CN108855138A - A kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst and preparation method thereof - Google Patents
A kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims description 91
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011858 nanopowder Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229940071125 manganese acetate Drugs 0.000 claims description 12
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 9
- 229960003067 cystine Drugs 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000006303 photolysis reaction Methods 0.000 abstract description 6
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- -1 washing Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
-
- 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
-
- 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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- 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 invention discloses a kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photo-catalyst and preparation method thereof belongs to inorganic functional material field.By Ag and Bi2WO6It is supported on Mn0.5Cd0.5Z-type structure Mn is prepared on S0.5Cd0.5S composite photo-catalyst, wherein Ag, Bi2WO6With Mn0.5Cd0.5S three's mass ratio is 0.01-0.05:0.5-2:1.In the present invention, the medium that Ag nano particle is conducted as electronics can be quickly by Bi2WO6Electronics transfer on conduction band is to Mn0.5Cd0.5S valence band simultaneously improves quantum efficiency and photolysis water hydrogen catalytic activity to effectively reduce the recombination rate of light induced electron and photohole in catalyst with hole-recombination in its valence band；Operation of the present invention mild condition, prepared photochemical catalyst have many advantages, such as that low reunion degree, good dispersion and photocatalytic activity are high.
Description
Technical field
The invention belongs to inorganic environment-friendly catalysis material technical fields, and in particular to a kind of Z-type structure Mn0.5Cd0.5S/Ag/
Bi2WO6Composite photocatalyst and preparation method thereof.
Background technique
Today's society brings huge energy to the world today due to the mankind's depending on unduly and using to fossil energy
The problems such as source crisis and environmental pollution, this has promoted the mankind to explore the new cleaning of exploitation, the recyclable energy.In renewable energy
In, solar energy is a kind of energy with very big researching value.Although there are many methods to explore using solar energy, such as：Too
Sunlight volt, converts solar energy directly as chemical energy, photolysis water hydrogen etc. at Columnating type solar generation technology.But final purpose is all
It is that water is resolved into H using sunlight2And O2, this is because water is that acquisition and cheap hydrogen energy source are easiest on the earth, tool
There are the unique advantages such as inexhaustible, cleaning.
Researchers have developed various semiconductor materials, for decomposing water under visible light illumination, still
The inefficient problem of its photogenerated charge separation and migration, hinders further mentioning for these semiconductor material photocatalysis performances
It is high.In many photochemical catalysts, metal oxide, sulfide, nitride etc. have grown up.In these photochemical catalysts,
Mn0.5Cd0.5S solid solution is studied recently, because it has good visible absorption and is suitble in photocatalysis hydrogen production
Conduction band, valence band.Since the separation rate of photoinduction carrier is low, Mn0.5Cd0.5S solid solution hydrogen manufacturing performance is still very low.
Summary of the invention
In order to further solve Mn0.5Cd0.5Two kinds of semiconductor materials are incorporated in one by S solid solution Photocatalyzed Hydrogen Production efficiency
It rises, using the difference on the two position of energy band, promotes photo-generated carrier to migrate between semiconductor, electrons and holes are reduced with this
It is compound, to improve the photocatalysis performance of semiconductor.
In many heterojunction photocatalysts, Z- system photocatalytic system process has more excellent separation light induced electron
With the ability in hole.Wherein precious metals ag is the medium transfer of electronics, improves photocatalytic activity by transfer electronics.Bi2WO6
Characteristic with relatively narrow band gap and absorption visible light.Ag is loaded into Mn in the present invention0.5Cd0.5On S solid solution, received using Ag
The medium that rice grain is conducted as electronics, can be quickly by Bi2WO6Electronics transfer on conduction band is to Mn0.5Cd0.5The valence band of S and with
Mn0.5Cd0.5On the one hand hole-recombination in S valence band can effectively reduce Mn in this way0.5Cd0.5Light induced electron and light in S catalyst
The recombination rate in raw hole, on the other hand maintains the reproducibility with higher of light induced electron in composite photo-catalyst again, thus
Improve quantum efficiency and Mn0.5Cd0.5S photolysis water hydrogen catalytic activity.Meanwhile Ag nano particle is urged as a kind of effectively help
Agent can be effectively reduced the overpotential of photocatalysis hydrolytic hydrogen production process, significantly improve hydrogen production rate, to improve Mn0.5Cd0.5S
The catalytic activity of photolysis water hydrogen has huge potential prospects for commercial application.
