CN108435169A - A kind of preparation method and application of gold-titanium dioxide nano tube catalyst - Google Patents
A kind of preparation method and application of gold-titanium dioxide nano tube catalyst Download PDFInfo
- Publication number
- CN108435169A CN108435169A CN201810192890.9A CN201810192890A CN108435169A CN 108435169 A CN108435169 A CN 108435169A CN 201810192890 A CN201810192890 A CN 201810192890A CN 108435169 A CN108435169 A CN 108435169A
- Authority
- CN
- China
- Prior art keywords
- preparation
- nano tube
- gold
- tube catalyst
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002071 nanotube Substances 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 88
- KAHROKHAOQFUTL-UHFFFAOYSA-N gold(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Au+3] KAHROKHAOQFUTL-UHFFFAOYSA-N 0.000 title claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 178
- 239000010931 gold Substances 0.000 claims abstract description 86
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 239000006286 aqueous extract Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 240000002924 Platycladus orientalis Species 0.000 claims description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 235000019253 formic acid Nutrition 0.000 claims description 25
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229920003266 Leaf® Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 241000902900 cellular organisms Species 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 241000218636 Thuja Species 0.000 claims 1
- 235000008109 Thuja occidentalis Nutrition 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract 5
- 239000002243 precursor Substances 0.000 abstract 2
- 239000004570 mortar (masonry) Substances 0.000 description 36
- 239000000284 extract Substances 0.000 description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 19
- 239000010935 stainless steel Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- 239000012263 liquid product Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 9
- 210000004700 fetal blood Anatomy 0.000 description 9
- 230000020477 pH reduction Effects 0.000 description 9
- 239000008279 sol Substances 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000003801 milling Methods 0.000 description 8
- 238000011017 operating method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- RMOGWMIKYWRTKW-UONOGXRCSA-N (S,S)-paclobutrazol Chemical compound C([C@@H]([C@@H](O)C(C)(C)C)N1N=CN=C1)C1=CC=C(Cl)C=C1 RMOGWMIKYWRTKW-UONOGXRCSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- -1 Acyl ammonia Chemical compound 0.000 description 1
- RMMXTBMQSGEXHJ-UHFFFAOYSA-N Aminophenazone Chemical compound O=C1C(N(C)C)=C(C)N(C)N1C1=CC=CC=C1 RMMXTBMQSGEXHJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 239000005985 Paclobutrazol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- 229960000212 aminophenazone Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DJGAAPFSPWAYTJ-UHFFFAOYSA-M metamizole sodium Chemical compound [Na+].O=C1C(N(CS([O-])(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 DJGAAPFSPWAYTJ-UHFFFAOYSA-M 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229960000282 metronidazole Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- FIDZUVLGQPMOIN-UHFFFAOYSA-N sodium oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Na+] FIDZUVLGQPMOIN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
-
- 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
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
- B01J37/0215—Coating
- B01J37/0232—Coating by pulverisation
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cosmetics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method and application of metal/titanic oxide nano tube catalyst, the preparation method of metal/titanic oxide nano tube catalyst includes the following steps：The aqueous extract of cacumen biotae is mixed with the aqueous solution of gold chloride, is reacted 1 10 minutes, aurosol is obtained；Titania nanotube is added in aurosol, stirs, the solid being obtained by filtration is dried in filtering, and grinding is to get to metal/titanic oxide precursor body of Nano tube；Obtained metal/titanic oxide precursor body of Nano tube is calcined at 300 400 DEG C, in oxidizing atmosphere to get to metal/titanic oxide nano tube catalyst.The Au/TiO of the present invention2Nano tube catalyst preparation process is simple, of low cost, nontoxic and pollution-free, has good both thermally and chemically stability and excellent catalysis characteristics, has good application prospect in fields such as electro-catalysis, hydrogenation catalyst, photocatalysis.
Description
Technical field
The present invention relates to a kind of preparation method and applications of gold-titanium dioxide nano tube catalyst, belong to precious metal catalyst
Agent preparation field.
