CN105664969B - A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof - Google Patents
A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof Download PDFInfo
- Publication number
- CN105664969B CN105664969B CN201610046441.4A CN201610046441A CN105664969B CN 105664969 B CN105664969 B CN 105664969B CN 201610046441 A CN201610046441 A CN 201610046441A CN 105664969 B CN105664969 B CN 105664969B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- platinum
- cobaltosic oxide
- catalysis material
- tri compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 20
- 239000010936 titanium Substances 0.000 title claims description 20
- 229910052719 titanium Inorganic materials 0.000 title claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 54
- 239000002055 nanoplate Substances 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- 239000003426 co-catalyst Substances 0.000 claims abstract description 14
- MACBSXIPRLPFDJ-UHFFFAOYSA-N oxygen(2-) platinum(2+) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Pt+2] MACBSXIPRLPFDJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003446 platinum oxide Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical group CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims description 5
- 235000015281 sodium iodate Nutrition 0.000 claims description 5
- 239000011697 sodium iodate Substances 0.000 claims description 5
- 229940032753 sodium iodate Drugs 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000002131 composite material Substances 0.000 description 14
- 239000011941 photocatalyst Substances 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 238000005286 illumination Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910002451 CoOx Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble 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
-
- 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
-
- 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
Landscapes
- 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 a kind of titanium dioxide platinum cobaltosic oxide tri compound catalysis material preparation methods.Titanium dioxide platinum cobaltosic oxide tri compound catalysis material, using the titanium dioxide nanoplate in exposure { 001 } and { 101 } face as carrier, using platinum and cobaltosic oxide nano particle as co-catalyst, platinum grain is supported on { 101 } face of titanium dioxide nanoplate, and cobaltosic oxide nano particulate load is on { 001 } face of titanium dioxide nanoplate.Its photochemical catalyzing hydrogen generation efficiency is high, and co-catalyst is tightly combined with titanium dioxide, and long-time service has good stability, and efficiently solving the problems, such as that photochemical catalyst electron hole is easily compound in the prior art causes photocatalysis efficiency to reduce.
Description
Technical field
The present invention relates to catalysis material synthesis technical fields, and in particular to a kind of titanium dioxide-platinum-cobaltosic oxide three
First composite photocatalyst material and preparation method thereof.
Background technology
With the development of modern technologies, energy crisis and problem of environmental pollution getting worse.To solve the above-mentioned problems, people
Continue to develop and innovate various methods, wherein most promising be exactly directly using abundant solar energy resources turn
Chemical energy is turned to, to reduce environmental pollution, solves the problems, such as energy shortage.In recent years, conductor photocatalysis decomposes aquatic products hydrogen skill
Art becomes a kind of environmentally friendly green technology with its cleaning and the feature of low cost, it can turn the solar energy of low-density
Turn to highdensity, storable Hydrogen Energy.The technology can utilize conductor photocatalysis material to be generated under sunlight irradiation
Light induced electron and hole, part electronics can move to semiconductor surface, and reduction reaction occurs with the proton in water or water, to
Generate hydrogen.
In numerous semiconductor light-catalysts, TiO2Because its excellent photocatalytic activity, chemical inertness, it is nontoxic the advantages that
And favor is received, thus obtained widest application.However, TiO2When photocatalysis Decomposition aquatic products hydrogen, photo-generated carrier is easily
Compound, it reduce TiO2The efficiency of photocatalysis Decomposition aquatic products hydrogen, to limit TiO2Large-scale application and popularization, therefore,
Novel photocatalysis material is developed, the recombination rate of light induced electron and hole is reduced, to improving current photochemical catalyzing hydrogen generation efficiency
It is of great significance.Recently, it has been found that, it can significantly improve Photocatalyzed Hydrogen Production effect in titanium dioxide surface deposition co-catalyst
Rate.Many effective co-catalysts have had been used on semiconductor light-catalyst, as reduced form co-catalyst (such as Pt, NiO,
Cu(OH)2,MoS2Deng) and oxidized form co-catalyst (such as IrO2,RuO2, CoOx, MnOx etc.), however, studies have shown that both
When co-catalyst is only deposited on corresponding oxide side or reduction face, it could play a role to the maximum extent, reduce photoproduction
Carrier it is compound.Therefore, make reduced form co-catalyst and oxidized form co-catalyst selective deposition, to significantly reduce photoproduction electricity
The compound probability of son and hole, and then Photocatalyzed Hydrogen Production performance is improved, become the research hotspot of this field.
Invention content
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of titanium dioxide
Titanium-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof, prepared composite material exhibits go out very high light
Catalysis production hydrogen activity and stability.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material is provided, with exposure { 001 } and { 101 } face
Titanium dioxide nanoplate be carrier, using platinum and cobaltosic oxide nano particle as co-catalyst, platinum grain is supported on titanium dioxide
On { 101 } face of titanium nanometer sheet, cobaltosic oxide nano particulate load is on { 001 } face of titanium dioxide nanoplate.
By said program, the platinum carrying capacity is 0.5-3wt%, and cobaltosic oxide carrying capacity is 0.5-5wt%.
By said program, the length of the titanium dioxide nanoplate is 80nm-110nm.
By said program, platinum particle size 1-3nm, cobaltosic oxide particle size is 2~5nm.
A kind of preparation method of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material is provided, steps are as follows：
1) titanium dioxide nanoplate is prepared：Hydrofluoric acid is added in butyl titanate, stirring makes solution be uniformly mixed, then
Hydro-thermal reaction is calcined after the obtained washed drying of precipitation in air atmosphere, you can is exposed { 001 } and { 101 } face
Titanium dioxide nanoplate；
2) preparing surface deposition has the titanium dioxide nanoplate of Pt nanoparticle：Chloroplatinic acid is dissolved in the mixing of water and methanol
In solution, the titanium dioxide nanoplate obtained by step 1) is added in the solution, be sufficiently stirred and with Xenon light shining, obtains surface
Deposition has the titanium dioxide nanoplate of Pt nanoparticle；
3) titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material is prepared：By the surface deposition obtained by step 2)
There is the titanium dioxide nanoplate powder of Pt nanoparticle to be added in the solution of excessive oxidant, adds cobalt saline solution, fully
It is dispersed with stirring and uses Xenon light shining, gained precipitation is post-treated to obtain titanium dioxide-platinum-cobaltosic oxide tri compound photocatalysis
Material.
By said program, the volume of hydrofluoric acid is the 0~40% of butyl titanate volume in step 1), hydro-thermal process temperature
At 160 DEG C~180 DEG C, processing time is 24~36h, and calcination temperature is 450 DEG C~550 DEG C, and calcination time is 1~3h.
By said program, the volume of hydrofluoric acid is preferably the 12%-18% of butyl titanate volume in step 1).The present invention
By controlling the ratio of hydrofluoric acid, it is 49%- that can control the ratio shared by titanium dioxide nanoplate { 001 } face by 10-80%
58%, and then can make acquisition material that there is higher electrons and holes separative efficiency, thus there is better catalytic performance.
By said program, the volume ratio of methanol described in step 2) and water is 1:1-1:3.
By said program, chloroplatinic acid is calculated as 0.5wt%~3wt% of titanium dioxide, step (3) with platinum element in step 2)
Middle cobalt salt is calculated as 0.5wt%~5wt% of titanium dioxide with cobaltosic oxide.
By said program, cobalt salt described in step 3) is cobalt nitrate or cobalt acetate, cobalt ions in the cobalt saline solution
A concentration of 1~5mg/mL.
By said program, oxidant described in step 3) is sodium iodate or Potassiumiodate, a concentration of 0.02~0.05mol/
L。
By said program, light application time is 1-3h in step 2)；Step 3) the Xenon light shining time is 3~5h.
By said program, the last handling process includes being used in combination deionized water and absolute ethyl alcohol to wash precipitation and centrifugal separation
It washs, washes away the foreign ion in solution, then vacuum drying obtains powdered samples.
