CN105854878A - Composite metal oxide loaded Pt-based nano metal catalyst and preparation method therefor - Google Patents
Composite metal oxide loaded Pt-based nano metal catalyst and preparation method therefor Download PDFInfo
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- CN105854878A CN105854878A CN201610178818.1A CN201610178818A CN105854878A CN 105854878 A CN105854878 A CN 105854878A CN 201610178818 A CN201610178818 A CN 201610178818A CN 105854878 A CN105854878 A CN 105854878A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 16
- 239000011591 potassium Substances 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 69
- 239000002905 metal composite material Substances 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 15
- 239000003863 metallic catalyst Substances 0.000 claims description 13
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 7
- 230000006911 nucleation Effects 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 deionized water compound Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 35
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 abstract description 24
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 239000012266 salt solution Substances 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 21
- 229940117916 cinnamic aldehyde Drugs 0.000 description 21
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 21
- 238000006555 catalytic reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a composite metal oxide loaded Pt-based nano metal catalyst and a preparation method therefor and belongs to the technical field of preparation of catalysts. A composite metal oxide of the composite metal oxide loaded Pt-based nano metal catalyst is one of CeO2-ZrO2, TiO2-ZrO2 and ZrO2-TiO2, the specific surface area of the catalyst is 250m<2>/g to 400m<2>/g, the average particle size of Pt particles is 2nm to 5nm, and the mass percentage of Pt is 1.0% to 5.5%. According to the method, a metal salt solution, a chloroplatinic acid solution and a potassium borohydride solution are mixed in a colloid mill and then are subjected to high-speed coring, then, a hydrothermal reaction is controlled by using kinetics, then, the compositing of metal oxides and the reduction of noble metals are achieved in one step, and finally, the composite metal oxide loaded Pt-based nano metal catalyst is prepared. By applying the catalyst to a reaction for preparing cinnamyl alcohol through selective hydrogenation of cinnamyl aldehyde, the conversion ratio of the cinnamyl aldehyde and the selectivity to the cinnamyl alcohol separately can reach 90% to 100% and 90% to 100%. The catalyst has the advantages that the dispersity of metal nanoparticles is high, the size is small, the carrier action is high, and the preparation method is simple.
Description
Technical field
The invention belongs to catalyst preparation technical field, particularly relate to the Pt Ji Na of a kind of metal composite oxide load
Rice metallic catalyst and preparation method.This catalyst is for the selective hydrogenation of cinnamic aldehyde.
Background technology
α, has a pair conjugated bonds (C=C and C=O key), its multiple choices hydrogenation products in beta-unsaturated aldehyde ketone structure
It it is raw material important in modern chemical industry.Wherein, cinnamic aldehyde is α, a kind of representative species in beta-unsaturated aldehyde ketone.Cortex Cinnamomi
The selection hydrogenation products cinnamyl alcohol of aldehyde is widely used in preparing flavor essence spice, the cosmetics such as Fructus Pruni, Fructus Persicae, Fructus Rubi, Lee
Essence and fragrance for detergents etc., and it is also used as organic synthesis intermediate for synthesizing the raw material of multi-medicament.
In alpha, beta-unsaturated aldehyde ketone hydrogenation reaction, load type metal catalyst is widely used.Loaded catalyst carries
The kind of body, surface nature, surface valence state and electronic structure all can affect the performance of catalyst.Traditional support type is urged
Agent mainly uses the method for aqueous impregnation, the catalyst of gained exists that pore passage structure is undeveloped, specific surface area is low,
The shortcoming such as more weak with active component active force.Oxide-based nanomaterial especially has the oxide of reducibility such as
CeO2、TiO2And ZrO2Deng, be widely used as due to the physical and chemical performance of self uniqueness catalyst carrier for photocatalysis,
The field of catalytic reactions such as hydrogenation, oxidation.Wherein: CeO2Because the fluorite structure of its uniqueness and storage oxygen excellent especially
/ oxygen release ability, oxygen flow ability, the dispersion promoting noble metal and activity, show much excellent physics and chemistry
Matter so that it is have huge using value [Ahmad at aspects such as optics, electronic device, catalysis material and magnetic materials
S,Gopalaiah K,et al.Inorg.Chem.,2014,53,2030-2039.】。ZrO2It is uniquely to have Acidity of Aikalinity and oxidoreduction concurrently
The tetravalent metal oxide of ability, owing to there being the existence of oxygen vacancies to enhance the effect between active component and zirconium dioxide
Power, the aspects such as catalytic hydrogenation reaction, oxidation reaction and Fischer-Tropsch synthesis or F-T reaction have a wide range of applications [Schneider J,
Matsuoka M,et al.Chem.Rev.2014,114,9919-9986.】。TiO2Show excellent in terms of stability and dielectric constant
Good character, shows good electric property.Have good optical property, chemical stability good, nontoxic and
Non-migratory, have a wide range of applications [Lin S H, Zhang X in fields such as catalysis material, coating, energy and environment
W,et al.Mater.Res.Bull.2013,48,4570-4575.】。
Metal composite oxide usually has as carrier compares the specific surface area that single carrier is bigger, with catalytic active component
Having stronger interaction, surface has more rich surface defect, thus provides for preparing high performance catalyst
Possible [Yuchao Li.et al.Catal.Sci.Technol.2015,5,3682].Support type platinum based catalyst is α, β-insatiable hunger
With heterogeneous catalyst conventional in aldehyde ketone catalytic hydrogenation.The preparation method of INVENTIONConventional metal-oxide carrier has microemulsion method
[Supakanapitak S.et al.Mater.Charact.2012,7,83-92.], Hydrolyze method [Zhong L S, Hu J S, et
And sol-gal process [Sreethawong T.et al.Chem.Eng. al.Chem.Mater.2007,19,1648-1655.]
J.2013,228,256-262.】.On the other hand, there are following problems in conventional load type Pt base catalyst: 1) urges
Agent specific surface area is little, dispersion is poor, poor stability, selectivity are low；2) preparation process complexity is time-consuming, needs high temperature
Calcining, reduction energy consumption is bigger.Therefore, there is electronic structure and the chemical property of uniqueness based on metal composite oxide,
Develop the platinum based catalyst that a kind of new metal composite oxide that can overcome traditional preparation methods and technical disadvantages loads
Tool is of great significance.
Summary of the invention
The improving eyesight of this is to provide Pt base metallic catalyst and the preparation method of a kind of metal composite oxide load,
And be efficiently applied in the reaction that cinnamyl alcohol is prepared in cinnamic aldehyde selective hydrogenation.This catalyst structure is novel, catalysis
Excellent performance, preparation technology green energy conservation, thus there is potential application prospect.Easy prepares composition metal oxidation
The high dispersive Pt base metallic catalyst of thing load, and use it for cinnamic aldehyde selective hydrogenation and prepare cinnamyl alcohol.
High speed nucleation after being mixed in colloid mill with solution of potassium borohydride by metal salt solution, platinum acid chloride solution, recycling is dynamic
Mechanics controls hydro-thermal reaction, and then a step realizes the compound of metal-oxide and the reduction of noble metal, final prepared compound
Metal oxide supported Pt base metallic catalyst.It is applied to cinnamic aldehyde selective hydrogenation and prepares cinnamyl alcohol
Reaction, the conversion ratio of cinnamic aldehyde and to cinnamyl alcohol selectivity respectively up to 90～100% and 90～100%.
The metal composite oxide of the Pt base metallic catalyst of the metal composite oxide load of the present invention is CeO2
-ZrO2、TiO2-ZrO2、ZrO2-TiO2In one, specific surface area of catalyst is 250～400m2/ g, Pt granule
Mean diameter be 2～5nm, the weight/mass percentage composition of Pt is 1.0～5.5%.
The preparation method is that addition boron hydrogen after first being mixed by difference tetravalent metal saline solution with platinum acid chloride solution
Change potassium solution and stir rapid nucleation in colloid mill high speed, form the nucleus with high surface energy, then place reaction liquid into
By dynamics Controlling hydro-thermal reaction in reactor, and then a step realizes being combined of metal-oxide and going back of noble metal
Former, the final Pt base metallic catalyst preparing metal composite oxide load.Compared with traditional method, prepared
Cheng Wuxu adds any surfactant or template, it is not required that through high-temperature roasting and reduction.Loaded catalyst
Specific surface area is 250～400m2The mean diameter of/g, Pt granule is 2～5nm, and the weight/mass percentage composition of Pt is
1.0～5.5%.Concrete technology step is as follows:
A. compound concentration is the tetravalent metal saline solution of 0.05～0.30mol/L, and compound concentration is 0.001
The platinum acid chloride solution of mol/L～0.01mol/L, compound concentration is the solution of potassium borohydride of 0.05～1.20mol/L；Institute
The tetravalent metal salt stated is any two kinds in zirconium nitrate, cerous nitrate and titanium tetrachloride.
B. the ratio of tetravalent metal saline solution, platinum acid chloride solution and solution of potassium borohydride 1:1:2 by volume is added simultaneously
Enter and colloid mill stirs under 5000～7000rpm 3～8min so that it is nucleation rapidly；Crystallization at 120～180 DEG C
12～36h, then centrifuge washing is to neutral, is finally vacuum dried at 60～90 DEG C, obtains metal composite oxide
(CeO2-ZrO2,CeO2-TiO2,ZrO2-TiO2) the Pt base metallic catalyst that loads.
The catalyst prepared is applied to liquid phase cinnamic aldehyde selective hydrogenation.Cinnamic aldehyde is dissolved in 10ml ethanol
In solvent, being configured to the cinnamic aldehyde solution that concentration is 2.8mmol/L, 0.02g catalyst is added simultaneously to reaction under high pressure
In still, it is passed through the H of 1.0MPa2, temperature rises to 60 DEG C of reactions, and after reaction 30min, hydrogenation on cinnamic aldehyde reaction turns
Rate and to cinnamyl alcohol selectivity respectively up to 90～100% and 90～100%.
The high dispersive metal composite oxide loaded nano Pt catalyst obtained is carried out structural characterization.By transmission electricity
Mirror (TEM) figure is it appeared that catalyst particle high dispersive is on composite oxide carrier surface, and grain size is little；Support type
The N of catalyst2Adsorption/desorption curve and graph of pore diameter distribution thereof prove that it has high specific surface area and little aperture；X
X-ray photoelectron spectroscopy X (XPS) result shows that Pt4f7/2's in catalyst goes out peak position near 70.7eV, and Pt4f5/2
Go out peak position near 74.1eV, the half-peak breadth of Pt4f7/2 and Pt4f5/2 is basically identical, shows that Pt species show
Go out metal state, and occur combining, to height, the trend that energy direction is moved, illustrate to exist very between active metal Pt and carrier
Strong interaction.
The present invention has following remarkable result: do not add any during (1) synthesis metal composite oxide carrier
Surfactant, does not use any template, breaks through traditional method with carbamide, sodium hydroxide and ammonia as precipitant,
Control being formed of metal composite oxide with potassium borohydride as precipitant be combined and the reduction of noble metal with reducing agent；(2)
The Pt metallic catalyst of metal composite oxide load, catalyst is obtained by colloid mill auxiliary hydro-thermal one-step synthesis
There is high specific surface area；(3), in the catalyst that one-step method is prepared, noble metal nano particles dispersion is high, particle diameter
Little, between carrier and nanoparticle, effect is strong, and the structural stability of catalyst is obviously improved；(4) catalyst is at cinnamic aldehyde
Hydrogenation reaction in embodied excellence catalytic performance, be 90～100% to cinnamic aldehyde aldehyde conversion ratio, to cinnamyl alcohol
Selectivity be 90～100%.
Accompanying drawing explanation
Fig. 1. for the Pt/CeO of embodiment 1 preparation2-ZrO2TEM schemes.
Fig. 2. for the Pt/CeO of embodiment 1 preparation2-ZrO2N2Adsorption/desorption curve chart.
Fig. 3 is the Pt/CeO of embodiment 1 preparation2-ZrO2N2The graph of pore diameter distribution of adsorption/desorption.
Fig. 4 is the Pt/CeO of embodiment 1 preparation2-ZrO2The XPS spectrum figure of middle Pt 4f.
Detailed description of the invention
Embodiment 1
Zirconium nitrate and cerous nitrate mixing salt solution, platinum acid chloride solution and solution of potassium borohydride is prepared, wherein with deionized water
Zirconium nitrate solution concentration is 0.0625mol/L, and cerous nitrate solution concentration is 0.0625mol/L, platinum acid chloride solution concentration
For 0.005mol/L, the concentration of potassium borohydride is 0.75mol/L, by tetravalent metal saline solution, platinum acid chloride solution and boron
The ratio of hydrofining solution 1:1:2 by volume is simultaneously introduced in colloid mill and is sufficiently stirred for 5min under 6000rpm, makes
Its rapid nucleation, then solution after reaction is transferred in hydrothermal reaction kettle, crystallization 24h at 150 DEG C, it is then centrifuged for
Washing, to neutral, be finally vacuum dried at 70 DEG C, obtain CeO2-ZrO2The Pt base of metal composite oxide load
Metallic catalyst.The surface area of catalyst is 390m2/ g, wherein the mean diameter of Pt is 3.0nm, catalyst
The weight/mass percentage composition of middle Pt element is 4.7%.
Hydrogenation on cinnamic aldehyde catalytic reaction, first toward autoclave is simultaneously introduced the reactant cinnamic aldehyde of 2.8mmol,
The catalyst obtained in 0.02g embodiment 1 and 10ml alcohol solvent, be passed through H2Gas starts to 1.0MPa, stirring
Reaction.When hydrogenation reaction proceeds to 30min, the conversion ratio of cinnamic aldehyde has reached 96%, the selectivity to cinnamyl alcohol
It is 98%.
Embodiment 2
Cerous nitrate and the mixed solution of titanium tetrachloride, platinum acid chloride solution and solution of potassium borohydride is prepared with deionized water, its
Middle cerous nitrate solution concentration is 0.125mol/L, and titanium tetrachloride solution concentration is 0.125mol/L, platinum acid chloride solution concentration
For 0.008mol/L, the concentration of potassium borohydride is 1mol/L.By tetravalent metal saline solution, platinum acid chloride solution and boron hydrogen
The ratio of change potassium solution 1:1:2 by volume is simultaneously introduced in colloid mill and is sufficiently stirred for 8min under 6500rpm so that it is
Nucleation rapidly, then solution after reaction is transferred in hydrothermal reaction kettle, hydro-thermal reaction 32h at 120 DEG C, then be centrifuged
Washing, to neutral, be finally vacuum dried at 80 DEG C, obtain CeO2-TiO2The Pt base of metal composite oxide load
Nano metal is catalyzed.The surface area of catalyst is 285m2/ g, wherein the mean diameter of Pt is 3.2nm, in catalyst
The weight/mass percentage composition of Pt element is 4.8%.
Hydrogenation on cinnamic aldehyde catalytic reaction, first toward autoclave is simultaneously introduced the reactant cinnamic aldehyde of 2.8mmol,
The catalyst obtained in 0.02g embodiment 2 and 10ml alcohol solvent, be passed through H2Gas starts to 1.0MPa, stirring
Reaction.When hydrogenation reaction proceeds to 30min, the conversion ratio of cinnamic aldehyde has reached 95%, the selectivity to cinnamyl alcohol
It is 92%.
Embodiment 3
Titanium tetrachloride and zirconium nitrate mixed solution, platinum acid chloride solution and solution of potassium borohydride is prepared, wherein with deionized water
Titanium tetrachloride solution concentration is 0.1mol/L, and zirconium nitrate solution concentration is 0.1mol/L, and platinum acid chloride solution concentration is
0.0039mol/L, the concentration of potassium borohydride is 1.0mol/L, by tetravalent metal saline solution, platinum acid chloride solution and boron hydrogen
The ratio of change potassium solution 1:1:2 by volume is simultaneously introduced in colloid mill and is sufficiently stirred for 5min under 6000rpm, makes
Its rapid nucleation, then solution after reaction is transferred in hydrothermal reaction kettle, hydro-thermal reaction 24h at 150 DEG C, then from
Heart washing, to neutral, be finally vacuum dried at 70 DEG C, obtain ZrO2-TiO2The Pt of metal composite oxide load
Base nano metal is catalyzed.The surface area of catalyst is 254m2/ g, wherein the mean diameter of Pt is 3.5nm, catalyst
The weight/mass percentage composition of middle Pt element is 2.8%.
Hydrogenation on cinnamic aldehyde catalytic reaction, first toward autoclave is simultaneously introduced the reactant cinnamic aldehyde of 2.8mmol,
The catalyst obtained in 0.02g embodiment 3 and 10ml alcohol solvent, be passed through H2Gas starts to 1.0MPa, stirring
Reaction.When hydrogenation reaction proceeds to 30min, the conversion ratio of cinnamic aldehyde has reached 92%, the selectivity to cinnamyl alcohol
It is 91%.
Claims (2)
1. a Pt base metallic catalyst for metal composite oxide load, method, it is characterised in that
Metal composite oxide is CeO2-ZrO2、TiO2-ZrO2、ZrO2-TiO2In one, catalyst specific surface
Amass is 250～400m2The mean diameter of/g, Pt granule is 2～5nm, and the weight/mass percentage composition of Pt is 1.0～5.5%.
2. the system of the Pt base metallic catalyst of the metal composite oxide load described in a claim 1
Preparation Method, it is characterised in that processing step is as follows:
A. with the tetravalent metal saline solution that deionized water compound concentration is 0.05～0.30mol/L, compound concentration is
The platinum acid chloride solution of 0.001mol/L～0.01mol/L, compound concentration be 0.05～1.20mol/L potassium borohydride molten
Liquid；Described tetravalent metal salt is any two kinds in zirconium nitrate, cerous nitrate and titanium tetrachloride；
B. the ratio of tetravalent metal saline solution, platinum acid chloride solution and solution of potassium borohydride 1:1:2 by volume is same
Time add colloid mill stir under 5000～7000rpm 3～8min so that it is nucleation rapidly；In 120～180 DEG C
Lower crystallization 12～36h, then centrifuge washing is to neutral, is finally vacuum dried at 60～90 DEG C, obtains composition metal
Oxide carried Pt base metallic catalyst, metal composite oxide is CeO2-ZrO2,CeO2-TiO2,
ZrO2-TiO2In one.
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