CN108275719A - A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material - Google Patents
A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material Download PDFInfo
- Publication number
- CN108275719A CN108275719A CN201810092030.8A CN201810092030A CN108275719A CN 108275719 A CN108275719 A CN 108275719A CN 201810092030 A CN201810092030 A CN 201810092030A CN 108275719 A CN108275719 A CN 108275719A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- tio
- anion
- doping
- sintering
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 243
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 84
- 239000000126 substance Substances 0.000 claims abstract description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 13
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 229910003083 TiO6 Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000005245 sintering Methods 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 150000001450 anions Chemical class 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- -1 metals cation Chemical class 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000005253 cladding Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003570 air Substances 0.000 claims description 7
- 238000000231 atomic layer deposition Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 229910003075 TiO2-B Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 3
- 238000003672 processing method Methods 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001483 high-temperature X-ray diffraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material belong to photocatalysis and technical field of lithium ion, specially a kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material.The titanium dioxide heterogeneous knot material of the present invention includes the titanic oxide material, the titanic oxide material through ion doping and coated and doped titanic oxide material of coated processing；Its agent structure is TiO6Octahedron, chemical formula TiO2；TiO simple, that ratio is controllable is prepared the object of the present invention is to provide a kind of2The preparation method of heterojunction material, TiO2Hetero-junctions is by anatase and TiO2B is formed, and the ratio of the two is arbitrarily adjustable, and anatase mole percent is 70% or more.
Description
Technical field
The invention belongs to technical field of lithium ion and catalysis material technical field, and in particular to a kind of Phase Proportion can
The TiO of control2The preparation of heterojunction material and method of modifying.
Background technology
TiO with heterojunction structure2It is that semiconductor functional material is ground in recent years with good electronic transport property
Study carefully hot spot, can be used for light-catalyzed reaction and lithium ion battery electrode material.There are four types of the common crystal forms of titanium dioxide, basic unit
By TiO6Octahedron is constituted, and by different connection types, forms rutile, anatase, brockite and TiO2The crystal forms such as-B.
Wherein rutile is Thermodynamically stable structure and is easily formed larger particle size；The nanostructure of Anatase is easily obtained；
TiO2- B and brockite are metastable state, the more difficult preparation of pure phase.Titanium dioxide between different crystal forms can by be simply heat-treated into
Row conversion is gradually changed into TiO such as using metatitanic acid as presoma by heating2- B, anatase, ultimately form Rutile Type.Pass through
Adjustment crystal form constructs heterojunction structure, can promote the separation of photo-generated carrier, reduces recombination probability；And nanocrystal boundary
Place can also further store up lithium, improve the capacity of material.By further accurately controlling crystal form ratio, and then realize the association of two-phase
Same effect is finally reached best photocatalysis/chemical property.The article or patent about composite construction reported at present mainly wrap
The compound phases such as rutile/anatase, brockite/anatase are included, it such as can be by depositing rutile on tubulose anatase surface
(Y.Luo, X.Y.Liu, J.G.Huang, CrystEngComm, 2013,15,5586), or with TT-2 type titanium dioxide be forerunner
Body, by sintering so that anatase is converted into rutile to formed heterojunction structure (T.Ohno, K.Tokieda,
S.Higashida,M.Matsumura,Appl.Catal.A-Gen.2003,244,383).It is solidifying by colloidal sol-to apply big east et al.
Titanium alkoxides and graphene oxide compound the processing such as are sintered by glue method, have obtained the anatase/rutile mixed phase material of mixed phase
Material, and use it for Photocatalyzed Hydrogen Production reaction (application number：201410243109.8 publication No.：CN 103991903A).Qiang Liang
It is raw et al. that anatase/rutile heterojunction structure is prepared for by the method for low temperature water-bath, and applied to photocatalysis field (application
Number：201210157404.2 publication No.：102674450A).Xie Yu et al. by hydro-thermal method be prepared for spherical anatase with it is rodlike
The heterojunction material of brockite, and it is applied to light-catalyzed reaction (application number：201510993747.6 publication No.：CN
105540656A).Although compound about two-phase heterojunction material report is more, about two-phase in the presence of when which kind of ratio
Its best results rare report.
Due to TiO2- B possesses all TiO under block or nano-scale2Highest theoretical capacity [Accounts in crystal form
Of chemical research, 2013,46,1104-1112], which has extensive research in terms of lithium battery.Pass through acid
Change hydro-thermal process and sintering [Journal of the American Chemical Society, 2005,127,6730-
6736], can be formed with TiO2The heterojunction material that-B is core, anatase is shell.By further controlling the hydro-thermal time, can adjust
Phase Proportion (Journal of the American Chemical Society, 2004,126,8380-8381) between the two.
With the K of preparationxTi2-x/3Lix/3O4Metatitanic acid presoma is obtained, after different temperatures is sintered by hydro-thermal process for presoma
Obtain anatase/TiO of different proportion2- B heterojunction materials show excellent chemical property under big multiplying power
(Advanced Energy Materials,2015,5,1401756).With unformed mesoporous TiO2For presoma, pass through hydro-thermal
Processing and proton exchange, obtain anatase/TiO of nucleocapsid2Micro-sphere structure (the Advanced Functional of-B
Materials 2017,1703270)。
Invention content
The purpose of the present invention is to propose to a kind of anatases and TiO that Phase Proportion is controllable2- B phases or Rutile Type or brockite
The heterojunction material and preparation method that one or more crystal forms in phase are constituted, and discuss out of phase component ratio, mesh
Be play different structure between synergistic effect, reach with beyond only it is single-phase in the presence of photocatalysis and chemical property.
Wherein anatase mole percent is 70% or more.
