CN105646550A - Silver coordination polymer and preparing method and application thereof - Google Patents
Silver coordination polymer and preparing method and application thereof Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title abstract description 23
- 229920001795 coordination polymer Polymers 0.000 title abstract description 23
- 238000000034 method Methods 0.000 title abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910052709 silver Inorganic materials 0.000 title abstract description 6
- 239000004332 silver Substances 0.000 title abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 21
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 19
- 229940012189 methyl orange Drugs 0.000 claims abstract description 19
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000004305 biphenyl Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 239000001048 orange dye Substances 0.000 abstract description 3
- 238000002411 thermogravimetry Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000000921 elemental analysis Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silver coordination polymer. The chemical formula of the silver coordination polymer is C24H20AgN4O2, 4,4'-di(parazole-1-methyl)-biphenyl is taken as the major ligand, terephthalic acid is taken as the auxiliary ligand, distilled water is taken as the solvent, the microwave heating reflux synthesis method is adopted, the first binode two-dimensional '4,4L10' topological network structure is formed, sufficient representation of the structure is achieved through elemental analysis, thermogravimetry and a single crystal X-ray diffractometer, and the luminescent property and degradation property on methyl orange dye of the structure are researched in detail too. The preparing process is simple, the yield and purity of crystals are high, high thermal stability and special luminescent property are realized, organic pollutants can be degraded through Fenton-like reaction, degradation efficiency is high, and the silver coordination polymer can serve as a catalyst and has great application prospects in the field of luminescent materials and environment protection.
Description
Technical field
The present invention relates to metal-organic coordination polymer material and preparation thereof and application, particularly a kind of Ag coordinated polymer and its preparation method and application.
Background technology
Metal organic coordination polymer is with its charming topological structure, and in the huge potential value that the fields such as catalysis, luminescence, gas storage, molecular magnetism, ion exchange exist, causes the concern of chemist. There is natural decomposition difficulty, decomposition cycle longer shortcoming for organic pollution, the catalysis material of coordination polymer is applied to the degraded of organic pollution and has caused and pay close attention to widely, and becomes a kind of green, stable, efficient environment restoring method. Construct outside multi-dimensional spatial structure except with multidentate ligand and symmetry part by covalent bond, low-dimensional coordination polymer can also be utilized to extend multidimensional network by the intermolecular weak interaction power of non-covalent bond, such as hydrogen bond, ��-pi-conjugated and other weak interaction. Wherein, some significant weak interaction forces, as passed through d10Electronic shell forms closed shell electrical arrangement and the argentophilicity (Ag Ag) that formed, and the coordination polymer of silver is formed material impact. Having of argentophilicity helps form special frame structure and then affect the carrying out of catalytic reaction; Induction high luminous performance. Therefore, these weak forces of systematic research are most important to the formation of metal coordinating polymer framework and the character of coordination polymer. Under normal circumstances, preparation method many employings hydro-thermal method of metal organic complex, the method needs the environment of High Temperature High Pressure, and reaction condition wants height, and power consumption height, the time is long, is unfavorable for the industrialized production of product.
Summary of the invention
Based on above technical Analysis and Problems existing, the invention provides a kind of Ag coordinated polymer and its preparation method and application, this Ag coordinated polymer has heat stability, fluorescence, and the degraded of organic pollution is had catalytic action, and technical scheme is as follows:
A kind of Ag coordinated polymer, chemical formula is C24H20AgN4O2With silver nitrate, main ligand L, assistant ligand p-phthalic acid for raw material, distilled water is solvent, microwave heating backflow synthetic method is adopted to prepare, wherein L=4,4 '-two (pyrazoles-1-methyl)-biphenyl, described ligand structure is anorthic system, space group P ��, cell parameter is: a=8.4155 (8), b=11.2864 (8), c=11.9091 (13), ��=82.8370 (9), ��=81.7250 (10), ��=71.1400 (10) ��;Infrared absorption peak is: 3109cm-1, 1569cm-1, 1518cm-1, 1400cm-1, 1281cm-1, 1093cm-1, 1055cm-1, 758cm-1, 744cm-1, 623cm-1��
Further, what the silver-colored central ion of described Ag coordinated polymer was formed is the pentacoordinate tetragonal pyramid space geometry configuration slightly distorted, ligand L overseas Chinese federation silver ion forms double-core secondary units, because two adjacent silver atoms distance (2.8483 (5)) define strong argentophilicity less than two silver atoms radius summation (2.89), secondary units is connected into further one-dimensional pearl type chain, one-dimensional chain forms first binode (4 by the connection of p-phthalic acid, 4) " 4 connected, 4L10 " two-dimensional layer topological structure, and it is expanded into Magnetic Properties of Three-Dimensional Supramolecular Complex structure further by hydrogen bond.
