain diameter of X nano is in below 8.5nm；Average grain diameter nanocrystalline PbX is in below 4.5nm；Average grain diameter nanocrystalline InY is in below 3nm；Single Ag can be realized2X nano is brilliant, PbX is nanocrystalline or the nanocrystalline production hydrogen of InY, without co-catalyst and other semiconductor carriers；And with more preferable photocatalysis efficiency, more preferable stability；Material environmental protection, pollution-free simultaneously.
Description
Technical field
The present invention relates to photocatalysis hydrogen production technical field, the catalyst and light that more particularly to a kind of photocatalysis prepares hydrogen are urged
The method that change prepares hydrogen.
Background technology
Hydrogen Energy is with a wide range of applications as a kind of Novel clean, regenerative resource.Using sunshine decomposition water system
Standby hydrogen is a kind of with low cost, approach of simple possible and great potential, and its core is development high efficiency photocatalyst.
The photochemical catalyst being currently known is generally inefficient, and light absorption range is narrower.Narrow band gap Ag2S absorption of crystal is reachable
More than 1300nm, how to realize and improve hydrogen generation efficiency using its excellent absorbing properties is that photocatalysis research field is generally closed
One of the problem of heart.
There are some document reports to utilize Ag2The nanocrystalline light absorbers that do of S aid in other semi-conducting materials (such as TiO2、CdS、
ZnS、In2S3Deng) photocatalysis prepares the work of hydrogen, such as Zhu has synthesized Ag2S-TiO2Composite catalyst, utilizes Ag2S, which is done, to be inhaled
Luminescent material sensitization TiO2 improves photocatalysis performance (Chinese Journal of Catalysis, 2012,33,254-260).
Shen etc. is prepared for Ag using two step sedimentations2S/CdS nanostructureds are simultaneously applied to photocatalysis, and they have found：Work as Ag2S contains
When measuring as 5wt%, Ag2S/CdS realizes higher Photocatalyzed Hydrogen Production efficiency (International Journal of
Hydrogen Energy,2010,35,7110-7115).Yang etc. has synthesized porous ZnS/Ag2S hybridized nanometer crystal, he
Find when Zn and Ag the ratio between atomicity is 33:When 26, the Photocatalyzed Hydrogen Production best results (ACS of hybridized nanometer crystal
applied materials&interfaces,2014,6,9078-9084).Although work, which is reported, above utilizes Ag2S width
Absorb and excellent electric charge transfer performance can aid in the yield of other semiconductors raising hydrogen, but use single Ag2S crystal does light
The method of catalyst preparation hydrogen there is no report.
The content of the invention
It is contemplated that overcoming existing narrow band gap Ag2The technology that S crystal is not applied very well in photocatalysis hydrogen production field
Problem can be used alone to photocatalysis hydrogen production, and the good photochemical catalyst of catalyzing manufacturing of hydrogen efficiency high, stability and photocatalysis there is provided one kind
The method for preparing hydrogen and the hydrogen prepared.
To achieve the above object, the present invention uses following technical scheme：
On the one hand, the present invention provides the catalyst that a kind of photocatalysis prepares hydrogen, and the catalyst is Ag2X nano is brilliant, PbX
One or more during nanocrystalline or InY is nanocrystalline, wherein, X=S, Se or Te；Y=P, As or Sb；The Ag2X nano crystalline substance,
The average grain diameter that PbX is nanocrystalline or InY is nanocrystalline is in below 8.5nm.
In some embodiments, Ag2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline has quantum size effect.
In some embodiments, catalyst is the Ag that surface carries metal Ion-hydrophilic Ligand2X nano is brilliant, PbX is nanocrystalline or InY nanometers
It is brilliant.
Yet another aspect, the present invention provides a kind of method that photocatalysis prepares hydrogen, and step includes using catalyst photocatalysis
The aqueous solution containing sacrifice agent prepares hydrogen, wherein, catalyst includes above-mentioned catalyst.
In some embodiments, catalyst is Ag2S is nanocrystalline, the Ag2Average grain diameter nanocrystalline S is in below 8.5nm.
In some embodiments, catalyst reacts 5min- for Ag sources are mixed with sulphur source at a temperature of 110 DEG C -190 DEG C
60min is obtained.
In some embodiments, Ag sources include solubility Ag salt；Sulphur source be selected from TGA, mercaptopropionic acid, 3-mercaptoethanol,
One or more in thiocarbamide or sulphur powder.
In some embodiments, catalyst reacts for Ag sources are mixed with sulphur source and part at a temperature of 110 DEG C -190 DEG C
5min-60min is obtained.
In some embodiments, part is selected from TGA, mercaptopropionic acid, 3-mercaptoethanol, oleic acid, tri octyl phosphine, 18
It is one or more of in alkene, octadecylamine.
In some embodiments, catalyst is the Ag of ligand exchange2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline.
In some embodiments, one or more of the part in TGA, mercaptopropionic acid, 3-mercaptoethanol.
In some embodiments, catalyst also contain cocatalyst, the co-catalyst include Pt, Au or Pd in one kind or
It is several.
In some embodiments, sacrifice agent is Na2S and/or Na2SO3, specific sacrifice agent can be Na2S and Na2SO3。
In some embodiments, sacrifice agent is one kind or several in ethanol, ethylene glycol, isopropanol, n-butanol or triethanolamine
Kind.
In some embodiments, sacrifice agent is one kind or several in ethanol, ethylene glycol, isopropanol, n-butanol or triethanolamine
Kind, and, Na2S and/or Na2SO3；In i.e. preferred scheme, sacrifice agent includes the first sacrifice agent and the second sacrifice agent, and first sacrifices
Agent is the one or more in ethanol, ethylene glycol, isopropanol, n-butanol or triethanolamine, and the second sacrifice agent is Na2S and/or
Na2SO3。
The present invention also provides a kind of hydrogen simultaneously, and the method that the hydrogen prepares hydrogen by above-mentioned photocatalysis is prepared.
The beneficial effects of the present invention are：
The present invention is by long-term experimental studies have found that single body phase Ag2S crystal bandgaps are narrow, and its conduction band positions is less than H+/H2
Reduction potential, causes electronics can not be from Ag2S conduction bands are to H+Transfer, so it can not be used alone to photocatalysis hydrogen production.And surprisingly send out
Now work as Ag2X crystal, PbX crystal or InY crystalline sizes constantly reduce, Ag2The brilliant average grain diameter of X nano is in below 8.5nm；PbX
Nanocrystalline average grain diameter is in below 4.5nm；Average grain diameter nanocrystalline InY is in below 3nm, Ag2X nano is brilliant, PbX nanometers
It is brilliant or InY is nanocrystalline can inherently produce good Photocatalyzed Hydrogen Production performance.Work as Ag2X nano is brilliant, diameter is further reduced to
During 7.2nm (absorb peak position in 800nm), its Photocatalyzed Hydrogen Production performance is further improved, light turn over number (TON) reach 3900 with
On.Ag2X nano is brilliant, the Photocatalyzed Hydrogen Production efficiency that PbX is nanocrystalline or InY is nanocrystalline and its particle diameter constantly reduce the quantum caused
Dimensional effect is relevant.The nanocrystalline of the present invention has larger band gap and smaller photocatalysis Preventing cough, so that for also
Protohydrogen gas provides bigger power.The present invention can be near red so as to realize using quantum size effect regulation and control narrow gap semiconductor
Outer response nano crystalline substance does high efficiency photocatalyst and prepares hydrogen.And this technology will substantially reduce the synthesis cost of catalyst, reduction
Complexity, and the pollution problem that the metal tapes such as Cd can be avoided are reacted, thus with important value.
The Ag of the present invention2X nano is brilliant, PbX is nanocrystalline or the nanocrystalline performances with Photocatalyzed Hydrogen Production of InY (and typically
Narrow gap semiconductor body phase Ag2X, PbX, InY material do not have the performance of Photocatalyzed Hydrogen Production), preferably realize (1) single
Ag2X nano is brilliant, PbX is nanocrystalline or the nanocrystalline production hydrogen of InY, without co-catalyst and other semiconductor carriers；(2) it is of the invention
Ag2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline has broader light abstraction width, and the effective uptake region of nanocrystal reaches
To more than 1100nm, with more preferable photocatalysis efficiency；(3) material environmental protection, pollution-free.
Brief description of the drawings
Fig. 1 is the Ag of the embodiment of the present invention 1, embodiment 2 and comparative example 12S absorption of crystal spectrograms.
Fig. 2 is the Ag of the embodiment of the present invention 1 and comparative example 12S crystal XRD (X-ray diffractogram).
The production hydrogen collection of illustrative plates of Fig. 3 embodiment of the present invention 1, embodiment 2 and comparative example 1.
The production hydrogen data of Fig. 4 embodiment of the present invention 1.
Fig. 5 is the nanocrystalline abosrption spectrograms of PbS of the embodiment of the present invention 5.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with accompanying drawing and specific implementation
Example, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain this hair
It is bright, without being construed as limiting the invention.
The invention provides the catalyst that a kind of photocatalysis prepares hydrogen, the catalyst is Ag2X nano is brilliant, PbX is nanocrystalline
Or InY it is nanocrystalline in one or more, wherein, X=S, Se or Te；Y=P, As or Sb；The Ag2The brilliant average grain of X nano
Footpath is in below 8.5nm, the PbX nanocrystalline average grain diameter in below 4.5nm, the InY nanocrystalline average grain diameter in 3nm
Hereinafter, single Ag can be realized2X nano is brilliant, PbX is nanocrystalline or the nanocrystalline production hydrogen of InY, is carried without co-catalyst and other semiconductors
Body；And the Ag of the present invention2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline has a broader light abstraction width, and nanocrystal has
Effect absorption region reaches more than 1100nm, with more preferable photocatalysis efficiency, more preferable stability；Material environmental protection simultaneously,
It is pollution-free.
In some embodiments, Ag2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline has quantum size effect, utilizes quantum
Dimensional effect regulation and control narrow gap semiconductor can be with so that realize that near-infrared response nano crystalline substance does high efficiency photocatalyst and prepares hydrogen.
Ag2The nanotopography that X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline can be point, line or face structure etc., and the present invention is not limited
System.
Specific preferred, catalyst is Ag2S is nanocrystalline, simple easily to prepare, environmental protection.
In some embodiments, catalyst is the Ag that surface carries metal Ion-hydrophilic Ligand2X nano is brilliant, PbX is nanocrystalline or InY nanometers
It is brilliant.It is more easy to play the performance of catalyst, high catalytic efficiency.
Meanwhile, the invention provides a kind of method that photocatalysis prepares hydrogen, step includes being contained with catalyst photocatalysis
The aqueous solution of sacrifice agent prepares hydrogen, wherein, catalyst includes above-mentioned catalyst.
Specific preferred catalyst is Ag2S is nanocrystalline, Ag2Average grain diameter nanocrystalline S is in below 8.5nm, catalytic efficiency
It is high.
When catalyst is Ag2When S is nanocrystalline, catalyst can be for Ag sources be mixed with sulphur source, in 110 DEG C of -190 DEG C of temperature
Lower reaction 5min-60min is obtained, and is specifically as follows at 145 DEG C and is reacted 10min.Wherein, Ag sources typically can be solubility Ag
Salt, such as AgNO3.Sulphur source can be selected from one kind in TGA, mercaptopropionic acid, 3-mercaptoethanol, thiocarbamide or sulphur powder or several
Kind.The present invention contains part in can also preferably reacting, i.e., mix in Ag sources with sulphur source and part, in 110 DEG C of -190 DEG C of temperature
Lower reaction 5min-60min obtains catalyst, wherein, part can be metal Ion-hydrophilic Ligand, such as TGA, mercaptopropionic acid, two mercaptos
Base ethanol etc.；Can also for oil phase part such as oleic acid, tri octyl phosphine, octadecylene, octadecylamine；I.e. part can be selected from sulfydryl
It is one or more of in acetic acid, mercaptopropionic acid, 3-mercaptoethanol, oleic acid, tri octyl phosphine, octadecylene, octadecylamine.When sulphur source is sulfydryl
When acetic acid, mercaptopropionic acid, 3-mercaptoethanol, itself can be used as part, you can not use extra ligand, can also select
Other kinds of part coordinates it to use.Other classes Ag2X nano is brilliant, the preparation that PbX is nanocrystalline or InY is nanocrystalline can also be joined
Prepared according to as above method using Hydrothermal Synthesiss or organic solvent thermal synthesis, typically using TGA, mercaptopropionic acid, two mercaptos
During the hydrophilic ligands such as base ethanol, gained is nanocrystalline to be directly used as photochemical catalyst；Using oleic acid, tri octyl phosphine, octadecylene, ten
During the oleophylic part such as eight amine, hydrogen, by ligand exchange into metal Ion-hydrophilic Ligand, can be produced available for photochemical catalyst by ligand exchange.
The method that then more specifically photocatalysis prepares hydrogen can be：By Ag sources such as AgNO3It is dissolved in organic solvent
For example in ethylene glycol, mercaptopropionic acid (MPA) is then added, mixed solution is led into nitrogen bubble such as 10min for a period of time, started
Heating.145 DEG C and then keeping temperature are to slowly warm up to, solution colour is changed into white cloud form from white clear, subsequently becomes yellow
Cloud form.Start timing when solution is eventually become when winestone is popular in bright color, it is that can obtain not that solution is taken out at different time points
With the nanocrystalline of particle diameter.Finally, solution is stopped heating and being progressively cooled to room temperature.By resulting solution add absolute methanol and from
The heart is that can obtain clean nanocrystalline sample.By this it is nanocrystalline be dispersed in again in deionized water or absolute methanol, and be transferred to light
Light-catalyzed reaction is carried out in catalytic reactor and prepares hydrogen.In light-catalyzed reaction, using sacrifice agent such as Na2S+Na2SO3Point
Dissipate in aqueous, using light such as AM1.5 (100mW/cm2) simulated solar light irradiation, by Ag2The nanocrystalline loading photocatalysis of S is anti-
Answer progress photocatalysis experiment in device.Stirred at ambient temperature using magnetic, the concentration of a hydrogen is surveyed every 15min.This reaction
Middle MPA is sulphur source, plays part again.
The Ag of the present invention2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline both can also use non-using synthesis in water
Synthesis in water.The nanocrystalline material that can not disperse in the aqueous solution can be such as changed into by ligand exchange using non-aqueous be combined to
The material that can disperse in the aqueous solution, i.e. catalyst are the Ag of ligand exchange2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline.Example
In such as some embodiments, first using the Ag on the part hydrophobic synthetic such as oleic acid or tri octyl phosphine, octadecylene surface2X nano crystalline substance,
PbX is nanocrystalline or InY is nanocrystalline, afterwards, and parent is can obtain using ligand exchanges such as TGA, mercaptopropionic acid, 3-mercaptoethanols
Nanocrystalline, i.e. Ag of the surface with metal Ion-hydrophilic Ligand of water2X nano is brilliant, PbX is nanocrystalline or InY is nanocrystalline.
It can also contain cocatalyst in some embodiments, in catalyst and further improve its performance, it is preferable that co-catalyst bag
Include the one or more in the heavy metal materials such as Pt, Au or Pd.
In some embodiments, sacrifice agent is Na2S and/or Na2SO3.Specific preferably sacrifice agent is Na2S and Na2SO3。
In some embodiments, sacrifice agent is one kind or several in ethanol, ethylene glycol, isopropanol, n-butanol or triethanolamine
Kind.
In some embodiments, sacrifice agent is one kind or several in ethanol, ethylene glycol, isopropanol, n-butanol or triethanolamine
Kind, and, Na2S and/or Na2SO3；In i.e. preferred scheme, sacrifice agent includes the first sacrifice agent and the second sacrifice agent, and first sacrifices
Agent is the one or more in ethanol, ethylene glycol, isopropanol, n-butanol or triethanolamine, and the second sacrifice agent is Na2S and/or
Na2SO3.By using the sacrifice agent of this combination, hydrogen-producing speed can be significantly improved.
The present invention also provides a kind of hydrogen simultaneously, and the method that the hydrogen prepares hydrogen by above-mentioned photocatalysis is prepared.System
Standby hydrogen purity is high.
The present invention is further described with reference to specific embodiment.
