CN108855070A - A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application - Google Patents
A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108855070A CN108855070A CN201810636396.7A CN201810636396A CN108855070A CN 108855070 A CN108855070 A CN 108855070A CN 201810636396 A CN201810636396 A CN 201810636396A CN 108855070 A CN108855070 A CN 108855070A
- Authority
- CN
- China
- Prior art keywords
- ceo
- composite catalyst
- nano composite
- load
- preparation
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002114 nanocomposite Substances 0.000 claims abstract description 32
- 235000019441 ethanol Nutrition 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 87
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 12
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical group Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 9
- 150000000703 Cerium Chemical class 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 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 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- 150000002828 nitro derivatives Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000006396 nitration reaction Methods 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 24
- 230000009467 reduction Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000010531 catalytic reduction reaction Methods 0.000 description 9
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 229910015371 AuCu Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- -1 cerium cation Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Ti/CeO of Pd load2Nano composite catalyst, the CeO adulterated with Ti2Nanometer sheet is carrier, on the carrier carrying transition metal Pd element, wherein load capacity≤0.19wt% of Pd element.The invention also discloses the Ti/CeO of Pd load2The preparation method of nano composite catalyst, including：Using ethyl alcohol as solvent, using organic acid and inorganic salts as raw material, rare earth oxide is prepared by precipitating reagent of water, then with ethylene glycol etc. for reducing agent, the CeO that Pd nanometer particle load is adulterated in Ti2On nanometer sheet carrier, appearance of nano material obtained is uniform, and each doped chemical is uniformly distributed, good to the catalysis reduction effect of p-nitrophenol, and reusing is high, has potential application in terms of sewage treatment.
Description
Technical field
The invention belongs to nano material preparation and catalytic fields, and in particular to a kind of Ti/CeO of Pd load2It is nano combined
Type catalyst and its preparation method and application.
Background technique
With the continuous development of China's industry, nitro compound gets worse the pollution of water body, attracts extensive attention.
P-nitrophenol (4-NP) and fragrant nitro compound have high toxicity and are difficult to degrade.And the reduzate para-aminophenol of 4-NP
(4-AP) has the advantages such as hypotoxicity, degradable, is the synthetic intermediate of many drugs.It at present will be right by catalytic reduction method
Nitrophenol is reduced to para-aminophenol and is widely used.
The key that p-nitrophenol is reduced to para-aminophenol is to the active component of catalyst and the selection of carrier.It is expensive
Metallic catalyst (Au, Ag, Pd, Pt, PdCu, PtNi and AuCu etc.) during compounds p-nitrophenol reduction reaction have compared with
Good catalytic performance, however active force is weaker between noble metal nano particles and catalyst carrier, during the reaction, noble metal is received
Rice corpuscles is easy to fall off from catalyst carrier.To solve this problem, a kind of way relatively conventional at present is by noble metal
It is embedded into mesoporous material hole wall, if the patent application of Publication No. CN107973390A is to be specifically blended the synthesis of crystallite lotion
Method, PtRu alloy nano particle is successfully imported into the micropore canals of multistage porous molecular sieve EMT-FAU/SBA-15, with
Prevent it from falling off in catalytic reduction process.
There are many kinds of the carriers of supported precious metal catalyst, as the patent application of Publication No. CN107349930A discloses
A kind of platinum attapulgite clay nano supported catalyst that nitrophenol is reduced to amino-phenol, the catalyst carrier are bumps
Stick soil, using the unique chain structure adsorption activity component platinum of attapulgite crystal, gold, preferably plays catalytic effect.But
The load capacity of the noble metal of the catalyst is 1.8~4.5wt%, relatively large, and industrial cost is high.
Titanium dioxide TiO2As common one of catalyst carrier, it has been widely used, and TiO2Itself there are band gap compared with
The disadvantages of wide and electron hole pair is easily compound, makes TiO2Catalytic activity is lower.
As important rare earth oxide, CeO2With high Oxygen storage capacity and either high redox, it is widely used in CO
Oxidation, three-way catalyst, photochemical catalyst etc..But the cerium cation and oxygen vacancies of simple cerium oxide are limited, catalysis is lived
Property is lower.