The present invention provides Z-type structure Mn that is a kind of easy to operate and being easily achieved0.5Cd0.5S/Ag/Bi2WO6Complex light is urged
Agent has many advantages, such as that photo-quantum efficiency is high, photocatalytic hydrogen production activity is good.
Composite photo-catalyst preparation method provided by the invention is as follows：
A kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photo-catalyst, which is characterized in that including such as
Lower step：
1) under stirring, manganese acetate and chromic acetate mixed solution is added in cystine, it is anti-to be subsequently placed in 130-150 DEG C of microwave
It answers；It is cooled to room temperature, is filtered through deionized water and ethyl alcohol, washing, be dried to obtain Mn0.5Cd0.5S nano-powder.
Further, in the above-mentioned technical solutions, the molar ratio of the cystine and chromic acetate and manganese acetate is 5:1:1.
2) under stirring, bismuth nitrate solution is added in sodium tungstate solution, ammonium hydroxide tune pH=7-9 is subsequently placed in 160-180 DEG C
Microwave reaction；After being cooled to room temperature, is filtered through deionized water and ethyl alcohol, washs, is dried to obtain Bi2WO6Nano-powder.
Further, in the above-mentioned technical solutions, the molar ratio of the bismuth nitrate and sodium tungstate is 2:1.
3) by Mn obtained by step 1)0.5Cd0.5S nano-powder is scattered in deionized water, is added with stirring methanol and nitric acid
Silver-colored solution is washed after xenon lamp irradiation, is dried, obtains Mn0.5Cd0.5S/Ag composite photocatalyst.
Further, in the above-mentioned technical solutions, the silver nitrate solution concentration is 0.1mol/L；Xenon lamp is selected from 300-
350W。
Further, in the above-mentioned technical solutions, the Mn0.5Cd0.5Mn in S/Ag composite photocatalyst0.5Cd0.5S with
The mass ratio of Ag is 1:0.01-0.05.
4) by Bi obtained by step 2)2WO6Mn obtained by micro-powder and step 3)0.5Cd0.5S/Ag nano-powder be scattered in from
Ultrasonic in sub- water, then 70-90 DEG C of circulating reflux, after being cooled to room temperature, filters, washing, drying through deionized water and ethyl alcohol, obtains
To Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst.
Further, in the above-mentioned technical solutions, the Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst
In, Mn0.5Cd0.5S and Bi2WO6Mass ratio be 1:0.5-2.
The composite photocatalyst being prepared according to the method described above have passed through XRD and XPS characterization, Mn in XRD0.5Cd0.5S
And Bi2WO6Diffraction maximum exist simultaneously, show that prepared sample exists simultaneously Mn0.5Cd0.5S and Bi2WO6Both substances,
Simultaneously because the load capacity of Ag is smaller, the diffraction maximum of Ag is not detected.XPS show in prepared sample comprising Mn, CdS,
Ag, Bi, W and O element further demonstrate the presence of Ag simple substance in prepared sample.
The Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6 composite photocatalyst prepared according to the method described above carries out production hydrogen
Experiment：
Operating condition：Light source：300W xenon lamp；The amount of catalyst：0.05g；The concentration of sacrifice agent：The Na of 0.35mol/L2S
With the Na of 0.25mol/L2SO3.It is found by Experimental comparison, pure Mn0.5Cd0.5The hydrogen-producing speed of S catalyst is 463 μm of ol g-1h-1, Mn0.5Cd0.5The hydrogen-producing speed of S/Ag catalyst is 753 μm of ol g-1h-1, and Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst
The hydrogen-producing speed of agent is up to 1020 μm of ol g-1h-1, show the photocatalysis hydrogen production performance being remarkably reinforced.
