CN114621262A - Preparation and application of metal nanocluster material for rapidly detecting methanol - Google Patents
Preparation and application of metal nanocluster material for rapidly detecting methanol Download PDFInfo
- Publication number
- CN114621262A CN114621262A CN202011476963.0A CN202011476963A CN114621262A CN 114621262 A CN114621262 A CN 114621262A CN 202011476963 A CN202011476963 A CN 202011476963A CN 114621262 A CN114621262 A CN 114621262A
- Authority
- CN
- China
- Prior art keywords
- ligand
- transition metal
- methanol
- organic
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 150000003573 thiols Chemical class 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 150000003623 transition metal compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- -1 transition metal salt Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017744 AgPF6 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001544 silver hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 16
- 229910052737 gold Inorganic materials 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 abstract description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007942 carboxylates Chemical class 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000004332 silver Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 239000010931 gold Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 208000008918 voyeurism Diseases 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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 System
- C07F1/10—Silver compounds
-
- 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 System
- C07F1/08—Copper compounds
-
- 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 System
- C07F1/12—Gold compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
Abstract
The invention discloses a metal nanocluster material for rapidly detecting methanol as well as a preparation method and application thereof, and belongs to the technical field of sensing detection. The structural formula of the metal nanocluster material prepared by the invention is Mn @ Lx(RCO2) y, wherein M is one or two of transition metals Au, Ag and Cu, L is organic ligand alkynyl ligand, thiol ligand, thiophenol ligand and RCO2Is organic carboxylate, trifluoroacetate, acetate, pentafluoropropionate or benzoate, n represents the number of metal atoms in the structure, x represents the number of organic ligands, and y represents the number of organic acid radicals. The synthesis method is simple and feasible, the yield is high, and the obtained metal nanocluster materialCan selectively detect the methanol, and has the advantages of good stability, repeated use and the like.
Description
Technical Field
The invention belongs to the technical field of sensing detection, and particularly relates to a metal nanocluster material for rapidly detecting methanol, and a preparation method and application thereof.
Background
Methanol is saturated monohydric alcohol with a simple structure, has a very stable structure, is difficult to decompose into water and carbon dioxide under natural conditions, is a basic raw material and an important solvent of various organic products, and is widely used in industries such as organic synthesis, dyes, medicines, coatings, national defense and the like. However, the lowest dose of oral methanol poisoning is about 100mg/kg body weight, and 0.3-1 g/kg oral intake can kill the human. With the improvement of environmental protection awareness and human safety awareness, it is important to detect the methanol residue in the environment. Although researchers in the prior art adopt metal oxide nanoparticles as gas-sensitive materials for detecting methanol gas, the defects of low sensitivity, poor selectivity, long response time and the like exist, and therefore, the development of a method for quickly detecting methanol in an anti-interference manner is a technical problem which needs to be solved urgently.
In recent years, metal nanocluster materials represented by gold and silver have attracted much attention of relevant researchers due to their unique optical and electrical properties and their great application prospects in the fields of new energy research, photoelectric information storage, biomedical science, industrial catalysis and the like. However, no report has been found on the research on the metal nanocluster material capable of rapidly and selectively detecting methanol and the application thereof.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a metal nanocluster material for rapid and selective detection of methanol and applications thereof.
The purpose of the invention is realized by the following modes:
the invention provides a metal nanocluster material which is a metal nanoparticle with a structural formula of Mn@Lx(RCO2)yM is one or two of transition metals (Au, Ag and Cu), L is an organic ligand (alkynyl ligand, thiophenol ligand or sulfur)Alcohol ligand), RCO2The organic carboxylate can be trifluoroacetate, acetate, pentafluoropropionate, benzoate and the like, n is a positive integer and represents the number of metal atoms in the structure, x is a positive integer and represents the number of organic ligands, and y is also a positive integer and represents the number of organic acid radicals.
Further, a direct-acting Ag-M bond (M is any one of Au, Ag and Cu) exists in the structure of the metal nanocluster material.
Further, the metal nanocluster material is a soluble solid powder and the formed solution is a liquid sol.
The invention provides a preparation method of the metal nanocluster material, which comprises the following steps:
(1) dissolving a transition metal compound in a certain amount of organic solvent, then dropwise adding the transition metal compound into an organic solvent solution in which an organic ligand and triethylamine are dissolved, and reacting for a period of time to obtain a solid;
(2) and (2) dispersing the solid obtained in the step (1) in an organic solvent, dropwise adding a transition metal salt dissolved in a proper amount of the organic solvent into the organic solution, reacting for a period of time to obtain a solid, and drying to obtain the metal nanocluster material.
