CN108383860A - A kind of 4,4`- is bis-（Imidazole radicals）The Keggin-type polyacid and its preparation method and application of biphenyl modification - Google Patents
A kind of 4,4`- is bis-（Imidazole radicals）The Keggin-type polyacid and its preparation method and application of biphenyl modification Download PDFInfo
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 24
- 239000004305 biphenyl Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000012986 modification Methods 0.000 title claims abstract description 11
- 230000004048 modification Effects 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229940005654 nitrite ion Drugs 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims abstract description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910009112 xH2O Inorganic materials 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910018557 Si O Inorganic materials 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 abstract description 2
- LDOMKUVUXZRECL-UHFFFAOYSA-N 2-aminobenzene-1,3-dicarboxylic acid Chemical class NC1=C(C(O)=O)C=CC=C1C(O)=O LDOMKUVUXZRECL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 238000011160 research Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- -1 salt compound Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/11—Electrochemical processes, e.g. electrodialysis
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/45—Inorganic substances containing nitrogen or phosphorus
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/27—Cadmium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It is bis- that the present invention discloses a kind of 4,4'（Imidazole radicals）The Keggin-type polyacid and its preparation method and application of biphenyl modification, belongs to Chemistry of Polyacids new material technology field.1D chain polyacid compounds are cubic system, and space group isPbca,a=23.5(8)Å,b=15.8(5)Å,c=23.8(7)Å,α=90°,β=90°,γ=90°,V=8856.6(5),Z=4,R1=0.0691,wR2=0.1634.It is bis- using silico-tungstic acid, 4,4'（Imidazole radicals）Biphenyl, cadmium nitrate, 5 amino isophthalic acids and N, N dimethylacetylamide are made of raw material.Performance：Polyacid compound of the present invention has good electro-chemical activity, has reducing power to nitrite ion.
Description
Technical field
The invention belongs to Chemistry of Polyacids fields, and in particular to 4,4'- of one kind is bis-（Imidazole radicals）The Keggin of biphenyl modification
Type polyacid compound and preparation method thereof and chemical property.
Background technology
As soon as polyoxometallate chemistry caused as the important research field in inorganic chemistry before more than 100 years
The concern of people.Polyoxometalates refer to formed by transition metal elements such as vanadium, niobium, tantalum, molybdenum and tungsten it is one big
The metal oxide cluster of anionoid type " molecular state "（M. T. Pope, Springer, Berlin, 1983；Li Y W,
Guo L Y, Su H F, et al. Inorganic Chemistry, 2017, 56(5).）.Due to polyoxometallic acid salinization
Closing object has molecular dimension by d-π tracks and the determined characteristic electron structure of d-pi-electron and nanometer scope, therefore table
Reveal the characteristics such as unusual light, electricity, magnetic, catalysis and pharmacology.Until modern age, due to the hair of X-radiocrystallgraphy hardware and software
Exhibition and the application of ESR, NMR spectroscopy and electrochemical method, just there is further the property of polyoxometalates
Understanding, especially application of the polyoxometallate as catalyst in actual operation promoted the research in this field to take
Obtained substantial progress.Although to polyoxometallate research oneself have more than 100 years history, due to there is novel knot always
The polyoxometallic acid salt compound of structure type be synthesized and characterize and its unique chemical reactivity and novelty purposes not
It is found disconnectedly, the research Chang Sheng in this field does not wane（S. Reinoso, P. Vitoria, L. S. Felices, et
al, Inorg. Chem., 2007, 46, 1237.）.
4,4'- is bis-（Imidazole radicals）Biphenyl（C18N4H18）As nitrogenous bridging ligand, it can influence the structure of final product,
The dimension that can be used for expanding polyacid Base Metal-organic compound, particularly suitable for open framework and microcellular structure chemical combination is constructed
Object.But 4,4'- is bis-（Imidazole radicals）The end group of biphenyl is monodentate containing n-donor ligand, this makes it have with transition metal ions coordination
A variety of possibilities, so that the more difficult prediction such as the frame structure finally constructed, dimension, needs to carry out same reaction system big
Amount experimental study simultaneously accumulates the experimental results, is likely to obtain relevant structure-composition related information, is closed for rational design
At research.Currently, in CP, the fields MOF have been obtained for widely studying（Meng X M, Zhang X Y, Wang X P,
et al. Polyhedron, 2017, 137.；Meng X M, Zhang X, Qi P F, et al. Rsc Advances,
2017, 7(9):4855-4871.）, but research report is less in polyacid system.