The beneficial effects of the present invention are：
In titanium dioxide-platinum provided by the present invention-cobaltosic oxide tri compound catalysis material, nano titania
Piece exposes { 001 } face and { 101 } face.For titanium dioxide, since conduction band positions ratio { 001 } face in { 101 } face is low,
Light induced electron can be transferred to { 101 } face from { 001 } face, and hole is transferred to { 001 } face from { 101 } face, and { 001 } face is caused to be in this way
Hole-rich face, i.e. oxide side；And { 101 } face is electron rich face, that is, restores face.This can make electrons and holes spatially
It separates, to reduce electron-hole recombination rate.Reduced form co-catalyst platinum is deposited on reduction face ({ 101 } face), by oxygen
Change type co-catalyst cobaltosic oxide is deposited on oxide side ({ 001 } face), can play the role of electron hole capturing agent, into
One step has the function that spatially to be automatically separated electron hole, is achieved in the raising of Photocatalyzed Hydrogen Production efficiency.
Further, the present invention makees block agent to nano titania by the dosage of regulation and control hydrofluoric acid using hydrofluoric acid
Platelet is looked unfamiliar long influence, by 10-80% controls it is 49%- by the ratio shared by titanium dioxide nanoplate { 001 } face
58%, it can make material that there is higher electrons and holes separative efficiency, thus there is better catalytic performance.
Titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material photocatalysis Decomposition aquatic products prepared by the present invention
Hydrogen efficiency is high, and co-catalyst is tightly combined with titanium dioxide, and long-time service has good stability, and efficiently solves existing skill
Photochemical catalyst electron hole easily compound the problem of causing photocatalysis efficiency to reduce in art.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of the composite photocatalyst material prepared by the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope picture of the composite photocatalyst material prepared by embodiment 1；The upper left corner is circle in figure in Fig. 2
Enclose the transmission electron microscope enlarged drawing of part.
Fig. 3 is the Photocatalyzed Hydrogen Production stability test figure of the composite photocatalyst material prepared by embodiment 1；
Fig. 4 be embodiment 1 prepared by composite photocatalyst material in cobalt element high-resolution x-ray photoelectron spectroscopy figure.
Fig. 5 be embodiment 1 prepared by composite photocatalyst material in platinum element high-resolution x-ray photoelectron spectroscopy figure.
Fig. 6 is the decahedral schematic diagram of titanium dioxide.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, below in conjunction with the accompanying drawings to the present invention make into
One step is described in detail.
Embodiment 1
1) 4.5mL hydrofluoric acid is rapidly joined in 25mL butyl titanates, mixed solution is under the action of magnetic stirring apparatus
Stirring is uniformly mixed for 1 hour to solution, then which is transferred to the hydro-thermal reaction of the polytetrafluoroethyllining lining of 100mL
In kettle, hydro-thermal reaction 24 hours at 180 DEG C, what is obtained is precipitated as after distilled water and ethyl alcohol wash repeatedly, is placed in 80 DEG C of bakings
It is 16 hours dry in case, and ground, it is calcined 2 hours for 450 DEG C in Muffle furnace, you can obtain titanium dioxide nanoplate.
2) preparing surface deposition has the titanium dioxide nanoplate of Pt nanoparticle：By the titanium dioxide powder of the above-mentioned gained of 50mg
Mixed solution (the methanol of 80mL water and methanol is added in end：Water=1:3) in, ultrasonic disperse 15 minutes makes titanium dioxide uniformly divide
It is dispersed in above-mentioned mixed solution, above-mentioned mixed solution is added with pipette accurate measuring 0.13mL platinum acid chloride solutions (1g/100mL)
In, chloroplatinic acid is calculated as the 1wt% of titanium dioxide with platinum, continues stirring 10 minutes, then continuous with xenon lamp under stirring conditions
Illumination 1 hour, gained precipitation are dry after deionized water and absolute ethyl alcohol washing, you can obtaining surface deposition has Pt nanoparticle
Titanium dioxide nanoplate；
3) titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material is prepared：Prepare the sodium iodate of 0.02mol/L
The surface deposition of the above-mentioned gained of 50mg is had the titania powder of Pt nanoparticle to be added by the cobalt nitrate solution of solution and 5g/L
In 80mL sodium iodide solutions, ultrasonic disperse makes its evenly dispersed in the solution for 15 minutes, then 0.23mL cobalt nitrate aqueous solutions is dripped
Above-mentioned solution is added, cobalt nitrate is made to be calculated as the 1wt% of titanium dioxide with cobaltosic oxide, continues stirring 10 minutes, is then stirring
Under conditions of mixing vacuum drying oven is placed on after deionized water and absolute ethyl alcohol washing with xenon lamp continuous illumination 3 hours, gained precipitation
In be dried in vacuo 16 hours at 40~50 DEG C, obtain titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material.
