CN109985639A - A method of with the Pt/ZnS-rGO photochemical catalyst of in-situ construction and its preparing hydrogen - Google Patents
A method of with the Pt/ZnS-rGO photochemical catalyst of in-situ construction and its preparing hydrogen Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000010276 construction Methods 0.000 title claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000004310 lactic acid Substances 0.000 claims description 18
- 235000014655 lactic acid Nutrition 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 9
- 230000001699 photocatalysis Effects 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000004519 grease Substances 0.000 claims description 8
- 239000004809 Teflon Substances 0.000 claims description 6
- 229920006362 Teflon® Polymers 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 5
- -1 Ethyl alcohol Chemical compound 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 61
- 239000005083 Zinc sulfide Substances 0.000 description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 229960004756 ethanol Drugs 0.000 description 15
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C01B2203/1076—Copper or zinc-based 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 photochemical catalyst field, specifically a kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction, preparation process includes following two steps: 1) synthesizing ZnS using hydro-thermal method；2) using gradually light deposition technique by ZnS made from Pt nano particle and step 1) in conjunction with rGO, obtain Pt/ZnS-rGO photochemical catalyst.Also disclose a kind of method for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction.The synthetic method is environmentally protective of Pt/ZnS-rGO photochemical catalyst of the present invention, easy to operate, functional, Pt/ZnS-rGO photochemical catalyst obtained has preferable Photocatalyzed Hydrogen Production performance, and under the Xe light irradiation of 300W, it is continuous and stablize to generate hydrogen.
Description
Technical field
The present invention relates to photochemical catalyst field, specifically a kind of Pt/ZnS-rGO photochemical catalyst and its system with in-situ construction
The method of standby hydrogen.
Background technique
The excessive use of fossil fuel causes serious energy shortage and environmental problem, and people is forced to be badly in need of further seeking
Green regenerative energy sources are looked for substitute.Hydrogen is as most clean fuel because of zero-emission pollutant after its burning and by huge
Research concern.The sustainable strategy that photocatalytic water splitting is converted as solar energy, it is considered to be cleaning is provided and high-performance is raw
The approach of hydrogen producing.
So far, people have been devoted to the high efficiency photocatalyst in exploitation water decomposition, must satisfy relatively low
The position conduction band (CB), suitable band gap, the electron transfer efficiency of effective visible absorption and raising.In various photochemical catalysts
In, metal sulfide, especially ZnS (zinc sulphide), since its nontoxic no metal and excellent chemical stability etc. are in photocatalysis
It is received significant attention in Material Field.
However, in photochemical catalyst water decomposition, electron-hole pair in the main body of photochemical catalyst or on surface in conjunction with
It is still a serious problem.In order to solve this negative effect, it has proved that building heterojunction structure, generate crystal defect,
Control form, addition co-catalyst or improvement crystallinity etc. are the effective ways for improving photocatalysis performance.Wherein, co-catalyst changes
Property be improve photocatalysis hydrogen production in carrier separation efficiency one of available strategy.It can not only reduce the overpotential for producing hydrogen,
Main body reactivity site can also be improved, to improve separation of charge efficiency, prevent the compound of photo-generated carrier.Graphene is made
For a kind of good two-dimentional (2D) material, due to its big specific surface area, active site abundant and excellent electric conductivity, institute
Can preferably promote separation of charge, therefore can be as the reason of ZnS nano particle photocatalysis hydrogen production with huge potentiality
Think composite material.
Therefore, for the above status, there is an urgent need to develop a kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction, with gram
Take the deficiency in currently practical application.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of the Pt/ZnS-rGO photochemical catalyst of in-situ construction and its preparation
The method of hydrogen, to solve the problems mentioned in the above background technology.