The structural model of Keggin type polyacid is to be proposed by English physicist J.F.Keggin for 1934, structure
General formula is [XM12O40]n-(X=P, Si, Ge, M=Mo, W), Keggin anion are in
Heart tetrahedron XO4Composition, by the shared metal oxygen octahedra MO in 12 corners and angle6It surrounds.（Kozhevnikov I V.
Chemical Reviews, 1998, 98(1): 171-198.；Zhao J W, Li Y Z, Chen L J, et al.
Chemical Communications, 2016, 52(24): 4418-4445.）In various heteropoly acids, Keggin
Type polyacid is most stable, and is easier acquisition, this is most important for catalysis.It also shows huge catalysis simultaneously
Activity, the stability with high redox state can participate in the multielectron transfer reaction of Rapid reversible（M.
Sadakane, E. Steckhan, Chem. Rev. 98 (1) (1998) 219e238.）.This makes Keggin types more
The reciprocal characteristics of sour electronics transfer are especially valuable for the design of redox active electrode, because swift electron shifts power
Be very suitable for high power operation.In the past ten years, nitrite, acid iodide are had focused largely on for the research of polyacid
The application that salt, hydrogen peroxide and bromate restore（F.M. Zonoz, F. Aliabadi, Inorg. Chim. Acta
444 (2016) 87–94.；Y. Yu, H. Pang, H. Ma, Y. Song, K. Wang, J. Clust. Sci. 24
(2013) 17–29.）.
Invention content
The object of the present invention is to provide a kind of 4,4'- is bis-（Imidazole radicals）The Keggin type polyacid compounds of biphenyl modification
And its preparation method and application.
The 4,4'- is bis-（Imidazole radicals）The Keggin type polyacid compounds of biphenyl modification, have following formula（1）'s
Molecular formula,
{Cd(bibp)0.5(DMA)4}2(SiW12O40)（bibp = C18N4H14, DMA=C4H9NO）.
Formula（1）
The polyacid compound is cubic system, and space group isPbca, a = 23.5(8) Å, b = 15.8(5) Å, c =
23.8(7) Å, α = 90°, β = 90°, γ = 90°.（Å：Length unit is equal to 100 pm）.
V=8856.6 (5) in the space group, Z=4, R1 = 0.0691, wR2= 0.1634；Formula（1）Change
Close polyoxoanion (SiW of the object by 1 keggin structure12O40)2-, Z fonts are connected by { Cd2 (bibp) } unit
Chain；Then three-dimensional is extended by intermolecular hydrogen bonding between Z print trains and Z print trains（3D）Frame；Wherein Cd2+Using six
Coordination mode, six coordination atoms are respectively from four DMA molecules, a polyoxoanion (SiW12O40)2-End oxygen and one
The nitrogen-atoms of a ligand bibp.
Above-mentioned formula（1）Compound crystal has the infrared signature vibration of Si-O, W-O, C-O, C-H and N-H
Absorption peak.
A kind of preparation method of Keggin types polyacid compound of the present invention, carries out according to the following steps：
By silico-tungstic acid（H4[Si(W3O10)4]·xH2O）, 4,4'- it is bis-（Imidazole radicals）Biphenyl（C18N4H18）, cadmium nitrate（Cd
(NO3)2）, 5-amino isophthalic acids（C8H7NO4）And N, N-dimethylacetylamide（C4H9NO）30 min are stirred in mixing,
It is subsequently placed in stainless steel cauldron interior sealing, the stainless steel cauldron of sealing is placed in the baking oven that temperature is 140 DEG C, heating 3
It, room temperature cooling obtains yellow bulk crystals, finally uses distilled water, ethyl alcohol washing and drying at room temperature successively, obtains polyacid crystalline substance
Body.
The 4,4'- is bis-（Imidazole radicals）Biphenyl（C18N4H18）It is prepared by following methods：4,4'- dibromos are joined
Benzene, imidazoles, K2CO3And CuSO4It mixes and is heated 12 hours at 180 DEG C；Mixture is cooled to room temperature, is washed with water, it is remaining
Object is extracted three times with ethyl alcohol；It by organic layer separation and is evaporated to dryness, obtains crude product, crude product with methanol and water recrystallization obtain
4,4'- is bis-（Imidazole radicals）Biphenyl.