In order to which the preparation of above-mentioned Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6 composite photocatalyst is further described
Method, more detailed operating procedure are as follows：
1) mixed solution for preparing certain density manganese acetate and chromic acetate, by a certain amount of cystine under stirring
It is add to the above mixed solution, wherein the molar ratio of added cystine and chromic acetate and manganese acetate is 5:1:1；Continue to stir
Above-mentioned solution is transferred in reaction kettle after 30-60min, then reaction kettle is put into microwave dissolver micro- in 130-150 DEG C
Wave reacts 20-30min；It after reacting end and being cooled to room temperature, is filtered through deionized water and ethyl alcohol, washing, drying can be obtained
Mn0.5Cd0.5S nano-powder.
2) certain density sodium tungstate solution is prepared, certain density nitre is added into sodium tungstate solution under stirring
Sour bismuth solution, wherein the molar ratio of added bismuth nitrate and sodium tungstate is 2:1；PH=7-9 is adjusted with ammonium hydroxide, when continuing one section of stirring
Between after be transferred in reaction kettle, then reaction kettle is put into microwave dissolver in 160-180 DEG C of microwave reaction 20-40min；To
Reaction terminates after being cooled to room temperature, and filters, washs through deionized water and ethyl alcohol, Bi can be obtained in drying2WO6Nano-powder.
3) by Mn obtained by step (1)0.5Cd0.5S nano-powder is scattered in deionized water, and 5- is added under stirring
The silver nitrate solution that 10mL methanol and a certain amount of concentration are 0.1mol/L, is irradiated after 1-2h with 350W xenon lamp and is washed, dried, obtained
To Mn0.5Cd0.5S/Ag composite photocatalyst.
4) by gained Bi in step (2)2WO6Gained Mn in micro-powder and step (3)0.5Cd0.5The dispersion of S/Ag nano-powder
It in deionized water, is transferred in water-bath after ultrasonic a period of time, 70-90 DEG C of circulating reflux 3-5h, after being cooled to room temperature, warp
Deionized water and ethyl alcohol are filtered, are washed, is dry, and Z-type structure Mn can be obtained0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst.
Further preferably, the molar concentration of chromic acetate is 0.001-0.01mol/L in mixed solution in step 1).
Further preferably, the concentration of sodium tungstate and bismuth nitrate is 0.01-0.02mol/L in step 2).
Further preferably, gained Mn in step 3)0.5Cd0.5Mn in S/Ag composite photocatalyst0.5Cd0.5The matter of S and Ag
Amount is than being 1:0.01-0.05.
Further preferably, gained Z-type structure Mn in step 4)0.5Cd0.5S/Ag/Bi2WO6In composite photocatalyst
Mn0.5Cd0.5S and Bi2WO6Mass ratio be 1:0.5-2.
Beneficial effect of the present invention：
1, the medium that Ag nano particle is conducted as electronics, can be quickly by Mn0.5Cd0.5Electronics transfer on S conduction band arrives
Mn0.5Cd0.5The valence band of S and and Mn0.5Cd0.5Hole-recombination in S valence band, on the one hand effectively reduces Mn0.5Cd0.5In S catalyst
On the other hand it is with higher to maintain light induced electron in composite photo-catalyst again for the recombination rate of light induced electron and photohole
Reproducibility, to improve quantum efficiency and Mn0.5Cd0.5S photolysis water hydrogen catalytic activity.
2, the excessively electric of photocatalysis hydrolytic hydrogen production process can be effectively reduced as a kind of effective co-catalyst in Ag nano particle
Position, significantly improves hydrogen production rate, to be also beneficial to Mn0.5Cd0.5The raising of S photolysis water hydrogen catalytic activity.
3, fast according to the microwave-hydrothermal method rate of heat addition, the features such as solution is heated evenly, crystalline substance is prepared using microwave-hydrothermal method
The grain high activity Mn that granularity is small, reunion degree is low0.5Cd0.5S nano-powder, and then effectively raise Mn0.5Cd0.5S/Ag/
Bi2WO6The activity of photochemical catalyst.