In terms of the catalysis reduction of 4-NP, if it is possible to develop the Performances of Novel Nano-Porous that noble-metal-supported amount is lower, stability is good
Nano composite material will be with particularly important meaning to effective improvement of 4-NP.
Summary of the invention
The present invention provides a kind of Ti/CeO of Pd load2Nano composite catalyst has high catalytic reduction and excellent
Different stability, and it is reusable, the present invention also provides the Ti/CeO of Pd load2The system of nano composite catalyst
Preparation Method, it is easy to operate, easy, it is suitble to industrialized production.
A kind of Ti/CeO of Pd load2Nano composite catalyst, the CeO adulterated with Ti2Nanometer sheet is carrier, described
Supported on carriers transition metal Pd element, wherein load capacity≤0.19wt% of Pd element；The CeO of the Ti doping2Nanometer sheet
With CeO2Nanometer sheet is parent, and Ti element is uniformly distributed in CeO2In lattice.
The present invention also provides the Ti/CeO of Pd load2The preparation method of nano composite catalyst, easy to operate,
It is easy, including：
(1) using alcohol as solvent, using water as precipitating reagent, complex reaction, reaction are carried out by raw material of cerium salt, titanium salt and organic acid
After, by being centrifuged, drying and obtaining rare earth oxide presoma；It is sintered to 2~5h in 400~650 DEG C and obtains Ti doping
CeO2Nanometer sheet carrier；
Wherein, the volume ratio of alcohol and water is 5~10:1；
(2) CeO of the Ti doping obtained step (1)2The alcohol that polyvinylpyrrolidone (PVP) is added in nanometer sheet carrier is molten
In liquid, after being uniformly dispersed, at a temperature of 70~120 DEG C, palladium salt aqueous solution is added, constant temperature stirs 2~4h, is centrifuged drying
Afterwards, the Ti/CeO of Pd load is obtained2Nano composite catalyst；
Wherein, the concentration of PVP is 0.5~1mg/mL in polyvinylpyrrolidone alcoholic solution；The aqueous solution of tetrachloro-palladium potassium chlorate
Concentration be 0.01~0.05M.
In step (1), the cerium salt is cerous nitrate and its hydrate or at least one of cerous acetate and its hydrate；
The titanium salt is at least one of butyl titanate, titanium tetrachloride or tetraisopropyl titanate；The organic acid be adipic acid,
At least one of M-phthalic acid, citric acid, phthalic acid, trimesic acid or Pyromellitic Acid.
In step (1), the molar ratio of the cerium salt and titanium salt is 5~9:1；The molar ratio of the cerium salt and organic acid
It is 1:1~1.2.
In step (1), the complex reaction temperature is 50~120 DEG C, and the reaction time is 1~5h.
In step (1), the alcohol is at least one of ethyl alcohol, propyl alcohol or ethylene glycol；In step (2), the alcoholic solution is
At least one of ethylene glycol, glycerine or isopropanol.
In step (2), the palladium salt is one or more of tetrachloro-palladium potassium chlorate, sodium tetrachloropallate or palladium chloride.
In step (2), the CeO of the palladium salt and Ti doping2The mass ratio of nanometer sheet carrier is 1:10~20.
The Ti/CeO of Pd load prepared by the present invention2Nano composite catalyst is uniform in nanometer sheet structure and size, respectively mixes
Miscellaneous element is in CeO2In be uniformly distributed, catalysis reduction effect it is good, property stablize, be heated to 1100 DEG C, 30min or more catalyst knot
Structure does not have any variation.
The present invention also provides the Ti/CeO of Pd load2Nano composite catalyst restores p-nitrophenol in catalysis
In application.
The Ti/CeO of Pd load prepared by the present invention2Nano composite catalyst, Ti are uniformly distributed in cerium oxide lattice,
Assign CeO2The more oxygen vacancies of nanometer sheet fertile material are easy to the absorption of nitro, while Pd is uniformly distributed in the CeO of Ti doping2
In the lattice of nanometer sheet carrier and on surface, active site is significantly increased, compound is urged so that prepared by the present invention
To environmental toxicity, greatly fragrant nitro compound has fabulous catalytic reduction efficiency to agent, especially restores effect to the catalysis of 4-NP
Fruit is good, and experimental result is shown, the catalytic reduction efficiency that 4-NP is reduced to para-aminophenol nearly 100%, in terms of sewage treatment
It has potential application.
In addition, the Ti/CeO of Pd load provided by the invention2Nano composite catalyst is reusable, can greatly reduce
Industrial cost.
The method of recycling is：It is in situ that p-nitrophenol and boron is added after solution colour is decorporated to the end of being catalyzed reaction
Sodium hydride, catalysis reaction continue, and experimental result is shown：Catalytic efficiency still keeps 96% or so after 5 catalysis reaction.
Compared with prior art, the invention has the advantages that：
(1) preparation method provided by the invention, simple production process, raw material is simple and easy to get, easy to industrialized production.
(2) Ti/CeO of Pd load provided by the invention2Nano composite catalyst, property are stablized, active component doping,
Load Balanced, internal synergistic effect makes catalyst have greater catalytic performance, for the reduction of 4-NP, catalytic reduction efficiency
Nearly 100%.
(3) Ti/CeO of Pd load provided by the invention2Nano composite catalyst is reusable, is recycled 5 times
Afterwards, catalytic efficiency still keeps 96% or so.
(4) Ti/CeO of Pd load provided by the invention2The load capacity of precious metals pd in nano composite catalyst≤
0.19wt% greatly reduces catalyst cost.
Detailed description of the invention
Fig. 1 is Ti/CeO obtained in the embodiment of the present invention 12The XRD diagram of@Pd.
Fig. 2 is Ti/CeO obtained in the embodiment of the present invention 12The EDS of@Pd schemes.
Fig. 3 is Ti/CeO made from the embodiment of the present invention 12The ultraviolet-visible spectrogram of@Pd catalysis reduction p-nitrophenol.
Fig. 4 is Ti/CeO obtained in the embodiment of the present invention 12The catalytic efficiency of@Pd with cycle-index variation diagram.
Fig. 5 is CeO made from comparative example 1 of the present invention2The ultraviolet-visible spectrogram of@Pd catalysis reduction p-nitrophenol.
Fig. 6 is the cerium oxide nano materials Ti/CeO of the doping of Ti made from comparative example 2 of the present invention2Catalysis reduction p-nitrophenyl
The ultraviolet-visible spectrogram of phenol.
Specific embodiment
For a further understanding of the present invention, below with reference to embodiment to a kind of Ti/CeO of Pd load provided by the invention2
Nano composite catalyst and its preparation method and application is specifically described, and however, the present invention is not limited to these examples, should
The non-intrinsically safe modifications and adaptations that field technical staff makes under core guiding theory of the present invention, still fall within protection of the invention
Range.
Embodiment 1
1) Ti/CeO of Pd load2The preparation of nano composite catalyst：
Six nitric hydrate cerium 0.3907g are dissolved in the in the mixed solvent (ethyl alcohol of 20mL ethyl alcohol and water：Water=7:1) in, add
After 20min is stirred at room temperature, ethanol solution (the 0.254g Pyromellitic Acid of Pyromellitic Acid is added in the butyl titanate for entering 34uL
It is dissolved in 20mL ethyl alcohol), above-mentioned mixed liquor is placed in 80 DEG C of oil baths and heats 1h, adds water quenching reaction, centrifugal drying, it is white heavy to obtain
Starch, yield 78%.
Obtained white depositions are placed in Muffle furnace, 500 DEG C of sintering 3h obtain Ti/CeO2Oxide.60mg is gathered
Vinylpyrrolidone is dissolved in 80mL glycerine, and 100mgTi/CeO is added2Oxide is placed in 120 DEG C of oil baths, and tetrachloro is added
The aqueous solution (8mg tetrachloro-palladium potassium chlorate is dissolved in 1.2mL water) of palladium acid potassium, constant temperature stir 2h, and be centrifuged at a high speed drying.It is negative to obtain Pd
The Ti/CeO of load2Nano composite catalyst (yield 70%), is denoted as Ti/CeO2@Pd nano material, wherein Pd content passes through electricity
Sense coupled plasma-mass spectrography (ICP-MS) measures, and see Table 1 for details.
