CN115382528B - Titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst and preparation method and application thereof - Google Patents
Titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst and preparation method and application thereof Download PDFInfo
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- CN115382528B CN115382528B CN202211030186.6A CN202211030186A CN115382528B CN 115382528 B CN115382528 B CN 115382528B CN 202211030186 A CN202211030186 A CN 202211030186A CN 115382528 B CN115382528 B CN 115382528B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010936 titanium Substances 0.000 title claims abstract description 81
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 81
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 52
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 title abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 230000015556 catabolic process Effects 0.000 claims abstract description 32
- 238000006731 degradation reaction Methods 0.000 claims abstract description 32
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 150000001868 cobalt Chemical class 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- -1 alkali metal salt Chemical class 0.000 claims description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 33
- 229960000907 methylthioninium chloride Drugs 0.000 description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- 238000001914 filtration Methods 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000002198 insoluble material Substances 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 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
- 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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst, and a preparation method and application thereof, and belongs to the field of photocatalytic degradation of organic pollutants. The invention adds titanium atoms into polyacid salt lattice, adopts titanium doped polyacrylate to modify the surface of titanium dioxide, can reduce the forbidden bandwidth of the titanium dioxide, and can improve the electron accepting capability, thus being capable of rapidly transferring TiO 2 E generated by light excitation ‑ Therefore, carriers are effectively separated, the recombination rate of carriers in the system is reduced, and the number of electrons and holes in the system is increased, so that the catalytic efficiency of the system is improved, and the degradation rate and the degradation effect of the composite catalyst on organic pollutants are improved.
Description
Technical Field
The invention relates to the field of photocatalytic degradation of organic pollutants, in particular to a titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst, and a preparation method and application thereof.
Background
With the development of technology, environmental pollution is also becoming more and more important. In modern times filled with energy crisis, traditional non-renewable energy sources such as coal and the like can produce waste during use to pollute the environment. Therefore, development of a novel energy source which is green, environment-friendly and renewable is urgent.
Titanium dioxide is a safe, non-toxic semiconductor material and has been favored in the field of photocatalysis. However, because of the large forbidden bandwidth (3.2 eV), only ultraviolet light in sunlight can be utilized, and the application of the ultraviolet light in photocatalysis is limited. Polyoxometallates are a class of metal oxygen cluster compounds formed from the bridging of transition metal (molybdenum, vanadium, tungsten, etc.) oxides by oxygen. The special structure of polyoxometalates gives them many excellent physicochemical properties such as strong acidity, high proton mobility, photochemical reducibility in aqueous solutions, non-toxicity and stable properties.
Heteropolyacid doped TiO as disclosed in the prior art 2 The catalyst of (2) has a problem of low catalytic efficiency.
Disclosure of Invention
In view of the above, the invention aims to provide a titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst, and a preparation method and application thereof. The composite catalyst prepared by the invention is doped with titanium atoms in the crystal lattice of cobalt (III) -containing polyacrylate, so that the catalytic efficiency is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst, which comprises the following steps:
mixing cobalt salt, metal acid salt and water for double decomposition reaction to obtain double decomposition products; the metal acid salt comprises one or more of tungstate, vanadate and molybdate;
mixing the double decomposition product with alkali metal salt to perform precipitation reaction to obtain a precipitation product;
dissolving the precipitate to obtain a solution;
mixing the solution with an oxidant for oxidation reaction to obtain cobalt (III) -containing polyacrylate;
mixing the cobalt (III) -containing polyacrylate with a first titanium source for reaction to obtain titanium doped cobalt (III) -containing polyacrylate;
and mixing the titanium doped cobalt (III) containing polyacrylate, a second titanium source and a dispersing agent for hydrothermal reaction to obtain the titanium doped cobalt (III) polyacrylate/titanium dioxide composite catalyst.
Preferably, the molar ratio of cobalt salt, metal acid salt and first titanium source is 5-10: 30-35: 0.1 to 13.
Preferably, the molar ratio of the titanium doped cobalt (iii) -containing polyacrylate to the second titanium source is 3.5 to 82: 450-9000.
