CN108993597A - A kind of catalyst and preparation method thereof for alkynes hydrogenation - Google Patents
A kind of catalyst and preparation method thereof for alkynes hydrogenation Download PDFInfo
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- CN108993597A CN108993597A CN201810862910.9A CN201810862910A CN108993597A CN 108993597 A CN108993597 A CN 108993597A CN 201810862910 A CN201810862910 A CN 201810862910A CN 108993597 A CN108993597 A CN 108993597A
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- gold
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- zif
- metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 53
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002086 nanomaterial Substances 0.000 claims abstract description 66
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 43
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 19
- -1 glyoxaline compound Chemical class 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 58
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 24
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 24
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 23
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 11
- 238000001228 spectrum Methods 0.000 claims description 11
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- 102100029880 Glycodelin Human genes 0.000 claims description 7
- 101000585553 Homo sapiens Glycodelin Proteins 0.000 claims description 7
- 239000013167 zeolitic imidazolate framework-1 Substances 0.000 claims description 7
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims 1
- 238000005253 cladding Methods 0.000 abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 26
- 239000011943 nanocatalyst Substances 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000010453 quartz Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000003708 ampul Substances 0.000 description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N diethyl maleate Chemical compound CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OVNWORSPZLORHV-UHFFFAOYSA-N 3-ethyl-3-methylpent-1-yne Chemical compound CCC(C)(CC)C#C OVNWORSPZLORHV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/19—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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/82—Metals of the platinum group
- B01J2523/824—Palladium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of catalyst for alkynes hydrogenation, are made of gold-palladium bimetal nano material with the ZIF metal-organic framework material for being coated on the gold-palladium bimetal nano material surface.Present invention also provides the preparation methods of above-mentioned catalyst, and gold-palladium bimetal nano material, glyoxaline compound are reacted in a solvent with zinc source, obtain the catalyst for alkynes hydrogenation.It is coordinated by metal center ionic zinc with glyoxaline compound in the present invention, is coated on gold-palladium bimetal nano material surface, prepare the catalyst of metal-organic framework material cladding bimetal nano material；The catalyst is used for optical drive alkynes hydrogenation reaction, shows excellent hydrogenation activity and olefin product selectivity.
Description
Technical field
The present invention relates to metal catalyst technology field more particularly to a kind of catalyst for alkynes hydrogenation and its
Preparation method.
Background technique
Solar energy is the energy of the forms such as electric energy, chemical energy by certain mediated transformation as cleaning, the sustainable energy
Amount, for solving the problems, such as lack of energy and environmental pollution.Semiconductor is common extinction medium, but most semiconductors
Material extinction is located at ultraviolet region, can not effectively absorb and utilize whole solar energies.Metal nano material is waited from sharp
Member can convert chemical energy for the visible and near infrared light for occupying 95% or more sunlight and be used for as a kind of important medium
Driving catalysis reaction.
Gold nanorods have good absorption visible and near infrared light characteristic, and the metal with catalytic activity is integrated into gold
Nanorod surfaces are the common methods for preparing phasmon catalyst.Such as the Chinese patent of 100549244 C of Publication No. CN
Disclose a kind of rectangle bimetallic nano rod with gold nucleus and palladium shell and preparation method thereof, the catalyst prepared using this method
For studying the reaction of optical drive organic hydrogenation；Such as " American Chemical Society " magazine (J.Am.Chem.Soc., 2016,138,6822)
It describes in conjunction with ultrafast absorption spectroscopy techniques research phasmon relaxation in the physical mechanism for realizing that luminous energy is converted to chemical energy, is
Material preparation basis has been established in the light-catalysed design studies of phasmon.
Preparing alkene by alkynes semihydrogenation reaction is a kind of common route of synthesis, such as the woods being widely used
Moral draw catalyst effectively olefin hydrocarbon molecules is inhibited further to be hydrogenated, but it is catalyst poisoning cause catalytic activity to reduce, and
The condition of high-temperature heating and the use of high-purity hydrogen carry out some potential safety problems to catalysis reaction zone.Exploitation is used for optical drive alkynes
The catalyst that hydrocarbon hydrogenation reaction generates alkene has a very important significance, and especially flexible modulation adds hydrogen under different hydrogen atmosphere
Activity and olefin product selectivity.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of catalyst for alkynes hydrogenation, which is being made
It is with higher active and olefin product highly selective during standby alkene.