The H4[Si(W3O10)4]·xH2O and C18N4H18 Molar ratio be 1:1；The H4[Si(W3O10)4]·xH2O
With Cd (NO3)2 Molar ratio be 1:1；The H4[Si(W3O10)4]·xH2O mole and C4H9The volume ratio of NO is
0.035mmol：5mL.
A kind of method of electrochemical reduction nitrite ion of the present invention, which is characterized in that the polyacid compound
It can electrochemical reduction nitrite ion.
Keggin types polyacid compound energy electrochemical reduction nitrite ion of the present invention.
The beneficial effects of the invention are as follows：1, the C that the present invention uses18N4H18The structure of final product can be influenced, its end
Base monodentate containing n-donor ligand makes it be coordinated there are many possibility with transition metal ions, so that the frame structure finally constructed,
The more difficult prediction such as dimension.2, the C that the present invention uses8H7NO4Play the role of environment modifier in preparation process, obtains height
The polyacid crystal compound of yield.Polyacid compound of the present invention has good electro-chemical activity, has to nitrite ion
Reducing power.
Description of the drawings
Fig. 1 is the molecular structure of 1 compound of formula provided by the invention（Omit DMA molecules）.
Fig. 2 is the 3D frame diagrams of 1 compound of formula provided by the invention（Omit DMA molecules）.
Fig. 3 is the infrared spectrogram of 1 compound of formula provided by the invention.
Fig. 4 is the thermogravimetric analysis figure of 1 compound of formula provided by the invention.
Fig. 5 is H of 1 compound of formula provided by the invention in 0.05mol/L, pH=12SO4Difference sweeps speed in solution（25
mv/s ~ 200 mV/s）Under cyclic voltammogram.
Fig. 6 is H of 1 compound of formula provided by the invention in 0.05mol/L, pH=12SO4Solution（I）With
The H of 0.05mol/L, pH=12SO4Solution and the NO for containing a concentration of 9.8 mmol/L2 -（II）In cyclic voltammogram.
Specific implementation mode
The present invention provides a kind of 4,4'- is bis-（Imidazole radicals）The Keggin type polyacid compounds of biphenyl modification, have formula
（1）Shown in molecular formula,
{Cd(bibp)0.5(DMA)4}2(SiW12O40)（bibp = C18N4H14, DMA=C4H9NO）
Formula（1）.
Wherein, by monocrystalline X-x ray diffraction to formula（1）The structure of shown compound is parsed, and the result is shown in Figure 1 ~
Fig. 2, Fig. 1 are the molecular structure of 1 compound of formula provided by the invention（Omit DMA molecules）, Fig. 2 is formula 1 provided by the invention
The 3D frame diagrams of compound（Omit DMA molecules）；Specifically, by single crystal diffraction result it is found that the compound be cubic system,
Space group isPbca, a = 23.5(8) Å, b = 15.8(5) Å, c = 23.8(7) Å, α = 90°, β = 90°,γ = 90°, V = 8856.6(5), Z = 4, R1 = 0.0691, wR2=0.1634,（Å：Length unit is equal to 100
pm）.Show formula by mono-crystalline structures parsing（1）Compound by 1 keggin structure polyoxoanion (SiW12O40)2-,
Z print trains are connected by { Cd2 (bibp) } unit.Then chain extends into three-dimensional by intermolecular hydrogen bonding（3D）Frame.Its
Middle Cd2+Using hexa-coordinate pattern, six coordination atoms are respectively from four DMA molecules, a polyoxoanion (SiW12O40
)2-End oxygen and a ligand bibp nitrogen-atoms.
The present invention also provides a kind of 4,4'- is bis-（Imidazole radicals）The system of the Keggin type polyacid compounds of biphenyl modification
Preparation Method, including：
By silico-tungstic acid（H4[Si(W3O10)4]·xH2O）, 4,4'- it is bis-（Imidazole radicals）Biphenyl（C18N4H18）, cadmium nitrate（Cd
(NO3)2）, 5-amino isophthalic acids（C8H7NO4）And N, N-dimethylacetylamide（C4H9NO）Mixing stirs 30 min, so
It is placed on stainless steel cauldron interior sealing, the stainless steel cauldron of sealing is placed in the baking oven that temperature is 140 DEG C, heating 3
It, room temperature cooling obtains brown color bulk crystals, finally uses distilled water, ethyl alcohol washing and drying at room temperature successively, obtains polyacid crystalline substance
Body.
The H4[Si(W3O10)4]·xH2O and C18N4H18Molar ratio be 1:1；The H4[Si(W3O10)4]·
xH2O and Cd (NO3)2Molar ratio be 1:1；The H4[Si(W3O10)4]·xH2O and C8H7NO4 Molar ratio be 1:
1；The H4[Si(W3O10)4]·xH2O mole and C4H9The volume ratio of NO is 0.035mmol：5mL.
Experiment base stock used：It is hydrated silico-tungstic acid H4[SiO4(W3O9)4]·xH2O （Chinese medicines group chemical reagent is limited
Company）；5-amino isophthalic acid C8H7NO4 （Sinopharm Chemical Reagent Co., Ltd.）；N, N-dimethylacetylamide
C4H9NO （Sinopharm Chemical Reagent Co., Ltd.）；4,4'- is bis-（Imidazole radicals）Biphenyl C18N4H18It is closed by following methods
At gained：By 4,4'- '-dibromobiphenyls, imidazoles, K2CO3And CuSO4It mixes and is heated 12 hours at 180 DEG C.By mixture
It is cooled to room temperature, is washed with water, residue is extracted three times with ethyl alcohol.It by organic layer separation and is evaporated to dryness, obtains crude product, it will
It is bis- with first alcohol and water recrystallization acquisition 4,4'-（Imidazole radicals）Biphenyl.
The advantageous effect of present embodiment is：1, the C that present embodiment uses18N4H18The structure of final product can be influenced,
Its end group monodentate containing n-donor ligand, making it, there are many possibilities with transition metal ions coordination, so that the frame finally constructed
The more difficult prediction such as frame structure, dimension.2, the C that present embodiment uses8H7NO4Environment modifier is played in preparation process
Effect, obtains the polyacid crystal compound of high yield.
Using infrared spectrometer, in 4000 cm-1 ~ 400 cm-1 It is scanned in wave-number range.Fig. 3 is that the present invention is more
The infrared spectrogram of acid compound shows the eigen vibration absorption peak of Si-O, W-O, C-O, C-H and N-H.
Using thermogravimetric analyzer, in N2Under protection system, heating rate is 15 DEG C/min, and temperature elevating range is 0-1000
Differential thermal analysis is carried out to polyacid compound of the present invention at DEG C, Fig. 4 is the hot weight curve of polyacid compound of the present invention, can by figure
Know, first step weightlessness is since 230 DEG C, until 400 DEG C or so end, measured value are 8.24 %, second step weightlessness is from 625 DEG C
Terminate to 934 DEG C or so, the penalty values of quality are 18.35 %.Corresponding according to the theoretical calculation first stage is ligand 4,
4'- is bis-（Imidazole radicals）Biphenyl（C18N4H18）Destruction（Calculated value is 7.11%）, corresponding second stage is N, N-dimethyl
Acetamide（C4H9NO）The removing of ion（Calculated value is 17.16%）.The two is substantially coincide.
Weigh formula prepared by the 5 mg present invention（1）Polyacid compound is simultaneously ground, and the polyacid crystal of grinding is placed in 0.1 mL
Ethyl alcohol and 0.05 mL Nafion mixed solutions in 30 min of ultrasonic disperse, obtain suspension, by suspension load in glass carbon
Working electrode is made in electrode surface, and using platinum electrode as auxiliary electrode, saturated calomel electrode is reference electrode, and chemical property exists
298 K, the H of electrolyte solution 0.05mol/L, pH=12SO4It is measured in solution.Fig. 5 is that the polyacid crystal of the present invention exists
The H of pH=1 0.05mol/L2SO4Cyclic voltammogram in solution, as shown in Figure 5 when sweep speed is changed to from 25 mV/s
When 200 mV/s, the position at peak does not have significant change.Peak value（II）The relationship of electric current and sweep speed is as shown in Fig. 5.By Fig. 5
It is found that under the sweep speed that 25 mV/s change to 200 mV/s, formula（1）The anode current of compound is with sweep speed at just
Than this shows that oxidation-reduction process is granule surface contral.
Fig. 6 is the formula of the present invention（1）H of the polyacid crystal in 0.05 mol/L, pH=12SO4Solution（I）, and 0.05
The H of mol/L, pH=12SO4Solution and contain the NO of 9.6 mmol/L2 -（II）In cyclic voltammogram, can from figure
Go out, with NO2 -Addition, all reduction peak currents significantly increase, and corresponding oxidation peak current decreases, and says
Bright NO2 -It is reduced.Polyacid compound of the present invention has good electro-chemical activity, has reducing power to nitrite ion.
Claims (8)
1. a kind of 4,4'- is bis-（Imidazole radicals）The Keggin-type polyacid compound of biphenyl modification, has formula（1）Molecular formula,
{Cd(bibp)0.5(DMA)4}2(SiW12O40)
Formula（1）, bibp=C in formula18N4H14, DMA = C4H9NO；
Formula（1）Compound is cubic system, and space group isPbca, a = 23.5(8) Å, b = 15.8(5) Å, c =
23.8(7) Å, α = 90°,β = 90°, γ = 90°。
2. bis- according to the 4,4'- described in claim 1（Imidazole radicals）The Keggin type polyacid compounds of biphenyl modification, it is special
Sign is, V=8856.6 (5) in the space group, Z=4, R1 = 0.0691, wR2= 0.1634；Formula（1）Change
Close polyoxoanion (SiW of the object by 1 keggin structure12O40)2-, Z fonts are connected by { Cd2 (bibp) } unit
Chain；Then three-dimensional is extended by intermolecular hydrogen bonding between Z print trains and Z print trains（3D）Frame；Wherein Cd2+Using six
Coordination mode, six coordination atoms are respectively from four DMA molecules, a polyoxoanion (SiW12O40)2-End oxygen and one
The nitrogen-atoms of a ligand bibp.
3. the 4,4'- according to claim 1 or 2 is bis-（Imidazole radicals）The Keggin type polyacid compounds of biphenyl modification,
It is characterized in that, formula（1）There is compound crystal the infrared signature vibration of Si-O, W-O, C-O, C-H and N-H to inhale
Receive peak.
4. a kind of preparation method of Keggin types polyacid compound, includes the following steps：
By silico-tungstic acid（H4[Si(W3O10)4]·xH2O）, 4,4'- it is bis-（Imidazole radicals）Biphenyl（C18N4H18）, cadmium nitrate（Cd
(NO3)2）, 5- amino isophthalic acids（C8H7NO4）And N, N- dimethylacetylamide（C4H9NO）Mixing stirs 30 min, so
It is placed on stainless steel cauldron interior sealing, the stainless steel cauldron of sealing is placed in the baking oven that temperature is 140 DEG C, heating 3
It, room temperature cooling obtains brown color bulk crystals, uses distilled water, ethyl alcohol washing and drying at room temperature successively, obtains polyacid crystal.
5. according to the preparation method described in claim 4, which is characterized in that 4, the 4'- is bis-（Imidazole radicals）Biphenyl
（C18N4H18）It is prepared by following methods：By 4,4'- '-dibromobiphenyls, imidazoles, K2CO3 And CuSO4It mixes and adds at 180 DEG C
Heat 12 hours；Mixture is cooled to room temperature, is washed with water, residue is extracted three times with ethyl alcohol；By organic layer separation and evaporate
To doing, crude product is obtained, it is bis- that crude product with methanol and water recrystallization obtain 4,4'-（Imidazole radicals）Biphenyl.
6. the preparation method according to claim 4 or 5, which is characterized in that the H4[Si(W3O10)4]·xH2O with
C18N4H18 Molar ratio be 1:1；The H4[Si(W3O10)4]·xH2O and Cd (NO3)2 Molar ratio be 1:1；The H4
[Si(W3O10)4]·xH2O and C8H7NO4Molar ratio be 1:1；The H4[Si(W3O10)4]·xH2O mole and C4H9NO
Volume ratio be 0.035mmol：5mL.
7. a kind of method of electrochemical reduction nitrite ion, which is characterized in that any described using claim 1-3
Polyacid compound electrochemical reduction nitrite ion.
8. any polyacid compound of claim 1-3 is applied to electrochemical reduction nitrite ion.
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| CN111057016A (en) * | 2019-12-11 | 2020-04-24 | 嘉兴学院 | Polyacid compound modified by multidentate bridging organic ligand |
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| CN110128326A (en) * | 2019-06-05 | 2019-08-16 | 哈尔滨理工大学 | Polyacid based supermolecular material and preparation method with difunctional electrocatalysis characteristic |
| CN111057016A (en) * | 2019-12-11 | 2020-04-24 | 嘉兴学院 | Polyacid compound modified by multidentate bridging organic ligand |
| CN111057016B (en) * | 2019-12-11 | 2021-06-25 | 嘉兴学院 | Polyacid compound modified by multidentate bridging organic ligand |
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