CN111450890A - Mixed isopolymolybdate organic-inorganic hybrid material and preparation method and application thereof - Google Patents
Mixed isopolymolybdate organic-inorganic hybrid material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 16
- 235000010323 ascorbic acid Nutrition 0.000 abstract description 8
- 229960005070 ascorbic acid Drugs 0.000 abstract description 8
- 239000011668 ascorbic acid Substances 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- 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
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Abstract
The invention belongs to the technical field of polyacid chemistry, and particularly relates to a mixed isopolymolybdate organic-inorganic hybrid material, and a preparation method and application thereof. The molecular formula of the mixed isopolymolybdate organic-inorganic hybrid material provided by the invention is [ Cu ]4(tpy)4(β‑Mo8O26)(γ‑Mo8O26)]·0.5H2O, the organic-inorganic hybrid material contains mixed isopolymolybdate which is based on β -Mo8O26And gamma-Mo8O26A unit and a Cu-terpyridine complex. The invention adopts a hydrothermal method to prepare the organic-inorganic hybrid material, has simple and convenient operation and simple structureThe preparation requirement is low, and the synthesis time is greatly saved. Meanwhile, the material has double electrocatalysis effects on reduction reaction of nitrite and oxidation reaction of ascorbic acid.
Description
Technical Field
The invention relates to the technical field of polyacid chemistry, in particular to a mixed isopolymolybdate organic-inorganic hybrid material and a preparation method and application thereof.
Background
Due to the adjustable structural characteristics and abundant redox properties of polyacid, polyacid is widely used for constructing organic-inorganic hybrid materials in crystal engineering. In addition, studies on the binding of transition metals to nitrogen-containing ligands have attracted attention from a number of researchers.
In recent years, the synthesis research of polyacid-based metal organic framework compounds has attracted the interest of numerous researchers, such materials have potential application prospects in the aspects of catalysis, material science, photoelectric materials, devices and the like, isopolymolybdate is an important component in the polyacid family, has an oxygen-rich surface and easily coordinated terminal oxygen atoms, therefore, the existing research generally utilizes isopolymolybdate as an inorganic ligand and a transition metal as a junction to form an organic-inorganic hybrid material based on isopolymolybdate (Wanli Zhou, Yanping Zheng, Gang Yuan, Jun Pen. Dalton Trans.,2019,48,2598-2605, Wanli Zhou, Ping L iu, Yaning Zheng, Jun Pen. catalysis Surveys, Asia, 2018,22,136-45, Wanli Zhong Zhang, Jung Ju et J.catalysis, Jun hybridization materials are inorganic hybrid materials with single-inorganic hybrid complexes, which have no restriction on synthesis of the polyoxolymolybdate, the unimorph materials are organic hybrid materials with enhanced performance, and the unimodal hybrid materials are organic hybrid materials with single inorganic ligands, no restriction on hybridization technology of the shortage of the transition metals 10993, and the unimodal hybrid materials.
Disclosure of Invention
The invention aims to provide a mixed isopolymolybdate organic-inorganic hybrid material, a preparation method and application thereof, wherein the mixed isopolymolybdate organic-inorganic hybrid material simultaneously contains mixed Mo8O26Clusters and transition metal complexes.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a mixed isopolymolybdate organic-inorganic hybrid material with a molecular formula of [ Cu4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O。
The invention provides a preparation method of the mixed isopolymolybdate organic-inorganic hybrid material in the technical scheme, which comprises the following steps:
mixing ammonium molybdate, copper nitrate, nitrogen heterocyclic ligand and water, adjusting the pH value of the obtained mixed solution to 4.2-4.3, and carrying out hydrothermal reaction to obtain a mixed isopolymolybdate organic-inorganic hybrid material;
the nitrogen heterocyclic ring ligand is 2,2 ', 6 ', 2 ' -tripyridine.
Preferably, the mass ratio of the ammonium molybdate to the copper nitrate to the nitrogen heterocyclic ligand is 5: 3-5: 1-2.
Preferably, the using amount ratio of the ammonium molybdate to the water is 0.15-0.20 g: 7-10 m L.
Preferably, the mixing is carried out under the condition of stirring, the stirring speed is 150-200 r/min, and the stirring time is 30-35 min.
Preferably, the reagent for adjusting the pH value is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 2 mol/L.
Preferably, the temperature of the hydrothermal reaction is 160-170 ℃ and the time is 4-5 d.
The invention provides the application of the mixed isopolymolybdate organic-inorganic hybrid material in the technical scheme or the mixed isopolymolybdate organic-inorganic hybrid material prepared by the preparation method in the technical scheme in electrocatalysis.
The invention provides a mixed isopolymolybdate organic-inorganic hybrid material with a molecular formula of [ Cu4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O, the organic-inorganic hybrid material contains mixed isopolymolybdate which is based on β -Mo8O26And gamma-Mo8O26Cell and Cu-The novel organic-inorganic hybrid material containing the mixed isopolymolybdate can play a role in the concerted catalysis of different types of isopolymolybdate in the catalytic property.
The invention provides a preparation method of the mixed isopolymolybdate organic-inorganic hybrid material, and the preparation method adopts a hydrothermal method to prepare the organic-inorganic hybrid material, so that the operation is simple and convenient, the equipment requirement is low, and the synthesis time is greatly saved.
The invention ensures that the material simultaneously contains mixed Mo by controlling the pH value of the hydrothermal reaction8O26Cluster (β -Mo)8O26And gamma-Mo8O26) And transition metal complexes (Cu-tripyridine complexes).
The invention provides application of the mixed isopolymolybdate organic-inorganic hybrid material in electrocatalysis. According to the embodiment, the material has double electrocatalytic effects on the reduction reaction of nitrite and the oxidation reaction of ascorbic acid.
Drawings
FIG. 1 is a schematic molecular structure diagram of a mixed isopolymolybdate organic-inorganic hybrid material according to the present invention;
FIG. 2 is an infrared spectrum of the material prepared in example 1;
FIG. 3 is a graph showing the electrochemical performance test of the material prepared in example 1;
FIG. 4 is an infrared spectrum of a material prepared in a comparative example.
Detailed Description
The invention provides a mixed isopolymolybdate organic-inorganic hybrid material with a molecular formula of [ Cu4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O。
The mixed isopolymolybdate organic-inorganic hybrid material contains two types of Mo8O26Units, in particular based on β -Mo8O26And gamma-Mo8O26The specific structure of the organic-inorganic hybrid material of the unit and the Cu-terpyridine (Cu-tpy) complex is shown in figure 1, wherein Cu1# 1 and Cu1#12#2 represents symmetric atoms of Cu1 and Cu2, the symmetric operation is #1-x,1-y,1-z, and #2-1-x, -y, 2-z., as can be seen from the figure, the molecular asymmetric unit comprises two copper atoms, two tripyridine ligands and β -Mo8O26And gamma-Mo8O26Unit, two Cu atoms are connected with a tri-pyridine ligand through three Cu-N bonds to form { Cu (tpy) }2+Building Unit, { Cu (tpy) }2+Connection β -Mo8O26And gamma-Mo8O26The anion clusters form a one-dimensional chain structure.
The invention provides a preparation method of the mixed isopolymolybdate organic-inorganic hybrid material in the technical scheme, which comprises the following steps:
mixing ammonium molybdate, copper nitrate, nitrogen heterocyclic ligand and water, adjusting the pH value of the obtained mixed solution to 4.2-4.3, and carrying out hydrothermal reaction to obtain a mixed isopolymolybdate organic-inorganic hybrid material; the nitrogen heterocyclic ring ligand is 2,2 ', 6 ', 2 ' -tripyridine.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In the present invention, the ammonium molybdate, preferably (NH), and the copper nitrate are preferably used in the form of hydrates4)6Mo7O24·4H2O, the copper nitrate is preferably (Cu (NO)3)2·6H2The mass ratio of the ammonium molybdate to the copper nitrate to the nitrogen heterocyclic ligand is preferably 5: 3-5: 1-2, more preferably 5: 3.2-3.5: 1.2-1.5, and the dosage ratio of the ammonium molybdate to the water is preferably 0.15-0.20 g: 7-10 m L, more preferably 0.16-0.18 g: 8-9 m L.
In the invention, the mixing is preferably carried out under the condition of stirring, the stirring speed is preferably 150-200 r/min, more preferably 160-180 r/min, and the stirring time is preferably 30-35 min, more preferably 32-34 min; after stirring was complete, a clear blue solution was obtained.