To further increase the comprehensive performance of titanium dioxide heterogeneous knot material, titanium dioxide heterogeneous knot material is being prepared
On the basis of further modification also has been carried out to it, including adulterate or/and coat, and wherein rutile titania mineral mole percent exists
70% or more.
A variety of analyses have been carried out, have been found in the titanium dioxide heterogeneous knot material of various ratios, when the composition ratio of anatase
When example is 70% or more mole percent, special performance boost can be obtained.When as photochemical catalyst, due to different alternate presence
Position of energy band difference, the separation of photo-generated carrier has been promoted；When as lithium cell negative pole material, alternate there is a large amount of phase boundaries
Face, interface electrons aggregation, it is possible to provide better comprehensive electrochemical.
At this moment, under the premise of specifying anatase composition, further the heterojunction material is modified, with into
The performance of one step promotion material, including titanium dioxide heterogeneous knot material, the titanium dioxide through ion doping of coated processing are different
Matter knot material and coated and doped titanium dioxide heterogeneous knot material, wherein titanium dioxide heterogeneous knot material can be
Micro-meter scale, nanoscale, and with one or more of macropore, mesoporous, micropore pore passage structure.The main body knot of these materials
Structure is TiO6Octahedron composition, chemical formula TiO2, the composition of anatase is 70% or more mole percent.
In the present invention, the ion doping of titanium dioxide heterogeneous knot material, doping type includes cation doping, anion
Doping or cation-anion co-doping are miscellaneous, and doping chemical formula is Ti1-XMXO2, TiO2-YNYOr Ti1-XMXO2-YNY, wherein M is selected from gold
Belong to cation, N is selected from negative valency element or anion, and X, Y are positive number, and X, Y are decimal or integer, and cation doping, anion are mixed
The mass percent range of miscellaneous doping is respectively 0%-10%.
In the present invention, doping metals cation is one or more of main group metal cation, transition-metal cation
Arbitrary mixing, wherein the main group metal cation includes：Li+, Na+, K+, Mg2+, Sr2+, Al3+, transition-metal cation
Including Fe2+, Fe3+, Co3+, Co4+, Zn2+, Ti3+；N is selected from C, S, P, F, Cl, Br, I, N；
In the present invention, the titanic oxide material of processing is coated, being (can not in titanium dioxide surface progress simple substance deposition
It is the type coated completely) or compound cladding acquisition；Simple substance is deposited as metal simple-substance, and metal simple-substance is selected from gold, silver, platinum；Packet
It covers material and is selected from carbons and inorganic compound.It is fixed that Carbon materials are selected from graphene, carbon nanotube, carbon fiber, carbon quantum dot, nothing
Type carbon；The inorganic compound is selected from titanium dioxide, silica, titanium nitride, carbonitride, iron oxide, cerium oxide, oxidation
Tin, five oxidation dioxies, molybdenum sulfide, cadmium sulfide；The number of plies of cladding is single-layer or multi-layer, and thickness 0-20nm, mass percent is
0-30%.
The present invention also provides the preparation methods of above-mentioned titanium dioxide heterogeneous knot material, including are based on titanium dioxide heterogeneous knot material
The preparation method of the method for the ion doping of material, the titanium dioxide heterogeneous knot material of simple substance deposition and compound cladding.
In the present invention, the method for the ion doping based on titanium dioxide heterogeneous knot material, including hydro-thermal method, solid phase
Different methods may be selected in sintering process, molte-salt synthesis, chemical etching method, gas phase doping method, different doping.
In order to facilitate elaboration, titanium dioxide heterogeneous knot material is with anatase and TiO below2- B constitute heterojunction material be
Example carries out preparation analysis, but is not limited only to anatase and TiO2- B heterojunction materials.
The first kind, hydro-thermal method, by titanium dioxide or TiO 2 precursor (such as butyl titanate, titanyl sulfate, tri-chlorination
Titanium, titanium tetrachloride) it is added in aqueous slkali (such as NaOH, KOH), titanate is obtained by hydro-thermal method；By cation to be adulterated
Metal salt or/and anion salt are added in the aqueous solution of above-mentioned titanate uniformly mixing (the mass ratio model of titanate and water
Enclose is 1:1-1:100), in certain temperature range stirring to carry out ion exchange, under certain temperature atmosphere (air, nitrogen,
Argon gas) under sintering a period of time obtain titanium dioxide heterogeneous knot material；
Or by cationic metal salt to be adulterated or/and carbon source and titanium dioxide or TiO 2 precursor or (such as titanium
Sour four butyl esters, titanyl sulfate, titanium trichloride, titanium tetrachloride) it is added in aqueous slkali (such as NaOH, KOH), it is obtained by hydro-thermal method
Titanate, by titanate and 0.05M HNO3Or desired anion acid solution mixing, under certain temperature and time stir with
Ion exchange is carried out, the titanium dioxide heterogeneous knot material of certain time acquisition is sintered under certain temperature atmosphere.
Above-mentioned anion salt is the acid selected from anion P, F, Cl, Br, I to be adulterated；A concentration of 5- of NaOH or KOH
15mol/L, hydrothermal temperature are 100-200 DEG C, and whipping temp is 20-200 DEG C, mixing time 1-48h, sintering temperature 400-
750 DEG C, sintering time 10min-4h, sintering atmosphere is air, nitrogen, argon gas.
Second class, molten-salt growth method, by cationic metal salt to be adulterated and titanium dioxide or TiO 2 precursor (such as metatitanic acid
Four butyl esters, titanyl sulfate, titanium trichloride, titanium tetrachloride) it is added in aqueous slkali (such as NaOH, KOH), after stirring is evaporated, it is added
One or more of appropriate low melting point salt (such as alkali metal chloride, alkali metal hydroxide), titanium is obtained at 200-800 DEG C
Hydrochlorate, by titanate and 0.05M HNO3Or the acid solution mixing of desired anion, it stirs and carries out under certain temperature and time
Ion exchange is sintered the titanium dioxide heterogeneous knot material of certain time acquisition under certain temperature atmosphere.
Or by the acid of simple titanate and cationic metal salt to be adulterated or/and desired anion, in certain temperature
And be stirred under the time to carry out ion exchange, the titanium dioxide heterogeneous knot of certain time acquisition is sintered under certain temperature atmosphere
Material.
Above-mentioned anion salt is the acid selected from anion P, F, Cl, Br, I to be adulterated；A concentration of 5- of NaOH or KOH
15mol/L；Whipping temp is 20-200 DEG C, mixing time 1-48h；Sintering temperature is 400-750 DEG C, and sintering time is
10min-4h, sintering atmosphere are air, nitrogen, argon gas.
Third class, solid sintering technology, by cationic metal salt to be adulterated and titanium dioxide or TiO 2 precursor
(e.g., butyl titanate, titanyl sulfate, titanium trichloride, titanium tetrachloride) is added in aqueous slkali (such as NaOH, KOH), and stirring is evaporated
Afterwards, doped titanate is obtained by the method for high temperature sintering, by titanate and 0.05M HNO3Or the acid solution of desired anion
Mixing, the stirring progress ion exchange under certain temperature and time are sintered certain time acquisition dioxy under certain temperature atmosphere
Change titanium heterojunction material.
Above-mentioned anion salt is the acid selected from anion P, F, Cl, Br, I to be adulterated；A concentration of 5- of NaOH or KOH
15mol/L；Whipping temp is 20-200 DEG C, mixing time 1-48h；Sintering temperature is 400-750 DEG C, and sintering time is
10min-4h, sintering atmosphere are air, nitrogen, argon gas.
4th class, chemical etching method, the titanium dioxide heterogeneous knot material that will be prepared, the acid with desired anion is certain
At a temperature of be stirred mixing, obtain titanium dioxide heterogeneous knot material.
Above-mentioned anion salt is the acid selected from anion P, F, Cl, Br, I to be adulterated；Whipping temp is 20-200 DEG C, is stirred
It is 1-48h to mix the time.
The metatitanic acid prepared is placed in tube furnace by the 5th class, gas phase doping method, by 400- under argon gas or nitrogen atmosphere
750 DEG C are heat-treated, and ammonia or hydrogen sulfide gas are passed through in insulating process to carry out N, S doping, it is 1min- to be passed through the time
1h then switchs to argon gas or nitrogen, and heat preservation total time is 10min-4h.
In the present invention, the preparation method of the titanium dioxide heterogeneous knot material of the cladding processing has ball-milling method, chemical gas
Phase sedimentation, ALD deposition method, local reduction way, one or more of hydro-thermal method.
The first kind, ball-milling method, by the titanium dioxide heterogeneous knot material prepared or the titanium dioxide heterogeneous knot material of doping
It is packed into ball grinder with covering material, and the abrasive body of proper proportion is added, can be coated after certain speed, time grinding
Titanium dioxide heterogeneous knot material.
Metatitanic acid presoma or the titania-doped heterojunction material prepared are placed in by the second class, chemical vapor deposition
In inert atmosphere, when calcining, is passed through the organic gas (such as toluene) for being easy to carbonization or is easy to the inorganic matter of distillation, passes through gas phase
Component is in the deposition of titanium dioxide surface, the titanium dioxide heterogeneous knot material or titania-doped hetero-junctions material that are coated
Material.
Titanium dioxide heterogeneous knot material is placed in atomic layer deposition room, by target coating by third class, ALD deposition method
Predecessor be alternately sent into reative cell in the form of gas pulses and control the thickness of sedimentary, realize the packet of thickness uniform, controllable
It covers.
4th class, local reduction way can be in titania-doped heterojunction materials when being Au, Ag, Pt for deposition simple substance
Chloroplatinic acid, gold chloride, silver nitrate are added in dispersion liquid, in-situ reducing (irradiation time 10min- is carried out under xenon source
2h), the titanium dioxide heterogeneous knot material of simple substance deposition is obtained.
Titanate is dispersed in appropriate solution (water or ethyl alcohol or the two mixed liquor) by the 5th class, hydro-thermal method, and carbon is added
Source obtains carbon-coated metatitanic acid in 100-200 DEG C of hydro-thermal 10min-24h, and certain time acquisition is sintered under certain temperature atmosphere
Titanium dioxide heterogeneous knot material.
Sintering temperature is 400-750 DEG C, sintering time 10min-4h, and sintering atmosphere is nitrogen or argon gas.
Or mix metatitanic acid with metal salt, reducing agent (such as sodium borohydride, citric acid) is added, is stirred at a certain temperature
Processing is mixed, to the titanium dioxide heterogeneous knot material of cladding.
Mixing time is 10min-24h, and temperature is 20-100 DEG C.
The titanium dioxide heterogeneous knot material of titanium dioxide heterogeneous knot material prepared by the present invention, cladding or doping treatment, packet
It covers and the titanium dioxide heterogeneous knot material of doping treatment, by Anatase and TiO2In-B phases or Rutile Type or brookite
One or more crystalline phases are constituted.Anatase content is in 70% or more mole percent, in terms of can be used for photocatalysis and electrochemistry.
Description of the drawings
Fig. 1 is 2D metatitanic acid in-situ high temperature XRD diagram.
Fig. 2 is the titanium dioxide heterogeneous knot material XRD diagram (feelings i.e. without adulterating and coating of the not in-phase proportion prepared
Condition).
Fig. 3 is the Phase Proportion result of calculation (i.e. without doping and cladding the case where) of titanium dioxide heterogeneous knot material.
Fig. 4 is titanium dioxide heterogeneous knot material boundary transmission plot (i.e. without doping and cladding the case where).
Fig. 5 is the photocatalytic degradation figure (i.e. without doping and cladding the case where) of titanium dioxide heterogeneous knot material.
Fig. 6 is pure Anatase and pure TiO2The photocatalytic degradation of-B phases compares figure.
Fig. 7 is the photocatalytic degradation figure of the titanium dioxide heterogeneous knot material of 3 gained Ag depositions of embodiment.
Specific embodiment
It can be better understood from the present invention from following embodiment, but the present invention is not limited solely to following embodiment.
Embodiment 1：By 0.5g TiO2It is added in 25ml, 10mol/l NaOH solution, each 30min is stirred by ultrasonic, then
It is transferred in 30ml water heating kettles, hydro-thermal 18h at 180 DEG C.After obtained solid titanate and 0.05M salpeter solutions are stirred for 24 hours
It filters, is dry, different time is heat-treated under 400-750 DEG C of air, and (preferential 620/640/660/680/700/720 DEG C of selection is right
Metatitanic acid is heat-treated 1h).
Above-mentioned institute's prepared material is subjected to Photocatalytic Degradation Property test respectively.Photocatalysis performance is tested, and the made powder of 50mg is taken
End is scattered in 80ml water, be added 0.5ml, 1mg/ml methyl orange solutions, dark place stirring 1h after carry out illumination, with LED (wavelength=
Be 365nm) light source, electric current takes 1A, and voltage 2.7V carries out degradation property test, and 4ml liquid is taken every 15min, carry out high speed from
The heart takes supernatant liquor and carries out test analysis using ultraviolet-visible spectrophotometer, draws degradation curve.According to formula C/C0Meter
Calculate its ratio of degrading.Wherein C is that temporally point samples methyl orange concentration, C0It is de- for the absorption-of methyl orange solution in original solution
Concentration when attached balance.
1. formation and the characterization of titanium dioxide heterogeneous knot
As shown in Figure 1, in situ under high temperature XRD test condition, with being stepped up for heat treatment temperature, metatitanic acid gradually phase
Become TiO2-B phases then mutually become Anatase, and the two is coexisting in certain temperature range, until TiO2-B phases are complete
It is converted into Anatase.At a temperature of different heat treatment, two-phase XRD structural analyses are as shown in Fig. 2, with heat treatment temperature liter
Height, TiO2-The feature peak intensity of B continuously decreases.It is calculated it is found that from 620-720 DEG C by structure refinement analysis, anatase contains
Amount is stepped up to 89%, as shown in Figure 3 from 30%.It can be seen that by the transmission plot of Fig. 4, titanium dioxide heterogeneous knot material has tight
The tactile boundary of contiguity, shows that metatitanic acid is that TiO is formed in situ2- B simultaneously mutually becomes Anatase, and crystallite dimension is in Nano grade.
2. influence of the different crystalline phase ratios to photocatalysis performance
Fig. 5 is the titanium dioxide heterogeneous knot material of different crystal forms ratio under ultraviolet light to the degradation of methyl orange song
Line, it can be seen that when anatase content is 82%, the heterojunction material catalytic effect is best.Compared to the pure phase material of two-phase
Expect (Fig. 6), the Titanium Dioxide effect with heterojunction structure is preferable.
Based on the above analysis, proposition of the present invention prepares Anatase and TiO2The heterojunction material of-B phases, and limit rutile titania
Mine phase content has preferable photocatalysis and chemical property in 70% or more mole percent.It is heterogeneous further to promote this
The comprehensive performance for tying material, can be doped it and the modified measures such as surface cladding, and wherein Anatase content is moles hundred
70% or more score
Embodiment 2：The titanium dioxide heterogeneous knot material or metatitanic acid presoma that prepare are subjected to ALD deposition TiO2, control
Deposition thickness (5nm)；680 DEG C of heat treatment 1h under hydrogen obtain carrying Ti3+The TiO of defect2Coated dissimilar knot material.
The material of above-mentioned gained is promoted according to method processing, test, performance in embodiment 1.
Embodiment 3：The silver nitrate of the titanium dioxide heterogeneous knot materials and 20ml, 0.04mg/ml of the 80mg prepared is water-soluble
Liquid is mixed, and 1h is irradiated under the xenon lamp of full spectrum and carries out in-situ reducing, obtains the titanium dioxide heterogeneous knot of Ag claddings
Material.
The material of above-mentioned gained is promoted according to method processing, test, performance in embodiment 1, as shown in Figure 7.
Embodiment 4：The 1g titanates prepared are mixed with mass fraction for 1% graphene oxide water solution, are added one
The surface charge of both quantitative 1M hydrochloric acid control realizes Electrostatic Absorption in turn, when there is notable sedimentation phenomenon, is centrifuged,
Obtained solid carries out hydro-thermal reaction in 80ml alcohol and/or aqueous solution, obtains metatitanic acid/graphene complex, then in Ar gas
Lower 680 DEG C of atmosphere carries out heat treatment 1h, obtains the titanium dioxide heterogeneous knot material of graphene coated.
The material of above-mentioned gained is promoted according to method processing, test, performance in embodiment 1.
Embodiment 4：The hydrofluoric acid solution of obtained 1g titanates and 20ml, 0.1M is stirred at 50 DEG C
For 24 hours, it is then centrifuged, by the 680 DEG C of progress 1h heat treatments under an argon atmosphere of obtained Fluorin doped metatitanic acid, obtains Fluorin doped
Titanium dioxide heterogeneous knot material.
The material of above-mentioned gained is promoted according to method processing, test, performance in embodiment 1.
Embodiment 5：1ml solution of tetrabutyl titanate is taken, water-acetic acid-chitosan (mass ratio 1 is distributed to:1:0.1) solution
In, after obtaining clear solution, the NaOH solution of 15ml, 10M is added, and be transferred in water heating kettle, 18h carries out water at 180 DEG C
Obtained solid is stirred in 0.05M salpeter solutions for 24 hours and filtration drying by thermal response, then under an argon atmosphere in
680 DEG C are heat-treated, and the titanium dioxide heterogeneous knot material of carbon doping/cladding is obtained.
The material of above-mentioned gained is promoted according to method processing, test, performance in embodiment 1.
Claims (9)
1. a kind of TiO that Phase Proportion is controllable2Heterojunction material, which is characterized in that TiO2Heterojunction material is anatase and TiO2-B
The heterojunction material that one or more crystal forms mutually or in Rutile Type or brookite are constituted, middle anatase mole percent exist
70% or more.
2. a kind of controllable TiO of Phase Proportion described in accordance with the claim 12Heterojunction material, which is characterized in that in TiO2It is heterogeneous
Further modification has also been carried out on the basis of knot material, including has adulterated or/and coats.
3. according to a kind of TiO that Phase Proportion is controllable as claimed in claim 1 or 22Heterojunction material, which is characterized in that titanium dioxide
Heterojunction material is micro-meter scale or nanoscale, and with one or more of macropore, mesoporous, micropore pore passage structure；This
The agent structure of a little materials is TiO6Octahedron composition, chemical formula TiO2。
4. a kind of TiO that Phase Proportion is controllable according to claim 22Heterojunction material, which is characterized in that titanium dioxide is different
Matter knot material is doped to ion doping, and doping type includes cation doping, anion doped or cation-anion co-doping is miscellaneous,
It is Ti that it, which adulterates chemical formula,1-XMXO2, TiO2-YNYOr Ti1-XMXO2-YNY, wherein M is selected from metal cation, and N is selected from negative valency member
Element or anion, X, Y be positive number, X, Y be decimal or integer, cation doping, anion doped doping mass percent
Range is respectively 0%-10%；Doping metals cation is main group metal cation, one kind in transition-metal cation or several
Kind arbitrary mixing, wherein the main group metal cation includes：Li+, Na+, K+, Mg2+, Sr2+, Al3+, transition metal sun from
Attached bag includes Fe2+, Fe3+, Co3+, Co4+, Zn2+, Ti3+；N is selected from C, S, P, F, Cl, Br, I, N；
Cladding processing is to carry out simple substance to deposit not being that the type coated completely or compound cladding obtain in titanium dioxide surface；
Simple substance is deposited as metal simple-substance, and metal simple-substance is selected from gold, silver, platinum；Covering material is selected from carbons and inorganic compound；Carbons material
Material is selected from graphene, carbon nanotube, carbon fiber, carbon quantum dot, agraphitic carbon；The inorganic compound is selected from titanium dioxide,
Silica, titanium nitride, carbonitride, iron oxide, cerium oxide, tin oxide, five oxidation dioxies, molybdenum sulfide, cadmium sulfide；The layer of cladding
Number is single-layer or multi-layer, thickness 0-20nm, mass percent 0-30%.
5. preparing a kind of controllable TiO of Phase Proportion as claimed in claim 1 or 22The method of heterojunction material, which is characterized in that packet
Include the method for the ion doping based on titanium dioxide heterogeneous knot material, the titanium dioxide heterogeneous knot of simple substance deposition and compound cladding
The preparation method of material；The method of the ion doping based on titanium dioxide heterogeneous knot material, including hydro-thermal method, solid phase are burnt
Connection, molte-salt synthesis, chemical etching method, gas phase doping method, different doping select different methods.
6. according to the method for claim 5, which is characterized in that doping includes following a few class methods：
Titanium dioxide or TiO 2 precursor are added in aqueous slkali by the first kind, hydro-thermal method, and metatitanic acid is obtained by hydro-thermal method
Salt；Cationic metal salt to be adulterated or/and anion salt are added in the aqueous solution of above-mentioned titanate and uniformly mixed, metatitanic acid
The mass ratio range of salt and water is 1:1-1:100, stirring is to carry out ion exchange in certain temperature range, in certain temperature
Sintering a period of time obtains titanium dioxide heterogeneous knot material under atmosphere；
Or by cationic metal salt to be adulterated or/and carbon source and titanium dioxide or TiO 2 precursor or it is added to alkali soluble
In liquid, titanate is obtained by hydro-thermal method, by titanate and 0.05M HNO3Or the acid solution mixing of desired anion, certain
Stirring is sintered the titanium dioxide heterogeneous knot of certain time acquisition to carry out ion exchange under certain temperature atmosphere under temperature and time
Material；
Anion salt is the acid selected from anion P, F, Cl, Br, I to be adulterated in above-mentioned first kind method；Alkali be selected from NaOH,
A concentration of 5-15mol/L of KOH, NaOH or KOH；Hydrothermal temperature is 100-200 DEG C, and whipping temp is 20-200 DEG C, when stirring
Between be 1-48h, sintering temperature be 400-750 DEG C, sintering time 10min-4h, sintering atmosphere be air, nitrogen, argon gas；
Cationic metal salt to be adulterated and titanium dioxide or TiO 2 precursor are added to alkali soluble by the second class, molten-salt growth method
In liquid, after stirring is evaporated, one or more of appropriate low melting point salt is added, titanate is obtained at 200-800 DEG C, by metatitanic acid
Salt and 0.05M HNO3Or the acid solution mixing of desired anion, the stirring progress ion exchange under certain temperature and time,
The titanium dioxide heterogeneous knot material of certain time acquisition is sintered under certain temperature atmosphere；
It is timely in certain temperature or by simple titanate and cationic metal salt to be adulterated or/and the acid of desired anion
Between under be stirred to carry out ion exchange, being sintered certain time under certain temperature atmosphere obtains titanium dioxide heterogeneous knot material
Material；
Above-mentioned second class method, anion salt are the acid selected from anion P, F, Cl, Br, I to be adulterated；NaOH's or KOH is dense
Degree is 5-15mol/L；Whipping temp is 20-200 DEG C, mixing time 1-48h；Sintering temperature is 400-750 DEG C, sintering time
For 10min-4h, sintering atmosphere is air, nitrogen, argon gas；
Cationic metal salt to be adulterated is added to by third class, solid sintering technology with titanium dioxide or TiO 2 precursor
In aqueous slkali, after stirring is evaporated, doped titanate is obtained by the method for high temperature sintering, by titanate and 0.05M HNO3Or mesh
The acid solution mixing of anion is marked, stirring progress ion exchange, is sintered under certain temperature atmosphere under certain temperature and time
Certain time obtains titanium dioxide heterogeneous knot material；
Third class method, above-mentioned anion salt are the acid selected from anion P, F, Cl, Br, I to be adulterated；Aqueous slkali NaOH or
A concentration of 5-15mol/L of KOH；Whipping temp is 20-200 DEG C, mixing time 1-48h；Sintering temperature is 400-750 DEG C,
Sintering time is 10min-4h, and sintering atmosphere is air, nitrogen, argon gas；
4th class, chemical etching method, the titanium dioxide heterogeneous knot material that will be prepared, the acid with desired anion is in certain temperature
Under be stirred mixing, obtain titanium dioxide heterogeneous knot material；
Above-mentioned anion salt is the acid selected from anion P, F, Cl, Br, I to be adulterated；Whipping temp is 20-200 DEG C, when stirring
Between be 1-48h；
The metatitanic acid prepared is placed in tube furnace by the 5th class, gas phase doping method, by 400-750 under argon gas or nitrogen atmosphere
It DEG C is heat-treated, ammonia or hydrogen sulfide gas is passed through in insulating process to carry out N, S doping, it is 1min-1h to be passed through the time,
Then switch to argon gas or nitrogen, heat preservation total time is 10min-4h.
7. according to the method for claim 6, which is characterized in that TiO 2 precursor be selected from butyl titanate, titanyl sulfate, three
Titanium chloride, titanium tetrachloride.
8. according to the method for claim 5, which is characterized in that the preparation of the titanium dioxide heterogeneous knot material of the cladding processing
Method has ball-milling method, chemical vapour deposition technique, ALD deposition method, local reduction way, one or more of hydro-thermal method；
The first kind, ball-milling method, by the titanium dioxide heterogeneous knot material prepared or the titanium dioxide heterogeneous knot material of doping with packet
It covers material and is packed into ball grinder, and abrasive body is added, the titanium dioxide heterogeneous knot material coated after grinding；
Metatitanic acid presoma or the titania-doped heterojunction material prepared are placed in inertia by the second class, chemical vapor deposition
In atmosphere, when calcining, is passed through the organic gas for being easy to carbonization or is easy to the inorganic matter of distillation, by gaseous component in titanium dioxide
The deposition on titanium surface, the titanium dioxide heterogeneous knot material coated or titania-doped heterojunction material；
Titanium dioxide heterogeneous knot material is placed in atomic layer deposition room, before target coating by third class, ALD deposition method
It drives object to be alternately sent into reative cell in the form of gas pulses and control the thickness of sedimentary, realizes the cladding of thickness uniform, controllable；
4th class, local reduction way can disperse when being Au, Ag, Pt for deposition simple substance in titania-doped heterojunction material
Chloroplatinic acid, gold chloride, silver nitrate are added in liquid, in-situ reducing is carried out under xenon source, irradiation time 10min-2h is obtained
The titanium dioxide heterogeneous knot material of simple substance deposition；
Titanate is dispersed in appropriate solution water or ethyl alcohol or the two mixed liquor by the 5th class, hydro-thermal method, and carbon source is added, in
100-200 DEG C of hydro-thermal 10min-24h, obtains carbon-coated metatitanic acid, and certain time acquisition dioxy is sintered under certain temperature atmosphere
Change titanium heterojunction material；
Sintering temperature is 400-750 DEG C, sintering time 10min-4h, and sintering atmosphere is nitrogen or argon gas；
Or mix metatitanic acid with metal salt, reducing agent is added, is stirred at a certain temperature, to the titanium dioxide of cladding
Heterojunction material；
Mixing time is 10min-24h, and temperature is 20-100 DEG C.
9. the controllable TiO of claim 1-4 any one of them Phase Proportions2The application of heterojunction material is used for photocatalysis or electrification
Learn reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810092030.8A CN108275719A (en) | 2018-01-30 | 2018-01-30 | A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810092030.8A CN108275719A (en) | 2018-01-30 | 2018-01-30 | A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108275719A true CN108275719A (en) | 2018-07-13 |
Family
ID=62807041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810092030.8A Pending CN108275719A (en) | 2018-01-30 | 2018-01-30 | A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108275719A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248675A (en) * | 2018-08-15 | 2019-01-22 | 四川省有色冶金研究院有限公司 | A kind of cerium oxide photochemical catalyst of doped yttrium and preparation method thereof |
| CN109701566A (en) * | 2019-02-26 | 2019-05-03 | 中国矿业大学 | A kind of codope TiO2Photochemical catalyst and preparation method thereof |
| CN109705853A (en) * | 2019-03-01 | 2019-05-03 | 惠科股份有限公司 | Quantum dot layer and preparation method thereof |
| CN110270363A (en) * | 2019-07-05 | 2019-09-24 | 河南大学 | A kind of preparation method and application of Li, C, N ternary codoping titanium dioxide nano material |
| CN110404524A (en) * | 2019-07-05 | 2019-11-05 | 武汉科技大学 | Carbon quantum dot/titanium dioxide composite photocatalyst preparation method and applications |
| CN110880589A (en) * | 2019-11-25 | 2020-03-13 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN111244416A (en) * | 2020-01-16 | 2020-06-05 | 中南大学 | Active quantum dot @ porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN112136830A (en) * | 2020-09-15 | 2020-12-29 | 青岛亿恩方能源环保科技有限公司 | Photocatalyst sterilization disinfectant based on Ag and N co-doped titanium dioxide/silver nitrate and preparation method and application thereof |
| CN113042070A (en) * | 2021-03-25 | 2021-06-29 | 江西理工大学 | In2S3@ CdS: yb and Er catalyst, preparation method and application |
| CN113097454A (en) * | 2020-01-09 | 2021-07-09 | 中国科学院上海硅酸盐研究所 | Porous confined multi-metal composite oxide material and preparation method and application thereof |
| CN113304742A (en) * | 2021-04-30 | 2021-08-27 | 昆明理工大学 | Ti3+Self-doping TiO2Preparation method of activated carbon-supported photocatalytic material |
| CN114162856A (en) * | 2021-12-07 | 2022-03-11 | 贵州民族大学 | Method for synthesizing iron-doped titanium oxide at high temperature and high pressure |
| CN114618471A (en) * | 2022-03-22 | 2022-06-14 | 吉林大学 | Europium ion doped yolk-shaped titanium dioxide difunctional composite material and preparation method and application thereof |
| CN114682249A (en) * | 2022-05-05 | 2022-07-01 | 中南大学 | Load type Mo-Ti double dopingHetero TiO 22Photocatalyst, preparation and application thereof |
| CN114700077A (en) * | 2022-04-24 | 2022-07-05 | 昆明理工大学 | Preparation method and application of ferric oxide doped double-phase titanium dioxide catalyst |
-
2018
- 2018-01-30 CN CN201810092030.8A patent/CN108275719A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| LIGANG GAI ET AL.: ""One-pot synthesis of nitrogen-doped TiO2 nanorods with anatase/brookitestructures and enhanced photocatalytic activity"", 《CRYSTENGCOMM》 * |
| WEIJIA ZHOU ET AL.: ""Phase transformation of TiO2 nanobelts and TiO2(B)/anatase interface", 《CRYSTENGCOMM》 * |
| XIAOQIANG AN ET AL.: ""Hierarchical Nanotubular Anatase/Rutile/TiO2(B) Heterophase Junction with Oxygen Vacancies for Enhanced Photocatalytic H2 Production"", 《LANGMUIR》 * |
| YAN ZHOU ET AL.: ""Stable Ti3+ Self-Doped Anatase-Rutile Mixed TiO2 with Enhanced Visible Light Utilization and Durability"", 《J. PHYS. CHEM. C》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248675A (en) * | 2018-08-15 | 2019-01-22 | 四川省有色冶金研究院有限公司 | A kind of cerium oxide photochemical catalyst of doped yttrium and preparation method thereof |
| CN109701566A (en) * | 2019-02-26 | 2019-05-03 | 中国矿业大学 | A kind of codope TiO2Photochemical catalyst and preparation method thereof |
| CN109705853A (en) * | 2019-03-01 | 2019-05-03 | 惠科股份有限公司 | Quantum dot layer and preparation method thereof |
| CN109705853B (en) * | 2019-03-01 | 2022-04-22 | 惠科股份有限公司 | Quantum dot layer and preparation method thereof |
| CN110270363A (en) * | 2019-07-05 | 2019-09-24 | 河南大学 | A kind of preparation method and application of Li, C, N ternary codoping titanium dioxide nano material |
| CN110404524A (en) * | 2019-07-05 | 2019-11-05 | 武汉科技大学 | Carbon quantum dot/titanium dioxide composite photocatalyst preparation method and applications |
| CN110880589A (en) * | 2019-11-25 | 2020-03-13 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN110880589B (en) * | 2019-11-25 | 2021-04-06 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN113097454A (en) * | 2020-01-09 | 2021-07-09 | 中国科学院上海硅酸盐研究所 | Porous confined multi-metal composite oxide material and preparation method and application thereof |
| CN113097454B (en) * | 2020-01-09 | 2022-07-12 | 中国科学院上海硅酸盐研究所 | Porous confined multi-metal composite oxide material and preparation method and application thereof |
| CN111244416A (en) * | 2020-01-16 | 2020-06-05 | 中南大学 | Active quantum dot @ porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111244416B (en) * | 2020-01-16 | 2021-04-09 | 中南大学 | Active quantum dot @ porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN112136830A (en) * | 2020-09-15 | 2020-12-29 | 青岛亿恩方能源环保科技有限公司 | Photocatalyst sterilization disinfectant based on Ag and N co-doped titanium dioxide/silver nitrate and preparation method and application thereof |
| CN113042070B (en) * | 2021-03-25 | 2023-03-21 | 江西理工大学 | In 2 S 3 @ CdS: yb and Er catalyst, preparation method and application |
| CN113042070A (en) * | 2021-03-25 | 2021-06-29 | 江西理工大学 | In2S3@ CdS: yb and Er catalyst, preparation method and application |
| CN113304742A (en) * | 2021-04-30 | 2021-08-27 | 昆明理工大学 | Ti3+Self-doping TiO2Preparation method of activated carbon-supported photocatalytic material |
| CN113304742B (en) * | 2021-04-30 | 2023-09-29 | 昆明理工大学 | Activated carbon supported Ti 3+ Self-doping TiO 2 Preparation method of photocatalytic material |
| CN114162856A (en) * | 2021-12-07 | 2022-03-11 | 贵州民族大学 | Method for synthesizing iron-doped titanium oxide at high temperature and high pressure |
| CN114162856B (en) * | 2021-12-07 | 2023-12-05 | 贵州民族大学 | Method for doping titanium oxide by using Cheng Tie under high temperature and high pressure |
| CN114618471B (en) * | 2022-03-22 | 2023-04-07 | 吉林大学 | Europium ion doped yolk-shaped titanium dioxide difunctional composite material and preparation method and application thereof |
| CN114618471A (en) * | 2022-03-22 | 2022-06-14 | 吉林大学 | Europium ion doped yolk-shaped titanium dioxide difunctional composite material and preparation method and application thereof |
| CN114700077A (en) * | 2022-04-24 | 2022-07-05 | 昆明理工大学 | Preparation method and application of ferric oxide doped double-phase titanium dioxide catalyst |
| CN114682249B (en) * | 2022-05-05 | 2023-07-18 | 中南大学 | Supported Mo-Ti double-dopedHetero TiO 2 Photocatalyst, preparation and application thereof |
| CN114682249A (en) * | 2022-05-05 | 2022-07-01 | 中南大学 | Load type Mo-Ti double dopingHetero TiO 22Photocatalyst, preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108275719A (en) | A kind of TiO that Phase Proportion is controllable2The preparation and application of heterojunction material | |
| Zhou et al. | Pristine Bi2WO6 and hybrid Au-Bi2WO6 hollow microspheres with excellent photocatalytic activities | |
| Zhang et al. | Facile formation of metallic bismuth/bismuth oxide heterojunction on porous carbon with enhanced photocatalytic activity | |
| Jampaiah et al. | Flower-like Mn3O4/CeO2 microspheres as an efficient catalyst for diesel soot and CO oxidation: Synergistic effects for enhanced catalytic performance | |
| Chen et al. | Room temperature synthesized BaTiO3 for photocatalytic hydrogen evolution | |
| Xu et al. | Controlled fabrication and enhanced photocatalystic performance of BiVO4@ CeO2 hollow microspheres for the visible-light-driven degradation of rhodamine B | |
| Salehabadi et al. | Green and facial combustion synthesis of Sr3Al2O6 nanostructures; a potential electrochemical hydrogen storage material | |
| Ming et al. | Fine control of titania deposition to prepare C@ TiO 2 composites and TiO 2 hollow particles for photocatalysis and lithium-ion battery applications | |
| Barhoum et al. | Synthesis, growth mechanism, and photocatalytic activity of zinc oxide nanostructures: porous microparticles versus nonporous nanoparticles | |
| Wang et al. | Crystalline phase regulation of anatase–rutile TiO 2 for the enhancement of photocatalytic activity | |
| Wang et al. | Pd cocatalyst on Sm-doped BiFeO 3 nanoparticles: synergetic effect of a Pd cocatalyst and samarium doping on photocatalysis | |
| Tamiolakis et al. | Mesoporous implantable Pt/SrTiO3: C, N nanocuboids delivering enhanced photocatalytic H2-production activity via plasmon-induced interfacial electron transfer | |
| Li et al. | Carbon and nitrogen co-doped bowl-like Au/TiO2 nanostructures with tunable size for enhanced visible-light-driven photocatalysis | |
| Yu et al. | Synthesis and characterization of mesoporous BiVO4 nanofibers with enhanced photocatalytic water oxidation performance | |
| CN102872774A (en) | Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof | |
| Shin et al. | Preparation of K-doped TiO2 nanostructures by wet corrosion and their sunlight-driven photocatalytic performance | |
| Long et al. | Nano-CdS confined within titanate nanotubes for efficient photocatalytic hydrogen production under visible light illumination | |
| Yang et al. | Synthesis of V 2 O 5@ TiO 2 core–shell hybrid composites for sunlight degradation of methylene blue | |
| Li et al. | Modulation of oxygen vacancy in hydrangea-like ceria via Zr doping for CO2 photoreduction | |
| Yao et al. | Improved photocatalytic activity of WO3/C3N4: By constructing an anchoring morphology with a Z-scheme band structure | |
| Yao et al. | Biomimetic Bi2WO6 with hierarchical structures from butterfly wings for visible light absorption | |
| Li et al. | Morphology-controlled WO3− x homojunction: hydrothermal synthesis, adsorption properties, and visible-light-driven photocatalytic and chromic properties | |
| Zheng et al. | Visible-light photocatalytic denitrogenation of nitrogen-containing compound in petroleum by metastable Bi20TiO32 | |
| Guo et al. | Facile synthesis of ZnFe2O4/SnO2 composites for efficient photocatalytic degradation of methylene blue | |
| Zhang et al. | Facile and robust construction of a 3D-hierarchical NaNbO 3-nanorod/ZnIn 2 S 4 heterojunction towards ultra-high photocatalytic H 2 production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180713 |