Preferably, the first and second titanium sources are independently titanium sulfate, titanyl sulfate, titanium tetrachloride, tetrabutyl titanate, or tetraethyl titanate.
Preferably, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 5-24 h.
Preferably, the dispersing agent is a mixture of water, ammonia water and hydrogen peroxide solution;
with NH 3 And H 2 O 2 The molar ratio of the ammonia water to the hydrogen peroxide solution to the water is 14-200: 15 to 155: 5X 10 3 ～1.1×10 4 。
Preferably, the process of mixing the titanium doped cobalt (III) -containing polyacrylate, the second titanium source and the dispersing agent comprises the steps of dissolving the titanium doped cobalt (III) -containing polyacrylate in water to obtain a titanium doped cobalt (III) -containing polyacid salt solution, and dripping the titanium doped cobalt (III) -containing polyacid salt solution into the mixture of the second titanium source, ammonia water, hydrogen peroxide and water, wherein the dripping speed is 1 drop/s.
The invention also provides the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst prepared by the preparation method.
The invention also provides application of the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst in the field of catalytic degradation of organic pollutants.
The invention provides a preparation method of a titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst, which comprises the following steps: mixing cobalt salt, metal acid salt and water for double decomposition reaction to obtain double decomposition products; the metal acid salt comprises one or more of tungstate, vanadate and molybdate; mixing the double decomposition product with alkali metal salt to perform precipitation reaction to obtain a precipitation product; dissolving the precipitate to obtain a solution; mixing the solution with an oxidant for oxidation reaction to obtain cobalt (III) -containing polyacrylate; mixing the cobalt (III) -containing polyacrylate with a first titanium source for reaction to obtain titanium doped cobalt (III) -containing polyacrylate; and mixing the titanium doped cobalt (III) -containing polyacrylate, a second titanium source and a dispersing agent for hydrothermal reaction to obtain the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst.
The invention adds titanium atoms into polyacid salt lattice, adopts titanium doped polyacrylate to modify the surface of titanium dioxide, can reduce the forbidden bandwidth of the titanium dioxide, and can improve the electron accepting capability, thus being capable of rapidly transferring TiO 2 E generated by light excitation - Therefore, carriers are effectively separated, the recombination rate of carriers in the system is reduced, and the number of electrons and holes in the system is increased, so that the catalytic efficiency of the system is improved, and the degradation rate and the degradation effect of the composite catalyst on organic pollutants are improved.
The titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst is prepared by a hydrothermal method with simple and convenient use, is low in cost, stable in property, large in surface area and good in dispersibility.
The invention also provides the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst prepared by the preparation method, and the composite catalyst has good degradation rate and degradation effect on organic pollutants, is a green and environment-friendly composite catalyst, improves the absorption and utilization of visible light, and accelerates the degradation rate on the organic pollutants. The polyacrylate in the composite catalyst can oxidize pollutants well, has reversible oxidation-reduction property, and can be continuously recycled.
Drawings
FIG. 1 is an ultraviolet-visible spectrum of cobalt (III) containing polyacid salt/titanium dioxide before and after titanium doping of example 1;
FIG. 2 is a composite catalyst CoTiW/TiO prepared in example 1 2 CoW/TiO prepared in comparative example 1 2 Degradation map for Methylene Blue (MB);
FIG. 3 is a composite catalyst CoTiW/TiO of example 2 2 CoTiW and TiO 2 Degradation map for Methylene Blue (MB);
FIG. 4 is a composite catalyst CoTiMo/TiO of example 3 2 CoTiMo and TiO 2 Degradation map for Methylene Blue (MB);
FIG. 5 is a composite catalyst CoTiV/TiO of example 4 2 CoTiV and TiO 2 Degradation profile for Methylene Blue (MB).