To achieve the above object, the embodiment of the present invention provides the following technical solutions:
A kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction, preparation process include following two steps:
1) ZnS is synthesized using hydro-thermal method；
2) using gradually light deposition technique by ZnS made from Pt (platinum) nano particle and step 1) and rGO (oxygen reduction fossil
Black alkene) it combines, obtain Pt/ZnS-rGO photochemical catalyst.
As a further solution of the present invention: in step 1), by the ZnCl of 5mmol under continuous magnetic agitation2(chlorination
Zinc) and the thioacetamide of 10mmol be dissolved in the mixture solution of ethyl alcohol containing 45mL and 15mL glycerol, and be continuously stirring to
Form clear solution；Then, by mixture in the stainless steel autoclave of teflon lined hydro-thermal 10h at 180 DEG C, and from
So it is cooled to room temperature；Sediment is collected by centrifugation, is then alternately washed three times with deionized water and dehydrated alcohol；After carrying out washing treatment,
Product is dried overnight at 60 DEG C, obtains ZnS.
As a further solution of the present invention: in step 2), gradually specific step is as follows for light deposition technique:
21) powdered graphite is aoxidized with improved Hummers method (a kind of method for preparing graphite oxide) and obtains GO (oxygen
Graphite alkene)；
22) GO of 1.6-14mg is dispersed in ultrasound 30min in 40mL ethyl alcohol, is then added in above-mentioned ethanol solution
The ZnS of 200mg；
23) Xe (xenon) light irradiation solution that 300W is used under continuous magnetic agitation, so that GO be made to restore；
24) H of 500 μ L is added2PtCl6(0.0072mM, 1wt%) makes Pt nanoparticle deposition on rGO；
25) powder is filtered and is dried in vacuum overnight, obtained the Pt/ZnS-rGO light containing 1wt%Pt and 2wt%rGO and urge
Agent.
As a further solution of the present invention: in step 22), the dosage of the GO is 4mg.
As a further solution of the present invention: in step 24), the H2PtCl6Concentration be 1wt%.
A method of hydrogen is prepared with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, comprising the following steps:
3) the Pt/ZnS-rGO photochemical catalyst and 100mL lactic acid aqueous solution for weighing 20mg are put into a top light-permeable
In 100mL quartz container, it is scattered in photochemical catalyst high uniformity in reaction solution by magnetic stirring apparatus；
4) it smears vacuum grease quartz container is connected on reaction unit, whole system first vacuumizes while leading to before the reaction
Entering condensed water guarantees reaction solution temperature at 19-21 DEG C；
5) under the Xe light irradiation of 300W, a sample is taken every a hour, is examined by the TCD (thermal conductivity) of gas chromatograph
It surveys device and carries out on-line analysis, obtain the amount of hydrogen product.
As a further solution of the present invention: in step 3), in lactic acid aqueous solution, the volume ratio of lactic acid and water is 1:4.
As a further solution of the present invention: in step 4), smearing vacuum grease for quartz container and be connected to reaction unit
On, whole system, which first vacuumizes while being passed through condensed water, before the reaction guarantees reaction solution temperature at 20 DEG C.
Compared with prior art, the beneficial effect of the embodiment of the present invention is:
The present invention has synthesized a kind of Pt/ZnS-rGO nanosphere by hydro-thermal-light deposition two-step method, using ZnS, GO and
Excellent interaction between Pt particle realizes the photoelectrocatalysis water decomposition of enhancing, is 2wt.% by adjusting compound dosage
RGO and 1wt.%Pt can synthesize the Pt/ZnS-rGO photochemical catalyst with optimum performance, and photocatalytic activity is than pure ZnS high 8
Times or so.
The synthetic method is environmentally protective of Pt/ZnS-rGO photochemical catalyst, easy to operate, functional, Pt/ZnS- obtained
RGO photochemical catalyst has preferable Photocatalyzed Hydrogen Production performance, and under the Xe light irradiation of 300W, it is continuous and stable to generate hydrogen.
Detailed description of the invention
Fig. 1 is the XRD schematic diagram that GO is synthesized in the embodiment of the present invention.