The scanning electron microscope and transmission electron microscope picture of composite photocatalyst material prepared by the present embodiment are as depicted in figs. 1 and 2,
As shown in Figure 1, which is nanometer plate shape, and average length is~80nm, and thickness is~30nm；Fig. 2 as it can be seen that this two
Titania surface deposition is there are two types of nano particle, and one kind is on { 101 } face, and for Pt nanoparticle, grain size 1-3nm is another to exist
{ 001 } it is cobaltosic oxide nano particle on face, grain size 2-5nm analyzes its lattice fringe, interplanar distance 0.143nm, with
The interplanar distance of cobaltosic oxide is coincide.And through characterization：The ratio in photochemical catalyst (001) face manufactured in the present embodiment is 58%.
The computational methods of 001 face ratio：
Wherein, θ indicates TiO2{ 001 } (68.3o, a indicate the length of side in { 001 } face, b tables to the theoretical angle in face and { 101 } face
Show { 101 } face length of side parallel with a.TiO2Crystal schematic diagram is as shown in Figure 6.
Fig. 4 and Fig. 5 is the high-resolution X-ray light of cobalt element and platinum element in the composite photocatalyst material that the present embodiment obtains
Electronic energy spectrum (XPS), as seen from the figure cobalt element exist in the form of cobaltosic oxide, platinum element exists in the form of metallic state.
The Photocatalyzed Hydrogen Production performance evaluation of photochemical catalyst manufactured in the present embodiment is at normal temperatures and pressures in 100mL three-necked bottles
It is carried out in reactor.The opening portion of the reactor is sealed with sillicon rubber blocking.Light source used is the xenon lamp of 350W.Light source face
The light intensity of reactor, horizontal distance 20cm, center is 130mW/cm2.The specific test method is as follows for it：By 50mg photochemical catalysts
Be added to 80mL first alcohol and waters mixed solution (volume ratio of methanol and water be 1:3) in.Then ultrasound keeps its evenly dispersed, connects
The air led to while agitating in nitrogen 30min removing reaction systems.After Xenon light shining 1h, measured with injector
Gas in 0.4mL reactors detects H2Yield, instrument are the GC-14C type gas chromatographs of Japanese Shimadzu Corporation's production
(TCD detectors, N2For carrier gas,Molecular sieve is chromatographic column).Photocatalysis stability experiment：It is surveyed with 50mg photochemical catalysts
Examination, testing procedure and photocatalytic activity testing procedure are essentially identical, continuous illumination 3h, per its primary photochemical catalyst of survey every other hour
Decompose hydrolysis production hydrogen activity.Catalyst is reused after the completion of primary experiment, sample is led into nitrogen 30min again, is removed anti-
The air and hydrogen for answering system to generate.Illumination is then proceeded to, loop test is carried out, is repeated 3 times altogether, tests its photostability.It is real
It tests the result shows that the aquatic products hydrogen efficiency of the composite photo-catalyst photocatalysis Decomposition 3h of gained can reach 0.9 μm of ol/h, has higher
Photocatalysis Decomposition aquatic products hydrogen activity, photocatalysis has good stability.
Quantum efficiency is tested：
At normal temperatures and pressures in carrying out in 100mL three-necked bottle reactors.The opening portion sillicon rubber blocking of the reactor
Sealing.Light source used is the LED light of 365nm.4 light sources are at angle face reactor perpendicular to each other, horizontal distance 1cm,
The light intensity at its center is 80mW/cm2.The specific test method is as follows for it：50mg photochemical catalysts are added to 80mL first alcohol and waters
(volume ratio of methanol and water is 1 to mixed solution:3) in.Then ultrasound keeps its evenly dispersed, then leads to nitrogen while agitating
30min removes the air in reaction system.With LED lamplight according to after 1h, gas in 0.4mL reactors, detection are measured with injector
H2Yield RH2, calculate quantum yield.