In the present invention, the reagent for adjusting the pH is preferably a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is preferably 2 mol/L.The invention adjusts the pH value to enable the subsequent hydrothermal reaction to be carried out under the acidic condition and promote β -Mo8O26And gamma-Mo8O26The formation of units and their bonding to Cu-tripyridine complexes.
In the invention, the temperature of the hydrothermal reaction is preferably 160-170 ℃, more preferably 165 ℃, the time is preferably 4-5 d, more preferably 4.5d8O26And gamma-Mo8O26The unit is characterized in that metal Cu is combined with an azacyclo ligand to form a Cu-tpy complex, and the three building units are linked through a Cu-O covalent bond to form the organic-inorganic hybrid material.
After the hydrothermal reaction is finished, the system is preferably naturally cooled to room temperature, and the mixed isopolymolybdate organic-inorganic hybrid material is obtained after crystallization.
The invention provides the application of the mixed isopolymolybdate organic-inorganic hybrid material in the technical scheme or the mixed isopolymolybdate organic-inorganic hybrid material prepared by the preparation method in the technical scheme in electrocatalysis. In the present invention, the application of the mixed isopolymolybdate organic-inorganic hybrid material in electrocatalysis is preferably electrocatalysis on reduction reaction of nitrite and oxidation reaction of ascorbic acid. The method of the present invention is not particularly limited, and a method known to those skilled in the art may be selected.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Will be (NH)4)6Mo7O24·4H2O(0.1500g)、Cu(NO3)2·6H2Adding O (0.1200g) and 2,2 ': 6 ', 2 ' -tripyridine (0.0430g) into 7m L distilled water, stirring for 30 min at 200r/min, adjusting pH of the obtained mixture to 4.3 with HCl solution (2 mol/L), placing the obtained mixture into a 25m L polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 5 days, cooling the obtained system to room temperature to obtain 0.0230g blue blocky crystals, namely [ Cu4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O, yield about 4.65% (based on elemental Mo).
Detection and Performance testing
1) For the product prepared in example 1, the Mo and Cu contents were determined using an L eeman metal element analyzer, and the C, H, N, C content was determined using a Perkin-Elmer 2400 element analyzer60H45N12O52.50Cu4Mo16The experimental values of elemental analysis (theoretical values) (%) of (1) were Mo 42.80(43.08), Cu 7.00(7.13), C20.00 (20.21), H1.35 (1.26), and N4.50 (4.72).
2) The product prepared in example 1 was subjected to infrared detection, and the obtained infrared spectrum was shown in FIG. 2, and the obtained infrared spectrum data was (cm)-1) 3450(s),3123(w)1586(s),1509(s),1315(s),1252(s),1134(m),1078(s),940(s),890(s),850(s),703(s)640(s)703 (w). Thus, the product is 640, 850 and 940cm-1The characteristic peak of (A) is attributed to β -Mo8O26And gamma-Mo8O26V (Mo ═ O) in aniont) And v (Mo-O-Mo),1078-1586cm-1The characteristic peak of (A) is attributed to the tripyridine ligand, 3450cm-1The characteristic peak of the water molecule is shown to indicate that the prepared product contains (β -Mo)8O26) And (gamma-Mo)8O26) And Cu-tpy and H2O。
3) Performing electrochemical performance test on the material prepared in example 1 by using a CHI-660E electrochemical workstation, wherein an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and a self-made carbon paste electrode is used as a working electrode; the manufacturing method of the self-made carbon paste electrode comprises the following steps: 0.01g of the material prepared in example 1 and 0.10g of carbon powder were mixed and ground uniformly, two drops of paraffin were added and stirred to a paste, and the paste was filled into a glass tube having an inner diameter of 2.0mm, and a copper wire was used as a wire.
The results of electrochemical detection of sodium nitrite and ascorbic acid by the above test method are shown in fig. 3, wherein (a) is the reduction current curve of the material prepared in example 1 for different concentrations of sodium nitrite (from top to bottom, the concentrations are 0,2,4,6, and 8mM, respectively), and (b) is the oxidation current curve of the material prepared in example 1 for different concentrations of ascorbic acid (from bottom to top, the concentrations are 0,2,4,6, and 8mM, respectively).
The results show that the material prepared in example 1 has dual electrocatalytic effects on the reduction of nitrite and oxidation of ascorbic acid, wherein the catalytic effect on the reduction of nitrite is attributed to β -Mo8O26And gamma-Mo8O26The catalytic effect of the unit, on the oxidation reaction of ascorbic acid, is due to the Cu-terpyridine complex.