A kind of Ag coordinated polymer closes preparation method and comprises the following steps:
(1) by silver nitrate, ligand L, p-phthalic acid and water are sequentially added in single port bottle, and stirring and dissolving at normal temperatures is placed in microwave reactor;
(2) being warming up to 100 DEG C in 15 minutes, and back flow reaction is after 30 minutes at 100 DEG C, then gradient cooling is cooled to room temperature, obtains colourless bulk crystals;
(3) product filtered and remove impurity with absolute ethanol washing and be placed in air natural drying and obtain this coordination compound.
Further, the mol ratio of described silver nitrate, 4,4 '-two (pyrazoles-1-methyl)-biphenyl and p-phthalic acid is: 1:1:2.
A kind of Ag coordinated polymer has photoluminescent property, as luminescent material; Methyl orange is had the effect of catalytic degradation by the Ag coordinated polymer that one kettle way is prepared when class Fenton, is used as the catalyst of the nitrogenous waste water from dyestuff of degraded.
The present invention compared with prior art, has the following advantages:
Preparation is simple for microwave heating, fast and homogeneous heating, has automatic thermal balance performance, will not produce superheating phenomenon, utilizes aqueous solvent to absorb microwave simultaneously and is heated heating up, and efficient energy-saving is beneficial to the industrialized production of product; Crystal yield (about 60%) and purity are higher simultaneously; This Ag coordinated polymer has higher heat stability and special photoluminescent property, can pass through class Fenton's reaction degradable organic pollutant, and degradation efficiency is higher, can as a kind of catalyst, the nitrogenous fuel waste water of catalytic degradation. The present invention not only facilitates the synthesis to crystalline material and carries out rational Design on Plane, and has huge application prospect at luminescent material and field of environment protection.
Accompanying drawing explanation
Fig. 1 is X-ray powder diffraction (XRPD) spectrogram of coordination polymer;
Fig. 2 is the thermogravimetric analysis figure of coordination polymer;
Fig. 3 is the environment map of coordination polymer;
Fig. 4 is the connection figure of coordination polymer;
Fig. 5 is the topological diagram of coordination polymer;
Fig. 6 is the Magnetic Properties of Three-Dimensional Supramolecular Complex structure chart of coordination polymer;
Fig. 7 is coordination polymer coordination compound and the Solid fluorescene spectrum of free ligand L;
Fig. 8 is the catalytic degradation methyl orange lab diagram of coordination polymer coordination compound.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is elaborated:
As shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8, a kind of Ag coordinated polymer, formula is C24H20AgN4O2With silver nitrate, main ligand L, assistant ligand p-phthalic acid for raw material, distilled water is solvent, adopt microwave heating backflow preparation, wherein L=4,4 '-two (pyrazoles-1-methyl)-biphenyl, described Ag coordinated polymer structure is anorthic system, space group P ��, cell parameter is: a=8.4155 (8), b=11.2864 (8), c=11.9091 (13), ��=82.8370 (9), ��=81.7250 (10), ��=71.1400 (10) ��;Infrared absorption peak is: 3109cm-1, 1569cm-1, 1518cm-1, 1400cm-1, 1281cm-1, 1093cm-1, 1055cm-1, 758cm-1, 744cm-1, 623cm-1��
What the silver-colored central ion of a kind of Ag coordinated polymer was formed is the pentacoordinate tetragonal pyramid space geometry configuration slightly distorted, ligand L overseas Chinese federation silver ion forms double-core secondary units, because two adjacent silver atoms distance (2.8483 (5)) define strong argentophilicity less than two silver atoms radius summation (2.89), secondary units is connected into further one-dimensional pearl type chain, one-dimensional chain forms first binode (4 by the connection of p-phthalic acid, 4) " 4 connected, 4L10 " two-dimensional layer topological structure, and it is expanded into Magnetic Properties of Three-Dimensional Supramolecular Complex structure further by hydrogen bond.