After tested, photochemical catalyst quantum efficiency of the invention is 11.28%.
Embodiment 2
1) 3mL hydrofluoric acid is rapidly joined in 25mL butyl titanates, mixed solution stirs under the action of magnetic stirring apparatus
It mixes 1 hour and is uniformly mixed to solution, then which is transferred to the hydrothermal reaction kettle of the polytetrafluoroethyllining lining of 100mL
In, hydro-thermal reaction 24 hours at 170 DEG C, what is obtained is precipitated as after distilled water and ethyl alcohol wash repeatedly, is placed in 80 DEG C of baking ovens
Middle drying 16 hours, and ground, it is calcined 2 hours for 450 DEG C in Muffle furnace, you can obtain titanium dioxide nanoplate.
2) preparing surface deposition has the titanium dioxide nanoplate of Pt nanoparticle：By the titanium dioxide powder of the above-mentioned gained of 50mg
Mixed solution (the methanol of 80mL water and methanol is added in end：Water=1:1) in, ultrasonic disperse 15 minutes makes titanium dioxide uniformly divide
It is dispersed in above-mentioned mixed solution, it is molten that above-mentioned mixing is added with pipette accurate measuring 0.065mL platinum acid chloride solutions (1g/100mL)
In liquid, chloroplatinic acid is calculated as the 0.5% of titanium dioxide with platinum, continues stirring 10 minutes, then continuous illumination 1 under stirring conditions
Hour, gained precipitation is dry after deionized water and absolute ethyl alcohol washing, you can obtaining surface deposition has the two of Pt nanoparticle
TiOx nano piece；
3) titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material is prepared：Prepare the sodium iodate of 0.03mol/L
The surface deposition of the above-mentioned gained of 50mg is had the titania powder of Pt nanoparticle to be added by the cobalt nitrate solution of solution and 5g/L
In 80mL sodium iodide solutions, ultrasonic disperse makes its evenly dispersed in the solution for 15 minutes, then 0.46mL cobalt nitrate aqueous solutions is dripped
Above-mentioned solution is added, cobalt nitrate is made to be calculated as the 2wt% of titanium dioxide with cobaltosic oxide, continues stirring 10 minutes, is then stirring
Continuous illumination 4 hours under conditions of mixing, gained precipitation after deionized water and absolute ethyl alcohol washing, be placed on 40 in vacuum drying oven~
It is dried in vacuo 16 hours at 50 DEG C, obtains titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material.
Reference implementation example 1 carries out phenetic analysis to composite photocatalyst material manufactured in the present embodiment, the results showed that：This implementation
The ratio in photochemical catalyst (001) face prepared by example is 49%, remaining characterization result is similar to Example 1.
Using method same as Example 1 and photocatalytic activity test and photocatalysis stability test, experimental result
Show that the composite photo-catalyst of gained has higher photocatalysis Decomposition aquatic products hydrogen activity, the aquatic products hydrogen efficiency of photocatalysis Decomposition 3h
0.8 μm of ol/h is can reach, photocatalysis has good stability.
Embodiment 3
1) 9mL hydrofluoric acid is rapidly joined in 25mL butyl titanates, mixed solution stirs under the action of magnetic stirring apparatus
It mixes 1 hour and is uniformly mixed to solution, then which is transferred to the hydrothermal reaction kettle of the polytetrafluoroethyllining lining of 100mL
In, hydro-thermal reaction 36 hours at 160 DEG C, what is obtained is precipitated as after distilled water and ethyl alcohol wash repeatedly, is placed in 80 DEG C of baking ovens
Middle drying 16 hours, and ground, it is calcined 3 hours for 500 DEG C in Muffle furnace, you can obtain titanium dioxide nanoplate.
2) preparing surface deposition has the titanium dioxide nanoplate of Pt nanoparticle：By the titanium dioxide powder of the above-mentioned gained of 50mg
Mixed solution (the methanol of 80mL water and methanol is added in end：Water=1:3) in, ultrasonic disperse 15 minutes makes titanium dioxide uniformly divide
It is dispersed in above-mentioned mixed solution, above-mentioned mixed solution is added with pipette accurate measuring 0.39mL platinum acid chloride solutions (1g/100mL)
In, chloroplatinic acid is calculated as the 3% of titanium dioxide with platinum, continues stirring 10 minutes, then continuous illumination 1 is small under stirring conditions
When, gained precipitation is dry after deionized water and absolute ethyl alcohol washing, you can obtaining surface deposition has the dioxy of Pt nanoparticle
Change titanium nanometer sheet；
3) titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material is prepared：Prepare the sodium iodate of 0.05mol/L
The surface deposition of the above-mentioned gained of 50mg is had the titania powder of Pt nanoparticle to be added by the cobalt nitrate solution of solution and 5g/L
In 80mL sodium iodide solutions, ultrasonic disperse makes its evenly dispersed in the solution for 15 minutes, then 1.15mL cobalt nitrate aqueous solutions is dripped
Above-mentioned solution is added, cobalt nitrate is made to be calculated as the 5wt% of titanium dioxide with cobaltosic oxide, continues stirring 10 minutes, is then stirring
Continuous illumination 5 hours under conditions of mixing, gained precipitation after deionized water and absolute ethyl alcohol washing, be placed on 40 in vacuum drying oven~
It is dried in vacuo 16 hours at 50 DEG C, obtains titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material.
Reference implementation example 1 carries out phenetic analysis to composite photocatalyst material manufactured in the present embodiment, the results showed that：This implementation
The ratio in photochemical catalyst (001) face prepared by example is 83%, remaining characterization result is similar to Example 1.
Using method same as Example 1 and photocatalytic activity test and photocatalysis stability test, experimental result
Show that the composite photo-catalyst of gained has higher photocatalysis Decomposition aquatic products hydrogen activity, the aquatic products hydrogen efficiency of photocatalysis Decomposition 3h
0.7 μm of ol/h is can reach, photocatalysis has good stability.
To sum up, titanium dioxide-platinum provided by the present invention-cobaltosic oxide tri compound catalysis material has good
Photochemical catalyzing H2-producing capacity and photocatalysis stability.
Claims (8)
1. a kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material, it is characterised in that：With exposure { 001 } and
{ 101 } titanium dioxide nanoplate in face is carrier, and using platinum and cobaltosic oxide nano particle as co-catalyst, platinum grain is supported on
On { 101 } face of titanium dioxide nanoplate, cobaltosic oxide nano particulate load is on { 001 } face of titanium dioxide nanoplate；
The platinum carrying capacity is 0.5-3wt%, and cobaltosic oxide carrying capacity is 0.5-5wt%.
2. titanium dioxide-platinum according to claim 1-cobaltosic oxide tri compound catalysis material, it is characterised in that：
The length of titanium dioxide nanoplate is 80nm-110nm, and platinum particle size 1-3nm, cobaltosic oxide particle size is 2 ~ 5nm.
3. the preparation method of titanium dioxide-platinum described in claim 1-cobaltosic oxide tri compound catalysis material, special
Sign is：Steps are as follows：
1）Prepare titanium dioxide nanoplate：Hydrofluoric acid is added in butyl titanate, stirring makes solution be uniformly mixed, then hydro-thermal
Reaction, after the obtained washed drying of precipitation, is calcined, you can exposed the dioxy in { 001 } and { 101 } face in air atmosphere
Change titanium nanometer sheet；
2）Preparing surface deposition has the titanium dioxide nanoplate of Pt nanoparticle：Chloroplatinic acid is dissolved in the mixed solution of water and methanol
In, by step 1）The titanium dioxide nanoplate of gained is added in the solution, is sufficiently stirred and with Xenon light shining, obtains surface deposition
There is the titanium dioxide nanoplate of Pt nanoparticle；
3）Prepare titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material：By step 2）The surface deposition of gained has platinum
The titanium dioxide nanoplate powder of nano particle is added in the solution of excessive oxidant, adds cobalt saline solution, is sufficiently stirred
Disperse and use Xenon light shining, gained precipitation is post-treated to obtain titanium dioxide-platinum-cobaltosic oxide tri compound photocatalysis material
Material；
Step 2）Middle chloroplatinic acid is calculated as 0.5wt% ~ 3wt% of titanium dioxide, step with platinum element（3）Middle cobalt salt is with cobaltosic oxide
It is calculated as 0.5wt% ~ 5wt% of titanium dioxide；
Step 3）The oxidant is sodium iodate or Potassiumiodate, a concentration of 0.02 ~ 0.05 mol/L.
