CN101995382A - Method for in-situ detection of nano noble metal catalyst - Google Patents
Method for in-situ detection of nano noble metal catalyst Download PDFInfo
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- CN101995382A CN101995382A CN 200910067408 CN200910067408A CN101995382A CN 101995382 A CN101995382 A CN 101995382A CN 200910067408 CN200910067408 CN 200910067408 CN 200910067408 A CN200910067408 A CN 200910067408A CN 101995382 A CN101995382 A CN 101995382A
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Abstract
The invention belongs to the technical field of nano material detection and in particularly relates to a method for in-situ detection of a nano noble metal catalyst, especially a gold/silver catalyst. In the method, SiO2 subjected to amino functional treatment and 4nm Ag sol or 2-4nm Au sol are used as raw materials and are compounded to form a SiO2-Ag or SiO2-Au composite material which has a core-shell structure and used as a catalyst, the SiO2-Ag composite material catalyst has an obvious catalytic action on the reduction reaction of a NaBH4 catalytic dye, and the SiO2-Au composite material catalyst has an obvious catalytic effect on catalyzing CO to be oxidized into CO2; and an in-situ detection is carried out on SiO2-Ag and SiO2-Au through an ultraviolet visible spectrum, the changes of SPR (Surface Plasmon Resonance) peak position and strength before and after catalyst reaction are compared so as to determine whether the nano silver/gold catalyst is inactivated after reaction or not and ensure the recycling of the nano silver/gold catalyst.
Description
Technical field
The invention belongs to the technical field that nano material detects, specifically a kind of in situ detection nano-noble metal, the particularly method of gold, silver catalyzer.
Background technology
When illumination is mapped on the metal nanoparticle surface, have interaction between light and the metal, when the irradiation light frequency equates with the natural mode shape of metallic particles, will produce surface plasma resonance.One big characteristics of metal nanoparticle have absorption band in the ultraviolet-visible district exactly, and this is because the surface of metal particles plasma resonance excites and causes.Mie proposed the earliest metallic colloid the conducting sphere model theory (Mie G..Ann.Physik, 1908,25:377).He utilizes the Maxwell equation to describe surface plasma resonance quantitatively, and the Maxwell equation requires spherical particle that suitable interface will be arranged, and is regarded as the summation of electromagnetism multiple dipole effect by the total delustring cross section that absorbs and scattering is formed.Its physics of particles with different sizes and optical property are also different, and total energy level is certain, and nano particle is more little, and the energy level difference in the particle between the adjacent energy level is big more, and plasma resonance absorption peak (SPR) position of metal colloid particles is blue shift thereupon also; Otherwise absorption peak increases and red shift with particle size.Therefore, absorption spectrum goes for the research of different shape particle in theory, to the accumulation of its research, make ultravioletvisible spectroscopy become research metallic colloid one of method the most simply and easily, it also is the main means of research gold or silver nano-grain and shell optical characteristics thereof.
Noble metal (gold or silver) nano particle is owing to its smaller particle size, higher surface activity and bigger specific surface area are widely used as catalyzer.Noble metal nano particles under proper condition can catalysis fracture H-H, C-H, C-C and C-O key.Because this particle do not have hole, can avoid because some subsidiary reaction that reactant causes to the slow diffusion of endoporus, thereby its activity all is higher than similar traditional catalyst with selectivity.In addition, utilize the catalysis characteristics of nano particle, and with superpolymer as carrier, can bring into play the high catalytic property of nano particle and the characteristics of selectivity catalysis, can make it to have long-acting stability again by the stabilization of superpolymer.As the new catalytic agent material that a class has the unique texture performance, noble metal Au or Ag nano material that particle size is little have higher surface/volume, so they have very high activity.Their configurations are abundant, particle diameter is even, determine it to have catalysis diversity and good selectivity, have widespread use at aspects such as immunoassay, sensor design, molectronicses, yet nobody mentions so far as the in-situ detection method of catalyzer to noble metal nano particles.Now, the flourish of composite nano materials will occupy special status in 21 century materials chemistry field undoubtedly.The optical property of composite particle can be led to the size of change nuclear and the thickness of shell is reconciled.People such as Halas point out that in conjunction with Mie scattering theory and colloidal growth chemistry, the optical property of core-shell particles has adjustable height.A betal can and the nuclear that insulate: as SiO
2The thickness of making the size of optical property that nuclear Ag makes the composite particle that shell forms and nuclear and betal can is relevant.Because pure SiO
2Particle does not absorb in the ultraviolet-visible light district.After the sedimentation of silver particle surface, at an interval absorption peak, the plasma resonance absorption peak of metallic silver particles that Here it is of occurring of 380-420nm.And in the 680-740nm interval, the plasma resonance peak of nanogold particle can occur, so we can adopt ultraviolet-visual spectrometer that metal colloid particles in the catalyzer is carried out in situ detection.
Summary of the invention
The objective of the invention is to provide a kind of SiO
2-Ag, SiO
2The in-situ detection method of the preparation of-Au nano composite material and this catalyst nano silver, gold, this method is simple, environmental protection, low cost; Detect rapid, repeatable high; Industrial organic dye waste water degraded detection is had broad application prospects.
The object of the present invention is achieved like this, and this method is to adopt APTMS to carry out the SiO that amino functional is handled
2With Ag colloidal sol or the 2-4nm Au colloidal sol of 4nm be raw material, the two is compounded to form the SiO of nucleocapsid structure
2-Ag, SiO
2-Au compound substance is as catalyzer, compound substance SiO
2-Ag is to NaBH
4Catalysis reducing dyes reaction has obvious catalysis, by ultraviolet-visible spectrum to SiO
2-Ag carries out in situ detection, the variation of SPR peak position and intensity in ultraviolet-visible spectrum 380-420nm, 680-740nm interval before and after 4nm Ag, the 2-4nm Au reaction among the comparative catalyst, determine Nano Silver, Au catalyst inactivation whether after reaction finishes, can recycle to guarantee nanometer Ag, Au catalyzer.
The inventive method is simple, environmental protection, low cost; Detect rapid, repeatable high; Industrial organic dye waste water degraded detection is had broad application prospects.
Description of drawings
Fig. 1 is SiO
2The transmission electron micrograph of-Ag compound substance.
Fig. 2 is low concentration SiO
2-Ag compound substance is as catalyzer, to catalyzing N aBH
4The ultraviolet-visible spectrum surveillance map of reduction rhodamine 6G reaction.
Fig. 3 is high concentration SiO
2-Ag compound substance is as catalyzer, to catalyzing N aBH
4The ultraviolet-visible spectrum surveillance map of reduction rhodamine 6G reaction.
Fig. 4 is SiO
2The transmission electron micrograph of-Au compound substance.
Fig. 5 is the ultraviolet-visible light spectrogram of 2-4nm Au.
Embodiment
Testing tool used in the present invention comprises: a ultraviolet-visual spectrometer (UV2550), quartz colorimetric utensil etc.
Embodiment 1:
One, preparation SiO
2The synthetic route of-Ag compound substance:
1., the SiO of synthetic different size
2Nano particle
1.7mL ammoniacal liquor is added in the 50.0mL absolute ethyl alcohol, and potpourri adopts the magnetic stirring apparatus vigorous stirring dropwise to add 1.5mL (about 6.7mmol) TEOS (ethyl orthosilicate) simultaneously, behind the solution stirring 6h, obtains the about 40nm SiO of white diameter
2Precipitation.When the ammoniacal liquor volume changes 2.5 or during 3.0mL respectively into by 1.7mL, said process can obtain 78 or 105nm SiO respectively
2Particle;
2., the SiO of synthesizing amino functionalization
2
Get the SiO of above-mentioned 1. middle 40nm, 78nm and 105nm
2Each 50mL of colloidal sol adds 150 μ L aminopropyl trimethoxysilane (APTMS is as amino functional reagent) and stirring rapidly respectively, behind the reaction 3h, obtains the SiO of the amino functional of white at drag
2The nano particle precipitation is with the SiO after the amino functional processing
2The particle centrifugal treating also is distributed to purifying in the ethanol;
3., SiO
2The preparation of-Ag core-shell structure nanometer particle
SiO
2The preparation process of the nano particle of-Ag nucleocapsid structure is: the SiO of amino functional
2Particle is put in the 100mL conical flask, adds to utilize NaBH
4The method of reduction newly prepares 4nm Ag colloidal sol; The conical flask vibration was left standstill 2h after 5-10 minute; Can obtain brown SiO
2-Ag nano-complex; The SiO of purifying
2-Ag particle washs 3 times through centrifugal, ethanol, and ultrasonic again being distributed to is saved to use in the deionized water; Promptly obtain SiO
2The nano-silver catalyst of-Ag nucleocapsid structure (seeing accompanying drawing 1).Rationally dilute as required again to reach best catalytic effect, minimum catalyst concn during use.
Two, the in situ detection of nano-silver catalyst:
Gained catalyzer in one is used for catalyzing N aBH
4Reduction rhodamine 6G etc. contains in the waste water system of organic dyestuff, utilizes UV-Vis spectrum that course of reaction is monitored in real time, can observe the deoxidization, degradation situation of rhodamine 6G.This method can be carried out in situ detection to the SPR peak of the regional Ag nano particle that occurs of 380-420nm.React the variation of SPR peak position, front and back and intensity by the comparative catalyst, can observe catalyzer inactivation whether after reaction: if reaction cross-reference SPR peak position and intensity no change, the not reunion after catalytic reaction of catalyst A g nano particle is described, there is not inactivation, can continue to use this catalyzer (seeing accompanying drawing 2, accompanying drawing 3); If obvious displacement has taken place in SPR peak position, reaction back, illustrate that catalyst A g nano particle reunites, can not continue use again; If reaction back SPR peak intensity dies down, illustrate that also catalyst concn diminishes, in time make-up catalyst.
Embodiment 2:
One, preparation SiO
2The synthetic route of-Au compound substance
1., the SiO of synthetic different size
2Nano particle
1.7mL ammoniacal liquor is added in the 50.0mL absolute ethyl alcohol, and potpourri adopts the magnetic stirring apparatus vigorous stirring dropwise to add 1.5mL (about 6.7mmol) TEOS (ethyl orthosilicate) simultaneously, behind the solution stirring 6h, obtains the about 40nm SiO of white diameter
2Precipitation.When the ammoniacal liquor volume changes 2.5 or during 3.0mL respectively into by 1.7mL, said process can obtain 78 or 105nm SiO respectively
2Particle;
2., the SiO of synthesizing amino functionalization
2
Get the SiO of above-mentioned 1. middle 40nm, 78nm and 105nm
2Each 50mL of colloidal sol adds 150 μ L aminopropyl trimethoxysilane (APTMS is as amino functional reagent) and stirring rapidly respectively, behind the reaction 3h, obtains the SiO of the amino functional of white at drag
2The nano particle precipitation is with the SiO after the amino functional processing
2The particle centrifugal treating also is distributed to purifying in the ethanol; Adopt four (methylol) phosphonic chloride (THPC) to make reductive agent and under the alkali condition that NaOH exists, reduce HAuCl
4The Au particle (accompanying drawing 4) of preparation 2-4nm;
3., with the SiO of amino functional
2Particle is placed in the conical flask, the Au nano particle in the adding 2., and conical flask jog 10-20 minute leaves standstill 2h then, can obtain SiO
2-Au nano-complex; Nano-complex is centrifugal, ethanol is washed and is handled the SiO that obtains purifying
2-Au particle, the SiO of purifying
2Ultrasonic being distributed to of-Au particle is saved to use in the water, rationally dilute as required to reach best catalytic effect, minimum catalyst concn more afterwards, promptly obtains SiO
2The nano catalyst of-Au nucleocapsid structure.
Two, the in situ detection of nano catalyst:
Utilize UV-Vis spectrum that synthetic Au nano particle catalysis CO oxidation is generated CO
2Course of reaction monitor (seeing accompanying drawing 5), by observation in the SPR peak intensity of the Au in 680-740nm zone nano particle and the variation of position, can in-situ monitoring SiO
2Nano-Au catalyst in-Au compound substance inactivation whether after reaction finishes: if if reaction cross-reference SPR peak position and intensity no change, the not reunion after catalytic reaction of catalyst A g nano particle is described, do not have inactivation, can continue to use this catalyzer (seeing accompanying drawing 2, accompanying drawing 3); If obvious displacement has taken place in SPR peak position, reaction back, illustrate that catalyst A g nano particle reunites, can not continue use again; If reaction back SPR peak intensity dies down, illustrate that also catalyst concn diminishes, in time make-up catalyst.
In a word, can carry out in situ detection to Nano Silver, Au catalyst with the method, operation is simple for the method, and detection speed is fast and accurate, is a kind of good method of in situ detection nano-noble metal catalyst.This in-situ detection method is applicable to that generally the liquid phase method detection has the noble metal gold, silver of spr signal etc. at uv-vis spectra.
Claims (4)
1. the method for an in situ detection nano-noble metal catalyst is characterized in that: this method is the SiO that adopts amino functional to handle
2With Ag colloidal sol or the 2-4nmAu colloidal sol of 4nm be raw material, the two is compounded to form the SiO of nucleocapsid structure
2-Ag or SiO
2-Au compound substance is as catalyzer, SiO
2-Ag composite catalyst is to NaBH
4The reaction of catalysis reducing dyes has obvious catalysis, SiO
2-Au composite catalyst is oxidized to CO to catalysis CO
2Catalytic effect is obvious; By uv-vis spectra to SiO
2-Ag, SiO
2-Au carries out in situ detection, and the variation of SPR peak position and intensity before and after the comparative catalyst reacts is determined Nano Silver, Au catalyst inactivation whether after reaction finishes, to guarantee recycling of Nano Silver, Au catalyst.
2. the method for a kind of in situ detection nano-silver catalyst according to claim 1 is characterized in that:
The concrete steps of this method are as follows:
(1), SiO
2The preparation of-Ag compound substance:
1., 1.7 parts of ammoniacal liquor are added in 50.0 parts of absolute ethyl alcohols, potpourri adopts the magnetic stirring apparatus vigorous stirring dropwise to add 1.5 parts of TEOS simultaneously, behind the solution stirring 6h, obtains the about 40nm SiO of white diameter
2Precipitation; When the ammoniacal liquor volume changed 2.5 or 3.0 parts respectively into by 1.7 parts, said process can obtain 78nm or 105nm SiO respectively
2Particle;
2., get the SiO of above-mentioned 1. middle 40nm, 78nm and 105nm
2Each 50 parts of colloidal sols add 150 μ L APTMS and stirring rapidly respectively, behind the reaction 3h, obtain the SiO of amino functional at drag
2Particle precipitation is with the SiO of amino functional
2The particle centrifugal treating also is distributed to purifying in the ethanol; Utilize NaBH
4The method of reduction prepares the 4nm silver sol;
3., with the SiO of amino functional
2Particle is placed in the conical flask, the Ag nano particle in the adding 2., and conical flask jog 10-20 minute leaves standstill 2h then, can obtain SiO
2-Ag nano-complex; Above-mentioned nano-complex is centrifugal, ethanol is given a baby a bath on the third day after its birth time and to be handled the SiO that obtains purifying
2-Ag particle, the SiO of purifying
2Ultrasonic being distributed to of-Ag particle is saved to use in the water, rationally dilute as required to reach best catalytic effect, minimum catalyst concn more afterwards, promptly obtains SiO
2The composite catalyst of-Ag nucleocapsid structure.
(2), the in situ detection of nano-silver catalyst:
1., with above-mentioned gained SiO
2-Ag catalyzer is used for catalyzing N aBH
4Reduction rhodamine 6G etc. contains in the waste water system of organic dyestuff, utilizes UV-Vis spectrum that course of reaction is monitored in real time, can observe the deoxidization, degradation situation of rhodamine 6G;
2., utilize SPR peak that ultraviolet-visible spectrometer detects the 4nmAg nano particle that occurs in the 380-420nm zone to compound substance in the nanometer Ag catalyzer carry out in situ detection; By the variation of SPR peak position and intensity before and after the catalyst A g reaction in the comparative composite, judge catalyzer inactivation whether after reaction;
3., when before and after the reaction when SPR peak position and intensity no change, the not reunion after catalytic reaction of catalyst A g nano particle be described, do not have inactivation, can continue to use this catalyzer; When obvious displacement has taken place in SPR peak position, reaction back, illustrate that catalyst A g nano particle reunites, catalyzer can not continue use again; When reaction back SPR peak intensity dies down, illustrate that catalyst concn diminishes, in time make-up catalyst.