A kind of Ag coordinated polymer closes preparation method and comprises the following steps:
(1) by silver nitrate, ligand L, p-phthalic acid and water are sequentially added in single port bottle, and stirring and dissolving at normal temperatures is placed in microwave reactor;
(2) being warming up to 100 DEG C in 15 minutes, and back flow reaction is after 30 minutes at 100 DEG C, then gradient cooling is cooled to room temperature, obtains colourless bulk crystals;
(3) product filtered and remove impurity with absolute ethanol washing and be placed in air natural drying and obtain this coordination compound.
A kind of method prepared by Ag coordinated polymer, the mol ratio of described silver nitrate, 4,4 '-two (pyrazoles-1-methyl)-biphenyl and p-phthalic acid is: 1:1:2.
A kind of Ag coordinated polymer has photoluminescent property, as luminescent material; Methyl orange is had the effect of catalytic degradation by the Ag coordinated polymer that one kettle way is prepared when class Fenton, is used as the catalyst of the nitrogenous waste water from dyestuff of degraded.
Embodiment 1:
1. the method step that an Ag coordinated polymer is standby is as follows:
(1) by 17.0mg silver nitrate (0.1mmol), 31.4mg ligand L (0.1mmol), 33.2mg p-phthalic acid (0.2mmol) and 12mL water are sequentially added in single port bottle, and stirring and dissolving at normal temperatures is placed in microwave reactor;
(2) in 15 minutes, be warming up to 100 DEG C, and at 100 DEG C back flow reaction after 30 minutes, gradient cooling, be slowly cooled to room temperature, obtain colourless bulk crystals;
(3) product filtered and remove impurity with absolute ethanol washing and be placed in air natural drying and obtain this coordination compound.
2. the Ag coordinated polymer of pair preparation characterizes:
(1) powder diffraction characterizes phase purity
X-ray powder diffraction (XRPD) spectrogram of coordination compound is as shown in Figure 1, wherein Simulated is the spectrogram that the single crystal structural data according to coordination polymer is simulated by Mercury software obtaining, As-synthesized is that coordination compound is in the scope of 5-50 ��, recorded by X-ray powder diffractometer, the powder diffractogram obtained by origin software processes. It can be seen that the position of critical peak mutually coincide very good, this coordination compound describing synthesis is pure phase, is practically free of impurity, also illustrates that this coordination compound is stable existence in laboratory conditions.
(2) thermogravimetric characterizes stability
For characterizing the heat stability of coordination compound comprehensively, we carry out thermogravimetric analysis to 800 DEG C with the thermograde of 10 DEG C/min from room temperature in a nitrogen atmosphere, determine the TG curve of coordination compound, as shown in Figure 2. Along with temperature raises, it is weightless that coordination compound shows two steps. The first step is C from 226 degree to 325 ��, and weightless 61.1%, what correspondence lost is L part (theoretical value is 62.1%);Second step from 371 �� of C to 503 �� of C, corresponding organic ligand H2Tpa decomposes, and final residual thing 25.0% is AgO(theoretical value 24.6%). Result shows that coordination polymer is stable before 226 DEG C.
(3) crystal structure determination
Choose under microscope that size is suitable, form is regular, internal structure is without the monocrystalline of obvious slight crack, it is bonded at a glass fibre top with binding agent, then monocrystalline is arranged on BrukerSmart1000CCDX-ray single crystal diffraction instrument, through the Mo-K alpha ray (l=0.71073) of graphite monochromator monochromatization, carry out crystallography Diffraction Data Collection with the scanning speed of ��-2 ��. All of diffraction data all adopts SADABS program to carry out semiempirical absorption correction. Data convert and structure elucidation use SAINT and SHELXTL program to complete respectively. Crystal structure direct method solves, and first determines whole non-hydrogen atom coordinate by difference functions method and method of least square, and obtains hydrogen atom position with theoretical hydrogenation method, then with method of least square, crystal structure is carried out refine
(4) Fig. 3 to be connection figure, Fig. 5 that coordination environment figure, Fig. 4 are this polymer of this coordination polymer be topological diagram of this polymer, Fig. 6 are the Magnetic Properties of Three-Dimensional Supramolecular Complex structure chart of this polymer.
3. Application Example
(1) photoluminescent property
We at room temperature determine coordination compound and the Solid fluorescene spectrum of free ligand L, as shown in Figure 4. Free ligand L, when excitation wavelength is 245nm, has strong emission peak at 389nm place, it is possible to speculate that peak is from n �� �� * or �� �� �� * transition. Coordination polymer is when excitation wavelength is 300nm, strong emission peak is had at 337nm place, compare with free ligand, emission peak positions generation blue shift 27nm, this shows the L part in coordination compound and silver ion coordination, forms interacting addicted to silver Ag Ag of part support, improves the rigidity of coordination compound, thus reducing skeletal vibration, the radiative decay being launched excited state by part reduces energy loss.
(2) catalytic property
The solid catalyst (coordination compound or silver nitrate) of 0.01mmol and the mixing of 0.04mmol sodium peroxydisulfate, it is added in methyl orange solution (20mg/L) solution of 100 milliliters, mixture is placed in the round-bottomed flask of 250 milliliters, magnetic agitation, utilizes circulation constant temperature water reaction temperature to be controlled at 40 �� of about C. At given interval, take out 3ml suspension, centrifugation, analyze under setted wavelength with visible spectrophotometer. Under the same conditions, utilizing the silver nitrate of equimolar amounts to do catalyst degraded methyl orange, experimental result compares with complex-catalyzed degradation results. Degradation efficiency can be expressed as variable color percentage ratio (%), it is considered to initial and final absorbance, and dye solution is at wavelength 496nm(respectively C0And CT).
The efficiency of degraded methyl orange can be defined as follows:
%D=[(C0-Ct)/C0] �� 100(1)
C0(mg/L) it is methyl orange initial concentration, Ct(mg/L) it is concentration after methyl orange degradation reaction t (min).
Catalytic degradation mechanism following (2-4):
AgI-MOCP+S2O8 2-��AgII-MOCP+SO4 ��-+SO4 2-(2)
AgII-MOCP+S2O8 2-��AgI-MOCP+2SO4 ��-(3)
azodye+SO4 ��-�� oxidationproducts(4)
As it is shown in figure 5, in controlled trial, Na2S2O8Highly stable with the absorbance of methyl orange mixture, it does not have any noticeable change, even if the response time was up to 110 minutes, the degradation rate of methyl orange is only 19.2%, it was shown that Na2S2O8With methyl orange occurs almost without between reaction, Na2S2O8Individually can not effectively degrade methyl orange. But, when being joined in system by coordination polymer, reaction causes the lighter of methyl orange, and at first in 30 minutes, methyl orange dye is by fast degradation, and the methyl orange dye of 71.9% is oxidized.After 110 minutes, the degradation efficiency of methyl orange is higher than 98.4%. Due to Ag(I) ion is likely to play a crucial role in the reaction, and the silver nitrate of equivalent carries out experimentation under the same conditions as catalyst, and compared with the catalytic degradation efficiency of coordination compound, the degradation efficiency of methyl orange is relatively low, and only 36.3%. In order to disclose the speed of catalytic reaction intuitively, we depict (C0/Ct) to change over figure, K value be 0.0020(K0), 0.0041(K1) and 0.0386(K2) control experiment, the reaction rate adding coordination compound is 10 times of the reaction rate adding silver nitrate. It is shown that this coordination compound is in similar Fenton system, methyl orange has high catalytic degradation activity.
The above; being only the specific embodiment of the present invention, but the protection domain of invention is not limited thereto, any those of ordinary skill in the art are in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should be encompassed within protection scope of the present invention.