Detailed description of the invention
Attached drawing 1 is Mn prepared by the embodiment of the present invention 10.5Cd0.5S/Ag/Bi2WO6The XRD diagram of composite photocatalyst；
A-h is Mn prepared by the embodiment of the present invention 1 in attached drawing 20.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst
XPS figure；
Attached drawing 3 is Mn prepared by the embodiment of the present invention 10.5Cd0.5S/Ag/Bi2WO6The photocatalytic water of composite photocatalyst
Produce hydrogen effect picture.
Specific embodiment：
The present invention is further described with reference to embodiments.It is noted that the present invention is not limited to following each embodiments.
Embodiment 1
Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst preparation：
1) the mixed solution 100mL of manganese acetate and chromic acetate is prepared, wherein the concentration of manganese acetate and chromic acetate is
2.403g cystine is add to the above mixed solution by 0.01mol/L under stirring；Continue stir 30min after will be upper
It states solution to be transferred in reaction kettle, then reaction kettle is put into microwave dissolver in 130 DEG C of microwave reaction 30min；Wait react
After end is cooled to room temperature, is filtered through deionized water and ethyl alcohol, washing, be dried to obtain Mn0.5Cd0.5S nano-powder.
2) compound concentration is the sodium tungstate solution 16.6mL of 0.01mol/L, is added under stirring into sodium tungstate solution
Entering concentration is 0.01mol/L bismuth nitrate solution 33.2mL；PH=7 is adjusted with ammonium hydroxide, continues to be transferred to instead after stirring a period of time
It answers in kettle, then reaction kettle is put into microwave dissolver in 160 DEG C of microwave reaction 40min；It is cooled to room temperature to the end of reacting
Afterwards, it filtered through deionized water and ethyl alcohol, wash, be dried to obtain Bi2WO6Nano-powder.
3) by Mn obtained by step 1)0.5Cd0.5S nano-powder is scattered in deionized water, and 5mL first is added under stirring
Pure and mild 0.2mL concentration is the silver nitrate solution of 0.1mol/L, is irradiated after 2h with 350W xenon lamp and is washed, dried, obtained
Mn0.5Cd0.5S/Ag composite photocatalyst.
4) by gained Bi in step 2)2WO6Gained Mn in micro-powder and step 3)0.5Cd0.5S/Ag nano-powder is scattered in
It in deionized water, is transferred in water-bath after ultrasonic a period of time, 90 DEG C of circulating reflux 3h, after being cooled to room temperature, through deionization
Water and ethyl alcohol are filtered, are washed, is dry, obtain Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst.Catalyst warp
Cross XRD and XPS characterization confirmation.
XRD diagram in attached drawing 1, it can be clearly seen that Mn0.5Cd0.5S and Bi2WO6Diffraction maximum exist simultaneously, prepared by explanation
Sample exist simultaneously Mn0.5Cd0.5S and Bi2WO6Both substances, simultaneously because the load capacity of Ag is smaller, the diffraction maximum of Ag is simultaneously
It does not detect.
XPS schemes in attached drawing 2, includes as can be seen from the figure Mn, CdS, Ag, Bi, W and O element in prepared sample, into
One step confirms the presence of Ag simple substance in prepared sample.
Embodiment 2
Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst preparation：
1) the mixed solution 100mL of manganese acetate and chromic acetate is prepared, wherein the concentration of manganese acetate and chromic acetate is
1.2015g cystine is add to the above mixed solution by 0.005mol/L under stirring；Continue to incite somebody to action after stirring 50min
Above-mentioned solution is transferred in reaction kettle, and then reaction kettle is put into microwave dissolver in 150 DEG C of microwave reaction 20min；To anti-
It should terminate after being cooled to room temperature, be filtered through deionized water and ethyl alcohol, washing, be dried to obtain Mn0.5Cd0.5S nano-powder.
2) compound concentration is the sodium tungstate solution 16.6mL of 0.01mol/L, is added under stirring into sodium tungstate solution
Entering concentration is 0.01mol/L bismuth nitrate solution 33.2mL；PH=8 is adjusted with ammonium hydroxide, continues to be transferred to instead after stirring a period of time
It answers in kettle, then reaction kettle is put into microwave dissolver in 180 DEG C of microwave reaction 20min；It is cooled to room temperature to the end of reacting
Afterwards, it filtered through deionized water and ethyl alcohol, wash, be dried to obtain Bi2WO6Nano-powder.
3) by Mn obtained by step 1)0.5Cd0.5S nano-powder is scattered in deionized water, and 7mL first is added under stirring
Pure and mild 0.2mL concentration is the silver nitrate solution of 0.1mol/L, is irradiated after 1h with 350W xenon lamp and is washed, dried, obtained
Mn0.5Cd0.5S/Ag composite photocatalyst.
4) by gained Bi in step 2)2WO6Gained Mn in micro-powder and step 3)0.5Cd0.5S/Ag nano-powder is scattered in
It in deionized water, is transferred in water-bath after ultrasonic a period of time, 70 DEG C of circulating reflux 3h, after being cooled to room temperature, through deionization
Water and ethyl alcohol are filtered, are washed, is dry, obtain Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst.Catalyst warp
Cross XRD and XPS characterization confirmation.
Embodiment 3
Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst preparation：
1) the mixed solution 100mL of manganese acetate and chromic acetate is prepared, wherein the concentration of manganese acetate and chromic acetate is
2.403g cystine is add to the above mixed solution by 0.001mol/L under stirring；Continue stir 60min after will be upper
It states solution to be transferred in reaction kettle, then reaction kettle is put into microwave dissolver in 140 DEG C of microwave reaction 30min；Wait react
It after end is cooled to room temperature, is filtered through deionized water and ethyl alcohol, washing, Mn can be obtained in drying0.5Cd0.5S nano-powder.
2) compound concentration is the sodium tungstate solution 3.32mL of 0.02mol/L, is added under stirring into sodium tungstate solution
Entering concentration is 0.02mol/L bismuth nitrate solution 6.64mL；PH=9 is adjusted with ammonium hydroxide, continues to be transferred to instead after stirring a period of time
It answers in kettle, then reaction kettle is put into microwave dissolver in 170 DEG C of microwave reaction 40min；It is cooled to room temperature to the end of reacting
Afterwards, it filters, wash through deionized water and ethyl alcohol, Bi can be obtained in drying2WO6Nano-powder.
3) by Mn obtained by step 1)0.5Cd0.5S nano-powder is scattered in deionized water, and 10mL is added under stirring
The silver nitrate solution that methanol and 0.1mL concentration are 0.1mol/L, is irradiated after 2h with 350W xenon lamp and is washed, dried, obtained
Mn0.5Cd0.5S/Ag composite photocatalyst.
4) by gained Bi in step 2)2WO6Gained Mn in micro-powder and step 3)0.5Cd0.5S/Ag nano-powder is scattered in
It in deionized water, is transferred in water-bath after ultrasonic a period of time, 80 DEG C of circulating reflux 3h, after being cooled to room temperature, through deionization
Water and ethyl alcohol are filtered, are washed, is dry, and Z-type structure Mn can be obtained0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst.The catalysis
Agent is by XRD and XPS characterization confirmation.
Embodiment 4
Catalyst obtained in embodiment 1 carries out producing hydrogen experiment：
Operating condition：Light source：300W xenon lamp；The amount of catalyst：0.05g；The concentration of sacrifice agent：The Na of 0.35mol/L2S
With the Na of 0.25mol/L2SO3.As can be known from Fig. 3, pure Mn0.5Cd0.5The hydrogen-producing speed of S catalyst is 463 μm of ol g-1h-1,
Mn0.5Cd0.5The hydrogen-producing speed of S/Ag catalyst is 753 μm of ol g-1h-1, and Mn0.5Cd0.5S/Ag/Bi2WO6Composite photo-catalyst
Hydrogen-producing speed be up to 1020 μm of ol g-1h-1, show the photocatalysis hydrogen production performance being remarkably reinforced.In conjunction with attached drawing 1,2 and of attached drawing
The provable the invention patent of the result of attached drawing 3 successfully produces the Z-type structure Mn with enhancing photocatalysis hydrogen production performance0.5Cd0.5S/
Ag/Bi2WO6Composite photo-catalyst, wherein Ag simple substance is located at Mn as electron conducting medium0.5Cd0.5S and Bi2WO6In catalyst
Between, it can be quickly by Bi2WO6Electronics transfer on conduction band is to Mn0.5Cd0.5The valence band of S, thus improve separation of charge efficiency and
Photocatalysis hydrogen production performance.