Detailed Description
The invention provides a preparation method of a titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst, which comprises the following steps:
mixing cobalt salt, metal acid salt and water for double decomposition reaction to obtain double decomposition products; the metal acid salt comprises one or more of tungstate, vanadate and molybdate;
mixing the double decomposition product with alkali metal salt to perform precipitation reaction to obtain a precipitation product;
dissolving the precipitate to obtain a solution;
mixing the solution with an oxidant for oxidation reaction to obtain cobalt (III) -containing polyacrylate;
mixing the cobalt (III) -containing polyacrylate with a first titanium source for reaction to obtain titanium doped cobalt (III) -containing polyacrylate;
and mixing the titanium doped cobalt (III) -containing polyacrylate, a second titanium source and a dispersing agent for hydrothermal reaction to obtain the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
The invention mixes cobalt salt, metal acid salt and water to carry out double decomposition reaction to obtain double decomposition products; the metal acid salt comprises one or more of tungstate, vanadate and molybdate.
In the present invention, the cobalt salt preferably includes cobalt acetate, cobalt nitrate or cobalt sulfate.
In the present invention, the tungstate preferably includes sodium tungstate, potassium tungstate, or ammonium tungstate.
In the present invention, the vanadate preferably includes sodium vanadate or ammonium vanadate.
In the present invention, the molybdate preferably includes potassium molybdate or ammonium molybdate.
In the present invention, the molar ratio of the cobalt element in the cobalt salt to the metal element in the metal acid salt is not particularly limited, and a cobalt (iii) -containing polyacid salt of keggin type may be formed.
Taking the tungstate as an example, the reaction equation of the double decomposition reaction of the cobalt salt and the tungstate is as follows:
8H 2 O+12WO 4 2- +Co(CH 3 COO) 2 →CoW 12 O 40 6- +2CH 3 COO - +16OH -
in the present invention, the metathesis reaction is preferably carried out under conditions of boiling in a water bath.
In the present invention, the mixing process is preferably: and (3) after mixing the metal acid salt and water, regulating the pH value of the obtained mixed solution to be 6-7, stirring in a water bath until the mixed solution is boiled, adding the cobalt salt, and continuously heating for 15-20 min.
In the present invention, the pH is preferably adjusted with an acid, preferably including hydrochloric acid, sulfuric acid or acetic acid, and the concentration and the amount of the acid are not particularly limited, so long as the pH can be reached.
After the double decomposition product is obtained, the double decomposition product is mixed with alkali metal salt for precipitation reaction to obtain a precipitation product.
In the present invention, the alkali metal salt is preferably potassium chloride or sodium chloride.
In the present invention, the molar ratio of cobalt element in the cobalt salt to alkali metal element in the alkali metal salt is preferably 1:1.
Taking tungstate and potassium chloride as examples, the precipitation product is K 6 CoW 12 O 40 Is a green precipitate.
In the present invention, after the completion of the precipitation reaction, the present invention preferably includes sequentially performing natural cooling to room temperature and filtration. The specific mode of naturally cooling to room temperature and filtering is not particularly limited in the present invention, and modes known to those skilled in the art may be adopted.
After the precipitated product is obtained, the precipitated product is dissolved to obtain a solution.
In the present invention, sulfuric acid is preferably used for the dissolution, and the concentration and the amount of sulfuric acid are not particularly limited, and the precipitated product may be completely dissolved.
After the dissolution, insoluble matters in the dissolved matters are preferably removed by filtration.
After the solution is obtained, the solution is mixed with an oxidant for oxidation reaction to obtain the cobalt (III) -containing polyacrylate.
In the present invention, the oxidizing agent preferably includes potassium persulfate, hydrogen peroxide, or ammonium persulfate.
The amount of the oxidizing agent used in the present invention is not particularly limited, and the solution may be completely oxidized. In the present invention, the oxidizing agent is preferably added in batches, and the batch and the amount of each batch are not particularly limited.
With said K 6 CoW 12 O 40 For example, the end point of the oxidation reaction is preferably a green to golden yellow solution.
In the present invention, the cobalt (iii) -containing polyacid salt is preferably a keggin-type CoW polyacrylate, coMo polyacrylate or CoV polyacrylate.
After cobalt (III) -containing polyacid salt is obtained, the cobalt (III) -containing polyacid salt is mixed with a first titanium source for reaction, and then the titanium doped cobalt (III) -containing polyacid salt is obtained.
In the present invention, the molar ratio of the cobalt salt, the metal acid salt and the first titanium source is preferably 5 to 10: 30-35: 0.1 to 13.
In the present invention, the molar ratio of the cobalt (iii) -containing polyacrylate to the first titanium source is preferably 10 to 50:1 to 15.