Fig. 2 is the XRD schematic diagram of different composite ratio Pt/ZnS-rGO photochemical catalyst in the embodiment of the present invention.
Fig. 3 is that different composite ratio Pt/ZnS-rGO photochemical catalyst produces under the Xe light irradiation of 300W in the embodiment of the present invention
Hydrogen amount schematic diagram.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction referring to FIG. 1-2, preparation process include following two
Step:
1) ZnS is synthesized using hydro-thermal method；
2) using gradually light deposition technique by ZnS made from Pt nano particle and step 1) in conjunction with rGO, obtain Pt/
ZnS-rGO photochemical catalyst.
Wherein, in step 1), by the ZnCl of 5mmol under continuous magnetic agitation2It is molten with the thioacetamide of 10mmol
In the mixture solution of Xie Han 45mL ethyl alcohol and 15mL glycerol, and it is continuously stirring to and forms clear solution；Then, by mixture
The hydro-thermal 10h at 180 DEG C in the stainless steel autoclave of teflon lined, and cooled to room temperature；Precipitating is collected by centrifugation
Then object is alternately washed three times with deionized water and dehydrated alcohol；After carrying out washing treatment, product is dried overnight at 60 DEG C, i.e.,
ZnS is made.
In step 2), gradually specific step is as follows for light deposition technique:
21) powdered graphite is aoxidized with improved Hummers method and obtains GO；
22) GO of 4mg is dispersed in ultrasound 30min in 40mL ethyl alcohol, is then added 200mg's in above-mentioned ethanol solution
ZnS；
23) the Xe light irradiation solution that 300W is used under continuous magnetic agitation, so that GO be made to restore；
24) H of 500 μ L is added2PtCl6(0.0072mM, 1wt%) makes Pt nanoparticle deposition on rGO；
25) powder is filtered and is dried in vacuum overnight, obtain the Pt/ZnS-rGO containing 1wt%Pt and 2wt%rGO
(PZG-2) photochemical catalyst.
Referring to Fig. 3, a kind of method for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, including following step
It is rapid:
3) Pt/ZnS-rGO (PZG-2) photochemical catalyst and 100mL lactic acid aqueous solution for weighing 20mg are put into a top can
In the 100mL quartz container of light transmission, it is scattered in photochemical catalyst high uniformity in reaction solution by magnetic stirring apparatus；
4) it smears vacuum grease quartz container is connected on reaction unit, whole system first vacuumizes while leading to before the reaction
Entering condensed water guarantees reaction solution temperature at 20 DEG C；
5) under the Xe light irradiation of 300W, take a sample every a hour, by the TCD detector of gas chromatograph into
Row on-line analysis show that (experiment show that after 4 hours of successive reaction, hydrogen output is up to 882 μm of ol for the amount of hydrogen product
h-1·g-1)。
Wherein, in step 3), in lactic acid aqueous solution, the volume ratio of lactic acid and water is 1:4.
Embodiment 2
A kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction referring to FIG. 1-2, preparation process include following two
Step:
1) ZnS is synthesized using hydro-thermal method；
2) using gradually light deposition technique by ZnS made from Pt nano particle and step 1) in conjunction with rGO, obtain Pt/
ZnS-rGO photochemical catalyst.
Wherein, in step 1), by the ZnCl of 5mmol under continuous magnetic agitation2It is molten with the thioacetamide of 10mmol
In the mixture solution of Xie Han 45mL ethyl alcohol and 15mL glycerol, and it is continuously stirring to and forms clear solution；Then, by mixture
The hydro-thermal 10h at 180 DEG C in the stainless steel autoclave of teflon lined, and cooled to room temperature；Precipitating is collected by centrifugation
Then object is alternately washed three times with deionized water and dehydrated alcohol；After carrying out washing treatment, product is dried overnight at 60 DEG C, i.e.,
ZnS is made.
In step 2), gradually specific step is as follows for light deposition technique:
21) powdered graphite is aoxidized with improved Hummers method and obtains GO；
22) GO of 1.6mg is dispersed in ultrasound 30min in 40mL ethyl alcohol, 200mg then is added in above-mentioned ethanol solution
ZnS；
23) the Xe light irradiation solution that 300W is used under continuous magnetic agitation, so that GO be made to restore；
24) H of 500 μ L is added2PtCl6(0.0072mM, 1wt%) makes Pt nanoparticle deposition on rGO；
25) powder is filtered and is dried in vacuum overnight, obtain the Pt/ZnS-rGO containing 1wt%Pt and 2wt%rGO
(PZG-0.8) photochemical catalyst.
Referring to Fig. 3, a kind of method for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, including following step
It is rapid:
3) Pt/ZnS-rGO (PZG-0.8) photochemical catalyst and 100mL lactic acid aqueous solution for weighing 20mg are put into a top
In the 100mL quartz container of light-permeable, it is scattered in photochemical catalyst high uniformity in reaction solution by magnetic stirring apparatus；
4) it smears vacuum grease quartz container is connected on reaction unit, whole system first vacuumizes while leading to before the reaction
Entering condensed water guarantees reaction solution temperature at 19 DEG C；
5) under the Xe light irradiation of 300W, take a sample every a hour, by the TCD detector of gas chromatograph into
Row on-line analysis show that (experiment show that after 4 hours of successive reaction, hydrogen output is up to 510 μm of ol for the amount of hydrogen product
h-1·g-1)。
Wherein, in step 3), in lactic acid aqueous solution, the volume ratio of lactic acid and water is 1:4.
Embodiment 3
A kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction referring to FIG. 1-2, preparation process include following two
Step:
1) ZnS is synthesized using hydro-thermal method；
2) using gradually light deposition technique by ZnS made from Pt nano particle and step 1) in conjunction with rGO, obtain Pt/
ZnS-rGO photochemical catalyst.
Wherein, in step 1), by the ZnCl of 5mmol under continuous magnetic agitation2It is molten with the thioacetamide of 10mmol
In the mixture solution of Xie Han 45mL ethyl alcohol and 15mL glycerol, and it is continuously stirring to and forms clear solution；Then, by mixture
The hydro-thermal 10h at 180 DEG C in the stainless steel autoclave of teflon lined, and cooled to room temperature；Precipitating is collected by centrifugation
Then object is alternately washed three times with deionized water and dehydrated alcohol；After carrying out washing treatment, product is dried overnight at 60 DEG C, i.e.,
ZnS is made.
In step 2), gradually specific step is as follows for light deposition technique:
21) powdered graphite is aoxidized with improved Hummers method and obtains GO；
22) GO of 10mg is dispersed in ultrasound 30min in 40mL ethyl alcohol, 200mg then is added in above-mentioned ethanol solution
ZnS；
23) the Xe light irradiation solution that 300W is used under continuous magnetic agitation, so that GO be made to restore；
24) H of 500 μ L is added2PtCl6(0.0072mM, 1wt%) makes Pt nanoparticle deposition on rGO；
25) powder is filtered and is dried in vacuum overnight, obtain the Pt/ZnS-rGO containing 1wt%Pt and 2wt%rGO
(PZG-5) photochemical catalyst.
Referring to Fig. 3, a kind of method for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, including following step
It is rapid:
3) Pt/ZnS-rGO (PZG-5) photochemical catalyst and 100mL lactic acid aqueous solution for weighing 20mg are put into a top can
In the 100mL quartz container of light transmission, it is scattered in photochemical catalyst high uniformity in reaction solution by magnetic stirring apparatus；
4) it smears vacuum grease quartz container is connected on reaction unit, whole system first vacuumizes while leading to before the reaction
Entering condensed water guarantees reaction solution temperature at 21 DEG C；
5) under the Xe light irradiation of 300W, take a sample every a hour, by the TCD detector of gas chromatograph into
Row on-line analysis show that (experiment show that after 4 hours of successive reaction, hydrogen output is up to 484 μm of ol for the amount of hydrogen product
h-1·g-1)。
Wherein, in step 3), in lactic acid aqueous solution, the volume ratio of lactic acid and water is 1:4.
Embodiment 4
A kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction referring to FIG. 1-2, preparation process include following two
Step:
1) ZnS is synthesized using hydro-thermal method；
2) using gradually light deposition technique by ZnS made from Pt nano particle and step 1) in conjunction with rGO, obtain Pt/
ZnS-rGO photochemical catalyst.
Wherein, in step 1), by the ZnCl of 5mmol under continuous magnetic agitation2It is molten with the thioacetamide of 10mmol
In the mixture solution of Xie Han 45mL ethyl alcohol and 15mL glycerol, and it is continuously stirring to and forms clear solution；Then, by mixture
The hydro-thermal 10h at 180 DEG C in the stainless steel autoclave of teflon lined, and cooled to room temperature；Precipitating is collected by centrifugation
Then object is alternately washed three times with deionized water and dehydrated alcohol；After carrying out washing treatment, product is dried overnight at 60 DEG C, i.e.,
ZnS is made.
In step 2), gradually specific step is as follows for light deposition technique:
21) powdered graphite is aoxidized with improved Hummers method and obtains GO；
22) GO of 14mg is dispersed in ultrasound 30min in 40mL ethyl alcohol, 200mg then is added in above-mentioned ethanol solution
ZnS；
23) the Xe light irradiation solution that 300W is used under continuous magnetic agitation, so that GO be made to restore；
24) H of 500 μ L is added2PtCl6(0.0072mM, 1wt%) makes Pt nanoparticle deposition on rGO；
25) powder is filtered and is dried in vacuum overnight, obtain the Pt/ZnS-rGO containing 1wt%Pt and 2wt%rGO
(PZG-7) photochemical catalyst.
Referring to Fig. 3, a kind of method for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, including following step
It is rapid:
3) Pt/ZnS-rGO (PZG-7) photochemical catalyst and 100mL lactic acid aqueous solution for weighing 20mg are put into a top can
In the 100mL quartz container of light transmission, it is scattered in photochemical catalyst high uniformity in reaction solution by magnetic stirring apparatus；
4) it smears vacuum grease quartz container is connected on reaction unit, whole system first vacuumizes while leading to before the reaction
Entering condensed water guarantees reaction solution temperature at 20 DEG C；
5) under the Xe light irradiation of 300W, take a sample every a hour, by the TCD detector of gas chromatograph into
Row on-line analysis show that (experiment show that after 4 hours of successive reaction, hydrogen output is up to 401 μm of ol for the amount of hydrogen product
h-1·g-1)。
Wherein, in step 3), in lactic acid aqueous solution, the volume ratio of lactic acid and water is 1:4.
The present invention has synthesized a kind of Pt/ZnS-rGO nanosphere by hydro-thermal-light deposition two-step method, using ZnS, GO and
Excellent interaction between Pt particle realizes the photoelectrocatalysis water decomposition of enhancing, is 2wt.% by adjusting compound dosage
RGO and 1wt.%Pt can synthesize the Pt/ZnS-rGO photochemical catalyst with optimum performance, and photocatalytic activity is than pure ZnS high 8
Times or so.
The synthetic method is environmentally protective of Pt/ZnS-rGO photochemical catalyst, easy to operate, functional, Pt/ZnS- obtained
RGO photochemical catalyst has preferable Photocatalyzed Hydrogen Production performance, and under the Xe light irradiation of 300W, it is continuous and stable to generate hydrogen.
In addition, the application successfully introduces rGO, and Pt abundant is assembled in ZnS by light deposition, this may be
Designing more reasonable CD-ROM drive heterostructure semiconductor opened up a new way, to develop its potential photocatalytic water splitting application.