4. the preparation method of titanium dioxide-platinum according to claim 3-cobaltosic oxide tri compound catalysis material,
It is characterized in that：Step 1）The volume of middle hydrofluoric acid be butyl titanate volume 0 ~ 40%, hydro-thermal process temperature 160 DEG C ~
180 DEG C, processing time is 24 ~ 36 h, and calcination temperature is 450 DEG C ~ 550 DEG C, and calcination time is 1 ~ 3h.
5. the preparation method of titanium dioxide-platinum according to claim 3-cobaltosic oxide tri compound catalysis material,
It is characterized in that：Step 1）The volume of middle hydrofluoric acid is the 12%-18% of butyl titanate volume.
6. the preparation method of titanium dioxide-platinum according to claim 3-cobaltosic oxide tri compound catalysis material,
It is characterized in that：Step 2）The volume ratio of the methanol and water is 1:1-1:3.
7. the preparation method of titanium dioxide-platinum according to claim 3-cobaltosic oxide tri compound catalysis material,
It is characterized in that：Step 3）The cobalt salt is cobalt nitrate or cobalt acetate, a concentration of the 1 of cobalt ions in the cobalt saline solution ~
5mg/mL。
8. the preparation method of titanium dioxide-platinum according to claim 3-cobaltosic oxide tri compound catalysis material,
It is characterized in that：Step 2）Middle light application time is 1-3h；Step 3）The Xenon light shining time is 3 ~ 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610046441.4A CN105664969B (en) | 2016-01-23 | 2016-01-23 | A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610046441.4A CN105664969B (en) | 2016-01-23 | 2016-01-23 | A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105664969A CN105664969A (en) | 2016-06-15 |
| CN105664969B true CN105664969B (en) | 2018-09-11 |
Family
ID=56302273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610046441.4A Expired - Fee Related CN105664969B (en) | 2016-01-23 | 2016-01-23 | A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105664969B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745534B (en) * | 2016-12-30 | 2020-07-07 | 浙江工商大学 | Composite photocatalytic electrode of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p-n heterojunction and preparation method thereof |
| CN110560172A (en) * | 2019-09-17 | 2019-12-13 | 南开大学 | Zirconium metal organic framework heterojunction material with photocatalytic performance and preparation method thereof |
| CN112604678B (en) * | 2020-12-17 | 2022-06-21 | 中国科学院过程工程研究所 | Photocatalytic composite particle and preparation method and application thereof |
| CN113000043B (en) * | 2021-02-21 | 2022-02-11 | 兰州大学 | Regulating and controlling process of crystal face structure exposed on surface of titanium dioxide quantum dot and composite photocatalyst constructed by regulating and controlling process and two-dimensional material |
| CN116173960A (en) * | 2023-03-09 | 2023-05-30 | 福州大学 | Preparation method and application of zirconia/cobalt/carbon composite catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001246264A (en) * | 2000-03-08 | 2001-09-11 | Mitsubishi Heavy Ind Ltd | Photocatalyst |
| CN1917966A (en) * | 2003-12-16 | 2007-02-21 | 开利公司 | Multi-layered photocatalyst/thermocatalyst for improving indoor air quality |
-
2016
- 2016-01-23 CN CN201610046441.4A patent/CN105664969B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001246264A (en) * | 2000-03-08 | 2001-09-11 | Mitsubishi Heavy Ind Ltd | Photocatalyst |
| CN1917966A (en) * | 2003-12-16 | 2007-02-21 | 开利公司 | Multi-layered photocatalyst/thermocatalyst for improving indoor air quality |
Non-Patent Citations (3)
| Title |
|---|
| Enhanced photocatalytic CO2-reduction activity of anatase TiO2 by coexposed {001} and {101} facets;Jiaguo Yu, et al;《J. Am. Chem. Soc.》;20140611;第136卷;第8839-8842页及支持信息 * |