Background technology
Formic acid (HCOOH) as one of basic Organic Chemicals, be widely used in pesticide, leather, medicine, rubber,
The industries such as printing and dyeing and industrial chemicals, are closely related with national economy.First, on medical industry, local excitants, convergence can be done
The important source materials such as agent and bubble cream, and production analgin, metronidazole, caffeine, aminopyrine, borneol, vitamin B1；Secondly,
In pesticide industry, formic acid can produce higher effective and lower toxic pesticide insecticidal ethers, triadimefon, paclobutrazol, and leather industry can manufacture leather
Tanning agent, deliming agent and neutralizer；Meanwhile in chemical industry industrial aspect, being mainly used in production formic acid ammonia, dimethylamino benzophenone
Acyl ammonia, various formates, anti-aging agent etc..In addition, being known as in " Energy Star " fuel cell of 21 century, majority uses methanol
(CH3OH it) is used as fuel that direct methanol fuel cell (DMFC) is made using however, methanol is stronger for the penetration of film
Mixed current potential is easily caused in the process.In view of formic acid electrochemistry oxidation performance is good, source very than wide, cheap, toxicity
It is small, for the advantages such as the penetration of proton membrane is weak, most researchers think that it is that methanol replaces in the DMFC for have very high potential
Dai Pin.
Due to industrial expansion, the long-time service of fossil fuel, the sharp increase of energy consumption and carbon dioxide are largely arranged
It puts caused energy shortage and serious environmental problem is greatly paid close attention to.How effectively to control and recycling
Carbon dioxide becomes the countermeasure for administering its pollution.Under such background, catalysis transform of carbon dioxide is generated with high added value
Organic chemical products are most promising approach in its utilization.In addition, in traditional formic acid synthesis, with carbon monoxide and
Aquatic production formic acid ratio is lower by sodium formate method production cost, but needs higher temperature (200-300 DEG C) and pressure (about
20.0MPa), energy expenditure is big, and equipment investment is high.And it is easy to operate to synthesize formic acid by catalytic hydrogenation of carbon dioxide, raw material utilizes
Rate is high, has Atom economy, meets contemporary green chemistry trend.Therefore, exploitation is prepared by catalytic hydrogenation of carbon dioxide
The technique of formic acid has prodigious potentiality and preferable application prospect, and the core technology break-through point of the reaction process is to be catalyzed
In the selection of agent.
Nanometer Au/TiO2Nano tube catalyst not only have good moisture resistant, sulfuration resistant performance, but also price relative to
The noble metals such as palladium, ruthenium are more cheap and resistance against physical chemistry and anti-optical corrosive effect it is strong, have in many fields and potentially urge
Change value.The valence state of active component, granularity, crystal form and carrier surface texture etc. be determine catalyst activity it is key because
Where plain, Au/TiO2The preparation method of nano tube catalyst is to influence the key technique of its performance.Carry out the catalyst preparation
The research of technology extends its application field and has great importance for improving the performance of catalyst.Au/TiO2Nanotube is urged
The preparation method type of agent is various, and be seen in report has solvated metal atom impregnation method, the condensation of low-pressure inert gas steam
Method, injection vapor condensing method, chemical vapour deposition, electrochemical control sedimentation etc..But all there is preparations for these methods
Process is complicated, increases production cost, and it is mostly the big chemical reagent of toxic to prepare raw material, this is largely limited
The large-scale production and application of catalyst, therefore it is necessary to the preparation method of catalyst further improved.
Invention content
In order to overcome the shortcomings of that current preparation method, biological in-situ of the present invention are restored the preparation method, carried with pure plant cacumen biotae
It is reducing agent to take liquid, is prepared for Au/TiO2Nano tube catalyst, and this catalyst is synthesized applied to catalytic hydrogenation of carbon dioxide
In the reaction of formic acid, good effect has been obtained.
The technical scheme is that a kind of preparation method of gold-titanium dioxide nano tube catalyst is provided, including it is following
Step：
(1) aqueous extract of cacumen biotae is mixed with the aqueous solution of gold chloride, is reacted 1-10 minutes, obtain aurosol；
(2) titania nanotube is added in the aurosol that step (1) obtains, stirs, filtering is consolidated what is be obtained by filtration
Soma is dry, and grinding is to get to gold-titania nanotube presoma；
(3) gold-titania nanotube presoma that step (2) obtains is forged at 300-400 DEG C, in oxidizing atmosphere
It burns to get to gold-titanium dioxide nano tube catalyst.
Preferably, the preparation method of the aqueous extract of the cacumen biotae is：Chinese Arborvitae Twig and Leaf is mixed with water, is stirred for 2
Hour or more, the filtrate that the mixed liquor after stirring obtains after filtering is the aqueous extract of cacumen biotae.
Preferably, it mixes, is stirred for 2-6 hours, after filtering with 100-120mL deionized waters per 1-1.2g Chinese Arborvitae Twig and Leafs
Obtained filtrate is the aqueous extract of cacumen biotae.
Preferably, by the aqueous solution of the aqueous extract of 50mL cacumen biotaes and the gold chloride of a concentration of 0.5-5g/L of 30-60mL
Mixing.It is highly preferred that a concentration of 1-2.5g/L of the aqueous solution of gold chloride.The chemical formula of gold chloride is HAuCl4, the application makes
It is three hydration gold chloride (H7AuCl4O3, molecular weight 394), so quality, the concentration of the gold chloride involved in the application are real
Border is calculated with the molecular weight of three hydration gold chlorides.
Preferably, the temperature of the aqueous solution of gold chloride is 60-90 DEG C, preferably 70-80 DEG C.
Preferably, the preparation method of the titania nanotube is：8-14mol/L hydroxides are added in titanium dioxide
Sodium solution, heating, then hydrochloric acid solution, side ultrasonic disperse is added in side, then filters, dry after obtained solid is washed, grinding
Up to titania nanotube.Nano titania prepared by commercial product or other methods can be used in titania nanotube
Pipe.
Preferably, in gold-titanium dioxide nano tube catalyst, the mass ratio of gold and titanium dioxide is 1-10:100.
Preferably, in step (3), calcination time 2-3h.The oxidizing atmosphere is air atmosphere.
The present invention also provides gold-titanium dioxide nano tube catalysts that above-mentioned preparation method obtains to add in carbon dioxide catalysis
Hydrogen synthesizes the application in the reaction of formic acid.
Preferably, in the reaction that catalytic hydrogenation of carbon dioxide synthesizes formic acid, when reaction originates, the titanium dioxide in reactor
Carbon partial pressure is 4-6MPa, hydrogen partial pressure 8-12MPa, and reaction temperature control is at 140-160 DEG C in reaction process.
The catalyst preparation scheme of the present invention is described in detail below：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (20-30 mesh).By 1-1.2g by grinding
The cacumen biotae of mill screening is added in 100-120mL deionized waters, with the speed of 300-500r/min in constant temperature blender with magnetic force
Rate stirs 3-4h.Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, so as to
For testing in next step.
(2) preparation of aurosol：
The gold chloride for weighing 0.04g, 0.06g, 0.08g and 0.10g respectively is dissolved in the deionized water of 30-50mL,
It is heated to 70-80 DEG C in constant temperature blender with magnetic force, is then quickly added into the Chinese arborvitae twig extract of 30-50mL, observes the change of color
Change (whole process about 2-3min), if there is apparent color change (faint yellow → light gray → darkviolet → brick-red), shows
The generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 8-10mol/L that 12-13g titanium dioxide is added to 100-120mL first, then
In oil bath pan 20-22h is kept the temperature at 110-120 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.1-0.12mol/L of 130-150mL,
And pass through ultrasonic disperse.Suction filtration processing, is washed with deionized to solution and is in neutrality (PH=7.0), be then put into vacuum drying
Case or air dry oven, the dry 5-6h at 70-80 DEG C.Finally solid particle is pulverized with agate mortar or ceramic mortar
End is to get titania nanotube.
(4)Au/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2-3g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2-3h is stirred with the rate of 300-500r/min on power blender.Then suspension is filtered, is put after being washed with deionized repeatedly
Enter vacuum drying chamber or air dry oven, the dry 5-6h at 70-80 DEG C.Finally use agate mortar or ceramic mortar by solid
Grain grind into powder, obtains Au/TiO2The presoma of nano tube catalyst.
(5)Au/TiO2The preparation of nano tube catalyst：
By Au/TiO2The presoma of nano tube catalyst calcining and activating 2-3h in air atmosphere at 300-400 DEG C, i.e.,
Obtain the Au/TiO of different gold loadings2Nano tube catalyst：Au (1.0wt%)/TiO2Nanotube, Au (1.5wt%)/TiO2It receives
Mitron, Au (2.0wt%)/TiO2Nanotube, Au (2.5wt%)/TiO2Nanotube.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (1-2.5wt%)/TiO2Nano tube catalyst (0.1-0.12g), solvent (15-18mL, ethyl alcohol), alkali (5-8mL, three
Ethamine) and stirring magneton be added sequentially in 50mL stainless steel high-pressure mini kettles, upper cover is closed.Checking system gas tightness.With
N2Displacement 3 times, the air being completely exhausted out in kettle.It is passed through CO2To 3-5MPa, hydrogen is passed through to 6-10MPa, is heated to 90-150 DEG C,
To thermal balance, start stirring and timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects II type gas of GC9790 after the acidification of 10-15% hydrochloric acid is added
Chromatograph (fid detector, FFAP capillary chromatographs).
The present invention uniformly mixes the aqueous solution of chloraurate of heating and Chinese arborvitae twig extract, first prepares aurosol, then
It is gold-nanoparticle-supported on titanium dioxide nano-tube support in aurosol, in situ also by Au (III) ion of carrier surface
Original is at golden simple substance.Compared with traditional titania support, modified titania nanotube enhance golden simple substance and carrier it
Between bond strength, there is higher activity, catalyst surface gold nano grain to be uniformly dispersed the load type gold catalyst of preparation, grain
Diameter is smaller.Compared with conventional chemical methods, biological in-situ reduction method preparation process is simple, it is easy to operate, clean and greenization, it is this
Preparation method has more application prospect and researching value.
The present invention is prepared for Au/TiO using gold chloride, titania nanotube and cacumen biotae as reaction raw materials2Nanotube is urged
Agent, on the one hand, have experimental raw it is simple, preparation process clean the characteristics of；On the other hand, the catalyst nanoparticles obtained
It is uniformly dispersed, and the activity and stability of catalytic hydrogenation of carbon dioxide Catalyzed by Formic Acid agent can be improved using this method.
The reaction of catalytic hydrogenation of carbon dioxide synthesis formic acid indicates as follows with chemical equation：
Compared with the existing technology, the beneficial effects of the present invention are：The Au/TiO of the present invention2Nano tube catalyst prepares work
Skill is simple, of low cost, nontoxic and pollution-free, has good both thermally and chemically stability and excellent catalysis characteristics, in electricity
There is good application prospect in the fields such as catalysis, hydrogenation catalyst, photocatalysis.
Description of the drawings
Fig. 1 is the Au/TiO of the embodiment of the present invention2The XRD diagram of nano tube catalyst.
Fig. 2 is the Au/TiO of the embodiment of the present invention2The reaction evaluating device flow chart of nano tube catalyst, in figure, 1- hydrogen
Gas cylinder, 2- carbon dioxide steel cylinders, 3- nitrogen cylinders, 4- check valves/check (non-return) valve, 5- stainless steel high-pressure minis reaction kettle, 6- pressures
Power table, 7- controllers.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Au (2.5wt%)/TiO in the present invention2Indicate that the mass fraction of Au in catalyst is 2.5%, it is convenient to write, it uses
Carrier TiO2Quality replaces the quality of catalyst, actually Au and TiO2Mass ratio is 2.5%.The gold chloride that the present invention uses
It is three hydration gold chlorides (relative molecular mass 394), 0.1g tri- is hydrated aurosol (0.05g containing gold) prepared by gold chloride and 2g is added
Titania nanotube, gold and TiO in the catalyst of preparation2Mass ratio is 2.5%.
Embodiment 1：
Au (2.5wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.10g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (2.5wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (2.5wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (2.5wt%)/TiO2The preparation of nano tube catalyst：
By Au (2.5wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (2.5wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (2.5wt%)/TiO2Nano tube catalyst (0.10g), solvent (15.0mL, ethyl alcohol), alkali (5.0mL, triethylamine) and
Stirring magneton is added sequentially in 50mL stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3
It is secondary, it is completely exhausted out air in kettle.It is passed through CO2To 5.0MPa, it is passed through hydrogen 10.0MPa, is heated to 90 DEG C, until thermal balance, starts
Stir simultaneously timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 2：
Au (2.5wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.10g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (2.5wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (2.5wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (2.5wt%)/TiO2The preparation of nano tube catalyst：
By Au (2.5wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (2.5wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by catalyst (0.10g, Au (2.5wt%)/TiO2Nanotube), solvent (15.0mL, ethyl alcohol), alkali (5.0mL, triethylamine) and
Stirring magneton is added sequentially in 50mL stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3
Air that is secondary, being completely exhausted out in kettle.It is passed through CO2To 5.0MPa, hydrogen is passed through to 10.0MPa, is heated to 120 DEG C, until thermal balance,
Start stirring and timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 3：
Au (2.5wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.10g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.5g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (2.5wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (2.5wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (2.5wt%)/TiO2The preparation of nano tube catalyst：
By Au (2.5wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (2.5wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (2.5wt%)/TiO2Nano tube catalyst (0.10g), solvent (15.0mL, ethyl alcohol), alkali (5.0mL, triethylamine) and
Stirring magneton is added sequentially in 50mL stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3
Air that is secondary, being completely exhausted out in kettle.It is passed through CO2To 3.0MPa, hydrogen is passed through to 6.0MPa, is heated to 150 DEG C, until thermal balance,
Start stirring and timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 4：
Au (2.5wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.10g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (2.5wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (2.5wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (2.5wt%)/TiO2The preparation of nano tube catalyst：
By Au (2.5wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (2.5wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (2.5wt%)/TiO2Nano tube catalyst (0.10g), solvent (15.0ml, ethyl alcohol), alkali (5.0ml, triethylamine) and
Stirring magneton is added sequentially in 50ml stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3
Air that is secondary, being completely exhausted out in kettle.It is passed through CO2To 4.0MPa, hydrogen is passed through to 8.0MPa, is heated to 150 DEG C, until thermal balance,
Start stirring and timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 5：
Au (1.0wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.04g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (1.0wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (1.0wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (1.0wt%)/TiO2The preparation of nano tube catalyst：
By Au (1.0wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (1.0wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (1.0wt%)/TiO2Nano tube catalyst (0.10g), solvent (15.0mL, ethyl alcohol), alkali (5.0mL, triethylamine) and
Stirring magneton is added sequentially in 50mL stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3
Air that is secondary, being completely exhausted out in kettle.It is passed through CO2To 5.0MPa, hydrogen is passed through to 10.0MPa, is heated to 150 DEG C, until thermal balance,
Start stirring and timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 6：
Au (1.5wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.06g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (1.5wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (1.5wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (1.5wt%)/TiO2The preparation of nano tube catalyst：
By Au (1.5wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (1.5wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (1.5wt%)/TiO2It nano tube catalyst (0.10g), solvent (15.0mL, ethyl alcohol), alkali (5.0mL triethylamines) and stirs
It mixes magneton to be added sequentially in 50mL stainless steel high-pressure mini kettles, upper cover is closed.Checking system gas tightness.Use N2Displacement 3 times,
The air being completely exhausted out in kettle.It is passed through CO2To 5.0MPa, hydrogen is passed through to 10.0MPa, is heated to 150 DEG C, until thermal balance, is opened
Begin to stir simultaneously timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 7：
Au (2.0wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1.0g by sieve of milling
The cacumen biotae divided is added in 100mL deionized waters, and 4.0h is stirred with the rate of 300r/min in constant temperature blender with magnetic force.It will
Mixture is filtered to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in real in next step
It tests.
(2) preparation of aurosol：
The gold chloride for weighing 0.08g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7.0), is then put into vacuum drying chamber or air dry oven, in
Dry 5.0h at 70 DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get nano titania
Pipe.
(4) Au (2.0wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (2.0wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (2.0wt%)/TiO2The preparation of nano tube catalyst：
By Au (2.0wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (2.0wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (2.0wt%)/TiO2Nano tube catalyst (0.10g), solvent (15.0mL, ethyl alcohol), alkali (5.0mL, triethylamine) and
Stirring magneton is added sequentially in 50mL stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3
Air that is secondary, being completely exhausted out in kettle.It is passed through CO2To 5.0MPa, hydrogen is passed through to 10.0MPa, is heated to 150 DEG C, until thermal balance,
Start stirring and timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
Embodiment 8：
Au (2.5wt%)/TiO2The preparation of nano tube catalyst, typical operating procedure are as follows：
(1) preparation of Chinese arborvitae twig extract：
Cacumen biotae is milled with blender or pulverizer first, then sieves (30 mesh).By 1g by screening of milling
Cacumen biotae be added in 100mL deionized waters, in constant temperature blender with magnetic force with the rate of 300r/min stir 4.0h.It will mix
Object filtering is closed to remove remaining biomass, and by filtrate (Chinese arborvitae twig extract) Cord blood, for use in testing in next step.
(2) preparation of aurosol：
The gold chloride for weighing 0.10g is dissolved in the deionized water of 30mL, and 70 DEG C are heated in constant temperature blender with magnetic force,
It is then quickly added into the Chinese arborvitae twig extract of 30mL, the variation (whole process about 2-3min) of color is observed, if there is apparent color
Change (faint yellow → light gray → darkviolet → brick-red), then shows the generation of aurosol.
(3) preparation of titania nanotube：
In the sodium hydroxide solution for weighing the 10.0mol/L that 12.50g titanium dioxide is added to 100mL first, then in oil
In bath 20.0h is kept the temperature at 110 DEG C.It is subsequently added into the hydrochloric acid solution of the 0.10mol/L of 150mL, and passes through ultrasonic disperse.It takes out
Filter is handled, and is washed with deionized to solution and is in neutrality (PH=7), vacuum drying chamber or air dry oven is then put into, in 70
Dry 5.0h at DEG C.Finally use agate mortar or ceramic mortar by solid particle grind into powder to get titania nanotube.
(4) Au (2.5wt%)/TiO2The preparation of the presoma of nano tube catalyst：
The immobilized aurosol of titania nanotube prepared by 2.0g is added after the complete colloidal sol 30min of gold chloride, in constant temperature magnetic
2.0h is stirred with the rate of 300r/min on power blender.Then suspension is filtered, is put into after being washed with deionized repeatedly true
Empty drying box or air dry oven, the dry 5.0h at 70 DEG C.Finally solid particle is ground with agate mortar or ceramic mortar
At powder, Au (2.5wt%)/TiO is obtained2The presoma of nano tube catalyst.
(5) Au (2.5wt%)/TiO2The preparation of nano tube catalyst：
By Au (2.5wt%)/TiO2The presoma of nano tube catalyst calcining and activating in air atmosphere at 350 DEG C
2.0h is to get required Au (2.5wt%)/TiO2Nano tube catalyst.
The reaction evaluating of catalytic hydrogenation of carbon dioxide synthesis formic acid can carry out in 50mL stainless steel high-pressure mini kettles.Reaction
It is preceding by Au (2.5wt%)/TiO2Catalyst (0.10g), solvent (15.0mL, ethyl alcohol), alkali (5.0mL, triethylamine) and stirring magnetic
Son is added sequentially in 50mL stainless steel high-pressure mini kettles, and upper cover is closed.Checking system gas tightness.Use N2Displacement 3 times, completely
The air in kettle is discharged.It is passed through CO2To 5.0MPa, hydrogen is passed through to 10.0MPa, is heated to 150 DEG C, until thermal balance, starts to stir
Mix simultaneously timing.
After reaction, autoclave is quickly cooled to room temperature in cold water.Kettle is opened after slow release.By solid-phase catalyst
It is recycled after filter centrifugation processing, obtains liquid product.Liquid product injects gas chromatographic analysis after the acidification of 10.0% hydrochloric acid is added
(fid detector, FFAP capillary chromatographs).
The reaction condition and result of catalyst performance evaluation are as shown in table 1 below：
1 catalyst performance evaluation table of table
Note：Catalyst usage amount (0.10g), solvent and usage amount (ethyl alcohol, 15mL), alkali and usage amount (triethylamine,
5mL), reaction kettle total volume (50mL), reaction total duration (2h), speed of agitator (500rpm), TON=generate the molal quantity of formic acid
(mmol) molal quantity (mmol) of/catalyst active center's component, TOF=TON/Time (h).
Claims (10)
1. a kind of preparation method of gold-titanium dioxide nano tube catalyst, which is characterized in that include the following steps：
（1）The aqueous extract of cacumen biotae is mixed with the aqueous solution of gold chloride, is reacted 1-10 minutes, aurosol is obtained；
（2）In step（1）Titania nanotube is added in the aurosol of acquisition, stirs, the solid being obtained by filtration is done in filtering
Dry, grinding is to get to gold-titania nanotube presoma；
（3）By step（2）Obtained gold-titania nanotube presoma is calcined at 300-400 DEG C, in oxidizing atmosphere, i.e.,
Obtain gold-titanium dioxide nano tube catalyst.
2. preparation method as described in claim 1, which is characterized in that the preparation method of the aqueous extract of the cacumen biotae is：
Chinese Arborvitae Twig and Leaf is mixed with water, is stirred for 2 hours or more, the filtrate that the mixed liquor after stirring obtains after filtering is arbor-vitae
The aqueous extract of leaf.
3. preparation method as claimed in claim 2, which is characterized in that gone per 1-1.2g Chinese Arborvitae Twig and Leafs and 100-120mL from
Sub- water mixing, is stirred for 2-6 hours, the filtrate obtained after filtering is the aqueous extract of cacumen biotae.
4. preparation method as described in claim 1, which is characterized in that the temperature of the aqueous solution of gold chloride is 60-90 DEG C.
5. preparation method as described in claim 1, which is characterized in that the aqueous extract of 50mL cacumen biotaes and 30-60mL is dense
Degree is the aqueous solution mixing of the gold chloride of 0.5-5g/L.
6. preparation method as described in claim 1, which is characterized in that the preparation method of the titania nanotube is：
8-14mol/L sodium hydroxide solutions are added in titanium dioxide, heating, then hydrochloric acid solution, side ultrasonic disperse is added in side, then takes out
Filter, the obtained washed rear drying of solid are ground up to titania nanotube.
7. preparation method as described in claim 1, which is characterized in that in gold-titanium dioxide nano tube catalyst, gold and two
The mass ratio of titanium oxide is 1-10: 100.
8. preparation method as described in claim 1, which is characterized in that step（3）In, calcination time 2-3h；The oxidation
Atmosphere is air atmosphere.
9. gold-titanium dioxide nano tube catalyst that claim 1-8 any one of them preparation methods obtain is in carbon dioxide
Catalytic hydrogenation synthesizes the application in the reaction of formic acid.
10. application as claimed in claim 9, which is characterized in that in the reaction that catalytic hydrogenation of carbon dioxide synthesizes formic acid, instead
When should originate, carbon dioxide in reactor partial pressure is 4-6MPa, hydrogen partial pressure 8-12MPa, reaction temperature in reaction process
Control is at 140-160 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810192890.9A CN108435169A (en) | 2018-03-09 | 2018-03-09 | A kind of preparation method and application of gold-titanium dioxide nano tube catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810192890.9A CN108435169A (en) | 2018-03-09 | 2018-03-09 | A kind of preparation method and application of gold-titanium dioxide nano tube catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108435169A true CN108435169A (en) | 2018-08-24 |
Family
ID=63193896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810192890.9A Pending CN108435169A (en) | 2018-03-09 | 2018-03-09 | A kind of preparation method and application of gold-titanium dioxide nano tube catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108435169A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264008A (en) * | 2020-11-23 | 2021-01-26 | 浙江师范大学 | Pd/TiO2- {100} composite catalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961651A (en) * | 2010-11-01 | 2011-02-02 | 浙江大学 | Method for preparing noble metal modified one-dimensional titanium dioxide Hg-removing catalyst |
| CN102120184A (en) * | 2011-01-25 | 2011-07-13 | 中国科学院山西煤炭化学研究所 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
| WO2012085174A1 (en) * | 2010-12-22 | 2012-06-28 | Solvay Sa | Process for the electrochemical synthesis of hydrogen peroxide and use of a catalyst therefore |
| CN102936037A (en) * | 2012-11-15 | 2013-02-20 | 天津工业大学 | Process for preparing stable high-dispersion Au/TiO2 catalyst |
| CN106378149A (en) * | 2016-10-11 | 2017-02-08 | 湖北大学 | Preparation method and application of titanium dioxide nano tube loaded dual-metal ruthenium and nickel nano catalyst |
-
2018
- 2018-03-09 CN CN201810192890.9A patent/CN108435169A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961651A (en) * | 2010-11-01 | 2011-02-02 | 浙江大学 | Method for preparing noble metal modified one-dimensional titanium dioxide Hg-removing catalyst |
| WO2012085174A1 (en) * | 2010-12-22 | 2012-06-28 | Solvay Sa | Process for the electrochemical synthesis of hydrogen peroxide and use of a catalyst therefore |
| CN102120184A (en) * | 2011-01-25 | 2011-07-13 | 中国科学院山西煤炭化学研究所 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
| CN102936037A (en) * | 2012-11-15 | 2013-02-20 | 天津工业大学 | Process for preparing stable high-dispersion Au/TiO2 catalyst |
| CN106378149A (en) * | 2016-10-11 | 2017-02-08 | 湖北大学 | Preparation method and application of titanium dioxide nano tube loaded dual-metal ruthenium and nickel nano catalyst |
Non-Patent Citations (3)
| Title |
|---|
| PRETI DEBORA 等: "Carbon Dioxide Hydrogenation to Formic Acid by Using a Heterogeneous Gold Catalyst", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| 潘润芝: "铜改性纳米TiO2催化剂光催化还原CO2性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 黄晓丹 等: "植物还原法制备负载型金纳米催化剂催化乙醇选择氧化反应", 《化学研究与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264008A (en) * | 2020-11-23 | 2021-01-26 | 浙江师范大学 | Pd/TiO2- {100} composite catalyst, preparation method and application thereof |
| CN112264008B (en) * | 2020-11-23 | 2023-08-18 | 浙江师范大学 | Pd/TiO 2 - {100} composite catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103028352B (en) | Preparation method for synthesizing MoS2/Fe3O4 nano composite material | |
| CN105289693B (en) | A kind of Zn0.5Co0.5Fe2O4/g‑C3N4The preparation method of composite photo-catalyst | |
| CN105772104B (en) | A kind of composite photo-catalyst and preparation method thereof based on nano-titanium dioxide and cyclization polyacrylonitrile | |
| CN108554439A (en) | A kind of photo-reduction CO2 ultra-thin Ti bases LDHs composite photo-catalysts and preparation method thereof | |
| CN109967072A (en) | A kind of lignin-base nano flower porous carbon support load Ru base catalyst and preparation method thereof and the application in lignin depolymerization | |
| CN109821528A (en) | A kind of nano heterogeneous material of Bi/ZnO and the preparation method and application thereof | |
| CN110201680B (en) | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde/ketone, preparation method and catalysis method | |
| CN108525694A (en) | A kind of preparation method of composite photo-catalyst | |
| CN104162432A (en) | A homo-dispersed efficient biomass reforming catalyst and a preparing method thereof | |
| CN107043124B (en) | A kind of cadmium sulfide nano is colored, prepares and its applies | |
| Guo et al. | Zn-doped Bi2O2CO3: Synthesis, characterization and photocatalytic properties | |
| CN106492772A (en) | A kind of titanium dioxide nanoplate and the preparation method of diatomite composite photocatalytic agent | |
| CN103433044A (en) | Preparation method of cobalt-nickel double metal hydroxide nano composite | |
| CN111992255B (en) | Flaky g-C for removing bisphenol A in water3N4ZIF-8/AgBr composite material and preparation method thereof | |
| Yu et al. | Porous wood decorated with gold nanoparticles as flow-through membrane reactor for catalytic hydrogenation of methylene blue and 4-nitrophenol | |
| CN106881085A (en) | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation | |
| Chen et al. | Fe/Zr-MOFs constructed by a sunlight-responsive ligand for efficient photocatalytic nitrogen fixation under ambient condition | |
| CN110302799A (en) | Electrochemically reducing carbon dioxide is the catalyst and preparation method thereof of carbon monoxide | |
| Zhang et al. | Construction of ZnIn2S4/MOF-525 heterojunction system to enhance photocatalytic degradation of tetracycline | |
| CN110420662A (en) | It is a kind of can efficient degradation stalk cellulose at low temperature composite catalyzing material and the preparation method and application thereof | |
| CN105148918B (en) | Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst | |
| CN108435169A (en) | A kind of preparation method and application of gold-titanium dioxide nano tube catalyst | |
| CN108940325A (en) | A kind of binary composite semiconductor light-catalyst materials A g2CrO4/ BiOI and its preparation and application | |
| CN109999791B (en) | Preparation method and application of attapulgite composite material with plasma resonance effect | |
| CN103816899B (en) | A kind of preparation method of Glucose Liquid phase oxidation Au catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180824 |