CN109225219B - Preparation method and application of copper-porous titanium dioxide composite material with Schottky junction structure - Google Patents
Preparation method and application of copper-porous titanium dioxide composite material with Schottky junction structure Download PDFInfo
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- CN109225219B CN109225219B CN201811007823.1A CN201811007823A CN109225219B CN 109225219 B CN109225219 B CN 109225219B CN 201811007823 A CN201811007823 A CN 201811007823A CN 109225219 B CN109225219 B CN 109225219B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000010949 copper Substances 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 235000014655 lactic acid Nutrition 0.000 claims description 13
- 239000004310 lactic acid Substances 0.000 claims description 13
- -1 titanium oxide glycolate Chemical compound 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 2
- 238000003421 catalytic decomposition reaction Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000002114 nanocomposite Substances 0.000 abstract description 13
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910000881 Cu alloy Inorganic materials 0.000 abstract 2
- 238000003795 desorption Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 239000012467 final product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
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- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 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
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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Abstract
The invention discloses a rod-shaped copper-porous titanium dioxide micro/nano composite material with a Schottky junction structure, which is prepared by loading cubic-phase nano Cu particles on anatase-type rod-shaped porous TiO2The surface of the copper alloy has a uniform rod-like structure, and the size of nano Cu attached to the surface of the copper alloy is small; the composite material adopts a green and efficient reducing agent and a coordination agent, and successfully constructs Cu @ TiO while obtaining a given porous shape2A Schottky structure; due to the special porous structure, the small-sized Cu and Schottky structure of the material, the material can promote the effective separation of photo-generated charges, simultaneously realize the proper adsorption of water molecules and the desorption of hydrogen, and improve the Cu @ TiO2Photocatalytic activity in the full light range. The porous rod-like micro/nano composite material obtained by the method has high reaction rate on hydrogen production by water decomposition under full light, has higher hydrogen production efficiency by photocatalytic water decomposition than titanium dioxide, and has important application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, functional materials and photocatalytic material preparation, and particularly relates to a preparation method and application of a copper-porous titanium dioxide composite material with a Schottky junction structure.
Background
For a long time, both "energy" and "environment" are two major worldwide problems that afflict mankind. On the one hand, the ever-increasing economy and the increasing material demand of people lead to the rapid consumption of energy; on the other hand, the environmental pollution is continuously intensified due to the consumption of energy, and people are suffering from atmosphere, water bodies and soilThe pollution is stereoscopic. "Hydrogen energy" has many advantages as a clean energy source, is non-toxic, burns cleanest with hydrogen compared to other fuels, and has the highest energy density among chemical fuels (142MJ kg)-1) And the water generated by combustion can be continuously used for producing hydrogen for repeated recycling, so that the water is a very promising energy source. However, hydrogen is still produced industrially mainly from coal, oil and natural gas, wherein greenhouse gases and pollutants are inevitably produced, and energy consumption is enormous. The photocatalytic technology is expected to solve the two problems by developing the photocatalyst capable of efficiently utilizing solar energy to decompose water to produce hydrogen. The anatase titanium dioxide micro-nano material is widely researched as an environment-friendly n-type semiconductor at present. However, due to the intrinsic characteristics of titanium dioxide, photogenerated carriers can be rapidly compounded, and surface active sites are few, so that the hydrogen production activity of photocatalytic water decomposition is severely limited.
The supported cocatalyst can delay the recombination of photo-generated electron-hole pairs to a great extent on titanium dioxide, can provide hydrogen production active sites, and reduces the activation energy in the hydrogen production process by photocatalytic water decomposition, thereby greatly improving the catalytic activity. In the past decades, traditional metals, especially noble metals such as Pt, Ru, Pd, Au, etc. have been the focus of research by researchers at home and abroad. Meanwhile, the method is also applied to hydrogen production by photocatalytic water decomposition, and has high activity of catalytically decomposing water to produce hydrogen. However, the noble metal has the defects that (1) in the full-water decomposition process, serious reverse reaction of oxygen reduction can occur; noble metals are limited by high cost and earth abundance; this makes it more valuable to develop efficient low cost non-noble metal promoters. Copper nanoparticles are particularly attractive in this regard. Because of high natural abundance and low cost of copper, various methods can directly prepare the copper-based nano material, and theoretical research also proves the potential of the copper-based nano material in the application of hydrogen production by photolysis of water. Among the synthesis processes for copper-based materials, the most popular synthesis process is based on "chemical treatment". This strategy has clear advantages in morphology or size selectivity. Among them, the "wet chemistry" technique is an effective method for preparing copper metal. It contains a reducing agent to provide an electron to reduce the copper salt. Reducing agents commonly used for this purpose include sodium borohydride, hydrazine hydrate, glucose, ascorbic acid, carbon monoxide, hydrogen or borane-like complexes. Various capping agents are also used to stabilize the resulting copper particles and control particle growth. The solid phase reducing agent with high activity is expensive and toxic, and the reaction condition of the gas phase reducing agent is harsh and dangerous; commonly used blocking agents such as polyvinylpyrrolidone, hexadecylamine, oleylamine, oleic acid have the disadvantage of being difficult to wash.
Disclosure of Invention
The invention mainly aims to provide a copper-porous titanium dioxide composite material with a Schottky junction structure aiming at the defects in the prior art, wherein the Schottky junction formed by the interface of copper and titanium dioxide is utilized to obviously improve the photocatalytic performance of the obtained composite material; the invention also provides a preparation method of the composite material, and the related preparation process is simple, low in cost, green and environment-friendly in production process, high in stability and suitable for popularization and application.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
a copper-porous titanium dioxide composite material with a Schottky junction structure has a chemical formula of Cu @ TiO2Anatase-type rod-like porous TiO supported by cubic-phase nano Cu particles2Wherein the nano Cu particles and the rod-like porous TiO are formed2The contact part of the structure forms a Schottky junction structure; the rod-shaped porous TiO2From TiO2And assembling the nano particles.
In the scheme, the specific surface area of the composite material is 140-160 m2Per g, wherein the porous TiO is rod-shaped2The length of the steel wire is 3-5 m, and the diameter of the steel wire is 0.8-1.5 m; the particle size of the nano Cu particles is 50-200 nm.
The preparation method of the copper-porous titanium dioxide composite material with the Schottky junction structure comprises the following steps:
1) synthesizing titanium oxyglycolate; adding a titanium source into ethylene glycol, then carrying out sol-gel reaction, and then carrying out centrifugal washing, drying and cooling to obtain a titanium oxyglycolate (TGP) precursor;
2) synthesizing porous titanium dioxide; adding titanium oxyglycolate into water, uniformly mixing, heating for hydrothermal reaction, and then carrying out centrifugal washing, drying and cooling to obtain a rod-shaped titanium dioxide material with a porous structure;
3) synthesizing a composite material; adding porous titanium dioxide, a copper source, lactic acid and sodium hydroxide into ethanol, uniformly mixing, heating to perform solvothermal reaction, and then performing centrifugal washing, drying and cooling to obtain the copper-porous titanium dioxide composite material with the Schottky junction structure.
In the scheme, the titanium source can be selected from titanium tetrachloride, titanium tetrafluoride, titanium sulfate, n-butyl titanate and isopropyl titanate; the copper source can be selected from copper sulfate, copper nitrate, copper chloride, and copper acetate.
In the scheme, the volume ratio of the titanium source to the ethylene glycol is 1 (10-500).
In the scheme, the sol-gel reaction temperature is 60-120 ℃, and the reaction time is 1-3 h.
In the scheme, the hydrothermal reaction temperature in the step 2) is 120-180 ℃, and the reaction time is 12-24 hours.
In the scheme, the solvothermal condition is that the reaction solution is placed in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and the reaction is carried out for 12-36 hours at the temperature of 140-160 ℃.
In the scheme, the molar ratio of the porous titanium dioxide to the copper source is (7-70): 1.
In the scheme, the molar ratio of the copper source to the lactic acid to the sodium hydroxide is 1 (0.5-20) to (4-500).
In the scheme, the dosage of the copper source relative to the ethanol is 1 (500-5000) mol: L.
The copper-porous titanium dioxide composite material with the Schottky junction structure obtained by the scheme is applied to preparing hydrogen by catalytically decomposing water under simulated sunlight, the hydrogen yield is far higher than that of the existing titanium dioxide product, and the copper-porous titanium dioxide composite material has great application potential.
The principle of the invention is as follows:
firstly, a titanium oxide glycolate prepolymer is constructed by a sol-gel method, then a hydrothermal reaction is carried out, and under the hydrothermal condition of high temperature and high pressure, water molecules enter the prepolymer to carry out hydrolysis reaction to generate porous titanium dioxide.
In the synthesis process of the copper-porous titanium dioxide composite material with the Schottky junction structure, Cu is firstly dissolved in an ethanol solvent2+Form complex dispersion with lactic acid, and then the excessive sodium hydroxide is added to compete with the lactic acid to complex Cu2+Make Cu2+Can be highly dispersed in a solvent; then adding titanium dioxide for ultrasonic dispersion, and obviously observing that the color of a dispersion system is gradually changed from white to light green in the process; description of Cu2+The complex of (a) is uniformly adsorbed on the porous titanium dioxide; finally, under the action of high-temperature and high-pressure solvent heat, the solvent ethanol is simultaneously used as a reducing agent to adsorb Cu on the titanium dioxide2+Reducing the complex into elemental copper; two coordination agents are adopted in the reaction system of the invention, so that Cu2+Can be well and stably dispersed on the porous titanium dioxide, and further inhibit the agglomeration growth of copper particles; further synthesizing the Cu @ TiO loaded by the small-size copper particles2The Schottky junction compound is beneficial to remarkably improving the catalytic performance and the cycle stability of the Schottky junction compound.
Compared with the prior art, the invention has the beneficial results that:
1) the invention firstly proposes that ethanol is simultaneously used as a solvent and a reducing agent, and 2 complexing agents of lactic acid and sodium hydroxide are used as Cu2+The stabilizer of (2) constructs a Schottky junction; resulting Cu @ TiO2The Schottky junction compound keeps a micron rod-shaped structure of porous titanium dioxide, a Schottky junction is formed by strong interaction force between copper nanoparticles attached to the surface of the porous titanium dioxide and the titanium dioxide, and the specific surface area of the obtained composite material is 140-160 m2The grain diameter of the nano Cu is 50-200 nm.
2) The invention adopts two coordination agents of sodium hydroxide and lactic acid to lead Cu to be2+Can be well and stably dispersed on the porous titanium dioxide, and further inhibit the agglomeration growth of copper particles; the catalytic performance of the obtained composite material is favorably and obviously improved.
3) Prepared Cu @ TiO2The Schottky junction structure formed by the micro/nano composite material can promote the effective separation of electron holes; moreover, the metallic copper as a cocatalyst is beneficial to promoting the adsorption and dissociation of water molecules, and simultaneously, the activation energy required by the reaction is reduced, so that the photocatalytic activity of the material is greatly improved; compared with pure titanium dioxide, the titanium dioxide has better activity of decomposing water into hydrogen by photocatalysis.
4) The preparation method disclosed by the invention is simple in preparation process, convenient to operate, low in cost, green and environment-friendly in production process, uniform in rod-shaped catalyst morphology, high in stability, capable of meeting actual production requirements and large in application potential.
Drawings
FIG. 1 is an X-ray diffraction analyzer (XRD) pattern of pure titanium dioxide, elemental Cu and final product obtained in example 1;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) spectrum of the final product obtained in example 1;
FIG. 3a is a Scanning Electron Microscope (SEM) of elemental copper, and FIGS. 3b and 3c are an SEM image and an X-ray energy spectrum elemental image (EDX-mapping), respectively, of the final product obtained in example 1;
FIG. 4 is a Transmission Electron Micrograph (TEM) and a High Resolution Transmission Electron Micrograph (HRTEM) of the final product obtained in example 1;
FIG. 5 is a graph showing adsorption/desorption isotherms and pore size distributions of the final product obtained in example 1;
FIG. 6 is a graph comparing the hydrogen evolution performance of the end product obtained in example 1 with that of the one-component titanium dioxide and commercial titanium dioxide by full photocatalytic decomposition; a hydrogen production amount; b, hydrogen production rate;
FIG. 7 is a diagram of the cyclic hydrogen production performance of the final product obtained in example 1; a hydrogen production amount; b, hydrogen production rate;
FIG. 8 is a graph of dehydrogenation performance of the final product obtained in example 1 in all-photocatalytic decomposition of ethanol, isopropanol and benzyl alcohol; a hydrogen production amount; b, hydrogen production rate;
FIG. 9 is an XRD pattern of the resulting product of comparative examples 1, 2;
FIG. 10a is a SEM image of elemental copper obtained in comparative example 2, and FIG. 10b is Cu @ TiO obtained in comparative example 22SEM picture of (1);
FIG. 11 is a graph of the final product obtained in example 1 versus the Cu @ TiO obtained in comparative example 22The hydrogen production activity of (A) is compared with that of (B).