In view of this, this application provides a kind of catalyst for alkynes hydrogenation, by gold-palladium bimetal nano material
The ZIF metal-organic framework material expected and be coated on the gold-palladium bimetal nano material surface forms.
Preferably, the gold-palladium bimetal nano material is by gold nanorods and the palladium group for being coated on the gold nanorods surface
At；The molar ratio of palladium and gold is (0.2~3.5): 1.
Preferably, the ZIF metal-organic framework material is ZIF-1 metal-organic framework material, ZIF-7 metal has machine frame
Frame material, ZIF-8 metal-organic framework material or ZIF-60 metal-organic framework material.
Present invention also provides a kind of preparation methods of catalyst for alkynes hydrogenation, comprising:
Gold-palladium bimetal nano material, glyoxaline compound are reacted in a solvent with zinc source, obtain hydrogenating for alkynes
The catalyst of reaction, the catalyst for alkynes hydrogenation is by gold-palladium bimetal nano material and is coated on the gold-palladium
The ZIF metal-organic framework material of bimetal nano material surface forms.
Preferably, the glyoxaline compound is selected from one or both of benzimidazole, 2-methylimidazole and imidazoles, institute
Stating zinc source is zinc nitrate hexahydrate.
Preferably, the gold-palladium bimetal nano material, glyoxaline compound and the mass ratio in zinc source be 1:(10.9~
307.7): (39.7~397).
Preferably, the time of the reaction is 10~120min or 12~for 24 hours.
Present invention also provides a kind of preparation methods of alkene, comprising:
Alkynes and catalyst are reacted under illumination condition in the atmosphere containing hydrogen, obtain alkene；The catalyst
By gold-palladium bimetal nano material and the ZIF metal-organic framework material group for being coated on the gold-palladium bimetal nano material surface
At.
Preferably, density of hydrogen is 2%~100% in the atmosphere containing hydrogen.
Preferably, the reaction carries out under the conditions of full spectrum light is shone, and the luminous intensity that the full spectrum light is shone is 50~100mW/
cm2；The time of the reaction is 2~12h.
This application provides a kind of catalyst for alkynes hydrogenation, by gold-palladium bimetal nano material and cladding
It is formed in the ZIF metal-organic framework material of the gold-palladium bimetal nano material surface.The present invention utilizes metal nano material
Phasmon effect, wherein the gold nanorods core in gold-palladium bimetal nano material as extinction center effectively absorb it is visible and
Near infrared light, and it is converted into heat-driven chemical reaction, palladium shell plays the role of catalytic hydrogenation reaction as active site, real
Solar energy is showed to chemical energy Efficient Conversion, in conjunction with metal-organic framework material to the coating function of catalyst surface, in hydrogen
Atmosphere in promote alkynes hydrogenation reaction, effectively promoted hydrogenation conversion and olefin product selectivity, avoid tradition
Energy consumption caused by thermal drivers and environmental pollution and high concentration hydrogen use bring security risk.The experimental results showed that this hair
The selectivity of bright alkene reaches as high as 100%.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo of gold nanorods prepared by the embodiment of the present invention 1；
Fig. 2 is the TEM photo of gold nanorods nucleus and palladium shell bimetal nanostructure prepared by the embodiment of the present invention 2；
Fig. 3 is the high-resolution TEM photo of gold nanorods nucleus and palladium shell bimetal nanostructure prepared by the embodiment of the present invention 2；
Fig. 4 is the TEM photo that ZIF-8 prepared by the embodiment of the present invention 3 coats bimetal nano catalyst；
Fig. 5 is the scanning electron microscope that ZIF-8 prepared by the embodiment of the present invention 3 coats bimetal nano catalyst
(SEM) photo；
The ZIF-8 cladding bimetal nano catalyst that Fig. 6 is prepared for the embodiment of the present invention 3 turns target X-ray powder diffraction
(XRD) spectrogram；
Fig. 7 is that gold nanorods nucleus and palladium shell bimetal nanostructure prepared by the embodiment of the present invention 2~3 and ZIF-8 cladding are double
Uv-visible absorption spectra (UV-vis) spectrogram of metal nano catalyst；
Fig. 8 is the TEM photo that ZIF-1 prepared by the embodiment of the present invention 4 coats bimetal nano catalyst；
Fig. 9 is the TEM photo that ZIF-60 prepared by the embodiment of the present invention 5 coats bimetal nano catalyst；
Figure 10 is the TEM photo that ZIF-7 prepared by embodiment 6 coats bimetal nano catalyst；
Figure 11 be the embodiment of the present invention 2 under 4% concentration hydrogen atmosphere the conversion ratio of hydrogenation reaction and selectivity at any time
Between change curve；
Figure 12 be the embodiment of the present invention 3 under 4% concentration hydrogen atmosphere the conversion ratio of hydrogenation reaction and selectivity at any time
Between change curve；
Figure 13 be in the embodiment of the present invention 2 and embodiment 3 under 4~100% concentration hydrogen atmospheres hydrogenation reaction conversion ratio
Histogram；
Figure 14 be the embodiment of the present invention 4~6 prepare catalyst under 4% concentration hydrogen atmosphere hydrogenation reaction conversion ratio
Column diagram.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of catalyst for alkynes hydrogenation, by gold-palladium bimetal nano material with
It is coated on the ZIF metal-organic framework material composition of the gold-palladium bimetal nano material surface.
Catalyst provided by the present application for alkynes hydrogenation is in catalysis alkynes reaction, under different hydrogen atmosphere
With flexible modulation hydrogenation activity and olefin product selectivity.
Above-mentioned catalyst is by gold-palladium bimetal nano material and the ZIF for being coated on the gold-palladium bimetal nano material surface
Metal-organic framework material composition.Specifically, the gold-palladium bimetal nano material is one kind using gold nanorods as core, it is with palladium
The bimetallic material of shell, the structure of gold-palladium bimetal nano material are specifically the cuboid of long 71.7nm, width 21.8nm, palladium and gold
Molar ratio be (0.2~3.5): 1, in a particular embodiment, the palladium and gold molar ratio be 1.62:1；The ratio increase or
The catalytic performance that reducing can all make catalyst under illumination condition reduces.The circle that gold nanorods are long 66nm, diameter is 16nm
Cylinder, draw ratio 4.1.
ZIF metal-organic framework material in the application catalyst can be ZIF-1, ZIF-7, ZIF-8 or ZIF-60；ZIF
Metal-organic framework material is zeolite imidazole ester frame structure material, is porous crystalline material；Wherein, organic imidazate crosslinking
It is connected on transition metal Zn, forms a kind of tetrahedral framework；Many different ZIF structures are crosslinked-crosslinking by simply adjusting
Interaction can be formed.In the application different ZIF metal-organic framework materials be due to the raw material of reaction is different and shape
At the ZIF metal-organic framework material of different structure.
Present invention also provides the preparation methods of the catalyst for alkynes hydrogenation, comprising:
Gold-palladium bimetal nano material, glyoxaline compound are reacted in a solvent with zinc source, obtain hydrogenating for alkynes
The catalyst of reaction, the catalyst for alkynes hydrogenation is by gold-palladium bimetal nano material and is coated on the gold-palladium
The ZIF metal-organic framework material of bimetal nano material surface forms.
In catalyst of the above-mentioned preparation for alkynes hydrogenation, the gold-palladium bimetal nano material is this field skill
Material known to art personnel, preparation method are carried out according to scheme well known to those skilled in the art；It is exemplary, by gold nanorods
Cetyl trimethylammonium bromide solution in sequentially add K2PdCl4Aqueous solution, hydrochloric acid solution and ascorbic acid solution, so
It is stood in oil bath pan afterwards, gold-palladium bimetal nano material is obtained after reaction.
The glyoxaline compound is selected from one or both of benzimidazole, 2-methylimidazole and imidazoles, the zinc source
For zinc nitrate hexahydrate；The gold-palladium bimetal nano material, glyoxaline compound and the mass ratio in zinc source be 1:(10.9~
307.7): (39.7~397)；The ratio in glyoxaline compound and zinc source is fixed in the synthesis process, thus it is possible to vary gold-palladium
The ratio of bimetal nano material and glyoxaline compound.For example, being closed when preparing the catalyst that core is ZIF-8 in order to reach
The concentration of suitable covered effect, two kinds of raw materials of control growth ZIF-8 is extremely low, is conducive to ZIF-8 in gold-palladium bimetal nano material
Material outside cladding；The dosage for improving glyoxaline compound and zinc source will lead to a large amount of ZIF-8 from growing, and can not be formed effective
Clad structure.For the gold-palladium bimetal nano material of ZIF-8 cladding, it is optimal that the mass ratio of three, which is 1:109:397,
Synthesis ratio, changing proportionate relationship will affect the clad structure pattern of catalyst.
In this application, according to the difference of reaction raw materials, it is different that gold-palladium bimetal nano material surface cladding can be prepared
ZIF metal-organic framework material.Specifically, coating ZIF-1 metal organic frame for gold-palladium bimetal nano material surface
The catalyst of material, the raw material used is imidazoles, zinc nitrate hexahydrate and gold-palladium bimetal nano material, solvent N, N- bis-
Methylformamide, time of reaction is 12~for 24 hours, the temperature of reaction is 20~30 DEG C；For gold-palladium bimetal nano material table
Bread covers the catalyst of ZIF-7 metal-organic framework material, and the raw material used is benzimidazole, zinc nitrate hexahydrate and gold-palladium
Bimetal nano material, solvent are n,N-Dimethylformamide, the time of reaction is 12~for 24 hours, the temperature of reaction is 20~30
℃；For the catalyst of gold-palladium bimetal nano material cladding ZIF-8 metal-organic framework material, the raw material used is 2- first
Base imidazoles, zinc nitrate hexahydrate and gold-palladium bimetal nano material, solvent are methanol, and the time of reaction is 10~120min, instead
It should be carried out in ice-water bath；The catalyst of ZIF-60 metal-organic framework material is coated for gold-palladium bimetal nano material,
The raw material used is imidazoles and 2-methylimidazole, zinc nitrate hexahydrate and gold-palladium bimetal nano material, solvent N, N- diformazan
Base formamide, time of reaction is 12~for 24 hours, the temperature of reaction is 80~90 DEG C.
During above-mentioned preparation is used for the catalyst of alkynes hydrogenation, by metal center ionic zinc and organic match
Body glyoxaline compound is coordinated, and is coated on gold-palladium bimetal nano material surface, has prepared ZIF metal organic frame material
The catalyst of material cladding bimetal nano material.
The preparation method for generating alkene is hydrogenated present invention also provides a kind of alkynes, comprising:
Alkynes and catalyst are reacted under illumination condition in the atmosphere containing hydrogen, obtain alkene；The catalyst
By gold-palladium bimetal nano material and the ZIF metal-organic framework material group for being coated on the gold-palladium bimetal nano material surface
At.
It is above-mentioned prepare alkene during, alkynes is alkynes well known to those skilled in the art, i.e., all alkynes is equal
It can be used as the raw material for preparing alkene, in a particular embodiment, the alkynes can be selected from diethyl butyn.It is described to contain hydrogen
Atmosphere in hydrogen concentration be 4%~100%；Within the scope of above-mentioned density of hydrogen, under 4% and 10% hydrogen atmosphere,
Catalyst to catalyzing hydrogenating activity and olefin product selectivity are higher.The time of the reaction is 2~12h, in a particular embodiment,
It was proved that: extend the reaction time under 4% hydrogen atmosphere, the gold-palladium bimetal nano catalyst of ZIF-8 cladding can be with
Maintain the selectivity of olefin product 84%, the gold-palladium bimetal nano catalyst yield without ZIF-8 cladding reaches
The selectivity for continuing to extend reaction time olefin product after 100% is decreased obviously, in the small Z- olefine selective at present of illumination 36
Only 64%.It follows that the gold-palladium bimetallic catalyst that surface has coated ZIF-8 can effectively maintain half hydrogenation reaction of alkynes
Selectivity.The temperature of the reaction is 20~30 DEG C, and applicant, which tests catalyst performance, to be carried out at 20 DEG C of room temperature, simultaneously
The catalytic performance under being protected from light at 50 DEG C is tested, two class catalyst of discovery are easier generation alkene at high temperature and add hydrogen to alkane
Reaction.Therefore lower environment temperature is conducive to the selectivity of olefin product.Above-mentioned reaction is carried out under illumination condition, into
One step is carried out under the conditions of full spectrum light is shone, and the luminous intensity that the full spectrum light is shone is 50~100mW/cm2。
The catalyst of ZIF metal-organic framework material cladding bimetal nano material is used for optical drive alkynes and added by the application
Hydrogen reaction, it is highly selective to show excellent hydrogenation activity and olefin product；Further, for low-concentration hydrogen atmosphere,
Catalyst provided by the present application also has excellent hydrogenation activity and olefin product highly selective.
For a further understanding of the present invention, urge below with reference to embodiment provided by the present invention for alkynes hydrogenation
Agent, preparation method and applications are described in detail, and protection scope of the present invention is not limited by the following examples.
The preparation of 1 gold nanorods of embodiment
It weighs 355.335mg cetyl trimethylammonium bromide (CTAB), the solution that 9.75mL water is made into 0.1M is added；It takes
The HAuCl of 0.25mL 0.01M4Solution, the NaBH that 0.6mL concentration is 0.01M4Solution, sequentially add wherein, vibrate 2min after
2h is stood at 30 DEG C, solution is in brown, as seed-solution；
The CTAB solution for taking 10mL 0.1M, sequentially adds 0.5mL 0.01MHAuCl4Solution, 0.1mL 0.01M AgNO3
The ascorbic acid (AA) that the HCl and 80 μ L concentration that solution, 0.2mL concentration are 1M are 0.1M, suitably rocks rear solution and becomes colourless,
As growth solution；From taking 15 μ L to be added in growth solution in seed-solution, 12h is stood, the Au NRs for obtaining brownish red is molten
Liquid；ICP is measured after using water to be centrifuged three times as solvent 8000r/min, is made into the gold nanorods that concentration containing gold element is 1mg/mL
Aqueous solution.
The present invention has carried out transmission electron microscope detection to gold nanorods used in the present embodiment, as a result as shown in FIG. 1, FIG. 1 is
The TEM photo of gold nanorods used in the present invention.
The preparation of 2 gold nanorods nucleus and palladium shell bimetal nanostructure of embodiment
Take 8.85mL concentration be 10mM CTAB aqueous solution, be added 0.5mL concentration be 1mg/mL gold nanorods, then according to
It is secondary that the K that 0.5mL concentration is 0.01M is added2PdCl4The HCl solution and 0.1mL concentration that aqueous solution, 0.1mL concentration are 1M are 0.2M
Ascorbic acid (AA), be placed in 50 DEG C of oil bath pans after mixing evenly and stand 2h；Use water as solvent 8000r/ after reaction
Min measures ICP after being centrifuged three times, and is made into the gold nanorods aqueous solution that concentration containing gold element is 1mg/mL.
The present invention has carried out transmission electron microscope inspection to gold nanorods nucleus and palladium shell bimetal nanostructure used in the present embodiment
It surveys, as a result as shown in Fig. 2, Fig. 2 is the TEM photo of gold nanorods used in the present invention；The present invention is to gold used in the present embodiment
Nanometer rods nucleus and palladium shell bimetal nanostructure has carried out high-resolution-ration transmission electric-lens detection, as a result as shown in figure 3, Fig. 3 is the present invention
The HRTEM photo of gold nanorods used.
Embodiment 3ZIF-8 coats bimetal nano catalyst
The gold nanorods nucleus and palladium shell bimetal nanostructure that the concentration of 0.05mL gold is 1mg/mL is taken, 10mL is sequentially added
Methanol solution and 10mL Zn containing the 37.2mg (NO of the 2-methylimidazole containing 10.25mg3)2·6H2The methanol solution of O, in ice-water bath
Middle stirring 10 minutes, uses acetonitrile to be centrifuged three times as solvent 8000r/min, last precipitating is dispersed in acetonitrile after reaction
For subsequent test.
The present invention has carried out transmission electron microscope detection to the cladding bimetal nano catalyst of ZIF-8 used in the present embodiment, ties
Fruit is as shown in figure 4, Fig. 4 is the TEM photo that ZIF-8 used in the present invention coats bimetal nano catalyst；
The present invention has carried out scanning electron microscope detection to the cladding bimetal nano catalyst of ZIF-8 used in the present embodiment, ties
Fruit is as shown in figure 5, Fig. 5 is the SEM photograph that ZIF-8 used in the present invention coats bimetal nano catalyst；
The present invention has carried out turning target x-ray powder spreading out to the cladding bimetal nano catalyst of ZIF-8 used in the present embodiment
Detection is penetrated, as a result as shown in fig. 6, Fig. 6 is the XRD spectra that ZIF-8 used in the present invention coats bimetal nano catalyst；
The present invention has carried out spectrum analysis to catalyst in embodiment 2~3, as a result as shown in fig. 7, Fig. 7 is that the present invention is real
Apply the UV-vis spectrogram of catalyst in example 2~3.
Embodiment 4ZIF-1 coats bimetal nano process for synthetic catalyst
The gold nanorods nucleus and palladium shell bimetal nanostructure that the concentration of 2mL gold is 1mg/mL is taken, 18mL is sequentially added and contains
DMF solution and 18mL Zn containing the 204.78mg (NO of 300mg imidazoles3)2·6H2The DMF solution of O stands 24 hours under 20 degree,
Acetonitrile is used to be centrifuged three times as solvent 8000r/min after reaction, last precipitating is dispersed in acetonitrile for subsequent survey
Examination.The present invention has carried out transmission electron microscope detection to the cladding bimetal nano catalyst of ZIF-1 used in the present embodiment, as a result as schemed
Shown in 8, Fig. 8 is the TEM photo that ZIF-1 used in the present invention coats bimetal nano catalyst.
Embodiment 5ZIF-60 coats bimetal nano process for synthetic catalyst
The gold nanorods nucleus and palladium shell bimetal nanostructure that the concentration of 2mL gold is 1mg/mL is taken, in the reaction kettle of 50mL
Sequentially add DMF solution and the 15mL Zn containing 267.8mg of 15mL imidazoles containing 183.8mg and 73.9mg2- methylimidazole
(NO3)2·6H2Reaction kettle is placed under 85 degree and reacts 12 hours, use after reaction after being vigorously stirred by the DMF solution of O
Acetonitrile is centrifuged three times as solvent 8000r/min, and last precipitating is dispersed in acetonitrile for subsequent test.The present invention is to this
The cladding bimetal nano catalyst of ZIF-60 used in embodiment has carried out transmission electron microscope detection, as a result as shown in figure 9, Fig. 9 is
The TEM photo of the cladding bimetal nano catalyst of ZIF-60 used in the present invention.
Embodiment 6ZIF-7 coats bimetal nano process for synthetic catalyst
The gold nanorods nucleus and palladium shell bimetal nanostructure that the concentration of 2mL gold is 1mg/mL is taken, in the reaction kettle of 50mL
Sequentially add DMF solution and 15mL Zn containing the 453mg (NO of 15mL benzimidazole containing 1154mg3)2·6H2The DMF solution of O, warp
Cross after being vigorously stirred, reaction kettle be placed under 20 degree and is reacted 24 hours, use after reaction acetonitrile as solvent 8000r/min from
The heart three times, last precipitating is dispersed in acetonitrile for subsequent test.The present invention coats ZIF-7 used in the present embodiment double
Metal nano catalyst has carried out transmission electron microscope detection, and the results are shown in Figure 10, and Figure 10 is ZIF-7 manufactured in the present embodiment cladding
The TEM photo of bimetal nano catalyst.
The alkynes hydrogenation reaction of optical drive under 4% hydrogen atmosphere of embodiment 7~8
Catalyst is prepared according to the method in embodiment 2, embodiment 7 carries out different light application times (6 hours~36 hours)
Lower catalytic hydrogenation reaction, taking the concentration of 0.1mL gold is that 1mg/mL catalyst is placed in 20mL quartz ampoule, measures 0.89mL acetonitrile and adds
Enter in above-mentioned quartz ampoule, ultrasonic disperse, 10 μ L diethyl butyns are added, use 4% hydrogen balloon with triple valve as hydrogen
Source excludes quartzy inner air tube by vacuumizing repeatedly；Use 100mW/cm2Full spectrum light irradiates quartz ampoule, while with 300r/min
Revolving speed stirring quartz ampoule in reaction solution, obtain the products such as butene dioic acid diethylester.
The present invention calculates the conversion ratio and selectivity of the corresponding hydrogenation reaction of catalyst in embodiment 7, as a result such as Figure 11
Shown, Figure 11 is the conversion ratio and selectivity curve figure of the hydrogenation reaction of catalyst prepared by the embodiment of the present invention 2.
Catalyst is prepared according to the method in embodiment 3, embodiment 8 carries out different light application times (2 hours~12 hours)
Lower catalytic hydrogenation reaction, taking the concentration of 0.1mL gold is that 1mg/mL catalyst is placed in 20mL quartz ampoule, measures 0.89mL acetonitrile and adds
Enter in above-mentioned quartz ampoule, ultrasonic disperse, 10 μ L diethyl butyns are added, use 4% hydrogen balloon with triple valve as hydrogen
Source excludes quartzy inner air tube by vacuumizing repeatedly；Use 100mW/cm2Full spectrum light irradiates quartz ampoule, while with 300r/min
Revolving speed stirring quartz ampoule in reaction solution, obtain the products such as butene dioic acid diethylester.
The present invention calculates the conversion ratio and selectivity of the corresponding hydrogenation reaction of catalyst of the preparation of embodiment 3, as a result such as
Shown in Figure 12, Figure 12 is the conversion ratio and selectivity curve figure of the hydrogenation reaction of catalyst prepared by the embodiment of the present invention 3.
Work as it can be seen from Figure 11 and Figure 12 and uses 100mW/cm2Full spectrum light irradiates quartz ampoule, and reaction 12 is small in embodiment 2
When diethyl butyn hydrogenation conversion be 35%, Z- olefine selective be 87%, extend the reaction time to 30 hours plus hydrogen
Conversion ratio is 100%, but Z- olefine selective is reduced to 78%.10 hours butine two are reacted under the same terms in embodiment 3
Diethyl phthalate hydrogenation conversion is that 96%, Z- olefine selective is 88%, extends the reaction time and to 12 hours hydrogenation conversions is
100%, but Z- olefine selective is reduced to 84%.Thus illustrate, coated the double gold of gold nanorods nucleus and palladium shell after ZIF-8
Belong to nanocatalyst to carry out with promoting alkynes hydrogenation reaction, and effectively controls the selectivity of olefin product.This time tolerance
The separation of olefins that alkynes hydrogenation reaction generates is extracted enough in industrial application, therefore, the method in the present invention has
Good prospects for commercial application.
The alkynes hydrogenation reaction of optical drive under the hydrogen atmosphere of 9 different hydrogen concentration of embodiment
Catalyst is prepared according to the method in embodiment 2~3 and carries out hydrogenation reaction, unlike, embodiment 9 makes respectively
With 4%, 10% and 100% concentration hydrogen, conversion ratio of the two class catalyst when reacting 10 hours, 4 hours and 10 minutes is obtained.
The present invention calculates the corresponding hydrogenation reaction of catalyst 10 hours, 4 hours and 10 minutes of the preparation of embodiment 2~3
Conversion ratio, as shown in figure 13, Figure 13 be 8 hydrogenation reaction of the embodiment of the present invention, 10 hours, 4 hours and 10 minutes conversion ratio columns
Shape figure.As seen from Figure 13, when with 100mW/cm2Full spectrum light irradiates quartz ampoule, in 4% and 10% hydrogen gas in embodiment 9
The alkynes hydrogenation activity of embodiment 3 is higher than embodiment 2 under atmosphere；The hydrogenation activity of embodiment 2 is higher under 100% hydrogen atmosphere,
But the selectivity of Z- olefine selective only has 66%, far below the 89% of embodiment 3.Compare the catalysis under different hydrogen concentration
Experimental result, it can be found that ZIF-8 cladding bimetal nano catalyst shows under low density of hydrogen and receives higher than bimetallic
The alkynes hydrogenation activity of rice catalyst, and there is higher hydrogenation of olefins selectivity of product under high density of hydrogen, it is one
Kind effectively control alkynes molecule is hydrogenated to the catalyst of olefin product.
The alkynes for the gold-palladium bimetallic catalyst optical drive that difference ZIF is coated under 10 4% hydrogen atmosphere of embodiment adds hydrogen anti-
It answers
Catalyst is prepared according to the method in embodiment 4~6, embodiment 10 carries out the gold-palladium bimetallic of different ZIF claddings
Catalyst takes the reality that the concentration of 0.1mL gold is 1mg/mL in 4% hydrogen atmosphere and the small catalytic hydrogenation reaction at present of light application time 10
The catalyst for applying the preparation of example 4~6 is placed in 20mL quartz ampoule, is measured 0.89mL acetonitrile and is added in above-mentioned quartz ampoule, ultrasonic disperse,
10 μ L diethyl butyns are added, use 4% hydrogen balloon with triple valve as hydrogen source, exclude quartz by vacuumizing repeatedly
Inner air tube；Use 100mW/cm2Full spectrum light irradiates quartz ampoule 10h, while stirring quartzy inner reaction tube with the revolving speed of 300r/min
Liquid obtains the products such as butene dioic acid diethylester.Such as Figure 14, Figure 14 be catalyst prepared by the embodiment of the present invention 4~6 plus hydrogen it is anti-
The conversion ratio column diagram answered.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of catalyst for alkynes hydrogenation by gold-palladium bimetal nano material and is coated on the gold-palladium bimetallic
The ZIF metal-organic framework material of nano-material surface forms.
2. catalyst according to claim 1, which is characterized in that the gold-palladium bimetal nano material by gold nanorods and
It is coated on the palladium composition on the gold nanorods surface；The molar ratio of palladium and gold is (0.2~3.5): 1.
3. catalyst according to claim 1, which is characterized in that the ZIF metal-organic framework material is ZIF-1 metal
Organic framework materials, ZIF-7 metal-organic framework material, ZIF-8 metal-organic framework material or ZIF-60 metal organic frame
Material.
4. a kind of preparation method of the catalyst for alkynes hydrogenation, comprising:
Gold-palladium bimetal nano material, glyoxaline compound are reacted in a solvent with zinc source, obtained for alkynes hydrogenation
Catalyst, the catalyst for alkynes hydrogenation is by gold-palladium bimetal nano material and is coated on the double gold of the gold-palladium
The ZIF metal-organic framework material on metal nanometer material surface forms.
5. the preparation method according to claim 4, which is characterized in that the glyoxaline compound is selected from benzimidazole, 2-
One or both of methylimidazole and imidazoles, the zinc source are zinc nitrate hexahydrate.
6. the preparation method according to claim 4, which is characterized in that the gold-palladium bimetal nano material, imidazoles
The mass ratio for closing object and zinc source is 1:(10.9~307.7): (39.7~397).
7. the preparation method according to claim 4, which is characterized in that the time of the reaction be 10~120min or 12~
24h。
8. a kind of preparation method of alkene, comprising:
Alkynes and catalyst are reacted under illumination condition in the atmosphere containing hydrogen, obtain alkene；The catalyst is by gold
Palladium bimetal nano material is formed with the ZIF metal-organic framework material for being coated on the gold-palladium bimetal nano material surface.
9. preparation method according to claim 8, which is characterized in that density of hydrogen is in the atmosphere containing hydrogen
2%~100%.
10. preparation method according to claim 8, which is characterized in that the reaction carries out under the conditions of full spectrum light is shone, institute
The luminous intensity for stating full spectrum light photograph is 50~100mW/cm2；The time of the reaction is 2~12h.
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