Claims (5)
1. an Ag coordinated polymer, it is characterised in that: chemical formula is C24H20AgN4O2With silver nitrate, main ligand L, assistant ligand p-phthalic acid for raw material, distilled water is solvent, microwave heating backflow synthetic method is adopted to prepare, wherein L=4,4 '-two (pyrazoles-1-methyl)-biphenyl, described Ag coordinated polymer structure is anorthic system, space group is P ��, and cell parameter is: a=8.4155 (8), b=11.2864 (8), c=11.9091 (13), ��=82.8370 (9), ��=81.7250 (10), ��=71.1400 (10) ��; Infrared absorption peak is: 3109cm-1, 1569cm-1, 1518cm-1, 1400cm-1, 1281cm-1, 1093cm-1, 1055cm-1, 758cm-1, 744cm-1, 623cm-1��
2. a kind of Ag coordinated polymer according to claim 1, it is characterized in that: the silver-colored central ion of described Ag coordinated polymer is tetragonal pyramid space geometry configuration, ligand L bridging silver ion forms double-core secondary units, due to the argentophilicity between silver ion, secondary units is connected into one-dimensional pearl type chain, one-dimensional chain forms first binode (4 by the connection of p-phthalic acid, 4) " 4; 4L10 " the two-dimensional layer topological structure connected, and it is expanded into Three-dimensional Supramolecular Network further by hydrogen bond.
3. the preparation method of an a kind of Ag coordinated polymer as claimed in claim 1, it is characterised in that comprise the following steps:
(1) by silver nitrate, ligand L, p-phthalic acid and water are sequentially added in single port bottle, and stirring and dissolving at normal temperatures is placed in microwave reactor;
(2) being warming up to 100 DEG C in 15 minutes, and back flow reaction is after 30 minutes at 100 DEG C, then gradient cooling is cooled to room temperature, obtains colourless bulk crystals;
(3) product filtered and remove impurity with absolute ethanol washing and be placed in air natural drying and obtain this coordination compound.
4. a kind of Ag coordinated polymer preparation method according to claim 3, it is characterised in that: the mol ratio of described silver nitrate, 4,4 '-two (pyrazoles-1-methyl)-biphenyl and p-phthalic acid is: 1:1:2.
5. the application of an a kind of Ag coordinated polymer as claimed in claim 1, it is characterised in that: described Ag coordinated polymer has photoluminescent property, as luminescent material; Methyl orange is had the effect of catalytic degradation by this polymer that microwave one kettle way is prepared when class Fenton, the catalyst of the nitrogenous waste water from dyestuff that can be used as degrading.
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| CN106501230A (en) * | 2016-12-22 | 2017-03-15 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN106496583A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | 4 silver formate polymer of pyrazoles and preparation method thereof |
| CN107149946A (en) * | 2017-04-25 | 2017-09-12 | 河南农业大学 | A kind of application of fenton catalyst in degraded organic pollutants |
| CN107913737A (en) * | 2016-10-11 | 2018-04-17 | 宁波大学 | A kind of double-core silver（I）Complex catalysis material and preparation method |
| CN113061258A (en) * | 2021-03-02 | 2021-07-02 | 华侨大学 | Nonlinear crystal material based on silver metal and organic framework, preparation method and application |
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| CN106279713A (en) * | 2016-08-09 | 2017-01-04 | 郑州大学 | Silver monobromide polyrotaxane supermolecule polymer, its preparation method and application |
| CN106279713B (en) * | 2016-08-09 | 2019-11-15 | 郑州大学 | Silver bromide polyrotaxane supermolecule polymer, preparation method and application |
| CN106496583A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | 4 silver formate polymer of pyrazoles and preparation method thereof |
| CN107913737A (en) * | 2016-10-11 | 2018-04-17 | 宁波大学 | A kind of double-core silver（I）Complex catalysis material and preparation method |
| CN106501230A (en) * | 2016-12-22 | 2017-03-15 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN106501230B (en) * | 2016-12-22 | 2019-01-08 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN107149946A (en) * | 2017-04-25 | 2017-09-12 | 河南农业大学 | A kind of application of fenton catalyst in degraded organic pollutants |
| CN107149946B (en) * | 2017-04-25 | 2019-06-11 | 河南农业大学 | A kind of application of fenton catalyst in degradation organic pollutants |
| CN113061258A (en) * | 2021-03-02 | 2021-07-02 | 华侨大学 | Nonlinear crystal material based on silver metal and organic framework, preparation method and application |
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