| Hydrogen production by photocatalytic water splitting over Pt/TiO2 nanosheets with exposed(001) facets;Jiaguo Yu, et al;《J. Phys. Chem. C》;20100713;第114卷(第30期);第13119页左栏第2-3段、第13120页左栏最后1段至第13122页右栏第1段 * |
| Nonaqueous synthesis of CoOx/TiO2 nanocomposites showing high photocatalytic activity of hydrogen generation;Yufen Wang , et al;《Applied Catalysis B:Environmental》;20130610;第142-143卷;第626页右栏第2段至第627页左栏第1段、第631页左栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105664969A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Aminated flower-like ZnIn2S4 coupled with benzoic acid modified g-C3N4 nanosheets via covalent bonds for ameliorated photocatalytic hydrogen generation | |
| US11345616B2 (en) | Heterojunction composite material consisting of one-dimensional IN2O3 hollow nanotube and two-dimensional ZnFe2O4 nanosheet, and application thereof in water pollutant removal | |
| Sun et al. | Oxygen vacancy-rich BiO2-x ultra-thin nanosheet for efficient full-spectrum responsive photocatalytic oxygen evolution from water splitting | |
| CN105664969B (en) | A kind of titanium dioxide-platinum-cobaltosic oxide tri compound catalysis material and preparation method thereof | |
| CN103316714B (en) | Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst | |
| CN110327920A (en) | A kind of monatomic catalyst and its preparation method and application | |
| CN103480353A (en) | Method for synthesis of carbon quantum dot solution by hydrothermal process to prepare composite nano-photocatalyst | |
| CN108786792B (en) | Metal/semiconductor composite photocatalyst and preparation and application thereof | |
| Huang et al. | Ti3C2 MXene supporting platinum nanoparticles as rapid electrons transfer channel and active sites for boosted photocatalytic water splitting over g-C3N4 | |
| CN109046424A (en) | A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof | |
| CN103263920B (en) | TiO2-loaded high dispersion metal catalyst and preparation method thereof | |
| Zhang et al. | Mechanism investigation of PtPd decorated Zn0. 5Cd0. 5S nanorods with efficient photocatalytic hydrogen production combining with kinetics and thermodynamics | |
| CN108054391B (en) | Synthesis method and application of dendritic Pd nanocrystal catalyst | |
| CN108620131A (en) | The in-situ preparation method of composite photocatalyst material | |
| CN110639620A (en) | Composite photocatalyst for degrading tetracycline and preparation method and application thereof | |
| Huang et al. | Visible light driven photocatalytic reduction of CO2 on Au-Pt/Cu2O/ReS2 with high efficiency and controllable selectivity | |
| CN113198496B (en) | Metallic indium-doped lead cesium bromide perovskite quantum dot photocatalyst, preparation method and application thereof in reduction of carbon dioxide | |
| CN109985618A (en) | A kind of H occupies BiVO4The catalysis material of-OVs, preparation method and applications | |
| CN112619647A (en) | Preparation method of Co-MOF derived cobaltosic oxide composite titanium dioxide heterojunction and application of electrolyzed water | |
| CN114534783B (en) | Method for preparing single-atom Pt-embedded covalent organic framework photocatalyst and application thereof | |
| CN113976110B (en) | Catalyst for photocatalytic hydrogen production in alcohol-water system and preparation method thereof | |
| CN113731466B (en) | MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst, preparation and application thereof | |
| Guan et al. | Engineering tandem double pn heterostructured CeO2@ CdS-Cu8S5 hollow spheres for remarkable photocatalytic CO2 reduction | |
| CN103191708B (en) | Quantum dot TiO2 loaded SiO2 photocatalyst and preparation method thereof | |
| Li et al. | Construction of a novel 2D–2D heterojunction by coupling a covalent organic framework and In 2 S 3 for photocatalytic removal of organic pollutants with high efficiency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180911 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |