CN109126870A - Multi-metal oxygen cluster is the preparation method that node constructs porous catalyst material - Google Patents
Multi-metal oxygen cluster is the preparation method that node constructs porous catalyst material Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 61
- 239000001301 oxygen Substances 0.000 title claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 7
- 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
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims description 2
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical class C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 10
- 238000001907 polarising light microscopy Methods 0.000 description 10
- 229920006324 polyoxymethylene Polymers 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- -1 salt ion Chemical class 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 238000000018 DNA microarray Methods 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/33—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to chemical synthesis process, and in particular to multi-metal oxygen cluster is the preparation method that node constructs porous catalytic agent material.Multi-metal oxygen cluster of the present invention constructs porous catalytic agent material for node and is converted into crystalline-state catalyst obtained from metal organic network at a suitable temperature as substituted type multi-metal oxygen cluster and organic bridge ligand, and chemical component is [ε-Keggin M4]L4/x, wherein L is organic bridge ligand, and M is metal ion, and x is the carboxyl number participated in organic bridge ligand with multi-metal oxygen cluster coordination.Multi-metal oxygen cluster of the present invention is that node constructs the limitation that porous catalyst has broken traditional polyacid, can effectively improve the stability of catalyst, selectivity and catalytic activity.Therefore, preparing multi-metal oxygen cluster is that node constructs porous catalyst and has great importance and potential application prospect.
Description
Technical field
The invention belongs to chemical synthesis process, and in particular to multi-metal oxygen cluster is the preparation that node constructs porous catalyst material
Method.
Background technique
Polyoxometallic acid salt ion (referred to as POMs) is a kind of construction unit for having nano-grade size, surface oxygen-enriched,
It is the ideal chose of design and customized framework material.In addition, more with redox active in many organic conversions
Oxometallate shows good prospect as oxidation reduction catalyst.Nevertheless, the biggish dissolution in reaction medium
The loss of degree, active site causes recyclability poor, this severely limits oxometallate as solid catalyst in reality
In extensive use.In order to improve recyclability, polyoxometallate be fixed on lewis acidity porous carrier (such as
Zeolite).However, these materials are often met difficulty in terms of synthesis, control and porous carrier filter out POMs.It exists simultaneously homogeneous
Form prevents the problems such as substrate is close to active site.Crystalline-state catalyst is due to its orderly crystal structure, rule and adjustable
Duct and high catalytic active site dot density.It can if organic ligand directly can be obtained even with multi-metal oxygen cluster key
Meet the crystalline-state catalyst of the polyacid base of the demand
Metal-organic framework (MOFs) is a kind of novel crystal of one kind with charming structure and excellent porous property
Material.Although, due to its lower conductivity, they are very it has been reported that MOFs material has good proton conductive property out
It is used as elctro-catalyst less.However, porosity and high surface area due to MOFs material, so that they may be in terms of electro-catalysis
With good advantage, such as evolving hydrogen reaction and oxygen reduction reaction (ORR).Various segments and biochip containing POM anion
Section (or metal-organic fragment) may construct POM base MOF material.It therefore, can in conjunction with the material of both POMs and MOFs advantage
Excellent catalytic activity is shown as elctro-catalyst or heterogeneous catalysis.Although POM base MOF material is as a kind of catalyst
It is widely studied, but so far, only minority POM base MOF material is as liberation of hydrogen catalyst.
The redox property of POM base MOF material combination polyoxometallate and the porosity of MOF are used as electrochemistry
Catalyst is advantageously possible for the generation of hydrogen.Furthermore under different pH value ranges, the stability of liberation of hydrogen catalyst in the solution is
It is vital.Therefore, it explores suitable polyoxometallate and suitable organic fragment synthesizes porous POM base MOF crystal material
Material is a task that is extremely important, being rich in challenge as non-precious metal base elctro-catalyst.
Summary of the invention
It is an object of the invention to provide a kind of with crystalline state, high selection according to the above deficiencies in the existing technologies
Property, high catalytic activity and multi-metal oxygen cluster the advantages that good stability be preparation method that node constructs porous catalyst material.
Based on multi-metal oxygen cluster node construct porous catalytic agent material by multi-metal oxygen cluster with organic bridge ligand suitable
PH and at a temperature of be converted into crystalline-state catalyst obtained from metal oxygen cluster-organic frame.This multi-metal oxygen cluster node is constructed
Porous catalytic agent material has broken the limitation of traditional polyacid, with good stability, selectivity and catalytic activity.
The preparation method of polyacid-like late transition metal-organic network catalyst material of the present invention includes the following steps:
(1) by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio；
(2) M salt (M includes Zn, Cd, Cu, Co, Ni, Zr, Hf, lanthanide series metal etc.), Asia is added in mixture in step (1)
Phosphoric acid and water stir 15 minutes；
(3) mixture that step (2) obtains adjusts pH value between 3 and 6, is fitted into autoclave, with 1-5 DEG C/min
Speed be warming up to 180 DEG C, keep the temperature 12 hours, then room temperature is down to 1-5 DEG C/min of speed, be added deionized water, filtering,
To reduce the residual M salt in surface or other impurity salts, bulk crystals i.e. [ε-Keggin M is obtained4]Cl4Multi-metal oxygen cluster；
(4) bulk [ε-Keggin M obtained step (3)4]Cl4Multi-metal oxygen cluster and organic bridge ligand are packed into high pressure
In reaction kettle, 180 DEG C are warming up to 1-5 DEG C/min of speed, keeps the temperature 12 hours, then room is down to 1-5 DEG C/min of speed
Deionized water is added in temperature, and filtering, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
Multi-metal oxygen cluster of the present invention constructs porous catalyst material catalyst for node and passes through the excellent of substituted type metal oxygen cluster
Gesture substitutes metal ion, synthesizing metal oxygen cluster-organic backbone.It avoids organic ligand and traditional oxygen-enriched POM cluster is difficult to
It is connected directly, reduces production cost and difficulty, enhance the structure designability and function controllability of material.With the prior art
It compares, the present invention has the advantage that first, the present invention is substituted metal ion using the advantage of substituted type metal oxygen cluster and answered
It closes functional group ligand and carries out self assembly coordination, to improve complex material structure diversification and stability.Second, this hair
Bright gained selects the organic ligand preparation of rigid benzene series carboxylic acid and the benzene series carboxylic acid of hydrophobic grouping modification to have isolated multicore position
Higher stability is presented to humidity and temperature in the porous catalyst of point and dynamics Subjective and Objective response characteristic, size adjustable, and
Stronger desulfurization characteristic can be showed.Third, simple synthetic method of the invention is feasible, operability with higher.Therefore, it prepares
Multi-metal oxygen cluster constructs porous catalytic agent material for node and has great importance and potential application prospect.
Detailed description of the invention
Fig. 1 is the resulting substituted type metal oxygen cluster basic cell structure figure of embodiment 1；
Fig. 2 is the structural formula of organic bridging ligand L；
Fig. 3 is that the resulting multi-metal oxygen cluster of embodiment 1 is the three-dimensional structure that node constructs porous catalytic agent material；
Fig. 4 is that the resulting multi-metal oxygen cluster of embodiment 1 is conventional photo and the scanning that node constructs porous catalytic agent material
Electromicroscopic photograph；
Fig. 5 is that the resulting multi-metal oxygen cluster of embodiment 1 is the acidproof alkaline stability survey that node constructs porous catalytic agent material
Examination.
Fig. 6 is that the resulting multi-metal oxygen cluster of embodiment 1 is the catalytic activity of hydrogen evolution survey that node constructs porous catalytic agent material
Examination.
Fig. 7 is that the resulting multi-metal oxygen cluster of embodiment 1 is the catalysate infrared light that node constructs porous catalytic agent material
Spectrum.
Specific embodiment
It is explained further the present invention with reference to embodiments, but embodiment does not do any type of limit to the present invention
It is fixed.
Embodiment 1
A kind of multi-metal oxygen cluster is that node constructs porous catalytic agent material, chemical component are as follows: [ε-Keggin Zn4]
L4/3。
Preparation method: by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio, and zinc salt, phosphorous acid and water (10ml) is added,
Stirring 15 minutes.Then mixture is adjusted pH value with dilute hydrochloric acid is to be fitted into autoclave between 3-6, with 1-5 DEG C/minute
The speed of clock is warming up to 180 DEG C, keeps the temperature 12 hours, then is down to room temperature with 1-5 DEG C/min of speed, and deionized water, mistake is added
Filter, to reduce the residual M salt in surface or other impurity salts, obtains bulk crystals i.e. [ε-Keggin Zn4]Cl4Multi-metal oxygen
Cluster.By obtained bulk [ε-Keggin Zn4]Cl4Multi-metal oxygen cluster and organic bridging ligand 1,3,5- tri- (4- carboxyl phenyl) benzene
It is fitted into autoclave, is warming up to 180 DEG C with 1-5 DEG C/min of speed, keeps the temperature 12 hours, then with 1-5 DEG C/min of speed
Degree is down to room temperature, deionized water is added, filtering, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
Embodiment 2
A kind of multi-metal oxygen cluster is that node constructs porous catalytic agent material, chemical component are as follows: [ε-Keggin La4]L2。
Preparation method: by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio, and lanthanum nitrate, phosphorous acid and water is added
(10ml) is stirred 15 minutes.Then mixture is adjusted pH value with dilute hydrochloric acid is to be fitted into autoclave between 3-6, with
1-5 DEG C/min of speed is warming up to 180 DEG C, keeps the temperature 12 hours, then be down to room temperature with 1-5 DEG C/min of speed, addition is gone
Ionized water, filtering, to reduce the residual M salt in surface or other impurity salts, obtains bulk crystals i.e. [ε-Keggin La4]Cl4
Multi-metal oxygen cluster.By obtained bulk [ε-Keggin La4]Cl4Multi-metal oxygen cluster and organic bridge ligand terephthalic acid (TPA) are packed into
In autoclave, 180 DEG C are warming up to 1-5 DEG C/min of speed, keeps the temperature 12 hours, then is dropped with 1-5 DEG C/min of speed
To room temperature, deionized water is added, filtering, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
Embodiment 3
A kind of multi-metal oxygen cluster is that node constructs porous catalytic agent material, chemical component are as follows: [ε-Keggin Zr4]
L4/3。
Preparation method: by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio, and acetic acid zirconium, phosphorous acid and water is added
(10ml) is stirred 15 minutes.Then mixture is adjusted pH value with dilute hydrochloric acid is to be fitted into autoclave between 3-6, with
1-5 DEG C/min of speed is warming up to 180 DEG C, keeps the temperature 12 hours, then be down to room temperature with 1-5 DEG C/min of speed, addition is gone
Ionized water, filtering, to reduce the residual M salt in surface or other impurity salts, obtains bulk crystals i.e. [ε-Keggin Zr4]Cl4
Multi-metal oxygen cluster.By obtained bulk [ε-Keggin Zr4]Cl4Multi-metal oxygen cluster and organic bridge ligand trimesic acid are packed into
In autoclave, 180 DEG C are warming up to 1-5 DEG C/min of speed, keeps the temperature 12 hours, then is dropped with 1-5 DEG C/min of speed
To room temperature, deionized water is added, filtering, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
Embodiment 4
A kind of multi-metal oxygen cluster is that node constructs porous catalytic agent material, chemical component are as follows: [ε-Keggin Zn4]L。
Preparation method: by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio, and zinc salt, phosphorous acid and water (10ml) is added,
Stirring 15 minutes.Then mixture is adjusted pH value with dilute hydrochloric acid is to be fitted into autoclave between 3-6, with 1-5 DEG C/minute
The speed of clock is warming up to 180 DEG C, keeps the temperature 12 hours, then is down to room temperature with 1-5 DEG C/min of speed, and deionized water, mistake is added
Filter, to reduce the residual M salt in surface or other impurity salts, obtains bulk crystals i.e. [ε-Keggin Zn4]Cl4Multi-metal oxygen
Cluster.By obtained bulk [ε-Keggin Zn4]Cl4(4- carboxyl phenyl) porphines-four in multi-metal oxygen cluster and organic bridge ligand
It is fitted into autoclave, is warming up to 180 DEG C with 1-5 DEG C/min of speed, keeps the temperature 12 hours, then with 1-5 DEG C/min of speed
Degree is down to room temperature, deionized water is added, filtering, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
Embodiment 5
A kind of multi-metal oxygen cluster is that node constructs porous catalytic agent material, chemical component are as follows: [ε-Keggin Co4]
L4/3。
Preparation method: by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio, and cobalt acetate, phosphorous acid and water is added
(10ml) is stirred 15 minutes.Then mixture is adjusted pH value with dilute hydrochloric acid is to be fitted into autoclave between 3-6, with
1-5 DEG C/min of speed is warming up to 180 DEG C, keeps the temperature 12 hours, then be down to room temperature with 1-5 DEG C/min of speed, addition is gone
Ionized water, filtering, to reduce the residual M salt in surface or other impurity salts, obtains bulk crystals i.e. [ε-Keggin Co4]Cl4
Multi-metal oxygen cluster.By obtained bulk [ε-Keggin Co4]Cl4Multi-metal oxygen cluster and organic bridge ligand trimesic acid are packed into
In autoclave, 180 DEG C are warming up to 1-5 DEG C/min of speed, keeps the temperature 12 hours, then is dropped with 1-5 DEG C/min of speed
To room temperature, deionized water is added, filtering, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
Effect example 1
We have carried out Catalysis experiments to synthesized embodiment 1, to measure its Electrocatalytic Property for Hydrogen Evolution.These experiment be
It is carried out in the solution (pH=0.16) of the H2SO4 of concentration 0.5M.Catalyst is in the H2SO4 solution that concentration is 0.5M, scanning
Polarization curve when rate is 5mVs-1.As a comparison, we also determine the compound of doping different proportion catalyst simultaneously
The electrocatalytic hydrogen evolution performance of material.The composite material ratio XC-72R modified electrode of catalyst doping XC-72R modified electrode has more
Activity.Meanwhile those pure catalyst of the current density ratio of composite material or XC- of catalyst doping XC-72R modified electrode
72R modified electrode is much larger lower than after -140mV.Hydrogen evolution activity after catalyst modified electrode doping carbon black is remarkably reinforced.