Further, in the step (1), the transition metal is one or more than two of gold, silver or copper.
Further, the transition metal compound in the step (1) is AgBF4、AgNO3、AgClO4，AgPF6、AgSbF6、Me2SAuCl, chloroauric acid, Cu (MeCN)4BF4Or Cu (BF)4)2One or more than two of them.
Further, the organic ligand in the step (1) is one or more of alkynyl ligand, thiophenol ligand or thiol ligand.
Further, the organic solvent in the step (1) and the step (2) is one or a mixture of more than two of methanol, dichloromethane, ethanol and acetone in any proportion.
Further, the transition metal salt in the step (2) is AgCO2CF3、AgCO2CH3、AgCO2C2F5、AgCO2C2H5Any one of them.
Further, the molar ratio of active H to triethylamine in the organic ligand in the step (1) is 1: (1-10).
Further, the molar ratio of the transition metal compound to the functional group of the organic ligand in step (1) is 1: (1-5).
Further, the molar amount of the transition metal salt in the step (2) is 2 to 5 times that of the transition metal compound in the step (1).
Further, the reaction conditions in the step (1) and the step (2) are room temperature and light-proof, and stirring reaction is carried out for 10min-2 h.
Further, the step (1) and the step (2) also comprise washing the obtained solid 3-5 times by using an organic solvent.
Further, the drying manner in step (2) includes vacuum drying.
The invention provides an application of the metal nanocluster material in rapid detection of methanol gas.
Further, the application mainly comprises the following steps: the metal nanocluster material is dispersed in an organic solvent, then sprayed on a PET plastic film with copper wires, under the irradiation of infrared light, methanol is atomized above the PET plastic film, and detection is carried out by using a detection device.
Furthermore, the detection device is an optoelectronic signal detection device, and the response condition of the electrical signal is recorded by an ammeter.
Compared with the prior art, the invention has the following beneficial effects:
1. the synthesis method of the gold/silver nano-particles of the methanol gas-sensitive material is simple and easy to implement and has high yield.
2. The methanol gas-sensitive material nano-particles have the advantages of high quantum yield, short response time and high sensitivity, and can generate obvious signal response to methanol under the irradiation of visible light and near infrared light.
3. The methanol gas-sensitive material nano-particles have good stability, can be repeatedly used, and can be widely applied to the aspects of methanol gas sensing and detection.
4. The methanol gas-sensitive material nano-particles have higher selectivity to methanol and have wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
Fig. 1 is a schematic structural view of silver nanoparticles prepared in example 1.
Fig. 2 is a powder diffraction pattern of the silver nanoparticles prepared in example 1.
Fig. 3 is a schematic diagram of an apparatus for detecting organic solvent gas by silver nanoparticles.
Fig. 4 is a graph showing the response of an electric signal when the silver nanoparticles are used for detecting methanol gas in example 2.
FIG. 5 is the response of silver nanoparticles to an electric signal in the detection of ethanol gas in example 3.
FIG. 6 is the response of silver nanoparticles to an electric signal when detecting acetone gas in example 4.
FIG. 7 is the response of silver nanoparticles to toluene gas in example 5.
Fig. 8 is a stability test of silver nanoparticles of example 6 under light.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Example 1:
process for preparing metal nanocluster material
157mg of 2-hydroxybenzonitrile is weighed and added into a 100mL round-bottom flask, 1 equivalent of triethylamine and 20mL of methanol are added, after stirring and reacting for several minutes, 1 equivalent of AgBF is weighed4Dissolved in 10ml of methanol and added dropwise slowly with rapid stirringTo a round bottom flask, the reaction was stirred at room temperature for 1h in the absence of light. After the reaction, the obtained white precursor was centrifuged and washed with methanol 3 to 5 times.
100mg of the precursor obtained by the reaction was weighed into a 100mL round-bottom flask, and 20mL of methanol was added. About 800mg of AgCO is taken2CF3Dissolving in 20ml of methanol, dropwise adding into a round-bottom flask, stirring and reacting for about 10min in the dark to obtain a light yellow solution, and performing rotary evaporation to obtain white silver nanoparticles with the yield of 80%.
The schematic structure of the silver nanoparticles prepared by the above method is shown in fig. 1, and the detection is performed by using powder XRD, and the result is shown in fig. 2.
Example 2:
use of metal nanocluster materials for methanol detection
Dispersing silver nanoparticles into n-hexane in a dark room, coating the n-hexane on a PET (polyethylene terephthalate) film with copper wires to form a silver nanoparticle film, connecting the copper wires to two poles of an ammeter respectively, drying the silver nanoparticle coating, spraying methanol above the silver nanoparticle coating through a spray can under the irradiation of a near-infrared lamp, and detecting the change of a current signal by means of the ammeter by controlling the on-off of the near-infrared lamp.
The change of the electric signal of the ammeter along with the time and the on-off of the infrared lamp is shown in fig. 4, and it can be seen from the graph that the silver nanoparticles have obvious electric signal response under illumination, and meanwhile, the electric signal has obvious on/off characteristics along with the existence of illumination.
Example 3:
use of metal nanocluster materials for ethanol detection
In a dark room, dispersing silver nanoparticles into n-hexane, coating the n-hexane on a PET (polyethylene terephthalate) film with copper wires to form a silver nanoparticle film, connecting the copper wires to two poles of an ammeter respectively, drying the silver nanoparticle coating, spraying ethanol above the silver nanoparticle coating through a spray can under the irradiation of a near-infrared lamp, and detecting the change condition of an electric signal by means of the ammeter by controlling the on-off of the near-infrared lamp.
The change of the electric signal of the ammeter along with the time and the on-off of the infrared lamp is shown in fig. 5, and it can be seen from the graph that the silver nanoparticles have a weaker electric signal response under illumination, and simultaneously, the electric signal has an on/off characteristic along with the presence or absence of illumination.
Example 4: use of metal nanocluster materials for acetone detection
In a dark room, dispersing silver nanoparticles into n-hexane, coating the n-hexane on a PET film with copper wires, respectively connecting the copper wires to two poles of an ammeter, drying the silver nanoparticle coating, spraying acetone above the silver nanoparticle coating through a spray can under the irradiation of a near-infrared lamp, and detecting the change of a current signal by means of the ammeter by controlling the on-off of the near-infrared lamp.
The change of the electric signal of the ammeter with time and the on-off of the infrared lamp is shown in fig. 6, and it can be seen from the graph that the silver nanoparticles have almost no electric signal response under the illumination.
Example 5: detection of toluene using metal nanocluster materials
Dispersing silver nanoparticles into n-hexane in a dark room, coating the n-hexane on a PET (polyethylene terephthalate) film with copper wires, respectively connecting the copper wires to two poles of an ammeter, drying the silver nanoparticle coating, spraying toluene above the silver nanoparticle coating through a spray can under the irradiation of a near-infrared lamp, and detecting the change of a current signal by means of the ammeter by controlling the on-off of lamplight.
The change of the electric signal of the ammeter with time and the on-off of the infrared lamp is shown in fig. 7, and it can be seen from the graph that the silver nanoparticles have almost no electric signal response under the illumination.
Example 6: detection of stability of silver nanoparticles by powder XRD
The powdery silver nanoparticles are spread on clean white paper, the white paper is irradiated for 1 hour in the sun, the color change of the silver nanoparticles before and after the irradiation is recorded by a camera, and the change of the internal structure of the silver nanoparticles is detected by a powder XRD spectrogram in a peeping way.
As shown in fig. 8, the silver nanoparticles showed good stability under light, and the silver nanoparticles showed no evidence of significant black decomposition in the color of the sample powder after 1 hour of light irradiation. And the powder XRD diffraction pattern of the sample is not obviously changed before and after illumination, further showing that the gas-sensitive silver nanoparticle material has good light stability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a metal nanocluster material, comprising the steps of:
(1) dissolving a transition metal compound in a certain amount of organic solvent, dropwise adding the transition metal compound into the organic solvent in which an organic ligand and triethylamine are dissolved, and reacting for a period of time to obtain a solid;
(2) and (2) dispersing the solid obtained in the step (1) in an organic solvent, then dropwise adding a transition metal salt dissolved in a proper amount of the organic solvent, reacting for a period of time to obtain a solid, and drying to obtain the metal nanocluster material.
2. The process according to claim 1, wherein the transition metal compound in the step (1) is AgBF4、AgNO3、AgClO4，AgPF6、AgSbF6、Me2SAuCl, chloroauric acid, Cu (MeCN)4BF4Or Cu (BF)4)2And the organic ligand is one or more than two of alkynyl ligand, thiophenol ligand or thiol ligand.
3. The method according to claim 2, wherein the transition metal salt in the step (2) is AgCO2CF3、AgCO2CH3、AgCO2C2F5、AgCO2C2H5Any one of them.
4. The method according to claim 1, wherein the organic solvent in step (1) and step (2) is one or more of methanol, dichloromethane, ethanol, and acetone mixed in any ratio.
5. The process according to any one of claims 1 to 4, wherein the molar ratio of active H to triethylamine in the organic ligand in step (1) is 1: (1-10), wherein the molar ratio of the transition metal compound to the functional group of the organic ligand is 1: (1-5).
6. The method according to claim 5, wherein the molar amount of the transition metal salt in the step (2) is 2 to 5 times the molar amount of the transition metal compound in the step (1).
7. The preparation method of claim 6, wherein the reaction conditions in step (1) and step (2) are room temperature and light-shielding, and stirring for 10min-2 h.
8. A metal nanocluster material produced by the production method of any one of claims 1 to 7.
9. Use of the metal nanocluster material of claim 8 for rapid detection of methanol gas.
10. The application according to claim 9, characterized in that it comprises the following steps: the metal nanocluster material according to any one of claims 1 to 7 dispersed in an organic solvent is sprayed on a PET plastic film with copper wires, methanol is atomized over the PET plastic film under irradiation of infrared light, and the response of an electric signal is recorded by an ammeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011476963.0A CN114621262B (en) | 2020-12-14 | 2020-12-14 | Preparation and application of metal nanocluster material for rapidly detecting methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011476963.0A CN114621262B (en) | 2020-12-14 | 2020-12-14 | Preparation and application of metal nanocluster material for rapidly detecting methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114621262A true CN114621262A (en) | 2022-06-14 |
| CN114621262B CN114621262B (en) | 2023-11-28 |
Family
ID=81896625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011476963.0A Active CN114621262B (en) | 2020-12-14 | 2020-12-14 | Preparation and application of metal nanocluster material for rapidly detecting methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114621262B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6699717B1 (en) * | 1997-02-12 | 2004-03-02 | The University Of Maryland Baltimore County | Method using luminescent transition metal-ligand complex for detecting polar solvents |
| CN101434612A (en) * | 2007-11-14 | 2009-05-20 | 中国科学院大连化学物理研究所 | Metal organic framework compound material, as well as preparation and application thereof |
| CN102675373A (en) * | 2012-04-06 | 2012-09-19 | 华中师范大学 | Methanol indicator and preparation method thereof |
| US20150268207A1 (en) * | 2012-04-13 | 2015-09-24 | University Of Maryland, College Park | Highly Selective Nanostructure Sensors and Methods of Detecting Target Analytes |
| CN105651835A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Methanol gas sensor and preparation method thereof |
| CN105699439A (en) * | 2016-02-25 | 2016-06-22 | 济南大学 | Preparation method and application of methanol gas sensor based on carbon nitride loaded metal and metal oxide composite |
| CN106053413A (en) * | 2016-06-13 | 2016-10-26 | 华东师范大学 | Metal organic fluorescent methanol sensing film and preparation method thereof |
| US20180172656A1 (en) * | 2012-04-13 | 2018-06-21 | University Of Maryland, College Park | Device having an array of sensors on a single chip |
| CN108398467A (en) * | 2018-03-06 | 2018-08-14 | 上海应用技术大学 | A kind of gas sensor and its construction method based on carbon nanotube and metal nanoparticle |
-
2020
- 2020-12-14 CN CN202011476963.0A patent/CN114621262B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6699717B1 (en) * | 1997-02-12 | 2004-03-02 | The University Of Maryland Baltimore County | Method using luminescent transition metal-ligand complex for detecting polar solvents |
| CN101434612A (en) * | 2007-11-14 | 2009-05-20 | 中国科学院大连化学物理研究所 | Metal organic framework compound material, as well as preparation and application thereof |
| CN102675373A (en) * | 2012-04-06 | 2012-09-19 | 华中师范大学 | Methanol indicator and preparation method thereof |
| US20150268207A1 (en) * | 2012-04-13 | 2015-09-24 | University Of Maryland, College Park | Highly Selective Nanostructure Sensors and Methods of Detecting Target Analytes |
| US20180172656A1 (en) * | 2012-04-13 | 2018-06-21 | University Of Maryland, College Park | Device having an array of sensors on a single chip |
| CN105651835A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Methanol gas sensor and preparation method thereof |