The composite photo-catalyst that embodiment 2-3 is prepared obtains similar production hydrogen effect.
Embodiment above describes basic principles and main features of the invention and advantages.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (9)
1. a kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photocatalyst, it is characterised in that including with
Lower step：
1) under stirring, manganese acetate and chromic acetate mixed solution is added in cystine, is subsequently placed in 130-150 DEG C of microwave reaction；It is cold
But it to room temperature, is filtered through deionized water and ethyl alcohol, washing, is dried to obtain Mn0.5Cd0.5S nano-powder；Wherein, cystine and vinegar
The molar ratio of sour chromium and manganese acetate is 5:1:1；
2) under stirring, bismuth nitrate solution is added in sodium tungstate solution, ammonium hydroxide tune pH=7-9 is subsequently placed in 160-180 DEG C of microwave
Reaction；After being cooled to room temperature, is filtered through deionized water and ethyl alcohol, washs, is dried to obtain Bi2WO6Nano-powder；Wherein, bismuth nitrate
Molar ratio with sodium tungstate is 2:1；
3) by Mn obtained by step 1)0.5Cd0.5S nano-powder is scattered in deionized water, is added with stirring methanol and silver nitrate is molten
Liquid is washed after xenon lamp irradiation, is dried, obtains Mn0.5Cd0.5S/Ag composite photocatalyst；
4) by Bi obtained by step 2)2WO6Mn obtained by micro-powder and step 3)0.5Cd0.5S/Ag nano-powder is scattered in deionized water
Middle ultrasound, then 70-90 DEG C of circulating reflux, after being cooled to room temperature, filters, washing, drying through deionized water and ethyl alcohol, obtains Z
Type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst.
2. Z-type structure Mn according to claim 10.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photocatalyst,
It is characterized in that：The molar concentration of chromic acetate is 0.001-0.01mol/L in mixed solution described in step 1).
3. Z-type structure Mn according to claim 10.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photocatalyst,
It is characterized in that：The concentration of sodium tungstate described in step 2) and bismuth nitrate is 0.01-0.02mol/L.
4. Z-type structure Mn according to claim 10.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photocatalyst,
It is characterized in that：Silver nitrate solution concentration described in step 3) is 0.1mol/L；Xenon lamp is selected from 300-350W.
5. Z-type structure Mn according to claim 10.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photocatalyst,
It is characterized in that：Mn described in step 3)0.5Cd0.5Mn in S/Ag composite photocatalyst0.5Cd0.5The mass ratio of S and Ag is 1:
0.01-0.05。
6. Z-type structure Mn according to claim 10.5Cd0.5S/Ag/Bi2WO6The preparation method of composite photocatalyst,
It is characterized in that：The Mn of Z-type structure described in step 4)0.5Cd0.5S/Ag/Bi2WO6Mn in composite photocatalyst0.5Cd0.5S with
Bi2WO6Mass ratio be 1:0.5-2.
7. a kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst, it is characterised in that：According to claim 1-6
Any one of the method preparation, catalyst structure confirmed by XRD and XPS.
8. the Z-type structure Mn according to claim 70.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst is in Photocatalyzed Hydrogen Production
In application.
9. the Z-type structure Mn according to claim 80.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst is in Photocatalyzed Hydrogen Production
In application, it is characterised in that：Operating condition is light source：300W xenon lamp；The amount of catalyst：0.05g；The concentration of sacrifice agent：
The Na of 0.35mol/L2The Na of S and 0.25mol/L2SO3。
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