In the present invention, the first titanium source is preferably titanium sulfate, titanyl sulfate, titanium tetrachloride, tetrabutyl titanate, or tetraethyl titanate.
In the present invention, the reaction is preferably carried out at a reflux temperature for a period of preferably 24 hours.
After the reaction is completed, the invention preferably further comprises natural cooling to room temperature, filtering and crystallizing sequentially.
The specific mode of the filtration and crystallization is not particularly limited in the present invention, and may be any mode known to those skilled in the art.
After the titanium doped cobalt (III) -containing polyacid salt is obtained, the titanium doped cobalt (III) -containing polyacid salt, a second titanium source and a dispersing agent are mixed for hydrothermal reaction, and the titanium doped cobalt (III) -containing polyacid salt/titanium dioxide composite catalyst is obtained.
In the present invention, the molar ratio of the titanium doped cobalt (iii) -containing polyacrylate to the second titanium source is preferably 3.5 to 82: 450-9000.
In the present invention, the second titanium source is preferably titanium sulfate, titanyl sulfate, titanium tetrachloride, tetrabutyl titanate, or tetraethyl titanate.
In the present invention, the dispersant is preferably a mixture of water, ammonia water and hydrogen peroxide solution; with NH 3 And H 2 O 2 The molar ratio of the ammonia water, the hydrogen peroxide solution and the water is preferably 14 to 200:15 to 155: 5X 10 3 ～1.1×10 4 The mass concentration of the ammonia water is preferably 25%, and the mass concentration of the hydrogen peroxide solution is preferably 30%.
In the present invention, the temperature of the hydrothermal reaction is preferably 120 to 180℃and the time is preferably 5 to 24 hours.
In the invention, the process of mixing the titanium doped cobalt (III) -containing polyacrylate, the second titanium source and the dispersing agent is preferably to dissolve the titanium doped cobalt (III) -containing polyacrylate in water to obtain a titanium doped cobalt (III) -containing polyacid salt solution, and drop the titanium doped cobalt (III) -containing polyacid salt solution into the mixture of the second titanium source, ammonia water, hydrogen peroxide and water, wherein the drop rate is 1 drop/s.
In the invention, the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst is in a sol state. The sol has small particle size and large surface area, is easy to adsorb the to-be-degraded substances, and can improve the degradation capability.
The invention also provides the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst prepared by the preparation method.
The invention also provides application of the titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst in the field of catalytic degradation of organic pollutants.
The specific mode of the application of the present invention is not particularly limited, and modes well known to those skilled in the art can be adopted.
For further explanation of the present invention, the titanium doped cobalt (iii) -containing polyacrylate/titanium dioxide composite catalyst, the preparation method and application thereof, provided by the present invention, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 10.0g of sodium tungstate into 20mL of deionized water, regulating the pH value to 6-7 by glacial acetic acid, stirring in a water bath until the solution is boiled, adding 1.30g of cobalt acetate, continuously heating for 15min, adding potassium chloride to obtain a green solution, cooling to room temperature, and filtering to obtain a green solid. The green solid was dissolved in 16ml of 2m sulfuric acid, warmed slightly and filtered to remove insoluble material. Continuously heating to boil, adding potassium persulfate in batches, and stopping adding after the solution turns from green to golden yellow. Heating to boiling was continued and 0.2g of titanyl sulfate was added to reflux for 24 hours. Cooling to room temperature, filtering, crystallizing at room temperature to obtain golden CoTiW rod-like crystal.
0.1g CoTiW crystal was dissolved in 30mL of water, and then 1.0mL of titanium tetrachloride, 6.0mL of ammonia, 5.0mL of hydrogen peroxide and 120mL of water (NH) were added at a rate of 1 drop/s 3 、H 2 O 2 And water in a molar ratio of 80:65:6667 Hydrothermal reaction at 140℃for 8 hours to give CoTiW/TiO 2 The composite catalyst is in a sol state, is uniformly dispersed in water and has the propertiesAnd (3) stability.