3. the method for a kind of in situ detection nano catalyst according to claim 1 is characterized in that:
The concrete steps of this method are as follows:
(1), SiO
2The preparation of-Au compound substance:
1., 1.7 parts of ammoniacal liquor are added in 50.0 parts of absolute ethyl alcohols, potpourri adopts the magnetic stirring apparatus vigorous stirring dropwise to add 1.5 parts of TEOS simultaneously, behind the solution stirring 6h, obtains the about 40nm SiO of white diameter
2Precipitation; When the ammoniacal liquor volume changed 2.5 or 3.0 parts respectively into by 1.7 parts, said process can obtain 78nm or 105nm SiO respectively
2Particle;
2., get the SiO of above-mentioned 1. middle 40nm, 78nm and 105nm
2Each 50 parts of colloidal sols add excessive APTMS and stirring rapidly respectively, behind the reaction 3h, obtain the SiO of amino functional at drag
2Particle precipitation is with the SiO of amino functional
2The particle centrifugal treating also is distributed to purifying in the ethanol; Utilize four (methylol) phosphonic chloride THPC to make reductive agent and under the alkali condition that NaOH exists, reduce HAuCl
4The Au particle of preparation 2-4nm;
3., with the SiO of amino functional
2Particle is placed in the conical flask, the Au nano particle in the adding 2., and conical flask jog 10-20 minute leaves standstill 2h then, can obtain SiO
2-Au nano-complex; It is centrifugal, ethanol washing is handled the SiO that obtains purifying 3 times
2-Au particle, the SiO of purifying
2Ultrasonic being distributed to of-Au catalyst particle is saved to use in the water, rationally dilute as required to reach best catalytic effect, minimum catalyst concn more afterwards, promptly obtains SiO
2The composite catalyst of-Au nucleocapsid structure.
(2), the in situ detection of nano catalyst:
1., with above-mentioned gained SiO
2-Au catalyzer is used for catalysis CO and is oxidized to CO
2In the reaction system, utilize UV-Vis spectrum to SiO
2The SPR peak of catalyst nano Au particle carries out in situ detection in reaction front-back direction and Strength Changes in-the Au compound substance, so judge catalyzer in the reaction front and back inactivation whether;
2., when the SPR peak position of nanometer Au before and after the reaction and intensity no change, the not reunion after catalytic reaction of catalyst A u nano particle be described, do not have inactivation, can continue to use this catalyzer; When obvious displacement has taken place in SPR peak position, reaction back, illustrate that catalyst A u nano particle reunites, catalyzer can not continue use again; When reaction back SPR peak intensity dies down, illustrate that the nano gold catalysis agent concentration diminishes, in time make-up catalyst.
4. according to the method for claim 2,3 described a kind of in situ detection nano-noble metal catalysts, it is characterized in that: the umber of described raw material ammonia water, absolute ethyl alcohol, ethyl orthosilicate, aminopropyl trimethoxysilane is meant volume parts.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959623A (en) * | 2015-06-12 | 2015-10-07 | 上海交通大学 | Method for preparing simple and controllable nanoscale silver-loaded monox |
| CN108906035A (en) * | 2018-07-31 | 2018-11-30 | 南京工业大学 | A kind of noble metal meso-porous titanium dioxide Si catalyst and its synthetic method with high stability |
| CN110681380A (en) * | 2019-10-22 | 2020-01-14 | 吉林师范大学 | Preparation of high-efficiency hydrogen production catalyst Au-HSTiO by liquid phase reduction2Method (2) |
| CN111610071A (en) * | 2020-04-28 | 2020-09-01 | 重庆大学 | Method for characterizing strength of denitration catalyst carrier titanium dioxide powder |
-
2009
- 2009-08-12 CN CN 200910067408 patent/CN101995382B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959623A (en) * | 2015-06-12 | 2015-10-07 | 上海交通大学 | Method for preparing simple and controllable nanoscale silver-loaded monox |
| CN108906035A (en) * | 2018-07-31 | 2018-11-30 | 南京工业大学 | A kind of noble metal meso-porous titanium dioxide Si catalyst and its synthetic method with high stability |
| CN108906035B (en) * | 2018-07-31 | 2021-04-16 | 南京工业大学 | Noble metal mesoporous silica catalyst with high stability and synthesis method thereof |
| CN110681380A (en) * | 2019-10-22 | 2020-01-14 | 吉林师范大学 | Preparation of high-efficiency hydrogen production catalyst Au-HSTiO by liquid phase reduction2Method (2) |
| CN111610071A (en) * | 2020-04-28 | 2020-09-01 | 重庆大学 | Method for characterizing strength of denitration catalyst carrier titanium dioxide powder |
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