Embodiment 1
By 0.17 gram of AgNO3It is dissolved in 50ml ethylene glycol, then adds 0.174ml mercaptopropionic acids (MPA).It will mix molten
Liquid leads to nitrogen bubble 10min, begins to warm up.145 DEG C and then keeping temperature are to slowly warm up to, solution colour is changed into from white clear
White cloud form, subsequently becomes yellow cloud form.Start timing when winestone is popular in bright color when solution eventually becomes, taken out after 15 minutes
Solution, and progressively it is cooled to room temperature.Resulting solution is added absolute methanol and centrifuged and can obtain clean Ag2The nanocrystalline samples of S,
By gained Ag2S is nanocrystalline to be disperseed in deionized water, the 25ml containing 10ml ethylene glycol to be added with 0.3mg/ml concentration again
Na2S(1M)+Na2SO3In (1M) aqueous solution, progress photocatalysis experiment in photo catalysis reactor is then charged into.Using AM1.5
(100mW/cm2) simulated solar light irradiation, at ambient temperature using magnetic stirring (600rpm), a hydrogen is surveyed every 15min
Concentration, test result is as shown in Fig. 3 QD800 and Fig. 4,596 μm of ol/g/h of hydrogen-producing speed.
Gained Ag is tested using high-resolution projection electron microscope2The particle diameter of the nanocrystalline samples of S, measures particle diameter for 7.2nm.
Gained Ag is tested using UV-Vis sub-ray spectrometers (UV absorption sub-ray spectrometer)2The absorption of the nanocrystalline samples of S
Spectrum, collection of illustrative plates is as shown in Fig. 1 QD800, and the absorption peak position of QD800 samples is 800nm.
Using X-ray diffraction spectra instrument to gained Ag2The nanocrystalline samples of S carry out X-ray diffraction, collection of illustrative plates such as Fig. 2 QD800
Shown, it belongs to β phase monoclinic systems.
Embodiment 2
By 0.17 gram of AgNO3It is dissolved in 50ml ethylene glycol, then adds 0.174ml mercaptopropionic acids (MPA).It will mix molten
Liquid leads to nitrogen bubble 10min, begins to warm up.145 DEG C and then keeping temperature are to slowly warm up to, solution colour is changed into from white clear
White cloud form, subsequently becomes yellow cloud form.Start timing when winestone is popular in bright color when solution eventually becomes, taken out after 20 minutes
Solution, and progressively it is cooled to room temperature.Resulting solution is added absolute methanol and centrifuged and can obtain clean Ag2The nanocrystalline samples of S,
By gained Ag2S is nanocrystalline to be disperseed in deionized water, the 25ml containing 10ml ethylene glycol to be added with 0.3mg/ml concentration again
Na2S(1M)+Na2SO3In (1M) aqueous solution, progress photocatalysis experiment in photo catalysis reactor is then charged into.Using AM1.5
(100mW/cm2) simulated solar light irradiation, at ambient temperature using magnetic stirring (600rpm), a hydrogen is surveyed every 15min
Concentration, test result is as shown in Fig. 3 QD1000.
Gained Ag is tested using the identical method and step of embodiment 12The particle diameter of the nanocrystalline samples of S, measuring particle diameter is
8.5nm。
Gained Ag is tested using the identical method and step of embodiment 12The absorption spectrum of the nanocrystalline samples of S, collection of illustrative plates is such as Fig. 1
Shown in QD1000, the absorption peak position of QD1000 samples is 1000nm.
Gained Ag is tested using the identical method and step of embodiment 12The XRD of the nanocrystalline samples of S, it belongs to β phase monocline
Crystallographic system.
Embodiment 3
By 0.17 gram of AgNO3It is dissolved in 50ml ethylene glycol, then adds 0.174ml mercaptopropionic acids (MPA).It will mix molten
Liquid leads to nitrogen bubble 10min, begins to warm up.145 DEG C and then keeping temperature are to slowly warm up to, solution colour is changed into from white clear
White cloud form, subsequently becomes yellow cloud form.Start timing when winestone is popular in bright color when solution eventually becomes, taken out after 15 minutes
Solution, and progressively it is cooled to room temperature.Resulting solution is added absolute methanol and centrifuged and can obtain clean Ag2The nanocrystalline samples of S.
By the nanocrystalline addition 0.1wt% of gained chloroplatinic acid (H2PtCl6) in solution, under nitrogen protective condition, the stirring of illumination magnetic
30min obtains the Ag of Pt co-catalysts modification2S is nanocrystalline.After centrifugation, by gained Ag2S is nanocrystalline to be dispersed in again
In deionized water, the Na of the 25ml containing 10ml ethylene glycol is added with 0.3mg/ml concentration2S(1M)+Na2SO3(1M) aqueous solution
In, it is then charged into progress photocatalysis experiment in photo catalysis reactor.Using AM1.5 (100mW/cm2) simulated solar light irradiation,
Using magnetic stirring (600rpm) under room temperature condition, the concentration of a hydrogen is surveyed every 15min, plus after Pt co-catalysts, production hydrogen effect
Rate can improve 1.4 times, reach 858 μm of ol/g/h.
Embodiment 4
By 0.17 gram of AgNO3It is dissolved in 50ml ethylene glycol, then adds 0.174ml mercaptopropionic acids (MPA).It will mix molten
Liquid leads to nitrogen bubble 10min, begins to warm up.145 DEG C and then keeping temperature are to slowly warm up to, solution colour is changed into from white clear
White cloud form, subsequently becomes yellow cloud form.Start timing when winestone is popular in bright color when solution eventually becomes, taken out after 15 minutes
Solution, and progressively it is cooled to room temperature.Resulting solution is added absolute methanol and centrifuged and can obtain clean Ag2The nanocrystalline samples of S,
By gained Ag2S is nanocrystalline to be disperseed in deionized water, Na to be added with 0.3mg/ml concentration again2S(1M)+Na2SO3(1M) water
In solution (common 25ml), progress photocatalysis experiment in photo catalysis reactor is then charged into.Using AM1.5 (100mW/cm2) simulation
Sunshine is irradiated, and at ambient temperature using magnetic stirring (600rpm), the concentration of a hydrogen, hydrogen-producing speed are surveyed every 15min
It can reach 54 μm of ol/g/h.
Embodiment 5
0.16g sulphur powders are dissolved in 15ml oleyl amines and 30min are kept at 120 DEG C, room temperature is cooled to and obtains sulphur precursor
Solution.Then, in three neck round bottom, 0.56g PbCl are added2With 10ml oleyl amines and be heated to 75-150 DEG C.After 30min,
Inject the mixed solution and 225 μ l trioctylphosphine oxygen phosphorus of 3ml sulphur precursor and 3ml oleyl amines.React after 5min, sequentially adding 20ml just
Reaction is quenched in butanol and 10ml methanol.After centrifugation, PbS is dispersed in toluene solution.Entered using mercaptopropionic acid (1mM, toluene)
After row surface ligand is exchanged, hydrophilic PbS is obtained nanocrystalline.By gained Ag2S it is nanocrystalline again disperse in deionized water, with
0.3mg/ml concentration adds the Na containing 10ml ethylene glycol2S(1M)+Na2SO3In (1M) aqueous solution (common 25ml), it is then charged into
Photocatalysis experiment is carried out in photo catalysis reactor.Using AM1.5 (100mW/cm2) simulated solar light irradiation, at ambient temperature
(600rpm) is stirred using magnetic, the concentration of a hydrogen is surveyed every 15min, hydrogen-producing speed can reach 385 μm of ol/g/h.
The particle diameter of the gained nanocrystalline samples of PbS is tested using the identical method and step of embodiment 1, particle diameter is measured for 3.7nm.
The absorption spectrum of the gained nanocrystalline samples of PbS, collection of illustrative plates such as Fig. 5 institutes are tested using the identical method and step of embodiment 1
Show.
Comparative example 1
Commercially available Ag is tested using the identical method and step of embodiment 12The particle diameter of S crystal powders, measures particle diameter for 15 microns.
Commercially available Ag is tested using the identical method and step of embodiment 12The absorption spectrum of S crystal powders, collection of illustrative plates such as Fig. 1 C-
Shown in Powder.
Commercially available Ag is tested using the identical method and step of embodiment 12The C-Powder of the XRD of S crystal powders, such as Fig. 2
It is shown.
By above-mentioned commercially available Ag2S crystal powders are configured to 0.3mg/ml Ag2The S aqueous solution, adds 25ml Na2S(1M)+
Na2SO3In (1M) aqueous solution, progress photocatalysis experiment in photo catalysis reactor is then charged into.Using AM1.5 (100mW/cm2) mould
Intend sunshine irradiation, at ambient temperature using magnetic stirring (600rpm), the concentration of a hydrogen is surveyed every 15min.Test knot
Fruit such as Fig. 3.
It can be seen that from above-mentioned test result：
As Fig. 1 shows the Ag of embodiment 1,22Absorption spectrum nanocrystalline S, wherein, the absorption of QD800 and QD1000 samples
Peak position is respectively 800nm and 1000nm, it can be seen that absorption peak position of the invention changes, and is exactly absorbed needed for the present invention
Peak, and commercially available Ag2S crystal powders are without absworption peak, i.e., commercially available Ag2S crystal powders are not solely used for photocatalysis hydrogen production, and this hair
Bright Ag2S is nanocrystalline to be preferably implemented separately catalyzing manufacturing of hydrogen.
Fig. 2 shows the Ag of the embodiment of the present invention 12XRD spectra nanocrystalline S, with commercially available Ag2The XRD spectra of S crystal powders
C-Powder is contrasted, the Ag of the embodiment of the present invention 12S is nanocrystalline with commercially available Ag2S crystal powders are monoclinic system.
Fig. 3 is the production hydrogen collection of illustrative plates of the embodiment of the present invention 1,2 and comparative example 1.The hydrogen generation efficiency of embodiment 1 is apparently higher than implementation
Example 2, and hydrogen generation efficiency is higher, and comparative example 1 is without obvious production hydrogen.
Fig. 4 is the production hydrogen data of the embodiment of the present invention 1, in AM1.5 (100mW/cm2) under the conditions of continuous illumination (96h) i.e.
By 4 days, hydrogen-producing speed still maintained 84%, and catalyst of the invention has preferable stability.
The embodiment of present invention described above, is not intended to limit the scope of the present invention..Any basis
Various other corresponding changes and deformation made by the technical concept of the present invention, should be included in the guarantor of the claims in the present invention
In the range of shield.
Claims (10)
1. a kind of photocatalysis prepares the catalyst of hydrogen, it is characterised in that the catalyst is Ag2X nano is brilliant, PbX is nanocrystalline or
One or more during InY is nanocrystalline, wherein, X=S, Se or Te；Y=P, As or Sb；The Ag2The brilliant average grain diameter of X nano
In below 8.5nm；The average grain diameter nanocrystalline PbX is in below 4.5nm；The average grain diameter nanocrystalline InY 3nm with
Under.
2. catalyst as claimed in claim 1, it is characterised in that the Ag2X nano is brilliant, PbX is nanocrystalline or the nanocrystalline tools of InY
There is quantum size effect.
3. catalyst as claimed in claim 1, it is characterised in that the catalyst is the Ag that surface carries metal Ion-hydrophilic Ligand2X receives
Meter Jing, PbX are nanocrystalline or InY is nanocrystalline.
4. a kind of method that photocatalysis prepares hydrogen, it is characterised in that step includes containing sacrifice agent with catalyst photocatalysis
The aqueous solution prepares hydrogen, and the catalyst includes the catalyst described in any one in claim 1-3.
5. method as claimed in claim 4, it is characterised in that the catalyst is Ag2S is nanocrystalline, the Ag2S is nanocrystalline
Average grain diameter is in below 8.5nm.
6. method as claimed in claim 5, it is characterised in that the catalyst for Ag sources are mixed with sulphur source, in 110 DEG C-
5min-60min is reacted at a temperature of 190 DEG C to obtain；It is preferred that, the Ag sources include solubility Ag salt；The sulphur source is selected from sulfydryl second
One or more in acid, mercaptopropionic acid, 3-mercaptoethanol, thiocarbamide or sulphur powder.
7. method as claimed in claim 6, it is characterised in that the catalyst is to mix in Ag sources with sulphur source and part, in
5min-60min is reacted at a temperature of 110 DEG C -190 DEG C to obtain；It is preferred that, the part is selected from TGA, mercaptopropionic acid, dimercapto
It is one or more of in ethanol, oleic acid, tri octyl phosphine, octadecylene, octadecylamine.
8. method as claimed in claim 4, it is characterised in that the catalyst is the Ag of ligand exchange2X nano is brilliant, PbX receives
Rice is brilliant or InY is nanocrystalline；It is preferred that, one or more of the part in TGA, mercaptopropionic acid, 3-mercaptoethanol.
9. method as claimed in claim 4, it is characterised in that the catalyst also contains cocatalyst, the co-catalyst
Including the one or more in Pt, Au or Pd.
10. scheme as claimed in claim 4, it is characterised in that the sacrifice agent is ethanol, ethylene glycol, isopropanol, n-butanol
Or the one or more in triethanolamine, and, Na2S and/or Na2SO3。
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