At 30mL containing CoTiW/TiO 2 1.2mg rhodamine B (40 mg/L) is added into the sol of the composite catalyst, and the mixture is stirred for 30min under dark condition, a photoreactor is utilized, an 800W LED lamp is adopted as a visible light source, and a magnetic stirrer is arranged, so that the reaction is carried out at normal temperature. 3mL samples were taken at intervals and tested in an ultraviolet-visible spectrophotometer to detect the degradation effect of the catalyst on MB.
Comparative example 1
Dissolving 10.0g of sodium tungstate into 20mL of deionized water, regulating the pH value to 6-7 by glacial acetic acid, stirring in a water bath until the solution is boiled, adding 1.30g of cobalt acetate, continuously heating for 15min, adding potassium chloride to obtain a green solution, cooling to room temperature, and filtering to obtain a green solid. The green solid was dissolved in 16ml of 2m sulfuric acid, warmed slightly and filtered to remove insoluble material. Continuously heating to boil, adding potassium persulfate in batches, and stopping adding after the solution turns from green to golden yellow. Heating to boiling, cooling to room temperature, filtering, crystallizing at room temperature to obtain golden CoW rod-like crystal.
0.1g of CoW crystals was dissolved in 30mL of water, which was then added at a rate of 1 drop/s to 1.0mL of titanium tetrachloride, 6.0mL of aqueous ammonia, 5.0mL of hydrogen peroxide and 120mL of water (NH) 3 、H 2 O 2 And water in a molar ratio of 80:65:6667 Hydrothermal reaction at 140 deg.c for 8 hr to obtain CoW/TiO 2 A composite catalyst.
Containing CoW/TiO in 30mL 2 1.2mg rhodamine B (40 mg/L) is added into the sol of the composite catalyst, and the mixture is stirred for 30min under dark condition, a photoreactor is utilized, an 800W LED lamp is adopted as a visible light source, and a magnetic stirrer is arranged, so that the reaction is carried out at normal temperature. 3mL samples were taken at intervals and tested in an ultraviolet-visible spectrophotometer to detect the degradation effect of the catalyst on MB.
FIG. 1 is an ultraviolet-visible spectrum of cobalt (III) -containing polyacid salt/titanium dioxide before and after titanium doping, and it is known that titanium-doped cobalt (III) -containing polyacid salt can improve the absorption of titanium dioxide to visible light, thereby having better catalytic degradation effect.
FIG. 2 is a composite catalyst CoTiW/TiO prepared in example 1 2 CoW/TiO prepared in comparative example 1 2 Degradation patterns of Methylene Blue (MB), from which CoTiW/TiO can be seen 2 Is superior to CoW/TiO in degradation effect 2 After 180min of illumination, coTiW/TiO 2 And CoW/TiO 2 The degradation rate for MB was 98.2% and 80.7%, respectively. FIG. 2 is an illustration of CoTiW/TiO prepared in example 1 2 Physical figures of the composite catalyst before and after degradation of Methylene Blue (MB).
Example 2
Synthesis of CoTiW
Dissolving 12.0g of potassium tungstate in 50mL of deionized water, regulating the pH to 6-7 by dilute hydrochloric acid, stirring in a water bath until the potassium tungstate is boiled, adding 1.30g of cobalt acetate, continuously heating for 20min, adding potassium chloride, cooling to room temperature, and filtering to obtain a solid. The solid was dissolved in 16ml of 2m sulfuric acid, slightly warmed, and the insoluble material was removed by filtration. Continuously heating to boiling, adding potassium persulfate in batches, and stopping adding after the solution turns to golden yellow. Heating to boiling was continued and 0.3g of titanium tetrachloride was added to reflux for 24 hours. Cooling to room temperature, filtering, crystallizing at room temperature to obtain golden CoTiW rod-like crystal.
0.1g CoTiW crystal was dissolved in 30mL of water, and then added at a rate of 1 drop/s to 1.0mL of tetraethyl titanate, 7.0mL of aqueous ammonia, 6.0mL of hydrogen peroxide and 120mL of water (NH) 3 、H 2 O 2 And water in a molar ratio of 94:77:6667) at 160 ℃ for 10 hours to obtain CoTiW/TiO 2 A composite catalyst.
At 30mL containing CoTiW/TiO 2 1.2mg rhodamine B (40 mg/L) is added into the composite catalyst sol, stirred for 30min under dark condition, a photoreactor is utilized, an 800W LED lamp is adopted as a visible light source, and a magnetic stirrer is arranged for reaction at normal temperature. 3mL of the sample is taken at intervals and tested in an ultraviolet-visible spectrophotometer, and the degradation effect of the catalyst on rhodamine B is detected.
FIG. 3 is a composite catalyst CoTiW/TiO of example 2 2 CoTiW and TiO 2 Degradation patterns of Methylene Blue (MB), from which CoTiW/TiO can be seen 2 The composite catalyst almost completely degrades MB (40 mg/L) after 60min of illumination, and CoTiW/TiO after 180min of illumination 2 CoTiW and TiO 2 The degradation rates for MB were 98.2%, 46.7% and 70.8%, respectively. FIG. 3 is an illustration showing the physical properties of the composite catalyst prepared in example 2 before and after degradation of Methylene Blue (MB).
Example 3
Synthesis of CoTiMo
6g of ammonium molybdate is dissolved in 40mL of deionized water, the pH is regulated to 6-7 by dilute sulfuric acid, the mixture is stirred in a water bath until the mixture is boiled, 1.80g of cobalt nitrate is added, the mixture is continuously heated for 20min, potassium chloride is added, and the mixture is cooled to room temperature and filtered to obtain a solid. The solid was dissolved in 16ml of 2m sulfuric acid, slightly warmed, and the insoluble material was removed by filtration. Adding 0.6g of titanium sulfate, continuously heating and stirring for 24 hours, evaporating and crystallizing at normal temperature to obtain CoTiMo crystals.
After 0.1g of CoTiMo crystals was dissolved in 30mL of deionized water, they were then added at a rate of 1 drop/s to 1.5mL of titanium tetrachloride, 6.0mL of ammonia, 5.0mL of hydrogen peroxide and 120mL of water (NH) 3 、H 2 O 2 And water in a molar ratio of 80:65:6667) at 120 ℃ for 12 hours to obtain CoTiMo/TiO 2 A composite catalyst.
Containing CoTiMo/TiO in 30mL 2 1.2mg rhodamine B (40 mg/L) is added into the composite catalyst sol, stirred for 30min under dark condition, a photoreactor is utilized, an 800W LED lamp is adopted as a visible light source, and a magnetic stirrer is arranged for reaction at normal temperature. 3mL of the sample is taken at intervals and tested in an ultraviolet-visible spectrophotometer, and the degradation effect of the catalyst on rhodamine B is detected.
FIG. 4 is a composite catalyst CoTiMo/TiO of example 3 2 CoTiMo and TiO 2 Degradation patterns of Methylene Blue (MB), from which CoTiMo/TiO can be seen 2 The composite catalyst almost completely degrades MB (40 mg/L) after 130min of illumination, 180min of illumination, coTiMo/TiO 2 CoTiMo and TiO 2 The degradation rates of MB are 90.7%, 52.3% and 70.8%, respectively. FIG. 4 is a diagram showing the actual conditions before and after the Methylene Blue (MB) is decomposed by the composite catalyst prepared in example 3.
Example 4
Synthesis of CoTiV
8.0g of ammonium vanadate is dissolved in 60mL of deionized water, the pH is regulated to 6-7 by dilute nitric acid, the mixture is stirred in a water bath until the mixture is boiled, 1.80g of cobalt nitrate is added, the mixture is continuously heated for 20min, sodium chloride is added, and the mixture is cooled to room temperature and filtered to obtain a solid. The solid was dissolved in 16ml of 2m sulfuric acid, slightly warmed, and the insoluble material was removed by filtration. 0.7g of titanium sulfate is added, heating and stirring are continued for 24 hours, evaporation and normal temperature crystallization are carried out, and CoTiV crystals are obtained.
After 0.1g of CoTiV crystals were dissolved in 20mL of deionized water, they were then added at a rate of 1 drop/s to 1.0mL of tetrabutyl titanate, 8.0mL of aqueous ammonia, 6.0mL of hydrogen peroxide, and 120mL of water (NH) 3 、H 2 O 2 And water in a molar ratio of 107:77:6667) at 180 ℃ for 11 hours to obtain CoTiV/TiO 2 A composite catalyst.