The above are merely the preferred embodiment of the present invention, it is noted that for those skilled in the art, not
Under the premise of being detached from present inventive concept, several modifications and improvements can also be made, these also should be considered as protection model of the invention
It encloses, these all will not influence the effect and patent practicability that the present invention is implemented.
Claims (8)
1. a kind of Pt/ZnS-rGO photochemical catalyst with in-situ construction, which is characterized in that its preparation process includes following two steps
It is rapid:
1) ZnS is synthesized using hydro-thermal method；
2) using gradually light deposition technique by ZnS made from Pt nano particle and step 1) in conjunction with rGO, obtain Pt/ZnS-
RGO photochemical catalyst.
2. the Pt/ZnS-rGO photochemical catalyst according to claim 1 with in-situ construction, which is characterized in that in step 1)
In, by the ZnCl of 5mmol under continuous magnetic agitation2Ethyl alcohol containing 45mL is dissolved in the thioacetamide of 10mmol and 15mL is sweet
In the mixture solution of oil, and it is continuously stirring to and forms clear solution；Then, by mixture in the stainless of teflon lined
Hydro-thermal 10h at 180 DEG C in steel autoclave, and cooled to room temperature；Sediment is collected by centrifugation, then with deionized water and anhydrous
Ethyl alcohol alternately washs three times；After carrying out washing treatment, product is dried overnight at 60 DEG C, obtains ZnS.
3. the Pt/ZnS-rGO photochemical catalyst according to claim 1 with in-situ construction, which is characterized in that in step 2)
In, gradually specific step is as follows for light deposition technique:
21) powdered graphite is aoxidized with improved Hummers method and obtains GO；
22) GO of 1.6-14mg is dispersed in ultrasound 30min in 40mL ethyl alcohol, 200mg then is added in above-mentioned ethanol solution
ZnS；
23) the Xe light irradiation solution that 300W is used under continuous magnetic agitation, so that GO be made to restore；
24) H of 500 μ L is added2PtCl6Make Pt nanoparticle deposition on rGO；
25) powder is filtered and is dried in vacuum overnight, obtain the Pt/ZnS-rGO photocatalysis containing 1wt%Pt and 2wt%rGO
Agent.
4. the Pt/ZnS-rGO photochemical catalyst according to claim 3 with in-situ construction, which is characterized in that in step 22)
In, the dosage of the GO is 4mg.
5. the Pt/ZnS-rGO photochemical catalyst according to claim 4 with in-situ construction, which is characterized in that in step 24)
In, the H2PtCl6Concentration be 1wt%.
6. a kind of side as described in any one in claim 1-5 for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction
Method, which comprises the following steps:
3) the Pt/ZnS-rGO photochemical catalyst and 100mL lactic acid aqueous solution that weigh 20mg are put into the 100mL of a top light-permeable
In quartz container, it is scattered in photochemical catalyst high uniformity in reaction solution by magnetic stirring apparatus；
4) it smears vacuum grease quartz container is connected on reaction unit, whole system is first vacuumized while being passed through cold before the reaction
Condensate guarantees reaction solution temperature at 19-21 DEG C；
5) under the Xe light irradiation of 300W, a sample is taken every a hour, is carried out by the TCD detector of gas chromatograph
Line analysis obtains the amount of hydrogen product.
7. the method according to claim 6 for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, feature
It is, in step 3), in lactic acid aqueous solution, the volume ratio of lactic acid and water is 1:4.
8. the method according to claim 7 for preparing hydrogen with the Pt/ZnS-rGO photochemical catalyst of in-situ construction, feature
It is, in step 4), smears vacuum grease and quartz container is connected on reaction unit, whole system first vacuumizes before the reaction
Being passed through condensed water simultaneously guarantees reaction solution temperature at 20 DEG C.
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