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
In the following examples, the XRD patterns were analyzed using a BrukeraxsD8 model X-ray diffraction analyzer; the XPS spectrum is obtained by analyzing a VG Multilab 2000 type X-ray electron energy spectrometer; the TEM image is obtained by observing a Philips TecnaiG2 type transmission electron microscope; the BET map is obtained by a Micromeritics ASAP 2020 type specific surface area analyzer; the hydrogen production performance map is obtained by testing a middle school gold source CEL-SPH2N-S9 type full-automatic photolysis water hydrogen production system.
Example 1
Porous rod-shaped Cu @ TiO with Schottky structure2The preparation method of the micro/nano composite material comprises the following steps:
1) adding 1mL of n-butyl titanate into 180mL of glycol solvent, placing the obtained reaction solution into a round-bottom flask, carrying out sol-gel reaction for 1h under the condition of an oil bath at the temperature of 120 ℃, and then carrying out centrifugal washing, drying and cooling to obtain the titanium oxo glycolate precursor.
2) 0.1g of titanyl glycolate precursor was added to 35mL of deionized water and dispersed with sonication. And then placing the obtained reaction solution in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 18 hours under the hydrothermal condition of 180 ℃, centrifugally washing to remove impurities, drying at 60 ℃, and cooling to obtain the rod-shaped titanium dioxide with the porous structure.
3) Adding 0.15mmol of copper acetate monohydrate, 0.15mmol of lactic acid, 5mmol of sodium hydroxide and 0.1g of porous titanium dioxide into 80mL of ethanol solution, ultrasonically dispersing into uniform solution, placing reaction liquid into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours under the condition of 140 ℃ solvothermal condition, centrifugally washing to remove impurities, drying at 60 ℃, and cooling to obtain the final product.
The final product obtained in this example was taken inX-ray diffraction analysis was performed, and the results are shown in FIG. 1; from FIG. 1, it can be seen that the characteristic peaks observed for pure cubic phase copper and pure anatase titanium dioxide were consistent with the standard spectra JCPDS 70-3039 and JCPDS 73-1764, and no other impurity peaks appeared, indicating that the final product was Cu @ TiO of high purity2And (c) a complex.
Fig. 2 is an XPS diagram of the final product obtained in this example, from which it can be seen that Cu exists in the 0-valent form, corresponding to the elemental copper peak in XRD, i.e. the synthesized material is a composite of metallic copper and anatase phase titanium dioxide.
Fig. 3a is an SEM image of Cu particles, and fig. 3b and fig. 4 are an SEM image, a TEM image and an HRTEM image, respectively, of the final product obtained in this example. As can be seen from the scanning electron micrograph, the Cu @ TiO prepared in the embodiment2The rod-shaped structure is uniform in size, the length is 3-5 mu m, and the diameter is 0.8-1.5 mu m; the particle size of the Cu particles is 50-200 nm; the resulting TiO can be seen by HRTEM2Is made of TiO2A porous rod-like structure assembled by nano particles; and the lattice fringes of titanium dioxide and elemental copper can be seen.
FIG. 5 shows the adsorption/desorption isotherms and pore distribution curves of the product obtained in this example, according to N2The specific surface area of the obtained sample was 157.6m by adsorption calculation2/g。
The rod-like titanium dioxide, the final product and the commercially available titanium dioxide (P25) product obtained in step 2) of this example were subjected to photocatalytic water splitting hydrogen production activity tests, and the results are shown in fig. 6; the results show that the porous rod-shaped Cu @ TiO obtained in this example2The photocatalytic activity of the micro/nano composite material is far higher than that of a pure titanium dioxide product.
Example 2
Porous rod-shaped Cu @ TiO with Schottky structure2The preparation method of the micro/nano composite material comprises the following steps:
1) adding 2mL of n-butyl titanate into 180mL of glycol solvent, placing the obtained reaction solution into a round-bottom flask, carrying out sol-gel reaction for 1h under an oil bath at the temperature of 60 ℃, and then carrying out centrifugal washing, drying and cooling to obtain a titanium oxo glycolate precursor;
2) adding 0.2g of titanium oxyglycolate precursor into 35mL of deionized water, and performing ultrasonic dispersion; placing the obtained reaction liquid in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12 hours under the hydrothermal condition of 80 ℃, centrifuging, washing to remove impurities, drying at 60 ℃, and cooling to obtain rod-shaped titanium dioxide with a porous structure;
3) adding 0.3mmol of copper acetate monohydrate, 0.3mmol of lactic acid, 5mmol of sodium hydroxide and 0.3g of porous titanium dioxide into 80mL of ethanol solution in sequence, ultrasonically dispersing the mixture into uniform solution, placing the obtained reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 20 hours under the solvothermal condition of 150 ℃, removing impurities through centrifugal washing, drying at 60 ℃, and cooling to obtain the Cu @ TiO with the Schottky junction structure2Micro/nano composite material.
Example 3
Porous rod-shaped Cu @ TiO with Schottky structure2The preparation method of the micro/nano composite material comprises the following steps:
1) adding 5mL of n-butyl titanate into 360mL of glycol solvent, placing the obtained reaction solution into a round-bottom flask, carrying out sol-gel reaction for 2h under the condition of an oil bath at 100 ℃, and then carrying out centrifugal washing, drying and cooling to obtain the titanium oxo glycolate precursor.
2) Adding 0.2g of titanium oxyglycolate precursor into 35mL of deionized water, and performing ultrasonic dispersion; placing the obtained reaction liquid in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 18 hours under the hydrothermal condition of 160 ℃, centrifuging, washing to remove impurities, drying at 60 ℃, and cooling to obtain rod-shaped titanium dioxide with a porous structure;
3) adding 0.5mmol of copper acetate monohydrate, 0.5mmol of lactic acid, 10mmol of sodium hydroxide and 0.5g of porous titanium dioxide into 80mL of ethanol solution in sequence, ultrasonically dispersing the mixture into uniform solution, placing the obtained reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 28 hours under the solvothermal condition of 150 ℃, centrifugally washing to remove impurities, drying at 60 ℃, and cooling to obtain the Cu @ TiO with the Schottky junction structure2Micro/nano composite material.
Example 4
Porous rod-shaped Cu @ TiO with Schottky structure2The preparation method of the micro/nano composite material comprises the following steps:
1) adding 10mL of n-butyl titanate into 500mL of glycol solvent, placing the obtained reaction solution into a round-bottom flask, carrying out sol-gel reaction for 3h under the condition of an oil bath at the temperature of 120 ℃, and then carrying out centrifugal washing, drying and cooling to obtain the titanium oxo glycolate precursor.
2) Adding 0.2g of titanium oxyglycolate precursor into 35mL of deionized water, and performing ultrasonic dispersion; placing the obtained reaction liquid in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours under the hydrothermal condition of 180 ℃, centrifuging, washing to remove impurities, drying at 60 ℃, and cooling to obtain rod-shaped titanium dioxide with a porous structure;
3) adding 1mmol of copper acetate monohydrate, 1mmol of lactic acid, 20mmol of sodium hydroxide and 1.0g of porous titanium dioxide into 80mL of ethanol solution in sequence, ultrasonically dispersing the mixture into uniform solution, placing the obtained reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 36 hours under the solvothermal condition of 160 ℃, removing impurities through centrifugal washing, drying at 60 ℃, and cooling to obtain Cu @ TiO with a Schottky junction structure2Micro/nano composite material.
Application example
The porous rod-shaped Cu @ TiO obtained in example 12The micro/nano composite material was tested for the performance of hydrogen production by photocatalytic water splitting and compared with the rod-like titanium dioxide obtained in step 2) and the commercially available titanium dioxide (P25), and the results are shown in fig. 6.
FIG. 7 is a graph of the cycle hydrogen production performance of the product obtained in example 1, which shows excellent cycle stability; FIG. 8 is a graph of dehydrogenation performance of the product obtained in example 1 by decomposing ethanol, isopropanol and benzyl alcohol with full photocatalytic activity, and the result shows that the product can exhibit excellent catalytic hydrogen production performance particularly under ethanol conditions.
The result shows that the porous rod-shaped Cu @ TiO prepared by the invention2The micro/nano composite material can exert excellent catalytic performance under the condition of visible light; and has good cycle stability.
Comparative example 1
The product was synthesized using lactic acid as a single complexing agent, and the result indicated that the product was cuprous oxide, and elemental copper in the examples could not be obtained, and the corresponding XRD is shown in fig. 9.
Comparative example 2
Sodium hydroxide is used as a single complexing agent to synthesize a product, the result shows that the product is elemental copper, and XRD of the corresponding product is shown in figure 9; comparative example metallic copper and Cu @ TiO2Is shown in fig. 10. From the figure, it can be seen that the elemental copper synthesized with sodium hydroxide as a single complexing agent has particles with a larger size and an irregular bulk structure than the elemental copper in the examples. And Cu @ TiO synthesized using the comparative example2In FIG. 10 can be found in TiO2Significantly larger copper particles were observed on the rods.
Further, Cu @ TiO of this comparative example 22With Cu @ TiO in the examples2The results of comparison of the activities of hydrogen production by photocatalytic water decomposition are shown in fig. 11, and the results show that the activity of the product obtained by the invention is improved by 1.66 times compared with the product in comparative example 2.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (9)
1. A preparation method of a copper-porous titanium dioxide composite material with a Schottky junction structure is characterized by comprising the following steps:
1) synthesizing titanium oxyglycolate; adding a titanium source into ethylene glycol, then carrying out sol-gel reaction, and then carrying out centrifugal washing, drying and cooling to obtain a titanium oxide glycolate precursor;
2) synthesizing porous titanium dioxide; adding titanium oxyglycolate into water, uniformly mixing, heating for hydrothermal reaction, and then carrying out centrifugal washing, drying and cooling to obtain a rod-shaped titanium dioxide material with a porous structure;
3) synthesizing a composite material; adding porous titanium dioxide, a copper source, sodium hydroxide and lactic acid into ethanol, uniformly mixing, heating to perform solvothermal reaction, and then performing centrifugal washing, drying and cooling to obtain the copper-porous titanium dioxide composite material with the Schottky junction structure;
the chemical formula is Cu @ TiO2Anatase-type rod-like porous TiO supported by cubic-phase nano Cu particles2Wherein the nano Cu particles and the rod-like porous TiO are formed2The contact portion of (a) constitutes a schottky junction structure.
2. The method of claim 1, wherein the specific surface area of the composite material is 140 to 160m2Per g, wherein the porous TiO is rod-shaped2The length of the glass is 3-5 micrometers, and the diameter of the glass is 0.8-1.5 micrometers; the particle size of the nano Cu particles is 50-200 nm.
3. The method of claim 1, wherein the titanium source is titanium tetrachloride, titanium tetrafluoride, titanium sulfate, n-butyl titanate, isopropyl titanate; the copper source is copper sulfate, copper nitrate, copper chloride, or copper acetate.
4. The preparation method according to claim 1, wherein the volume ratio of the n-butyl titanate to the ethylene glycol is 1 (10-500).
5. The preparation method according to claim 1, wherein the sol-gel reaction temperature is 60-120 ℃ and the reaction time is 1-3 h.
6. The preparation method according to claim 1, wherein the hydrothermal reaction temperature in the step 2) is 120 to 180 ℃ and the reaction time is 12 to 24 hours.
7. The preparation method of claim 1, wherein the solvothermal condition is that the reaction solution is placed in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts at the temperature of 140-160 ℃ for 12-36 h.
8. The preparation method according to claim 1, wherein the molar ratio of the porous titanium dioxide to the copper source is (7-70): 1; the molar ratio of the copper source to the lactic acid to the sodium hydroxide is 1 (0.5-20) to (4-500); the dosage of the copper source relative to the ethanol is 1 (500-5000) mol: L.
9. The application of the copper-porous titanium dioxide composite material with the Schottky junction structure prepared by the preparation method of any one of claims 1 to 8 in the field of hydrogen production through catalytic decomposition under sunlight.
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