The Ti/CeO2The XRD diagram of@Pd nano material is as shown in Figure 1, Fig. 1 only shows CeO2Signal peak, furtherly
Bright Pd, Ti can uniformly mix CeO2In lattice, soluble solids is formed.
The Ti/CeO2The EDS of@Pd nano material schemes as shown in Fig. 2, Pd, Ti uniformly divide in nanometer sheet as shown in Figure 2
It dissipates.
2)Ti/CeO2The catalysis reduction p-nitrophenol test of@Pd nano material：
1mL NaBH is added in 4-NP (4mM) aqueous solution of 0.1mL4(0.02M) aqueous solution, is put into quartz colorimetric utensil,
It is diluted to 3mL, 0.1mL Ti/CeO is added2@Pd (0.2mg/mL), is surveyed every 3min with ultraviolet-uisible spectrophotometer
Amount, the Ti/CeO2The ultraviolet-visible spectrogram of the catalysis reduction p-nitrophenol of@Pd nano material is as shown in figure 3, by Fig. 3
It is found that signal peak when 25min at 400nm disappears, while the peak at 317nm reaches maximum value, illustrates the complete conversion of 4-NP,
Its catalytic reduction efficiency nearly 100%.
3) catalyst Ti/CeO2The recycling performance of@Pd is tested：
It is in situ to be added p-nitrophenol and sodium borohydride after solution colour is decorporated to the end of being catalyzed reaction, catalysis reaction after
It is continuous to carry out, the Ti/CeO2The catalytic efficiency of@Pd catalyst with the variation diagram of cycle-index as shown in figure 4, as shown in Figure 4, to
5 catalysis post catalyst reaction Ti/CeO2The catalytic efficiency of@Pd still keeps 96% or so.
Embodiment 2
1) Ti/CeO of Pd load2The preparation of nano composite catalyst：
Cerous acetate 0.3096g is dissolved in the in the mixed solvent (ethyl alcohol of 20mL ethyl alcohol and water：Water=5:1) in, 34uL is added
Tetraisopropyl titanate, after 20min is stirred at room temperature, the ethanol solution of phthalic acid is added, and (0.1661g phthalic acid is dissolved in
20mL ethyl alcohol), above-mentioned mixed liquor is placed in 50 DEG C of oil baths and heats 1h, adds water quenching reaction, centrifugal drying obtains white precipitate
Object, yield 75%.
Obtained white depositions are placed in Muffle furnace, 400 DEG C of sintering 5h obtain Ti/CeO2Oxide.40mg is gathered
Vinylpyrrolidone is dissolved in 80mL isopropanol, and 100mgTi/CeO is added2Oxide is placed in 70 DEG C of oil baths, and tetrachloro palladium is added
The aqueous solution (10mg sodium tetrachloropallate potassium is dissolved in 1.2mL water) of sour sodium, constant temperature stir 4h, and be centrifuged at a high speed drying.Obtain Ti/
CeO2@Pd nano material (yield 73%), wherein Pd content is measured by inductively coupled plasma mass spectrometry method (ICP-MS),
See Table 1 for details；It is tested through XRD and EDS, the Ti/CeO2Pd, Ti can uniformly mix CeO in@Pd nano material2In lattice and table
Face.
2)Ti/CeO2The catalysis reduction p-nitrophenol test of@Pd nano material：
1mL NaBH is added in 4-NP (4mM) aqueous solution of 0.1mL4(0.02M) aqueous solution, is put into quartz colorimetric utensil,
It is diluted to 3mL, 0.1mL Ti/CeO is added2@Pd (0.2mg/mL), is surveyed every 3min with ultraviolet-uisible spectrophotometer
Amount, by Ti/CeO2The ultraviolet-visible spectrogram of the catalysis reduction p-nitrophenol of@Pd nano material is it is found that its catalysis reduction effect
Rate is about 99%.
3) catalyst Ti/CeO2The recycling performance of@Pd is tested：
It is in situ to be added p-nitrophenol and sodium borohydride after solution colour is decorporated to the end of being catalyzed reaction, catalysis reaction after
It is continuous to carry out, to 5 catalysis post catalyst reaction Ti/CeO2The catalytic efficiency of@Pd still keeps 93% or so.
Embodiment 3
1) Ti/CeO of Pd load2The preparation of nano composite catalyst：
Cerous acetate hydrate 0.3096g is dissolved in the in the mixed solvent (ethylene glycol of 20mL ethylene glycol and water：Water=10:1)
In, the titanium tetrachloride of 5uLg is added, after 20min is stirred at room temperature, the ethylene glycol solution of citric acid is added, and (0.192g citric acid is dissolved in
20mL ethylene glycol), above-mentioned mixed liquor is placed in 50 DEG C of oil baths and heats 1h, adds water quenching reaction, centrifugal drying obtains white precipitate
Object, yield 82%.
Obtained white depositions are placed in Muffle furnace, 400 DEG C of sintering 5h obtain Ti/CeO2Oxide.80mg is gathered
Vinylpyrrolidone is dissolved in 80mL ethylene glycol, and 100mgTi/CeO is added2Oxide is placed in 100 DEG C of oil baths, and chlorination is added
The aqueous solution (10.6mg palladium chloride tetrachloro-palladium potassium chlorate is dissolved in 1.2mL water) of palladium, constant temperature stir 4h, and be centrifuged at a high speed drying.?
Ti/CeO2@Pd nano material (yield 77%), wherein Pd content is surveyed by inductively coupled plasma mass spectrometry method (ICP-MS)
, see Table 1 for details；It is tested through XRD and EDS, the Ti/CeO2Pd, Ti can uniformly mix CeO in@Pd nano material2In lattice and
Surface.
2)Ti/CeO2The catalysis reduction p-nitrophenol test of@Pd nano material：
1mL NaBH is added in 4-NP (4mM) aqueous solution of 0.1mL4(0.02M) aqueous solution, is put into quartz colorimetric utensil,
It is diluted to 3mL, 0.1mL Ti/CeO is added2@Pd (0.2mg/mL), is surveyed every 3min with ultraviolet-uisible spectrophotometer
Amount, by Ti/CeO2The ultraviolet-visible spectrogram of the catalysis reduction p-nitrophenol of@Pd nano material is it is found that its catalysis reduction effect
Rate is about 97%.
3) catalyst Ti/CeO2The recycling performance of@Pd is tested：
It is in situ to be added p-nitrophenol and sodium borohydride after solution colour is decorporated to the end of being catalyzed reaction, catalysis reaction after
It is continuous to carry out, to 5 catalysis post catalyst reaction Ti/CeO2The catalytic efficiency of@Pd still keeps 95% or so.
Comparative example 1
1) CeO of Pd load2The preparation of nano composite catalyst：
Six nitric hydrate cerium 0.3907g are dissolved in 20mL ethyl alcohol, after 20min is stirred at room temperature, trimesic acid is added
Ethanol solution (0.254g Pyromellitic Acid is dissolved in 20mL ethyl alcohol), above-mentioned mixed liquor is placed in 80 DEG C of oil baths and heats 1h, centrifugation
It is dry, obtain white depositions.Yield 83%.
Obtained white depositions are placed in Muffle furnace, 500 DEG C of sintering 3h obtain CeO2Oxide.By the poly- second of 60mg
Alkene pyrrolidone is dissolved in 80mL ethylene glycol, and 100mg rare earth oxide is added, is placed in 120 DEG C of oil baths, and tetrachloro-palladium potassium chlorate is added
Aqueous solution (8mg tetrachloro-palladium potassium chlorate is dissolved in 1.2mL water), constant temperature stir 2h, be centrifuged at a high speed drying, obtain Pd load
CeO2Nano material is denoted as CeO2@Pd nano material, yield 73%.
2)CeO2The catalysis reduction p-nitrophenol test of@Pd nano material：
1mL NaBH is added in 4-NP (4mM) aqueous solution of 0.1mL4(0.02M) aqueous solution, is put into quartz colorimetric utensil,
It is diluted to 3mL, 0.1mL CeO is added2@Pd (0.2mg/mL), is measured every 3min with ultraviolet-uisible spectrophotometer, by
CeO2The ultraviolet-visible spectrogram of the catalysis reduction p-nitrophenol of@Pd nano material is as shown in figure 5, as shown in Figure 5,40min
Catalytic efficiency is basically unchanged afterwards, and catalytic reduction efficiency is about 76%.
Comparative example 2
1) the cerium oxide nano materials Ti/CeO of Ti doping2Preparation：
Six nitric hydrate cerium 0.3907g are dissolved in 20mL ethyl alcohol, the butyl titanate of 34uL is added, is stirred at room temperature
After 20min, the ethanol solution (0.254g Pyromellitic Acid is dissolved in 20mL ethyl alcohol) of M-phthalic acid is added, above-mentioned mixed liquor is set
1h, centrifugal drying are heated in 80 DEG C of oil baths, obtained white depositions are the cerium oxide nano materials Ti/CeO of Ti doping2,
Yield 80%.
2)Ti/CeO2Nano material catalysis reduction p-nitrophenol test：
1mL NaBH is added in 4-NP (4mM) aqueous solution of 0.1mL4(0.02M) aqueous solution, is put into quartz colorimetric utensil,
It is diluted to 3mL, 0.1mL Ti/CeO is added2(0.2mg/mL), is measured every 3min with ultraviolet-uisible spectrophotometer, by
Ti/CeO2The ultraviolet-visible spectrogram of the catalysis reduction p-nitrophenol of nano material is as shown in fig. 6, it will be appreciated from fig. 6 that 10min
Catalytic efficiency is basically unchanged afterwards, and catalytic reduction efficiency is about 10%.
Table 1
Claims (10)
1. a kind of Ti/CeO of Pd load2Nano composite catalyst, which is characterized in that the CeO adulterated with Ti2Nanometer sheet is to carry
Body, on the carrier carrying transition metal Pd element, wherein load capacity≤0.19wt% of Pd element.
2. the Ti/CeO of Pd load according to claim 12Nano composite catalyst, which is characterized in that the Ti doping
CeO2Nanometer sheet is with CeO2Nanometer sheet is parent, and Ti element is uniformly distributed in CeO2In lattice.
3. the Ti/CeO of Pd load according to claim 1 or 22The preparation method of nano composite catalyst, including：
(1) using alcohol as solvent, using water as precipitating reagent, complex reaction is carried out by raw material of cerium salt, titanium salt and organic acid, reaction terminates
Afterwards, by being centrifuged, drying and obtaining rare earth oxide presoma；It is sintered to 2~5h in 400~650 DEG C and obtains Ti doping
CeO2Nanometer sheet carrier；
Wherein, the volume ratio of alcohol and water is 5~10:1；
(2) CeO of the Ti doping obtained step (1)2Nanometer sheet carrier is added in the alcoholic solution of polyvinylpyrrolidone, dispersion
After uniformly, at a temperature of 70~120 DEG C, palladium salt aqueous solution is added, constant temperature stirs 2~4h, and after being centrifuged drying, it is negative to obtain Pd
The Ti/CeO of load2Nano composite catalyst.
4. the Ti/CeO of Pd load according to claim 32The preparation method of nano composite catalyst, which is characterized in that
The cerium salt is cerous nitrate and its hydrate or at least one of cerous acetate and its hydrate；The titanium salt is metatitanic acid four
At least one of butyl ester, titanium tetrachloride or tetraisopropyl titanate；The organic acid be adipic acid, M-phthalic acid, citric acid,
At least one of phthalic acid, trimesic acid or Pyromellitic Acid；The palladium salt is tetrachloro-palladium potassium chlorate, tetrachloro-palladium acid
One or more of sodium or palladium chloride.
5. the Ti/CeO of Pd load according to claim 3 or 42The preparation method of nano composite catalyst, feature exist
In in step (1), the molar ratio of the cerium salt and titanium salt is 5~9:1；The molar ratio of the cerium salt and organic acid is 1:1
~1.2.
6. the Ti/CeO of Pd load according to claim 32The preparation method of nano composite catalyst, which is characterized in that
In step (1), the complex reaction temperature is 50~120 DEG C, and the reaction time is 1~5h.
7. the Ti/CeO of Pd load according to claim 32The preparation method of nano composite catalyst, which is characterized in that
In step (2), the CeO of the palladium salt and Ti doping2The mass ratio of nanometer sheet carrier is 1:10~20.
8. the Ti/CeO of Pd load according to claim 32The preparation method of nano composite catalyst, which is characterized in that
In step (2), the concentration of polyvinylpyrrolidone is 0.5~1mg/mL in the polyvinylpyrrolidone alcoholic solution；The palladium
The concentration of saline solution is 0.01~0.05M.
9. the Ti/CeO of Pd load according to claim 32The preparation method of nano composite catalyst, which is characterized in that
In step (1), the alcohol is at least one of ethyl alcohol, propyl alcohol or ethylene glycol；In step (2), the alcohol is ethylene glycol, the third three
At least one of alcohol or isopropanol.
10. the Ti/CeO of Pd load according to claim 1 or 22Nano composite catalyst restores fragrant nitration in catalysis
Close the application in object, which is characterized in that the fragrant nitro compound is p-nitrophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810636396.7A CN108855070A (en) | 2018-06-20 | 2018-06-20 | A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810636396.7A CN108855070A (en) | 2018-06-20 | 2018-06-20 | A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108855070A true CN108855070A (en) | 2018-11-23 |
Family
ID=64339692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810636396.7A Pending CN108855070A (en) | 2018-06-20 | 2018-06-20 | A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108855070A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303368A (en) * | 2020-04-22 | 2020-06-19 | 深圳飞扬骏研新材料股份有限公司 | Water-based polyaspartic acid ester resin and preparation method thereof |
| CN112108645A (en) * | 2020-09-04 | 2020-12-22 | 吉林师范大学 | Superparamagnetic small-size alloy nanoparticle and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498783A (en) * | 2016-01-28 | 2016-04-20 | 郑州航空工业管理学院 | Fe3O4/CeO2 nanometer composite material, preparation method and application |
| CN106588964A (en) * | 2016-12-02 | 2017-04-26 | 浙江大学 | Rare earth coordination complex nano materials as well as preparation method and application thereof |
| CN107638878A (en) * | 2017-11-14 | 2018-01-30 | 济南大学 | A kind of preparation method of sandwich structure nano-tube composite catalyst |
-
2018
- 2018-06-20 CN CN201810636396.7A patent/CN108855070A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498783A (en) * | 2016-01-28 | 2016-04-20 | 郑州航空工业管理学院 | Fe3O4/CeO2 nanometer composite material, preparation method and application |
| CN106588964A (en) * | 2016-12-02 | 2017-04-26 | 浙江大学 | Rare earth coordination complex nano materials as well as preparation method and application thereof |
| CN107638878A (en) * | 2017-11-14 | 2018-01-30 | 济南大学 | A kind of preparation method of sandwich structure nano-tube composite catalyst |
Non-Patent Citations (3)
| Title |
|---|
| FAN WANG ET AL.: "Decoration of Pt on Cu/Co double-doped CeO2 nanospheres and their greatly enhanced catalytic activity", 《CHEM. SCI.》 * |
| SAI ZHANG ET AL.: "High Catalytic Activity and Chemoselectivity of Sub-nanometric Pd Clusters on Porous Nanorods of CeO2 for Hydrogenation of Nitroarenes", 《J. AM. CHEM. SOC.》 * |
| ZHENYUAN JI ET AL.: "Anchoring noble metal nanoparticles on CeO2 modified reduced graphene oxide nanosheets and their enhanced catalytic properties", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303368A (en) * | 2020-04-22 | 2020-06-19 | 深圳飞扬骏研新材料股份有限公司 | Water-based polyaspartic acid ester resin and preparation method thereof |
| CN111303368B (en) * | 2020-04-22 | 2021-09-17 | 深圳飞扬骏研新材料股份有限公司 | Water-based polyaspartic acid ester resin and preparation method thereof |
| CN112108645A (en) * | 2020-09-04 | 2020-12-22 | 吉林师范大学 | Superparamagnetic small-size alloy nanoparticle and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiong et al. | Efficiently multifunctional catalysts of 3D ordered meso-macroporous Ce0. 3Zr0. 7O2-supported PdAu@ CeO2 core-shell nanoparticles for soot oxidation: Synergetic effect of Pd-Au-CeO2 ternary components | |
| Mohamed et al. | Characterization and Catalytic Properties of Nano‐Sized Au Metal Catalyst on Titanium Containing High Mesoporous Silica (Ti‐HMS) Synthesized by Photo‐Assisted Deposition and Impregnation Methods | |
| Hidalgo et al. | Effect of sulfate pretreatment on gold-modified TiO2 for photocatalytic applications | |
| Zhang et al. | Preparation of Ag/UiO-66-NH 2 and its application in photocatalytic reduction of Cr (VI) under visible light | |
| CN103418371B (en) | A kind of MOx@SiO2the preparation method of shell-core structure catalyst | |
| CN107456965B (en) | It is a kind of using cerium oxide as load type palladium catalyst of carrier and preparation method thereof | |
| CN106000402B (en) | A kind of preparation method and application of the titanium dioxide nanometer composite particles of supporting Pt-Au alloy | |
| CN103301850B (en) | Three-dimensional sequential macroporous Co3O4 loaded nanometer Au catalyst as well as preparation method and application thereof | |
| Taratayko et al. | Ag–CeO2/SBA-15 composite prepared from Pluronic P123@ SBA-15 hybrid as catalyst for room-temperature reduction of 4-nitrophenol | |
| CN107855123B (en) | Pd/SiO2@Al2O3Nanocrystalline material and preparation method and application thereof | |
| Devaiah et al. | Structure dependent catalytic activity of Ce0. 8Tb0. 2O2− δ and TiO2 supported Ce0. 8Tb0. 2O2− δ solid solutions for CO oxidation | |
| CN104888767A (en) | Noble metal oxide catalyst, and preparation and application thereof | |
| CN107159205A (en) | A kind of three-dimensional ordered macroporous meso-hole structure cerium zirconium aluminum composite oxides metal supported catalyst and preparation method thereof | |
| CN102101051B (en) | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides | |
| CN104741118A (en) | Preparation method of high-dispersion load type noble metal alloy catalyst | |
| Wen et al. | Tuning the structural properties of CeO2 by Pr and Fe codoping for enhanced visible‐light catalytic activity | |
| CN108855070A (en) | A kind of Ti/CeO of Pd load2Nano composite catalyst and its preparation method and application | |
| CN107442117B (en) | A kind of exhaust gas catalytic conversion | |
| CN103041865A (en) | Organic anthraquinone dye sensitized and precious metal supported inorganic semiconductor visible-light photocatalyst, and preparation method and application of photocatalyst | |
| CN104001523B (en) | Cobalt/noble metal/cobalt hydroxide nano-composite material, and preparation method and application thereof | |
| CN103691438A (en) | Controllable preparation method of Ag-manganese monoxide nanorods | |
| CN101654256B (en) | Method for in situ synthesis of titanium-silicon molecular sieve material containing noble metal | |
| CN109603798A (en) | A kind of meso-porous titanium oxide-oxidation silicon oxide composite material and its preparation method and application | |
| CN101618323B (en) | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof | |
| CN103041799A (en) | Preparation method of lanthanum and boron codoped titanium dioxide visible-light-induced photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181123 |