Effect example 2
We have carried out Catalysis experiments to synthesized embodiment 1, to measure its desulfurization catalyst performance.Take 50mL dibenzo thiophene
The isooctane solution (0.01mol/L) of pheno (DBT), heating and maintaining solution temperature is 80 DEG C, is added that 0.1g is compound urges thereto
Agent, blasts oxygen while being stirred continuously solution, and catalytic oxidation starts to carry out.Dibenzothiophenes is by catalysis oxidation
Process is monitored by uv-visible absorption spectra instrument, and at interval of certain time, equivalent is taken out from reaction mixture with syringe
Solution, after being diluted to same concentrations with isooctane, test its uv-visible absorption spectra and change with time.Reaction terminates
Afterwards, it is centrifugated catalyst, the DBT content in final isooctane solution passes through gas chromatograph and flame ionic detector
(GC-FID) it analyzes, as a result, it has been found that only 0.45mg DBT is not oxidized, 95% or more DBT is successfully stripped of.DBT's
Oxidation product is confirmed as dibenzothiophene sulphone through infrared spectrum analysis.
Claims (3)
1. multi-metal oxygen cluster is that node constructs porous catalyst material, which is characterized in that the porous catalyst material is with multi-metal oxygen cluster
Centered on be coordinated with rigid organic ligand L and then form three-dimensional porous crystal catalysis material.
2. multi-metal oxygen cluster includes the following steps: for the preparation method that node constructs porous catalyst material
(1) by molybdate and molybdenum powder, 5:1 is ground uniformly in molar ratio；
(2) M salt (M includes Zn, Cd, Cu, Co, Ni, Zr, Hf, lanthanide series metal etc.), phosphorous acid is added in mixture in step (1)
And water, it stirs 15 minutes；
(3) mixture for obtaining step (2) adjusts pH value between 3 and 6, is fitted into autoclave, with 1-5 DEG C/min
Speed is warming up to 180 DEG C, keeps the temperature 12 hours, then is down to room temperature with 1-5 DEG C/min of speed, and deionized water is added, and filters, with
The residual M salt in surface or other impurity salts are reduced, bulk crystals i.e. [ε-Keggin M is obtained4]Cl4Multi-metal oxygen cluster；
(4) bulk [ε-Keggin M obtained step (3)4]Cl4Multi-metal oxygen cluster and organic bridge ligand are packed into reaction under high pressure
In kettle, 180 DEG C are warming up to 1-5 DEG C/min of speed, 12 hours is kept the temperature, then room temperature is down to 1-5 DEG C/min of speed, adds
Enter deionized water, filter, it is that node constructs porous catalytic agent material that multi-metal oxygen cluster, which can be obtained,.
3. multi-metal oxygen cluster is the general formula that node constructs porous catalytic agent material: [ε-Keggin M4]L4/x, wherein L is organic bridge
Join ligand (include terephthalic acid (TPA), trimesic acid, 1,3,5- tri- (4- carboxyl phenyl) benzene, in-four (4- carboxyl phenyl) porphines
Deng rigid carboxylic acid organic ligand), M includes Zn, Cd, Cu, Co, Ni, Zr, Hf, lanthanide series metal etc., and x is to join in organic bridge ligand
With the carboxyl number being coordinated with multi-metal oxygen cluster.
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