Comparative example
The material was prepared as described in example 1, except that the pH of the resulting mixture was adjusted to 4.15 to obtain an organic-inorganic hybrid material [ Cu ]2(tpy)2(H2O)2(β-Mo8O26)]。
Performing infrared detection on the organic-inorganic hybrid material in a comparative ratio, wherein the obtained infrared spectrum is shown in figure 4, and the obtained infrared spectrum data is (cm)-1) 3560(s),1605(s),1475(s),1328(s),1088(m),943(s),882(s),720(s),550 (m). From this infrared data, the material was found to be 720, 882 and 943cm-1The characteristic peak of (A) is attributed to β -Mo8O26V (Mo ═ O) in aniont) And v (Mo-O-Mo),1088-1605cm-1The characteristic peak of (A) is attributed to the tripyridine ligand, which indicates that the material contains single Mo8O26Clustered organic-inorganic hybrid materials [ Cu ]2(tpy)2(H2O)2(β-Mo8O26)]。
Example 2
Will be (NH)4)6Mo7O24·4H2O(0.1508g)、Cu(NO3)2·6H2Adding O (0.1300g) and 2,2 ': 6 ', 2 ' -tripyridine (0.0420g) into 7m L distilled water, stirring at 200r/min for 35min, adjusting pH of the obtained mixture to 4.2 with HCl solution (2 mol/L), placing the obtained mixture into a 25m L polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 4 days, cooling the obtained system to room temperature to obtain blue blocky crystals, namely [ Cu4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O。
Example 3
Will be (NH)4)6Mo7O24·4H2O(0.1506g)、Cu(NO3)2·6H2Adding O (0.1450g) and 2,2 ': 6 ', 2 ' -tripyridine (0.0346g) into 10m L distilled water, stirring at 180r/min for 35min, regulating the pH value of the obtained mixed solution to 4.2 with HCl solution (2 mol/L), placing the obtained mixture into a 25m L polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 5 days, cooling the obtained system to room temperature to obtain blue blocky crystals, namely [ Cu4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O。
The embodiment shows that the invention provides the mixed isopolymolybdate organic-inorganic hybrid material, the preparation method and the application thereof, and the organic-inorganic hybrid material contains the mixed isopolymolybdate which is based on β -Mo8O26And gamma-Mo8O26A unit and a Cu-terpyridine complex. Meanwhile, the material has double electrocatalysis effects on reduction reaction of nitrite and oxidation reaction of ascorbic acid.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. Mixed isopolymolybdate organicAn inorganic hybrid material characterized in that the molecular formula is [ Cu ]4(tpy)4(β-Mo8O26)(γ-Mo8O26)]·0.5H2O。
2. The method for preparing mixed isopolymolybdate organic-inorganic hybrid materials as claimed in claim 1, which comprises the following steps:
mixing ammonium molybdate, copper nitrate, nitrogen heterocyclic ligand and water, adjusting the pH value of the obtained mixed solution to 4.2-4.3, and carrying out hydrothermal reaction to obtain a mixed isopolymolybdate organic-inorganic hybrid material;
the nitrogen heterocyclic ring ligand is 2,2 ', 6 ', 2 ' -tripyridine.
3. The preparation method according to claim 2, wherein the mass ratio of ammonium molybdate to copper nitrate to nitrogen heterocyclic ligand is 5: 3-5: 1-2.
4. The preparation method according to claim 2 or 3, wherein the amount ratio of the ammonium molybdate to the water is 0.15-0.20 g: 7-10 m L.
5. The method according to claim 2, wherein the mixing is carried out under stirring conditions, wherein the stirring speed is 150 to 200r/min, and the stirring time is 30 to 35 min.
6. The method according to claim 2, wherein the agent for adjusting the pH is a hydrochloric acid solution having a concentration of 2 mol/L.
7. The preparation method according to claim 2, wherein the temperature of the hydrothermal reaction is 160-170 ℃ and the time is 4-5 days.
8. Use of the mixed isopolymolybdate organic-inorganic hybrid material described in claim 1 or the mixed isopolymolybdate organic-inorganic hybrid material prepared by the preparation method described in any one of claims 2 to 7 in electrocatalysis.
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