At 30mL containing CoTiV/TiO 2 1.2mg rhodamine B (40 mg/L) is added into the composite catalyst sol, stirred for 30min under dark condition, a photoreactor is utilized, an 800W LED lamp is adopted as a visible light source, and a magnetic stirrer is arranged for reaction at normal temperature. 3mL of the sample is taken at intervals and tested in an ultraviolet-visible spectrophotometer, and the degradation effect of the catalyst on rhodamine B is detected.
FIG. 5 is a composite catalyst CoTiV/TiO of example 4 2 CoTiV and TiO 2 Degradation patterns of Methylene Blue (MB), from which CoTiV/TiO can be seen 2 The MB (40 mg/L) of the composite catalyst is almost completely degraded after 130min of illumination, and the composite catalyst CoTiV/TiO after 180min of illumination 2 CoTiV and TiO 2 The degradation rates of MB are 88.7%, 42.5% and 70.8%, respectively. FIG. 5 is a diagram showing the actual conditions before and after the Methylene Blue (MB) is decomposed by the composite catalyst prepared in example 4.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the titanium doped trivalent cobalt-containing polyacid salt/titanium dioxide composite catalyst is characterized by comprising the following steps of:
mixing cobalt salt, metal acid salt and water for double decomposition reaction to obtain double decomposition products; the mixing process comprises the following steps: after mixing the metal acid salt and water, regulating the pH value of the obtained mixed solution to 6-7, stirring in a water bath until the mixed solution is boiled, adding the cobalt salt, and continuously heating for 15-20 min; the metal acid salt is one or more of tungstate, vanadate and molybdate;
mixing the double decomposition product with alkali metal salt to perform precipitation reaction to obtain a precipitation product;
dissolving the precipitate by using sulfuric acid to obtain a solution;
mixing the solution with an oxidant for oxidation reaction to obtain a polyacid salt containing trivalent cobalt; the oxidant is potassium persulfate, hydrogen peroxide or ammonium persulfate;
mixing the trivalent cobalt-containing polyacrylate with a first titanium source for reaction to obtain titanium doped trivalent cobalt-containing polyacrylate; the reaction is carried out at reflux temperature for 24 hours;
mixing the titanium doped trivalent cobalt-containing polyacrylate, a second titanium source and a dispersing agent for hydrothermal reaction to obtain the titanium doped trivalent cobalt-containing polyacid salt/titanium dioxide composite catalyst; the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 5-24 hours; the dispersing agent is a mixture of water, ammonia water and hydrogen peroxide solution; with NH 3 And H 2 O 2 The molar ratio of the ammonia water to the hydrogen peroxide solution to the water is 14-200: 15-155: 5X 10 3 ~1.1×10 4 。
2. The preparation method of claim 1, wherein the molar ratio of cobalt salt, metal acid salt and first titanium source is 5-10: 30-35: 0.1 to 13.
3. The method of claim 1, wherein the molar ratio of the titanium doped trivalent cobalt-containing polyacrylate to the second titanium source is 3.5 to 82: 450-9000.
4. The method according to any one of claims 1 to 3, wherein the first titanium source and the second titanium source are independently titanium sulfate, titanyl sulfate, titanium tetrachloride, tetrabutyl titanate, or tetraethyl titanate.
5. The method according to claim 1, wherein the mixing process of the titanium doped trivalent cobalt-containing polyacrylate, the second titanium source and the dispersing agent is that firstly, the titanium doped trivalent cobalt-containing polyacrylate is dissolved in water to obtain a titanium doped trivalent cobalt-containing polyacid salt solution, the titanium doped trivalent cobalt-containing polyacid salt solution is dripped into the mixture of the second titanium source, water, ammonia water and hydrogen peroxide, and the dripping speed is 1 drop/s.
6. The titanium-doped trivalent cobalt-containing polyacid salt/titanium dioxide composite catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the titanium doped trivalent cobalt-containing polyacid salt/titanium dioxide composite catalyst according to claim 6 in the field of catalytic degradation of organic pollutants.
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