| CN105699439A (en) * | 2016-02-25 | 2016-06-22 | 济南大学 | Preparation method and application of methanol gas sensor based on carbon nitride loaded metal and metal oxide composite |
| CN106053413A (en) * | 2016-06-13 | 2016-10-26 | 华东师范大学 | Metal organic fluorescent methanol sensing film and preparation method thereof |
| CN108398467A (en) * | 2018-03-06 | 2018-08-14 | 上海应用技术大学 | A kind of gas sensor and its construction method based on carbon nanotube and metal nanoparticle |
Non-Patent Citations (3)
| Title |
|---|
| KAISA HELTTUNEN等: ""Inverted molecular cups：1-D and 2-D Ag（I）coordination polymers from resorcinarene bis-thiacrowns"", 《KAISA HELTTUNEN等》, vol. 18, pages 4944 - 4951 * |
| MASAHIKO IYODA等: ""Synthesis and complexation properties of a synthetic receptor，Z-tetrabenzohexadehydro[16]annulene"", 《TETRAHEDRON LETTERS》, vol. 21, pages 6883 - 6886 * |
| NICKY SAVJANI等: ""Gold(III) Olefin Complexes"", 《ANGEW. CHEM. INT. ED》, vol. 52, pages 874 - 877, XP072073973, DOI: 10.1002/anie.201208356 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114621262B (en) | 2023-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Abdelhameed et al. | Employable metal (Ag & Pd)@ MIL-125-NH2@ cellulose acetate film for visible-light driven photocatalysis for reduction of nitro-aromatics | |
| Zhao et al. | Enhanced photocatalytic activity of Ag-CsPbBr3/CN composite for broad spectrum photocatalytic degradation of cephalosporin antibiotics 7-ACA | |
| Li et al. | Preparation and enhanced visible light-driven catalytic activity of ZnO microrods sensitized by porphyrin heteroaggregate | |
| WO2016158806A1 (en) | Novel composite of iron compound and graphene oxide | |
| CN105241860B (en) | A kind of preparation method of magnetic fluorescence graphene composite Nano ion probe | |
| Urbaniak et al. | Properties and application of diketones and their derivatives | |
| Hayati et al. | Influences of temperature, power ultrasound and reaction time on the morphological properties of two new mercury (II) coordination supramolecular compounds | |
| CN113176305B (en) | Composite gas-sensitive material and preparation method thereof, ethanol gas sensor and preparation method thereof | |
| Imadadulla et al. | Solvent dependent dispersion behaviour of macrocycle stabilized cobalt nanoparticles and their applications | |
| Kaewtong et al. | Highly selective detection of Au3+ using rhodamine-based modified polyacrylic acid (PAA)-coated ITO | |
| Young et al. | pH responsive histidin-2-ylidene stabilized gold nanoparticles | |
| Su et al. | MOF-Derived hierarchical porous 3D ZnO/Ag nanostructure as a reproducible SERS substrate for ultrasensitive detection of multiple environmental pollutants | |
| Chen et al. | A low-cost 3D core-shell nanocomposite as ultrasensitive and stable surface enhanced Raman spectroscopy substrate | |
| Gómez et al. | Novel super-structures resulting from the coordination of chiral oxazolines on platinum nanoparticles | |
| Ali et al. | Synthesis and characterization of MnII and CoII complexes with poly (vinyl alcohol-nicotinic acid) for photocatalytic degradation of Indigo carmine dye | |
| CN114621262A (en) | Preparation and application of metal nanocluster material for rapidly detecting methanol | |
| Fu et al. | A polydiacetylene-based smart cellulose aerogel functionalized by ZnO/MoS2 heterojunction for simultaneous visual detection and photocatalytic degradation of gaseous VOCs | |
| Cormode et al. | Anion sensing porphyrin functionalized nanoparticles | |
| Gupta et al. | Enhanced sensitivity of caterpillar-like ZnO nanostructure towards amine vapor sensing | |
| Nian et al. | Does the intrinsic photocontrollable oxidase-mimicking activity of 2-aminoterephthalic acid dominate the activity of metal–organic frameworks? | |
| Najjar et al. | Photocatalytic activity of the novel triazine-based magnetic core–shell Cu nanocomposite for degradation of RhB and MB via air oxidation and Cr (VI) reduction | |
| Hata et al. | Preparation and electrochemical polymerization of new multifunctional pyrrolethiolate-stabilized gold and palladium nanoparticles | |
| Hu et al. | Highly dispersed Cu 2 O quantum dots (about 2 nm) constructed by a simple functional group anchoring strategy boost the photocatalytic water splitting ability by 72 times | |
| Künneth et al. | Heterogeneous photocatalysis XI. Zinc sulphide catalysed dehydrodimerization of dihydropyrans and cyclohexene | |
| CN114632517A (en) | Function-integrated magnetic-response nanorod catalyst with limited nano-particles, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |