CN116020453A - Gold-silver nano alloy and ultra-clean preparation method and application thereof - Google Patents
Gold-silver nano alloy and ultra-clean preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a gold-silver nano alloy, an ultra-clean preparation method and application thereof, and relates to the technical field of nano particle preparation. The ultra-clean preparation method of the gold-silver nano alloy provided by the invention comprises the following steps: mixing tetrachloroauric acid trihydrate, silver nitrate and an organic mixed solvent to obtain a precursor mixed solution; suspending the precursor mixed solution under the action of a non-contact ultrasonic field to obtain a precursor suspension; and maintaining the suspension state of the precursor mixed solution, adding a reducing agent into the precursor suspension, and carrying out reduction reaction to obtain the gold-silver nano alloy. The gold-silver nano alloy is prepared in an ultra-clean environment by utilizing a non-contact ultrasonic suspension manipulation technology, heterogeneous nucleation can be avoided, the prepared gold-silver nano alloy is smaller in size and more concentrated in particle size distribution, and the catalytic activity of the gold-silver nano alloy prepared by the method is remarkably improved.
Description
Technical Field
The invention relates to the technical field of nanoparticle preparation, in particular to a gold-silver nano alloy and an ultra-clean preparation method and application thereof.
Background
Noble metal nanoparticles (gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.) are of great interest due to their unique optical properties, excellent catalytic properties, and broad application prospects. Compared with single metal nano particles, the binary noble metal nano alloy has greatly improved catalytic activity under the action of synergistic effect (H.L.Jiang, T.Akita, T.Ishida, M.Haruta, Q.Xu, synergistic catalysis of Au@Ag core-shell nanoparticles stabilized on metal-organic framework [ J ]. Journal of the American Chemical Society,2011,133 (5): 1304-1306'), so that the binary noble metal nano alloy is more suitable for being used as a catalyst for pollutant treatment. For example, patent CN112354567a discloses a preparation method of gold-silver bimetallic nanoclusters and application thereof in sewage degradation. Currently, the preparation method of the nano gold-silver alloy comprises a co-reduction method, a seed growth method, a laser ablation method, an anodic dissolution method and the like. For example, patent CN108031862a uses fructose to co-reduce gold and silver ion solution under boiling condition to obtain gold-silver nano-particles; patent CN103157811B discloses a scheme for synthesizing a gold-silver core-shell structure by using a seed growth method. Among them, the co-reduction method is widely used because of its simplicity and easiness and mild reaction conditions. However, the catalytic activity of the gold-silver nano alloy prepared by the existing co-reduction method still needs to be further improved.
The ultrasonic technology has been applied to the field of nano material preparation (B.J.H.Bang, K.S.Suslick, applications of Ultrasound to the Synthesis of Nanostructured Materials [ J ]. Adv. Mater.2010,22, 1039-1059), cavitation bubbles collapse and collapse under the action of ultrasound, resulting in local high temperature and pressure (about 5000K,1000 bar), and a new phenomenon different from common chemical reactions. However, in an ultrasonic device in which a conventional ultrasonic probe is inserted into a reaction solution, contact of the probe with the solution may introduce heterogeneous nucleation, affecting nucleation and growth of crystals. In addition, high intensity ultrasound can be accompanied by severe thermal effects, which can cause destructive damage to portions of the material.
Disclosure of Invention
The invention aims to provide a gold-silver nano alloy, an ultra-clean preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an ultra-clean preparation method of gold-silver nano alloy, which comprises the following steps:
mixing tetrachloroauric acid trihydrate, silver nitrate and an organic mixed solvent to obtain a precursor mixed solution;
suspending the precursor mixed solution under the action of a non-contact ultrasonic field to obtain a precursor suspension;
and maintaining the suspension state of the precursor mixed solution, adding a reducing agent into the precursor suspension, and carrying out reduction reaction to obtain the gold-silver nano alloy.
Preferably, the organic mixed solvent is a mixed solvent of a stabilizer and an organic solvent.
Preferably, the stabilizer is oleylamine; the organic solvent is toluene.
Preferably, the volume ratio of the stabilizer to the organic solvent in the organic mixed solvent is 1:1-2.
Preferably, the total concentration of the tetrachloroauric acid trihydrate and the silver nitrate in the precursor mixed solution is 20-30 mmol/L.
Preferably, the reducing agent is a borane tert-butylamine complex solution.
Preferably, the volume ratio of the reducing agent to the precursor suspension is 1:10.
preferably, the temperature of the reduction reaction is room temperature, and the time of the reduction reaction is 2-10 min.
The invention provides the gold-silver nano alloy prepared by the ultra-clean preparation method, which is granular.
The invention provides application of the gold-silver nano alloy in reduction of p-nitrophenol.
The invention provides an ultra-clean preparation method of gold-silver nano alloy, which is used for preparing gold-silver nano alloy in an ultra-clean container-free environment provided by a non-contact ultrasonic field, and can avoid introducing heterogeneous nuclei and improve the catalytic activity of the gold-silver nano alloy. Under the action of ultrasound, the particle size is refined and very uniform, the collapse of cavitation bubbles can generate local high temperature and high pressure, the formation of active free radicals in water is promoted, the reduction of metal salt precursors is accelerated, and according to the Lamer theory, the rapid reduction of the precursor quantity can lead to insufficient monomer supply required in the growth stage, so that particles with smaller size are formed; in addition, the flow inside the liquid drop can be induced under the action of the sound flow, so that the crystallization behaviors such as fusion and condensation in the growth stage of the particles are influenced, the small particles are ablated and the large particles continue to grow according to the Ostwald ringing theory, and the particles under the action of the sound flow are fused or inhibited, so that the particle size distribution is more concentrated than that of the conventional gold-silver nano alloy, and therefore, the particle size distribution is more concentrated compared with that of the gold-silver nano alloy prepared by the conventional co-reduction method.
In a specific embodiment of the invention, a standing wave ultrasonic field is formed between the transmitting end and the reflecting end by utilizing the acoustic radiation force generated by the high-intensity acoustic nonlinear effect. According to the invention, by limiting the ultrasonic frequency, the ultrasonic power and the distance between the transmitting end and the reflecting end, an ultrasonic potential well which is beneficial to the ultra-clean preparation of liquid drop suspension is formed between the transmitting end and the reflecting end. Experimental results show that the gold-silver nano alloy prepared by the non-contact ultrasonic suspension manipulation technology in an ultra-clean environment is smaller in size, more concentrated in particle size distribution and remarkably improved in catalytic activity.
Drawings
FIG. 1 is a TEM image of gold-silver nanoalloys prepared in comparative example 1 and example 1;
FIG. 2 is a graph showing the comparison of particle size distribution curves of the gold-silver nano-alloy prepared in comparative example 1 and example 1;
FIG. 3 is an ultraviolet-visible spectrum monitoring image of the gold-silver nano alloy prepared in comparative example 1 and example 1 in the catalysis treatment of p-nitrophenol;
fig. 4 is a graph showing the comparison of catalytic reaction kinetics curves of the gold-silver nano alloy prepared in comparative example 1 and example 1.
Detailed Description
The invention provides an ultra-clean preparation method of gold-silver nano alloy, which comprises the following steps:
mixing tetrachloroauric acid trihydrate, silver nitrate and an organic mixed solvent to obtain a precursor mixed solution;
suspending the precursor mixed solution under the action of a non-contact ultrasonic field to obtain a precursor suspension;
and maintaining the suspension state of the precursor mixed solution, adding a reducing agent into the precursor suspension, and carrying out reduction reaction to obtain the gold-silver nano alloy.
The invention mixes the tetrachloroauric acid trihydrate, the silver nitrate and the organic mixed solvent to obtain the precursor mixed liquid. In the present invention, the organic mixed solvent is preferably a mixed solvent of a stabilizer and an organic solvent. In the present invention, the stabilizer is preferably oleylamine; the organic solvent is preferably toluene. In the invention, the volume ratio of the stabilizer to the organic solvent in the organic mixed solvent is preferably 1:1-2. In the invention, toluene is insoluble in water, but can be mixed with carbon disulfide, alcohol and diethyl ether in any proportion, and has good solubility in chloroform, acetone and most other common organic solvents; the oleylamine is a high-boiling-point polar substance, can effectively cover the surfaces of nano particles, and maintains the stability and dispersibility of the particles.
In the present invention, the mixing of the tetrachloroauric acid trihydrate, silver nitrate and the organic mixed solvent preferably comprises: the tetrachloroauric acid trihydrate and silver nitrate are respectively dissolved in an organic mixed solvent, and then mixed.
In the invention, the molar ratio of the gold element to the silver element in the precursor mixed solution is preferably 10:1 to 1:10.
in the invention, the total concentration of the tetrachloroauric acid trihydrate and the silver nitrate in the precursor mixed solution is preferably 20-30 mmol/L.
In the invention, the mixing of the tetrachloroauric acid trihydrate, the silver nitrate and the organic mixed solvent is preferably carried out under the condition of ultrasonic dispersion; the time of the ultrasonic dispersion is preferably 1 to 5 minutes.
After the precursor mixed solution is obtained, the precursor mixed solution is suspended under the action of a non-contact ultrasonic field to obtain a precursor suspension. In the invention, the ultrasonic power of the non-contact ultrasonic field is 350-500W, preferably 400-450W; the ultrasonic frequency is 21-21.5 kHz, preferably 21.1-21.3 kHz; the distance between the emitting end and the reflecting end is 20-40 mm, preferably 26-30 mm. In a specific embodiment of the present invention, the emitting end and the reflecting end are disposed on the same axis.
In the present invention, the means for providing the non-contact ultrasound field is preferably an acoustic suspension means; the acoustic suspension instrument preferably adopts a plane emitting end, and the radius of the cross section of the emitting end is preferably 5-20 mm, more preferably 10-15 mm. In the invention, the acoustic suspension instrument preferably adopts a concave spherical reflecting end, and the radius of the cross section of the reflecting end is preferably 15-20 mm, more preferably 16-18 mm; the radius of curvature is preferably 40 to 45mm, more preferably 42.5 to 44mm. In the present invention, when a concave spherical reflecting end is used, the distance between the emitting end and the reflecting end refers to the distance from the lowest point of the concave surface to the bottom surface of the emitting end.
In the present invention, the suspension is preferably carried out at normal temperature and pressure. In a specific embodiment of the present invention, the acoustic wave propagation medium of the non-contact ultrasound field is air, and the ambient temperature is 20 ℃.
The invention has no special requirements on the type of the instrument for providing the non-contact ultrasonic field, and the acoustic suspension instrument well known in the field can be used. In the embodiment of the invention, a uniaxial acoustic suspension device is specifically disclosed by a spatial material science and technology emphasis laboratory of the northwest industrial university where the applicant is located through a doctor paper acoustic suspension optimal design theory and application research thereof (Jie Wenjun, 2002).
In the specific embodiment of the invention, the position of an ultrasonic potential well is detected through preset liquid drops, and then the precursor mixed liquid is placed in the ultrasonic potential well by using a liquid-transferring gun, so that stable suspension of the precursor mixed liquid is realized.
After the precursor suspension is obtained, the invention maintains the suspension state of the precursor mixed solution, and a reducing agent is added into the precursor suspension for reduction reaction to obtain the gold-silver nano alloy. In the present invention, the reducing agent is preferably a borane tert-butylamine complex solution. In the invention, the solvent of the borane tert-butylamine complex solution is preferably a mixed solution of oleylamine and toluene; the volume ratio of the oleylamine to the toluene in the mixed liquid of the oleylamine and the toluene is preferably 1:1; the concentration of the borane tert-butylamine complex solution is preferably 40-50 mmol/L. In the invention, the reducing agent is more stable, which is beneficial to improving the quality of gold-silver nano alloy.
In the present invention, the volume ratio of the reducing agent to the precursor suspension is preferably 1:10.
in the present invention, the temperature of the reduction reaction is preferably room temperature, and the time of the reduction reaction is preferably 2 to 10 minutes.
The method is characterized in that suspended gold-silver nano alloy sol droplets are collected after the reduction reaction, and the gold-silver nano alloy is obtained after standing and centrifugal washing are sequentially carried out. In the present invention, the time of the standing is preferably 1h. In the present invention, the rotational speed of the centrifugal washing is preferably 7000 to 10000rpm, more preferably 8000 to 10000rpm; the time for the centrifugal washing is preferably 3 to 10 minutes, more preferably 5 to 8 minutes. In the invention, the washing liquid used for centrifugal washing is preferably a mixed liquid of ethanol and n-hexane; the volume ratio of the ethanol to the n-hexane is preferably 1:3 to 4.
In a specific embodiment of the invention, the gold-silver nano alloy obtained is dispersed in normal hexane or methylene dichloride for storage.
The invention provides the gold-silver nano alloy prepared by the ultra-clean preparation method, which is granular.
The invention provides application of the gold-silver nano alloy in reduction of p-nitrophenol. In the present invention, the application preferably includes: p-nitrophenol solution, solvent and NaBH 4 And mixing the solution with the gold-silver nano alloy, and carrying out reduction reaction. In the invention, the solvent of the p-nitrophenol solution is preferably a mixed solution of dichloromethane and methanol; the volume ratio of the dichloromethane to the methanol is preferably 2-3: 1, a step of; the concentration of the p-nitrophenol solution is preferably 0.2-0.5 mmol/L. In the present invention, the solvent is preferably a mixed solution of dichloromethane and methanol; the volume ratio of the dichloromethane to the methanol is preferably 2-3: 1. in the present invention, the NaBH 4 The solvent of the solution is preferably a mixed solution of dichloromethane and methanol; the volume ratio of the dichloromethane to the methanol is preferably 2-3: 1, a step of; the NaBH 4 The concentration of the solution is preferably 80 to 100mmol/L. In the present invention, the p-nitrophenol solution, solvent and NaBH 4 The volume ratio of the solutions is preferably 1:1.4:0.1. In the present invention, the temperature of the reduction reaction is preferably room temperature. The invention uses gold-silver nano alloy to catalyze and reduce the p-nitrophenol into the p-aminophenol, and has the advantages of mild reaction condition, high speed, high efficiency, environmental protection and the like.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) The volume ratio of oleylamine to toluene is 1:1 mixing as a solvent; 9.85mg of HAuCl was weighed out with a balance 4 ·3H 2 O powder with 4.25mg AgNO 3 Powders, each dissolved in 2mL solvent; HAuCl 4 ·3H 2 Diluting the O solution to 12.5mmol/L, and adding AgNO 3 The solution was diluted to 12.5mmol/L and 1mL of each of the resulting HAuCl was taken 4 ·3H 2 Dilute solution of O and AgNO 3 Is of (2)Mixing the release solution (namely mixing according to the molar ratio of gold element to silver element of 1:1), and dispersing for 3min by using ultrasonic to obtain the precursor mixed solution.
(2) The ultrasonic transmitting end and the reflecting end are arranged on the same axis, the radius of the cross section of the plane transmitting end is 15mm, the radius of the cross section of the concave spherical reflecting end is 20mm, and the radius of curvature is 42.5mm; opening an ultrasonic generator switch, setting the ultrasonic power input into an ultrasonic transducer to be 350W and the ultrasonic frequency to be 21.3kHz; detecting an ultrasonic field between an ultrasonic transmitting end and a reflecting end by using a preset liquid drop method, searching an ultrasonic potential well, and controlling a tuning handle of the ultrasonic reflecting end to enable the distance between the reflecting end and the transmitting end to be 26mm, so that the ultrasonic potential well formed between the ultrasonic transmitting end and the reflecting end is beneficial to suspension; and stably suspending the prepared 50 mu L of precursor mixed solution by adopting a pipetting gun to obtain precursor suspension.
(3) Sucking 5 mu L of borane tert-butylamine complex solution with the concentration of 50mmol/L by adopting a pipetting gun (the solvent is a mixed solution of oleylamine and toluene, the volume ratio of oleylamine to toluene in the mixed solution of oleylamine and toluene is preferably 1:1), rapidly injecting the solution into a precursor mixed solution which is stably suspended, adjusting the distance between a reflecting end and a reflecting end to adjust the suspension state of liquid drops so as to prevent the liquid drops from falling, and collecting the liquid drops by using the pipetting gun after acting for 5min in an ultrasonic potential well.
(4) Standing the collected liquid drops for 1h, and placing the liquid drops in a centrifugal machine with the rotating speed of 8000rpm for 5min, wherein the washing liquid is a mixed liquid of ethanol and n-hexane, and the volume ratio of the ethanol to the n-hexane is 1:4, re-dispersing in n-hexane (the volume of the collected liquid drops is the same) to obtain gold and silver nano alloy sol.
Comparative example 1
(1) The volume ratio of oleylamine to toluene is 1:1 mixing as a solvent; 9.85mg of HAuCl was weighed out with a balance 4 ·3H 2 O powder with 4.25mg AgNO 3 Powders, each dissolved in 2mL solvent; HAuCl 4 ·3H 2 Diluting the O solution to 12.5mmol/L, and adding AgNO 3 The solution was diluted to 12.5mmol/L and 1mL of each of the resulting HAuCl was taken 4 ·3H 2 Dilute solution of O and AgNO 3 Mixing the diluted solutions of (i.e. according to gold element andsilver element mole ratio 1: 1) and dispersing for 3min by using ultrasonic to obtain a precursor mixed solution.
(2) 200 mu L of borane tert-butylamine complex solution with the concentration of 50mmol/L (solvent is mixed solution of oleylamine and toluene, wherein the volume ratio of oleylamine to toluene in the mixed solution of oleylamine and toluene is preferably 1:1) is quickly injected into the precursor mixed solution, and after standing for 1h, the solution is placed in a centrifugal machine with the rotating speed of 8000rpm for 5min, the washing solution is mixed solution of ethanol and normal hexane, and the volume ratio of ethanol to normal hexane is 1:4, dispersing in n-hexane again to obtain gold-silver nano alloy sol.
Example 2
Substantially the same as in example 1, except that HAuCl was used 4 ·3H 2 The concentration of the diluted solution of O is adjusted from 12.5mmol/L to 2.5 mmol/L; agNO is to be carried out 3 The concentration of the diluted solution of (C) is adjusted from 12.5mmol/L to 22.5mmol/L, namely, the precursor mixed solution is prepared by mixing according to the mole ratio of gold element to silver element of 1:9.
Comparative example 2
Substantially the same as in comparative example 1, except that HAuCl was added 4 ·3H 2 The concentration of the diluted solution of O is adjusted from 12.5mmol/L to 2.5 mmol/L; agNO is to be carried out 3 The concentration of the diluted solution of (C) is adjusted from 12.5mmol/L to 22.5mmol/L, namely, the precursor mixed solution is prepared by mixing according to the mole ratio of gold element to silver element of 1:9.
Example 3
Substantially the same as in example 1, except that HAuCl was used 4 ·3H 2 The concentration of the diluted solution of O was adjusted from "12.5mmol/L" to "22.5mmol/L"; agNO is to be carried out 3 The concentration of the diluted solution of (C) is adjusted to be 2.5mmol/L from 12.5mmol/L, namely, the precursor mixed solution is prepared by mixing according to the mol ratio of gold element to silver element of 9:1.
Comparative example 3
Substantially the same as in comparative example 1, except that HAuCl was added 4 ·3H 2 The concentration of the diluted solution of O was adjusted from "12.5mmol/L" to "22.5mmol/L"; agNO is to be carried out 3 Dilution of (2)The concentration of the solution is adjusted from 12.5mmol/L to 2.5mmol/L, namely, the precursor mixed solution is prepared by mixing according to the mol ratio of gold element to silver element of 9:1.
Test example 1
The gold-silver nano alloy sol prepared in the example 1 and the comparative example 1 is diluted to a proper concentration and then deposited on a 400-mesh carbon film copper mesh, and a TEM image thereof is shown in fig. 1, wherein (a) of fig. 1 is comparative example 1, and (b) of fig. 1 is example 1; and carrying out statistical analysis on the particle size, wherein the average particle size of the gold-silver nano alloy in comparative example 1 is 11.0+/-3.9 nm, and the average particle size of the gold-silver nano alloy in example 1 is 8.1+/-2.2 nm; and carrying out Gaussian fitting according to the frequency distribution histogram to obtain a particle size distribution image of the frequency distribution histogram, wherein the particle size distribution image is shown in figure 2.
Test example 2
The ultraviolet band is 250-600 nm when the catalytic reaction system is monitored, the solvent is a mixed solution of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 2:1.
1mL of a 0.2mmol/L p-nitrophenol solution (the solvent is a mixed solution of dichloromethane and methanol in a volume ratio of 2:1) was added to 1.4mL of the solvent, followed by 100. Mu.L of 100mmol/L NaBH 4 A solution (the solvent is a mixed solution of dichloromethane and methanol in a volume ratio of 2:1) and 100 mu L of the gold-silver nano alloy sol prepared in comparative example 1 or example 1.
The p-nitrophenol had a characteristic absorption peak at 400nm, and the peak at 400nm was continuously decreased and then remained unchanged as the catalytic reaction proceeded, as shown in fig. 3, wherein fig. 3 (a) is comparative example 1 and fig. 3 (b) is example 1. The catalytic rate can be characterized by the change in ultraviolet absorbance peak at 400nm over time, as shown in fig. 4.
As can be seen from FIG. 4, the catalytic rate of the gold-silver nano alloy prepared in comparative example 1 is 7.37X10 -3 s -1 The catalytic rate of the gold-silver nano alloy prepared in example 1 is 1.64×10 -2 s -1 Example 1 is much higher than comparative example 1, demonstrating that the catalytic rate of the gold-silver nanoalloy prepared by the invention is significantly improved.
Examples 2 to 3 and comparative examples 2 to 3 were examined in the same manner as in test examples 1 to 2, and the results obtained are shown in Table 1.
As can be seen from Table 1, for gold and silver nano-alloys with various molar ratios, the gold and silver nano-alloys prepared by the non-contact ultrasonic field of the invention have smaller size, more concentrated particle size distribution and remarkably improved catalytic activity compared with gold and silver nano-alloys obtained under the conventional container contact condition.
Table 1 experimental results of examples 1 to 3 and comparative examples 1 to 3
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An ultra-clean preparation method of gold and silver nano alloy comprises the following steps:
mixing tetrachloroauric acid trihydrate, silver nitrate and an organic mixed solvent to obtain a precursor mixed solution;
suspending the precursor mixed solution under the action of a non-contact ultrasonic field to obtain a precursor suspension;
and maintaining the suspension state of the precursor mixed solution, adding a reducing agent into the precursor suspension, and carrying out reduction reaction to obtain the gold-silver nano alloy.
2. The method according to claim 1, wherein the organic mixed solvent is a mixed solvent of a stabilizer and an organic solvent.
3. The ultra-clean preparation method according to claim 2, wherein the stabilizer is oleylamine; the organic solvent is toluene.
4. The ultra-clean preparation method according to claim 2, wherein the volume ratio of the stabilizer to the organic solvent in the organic mixed solvent is 1:1-2.
5. The ultra-clean preparation method according to claim 1, wherein the total concentration of the tetrachloroauric acid trihydrate and the silver nitrate in the precursor mixed solution is 20-30 mmol/L.
6. The method of claim 1, wherein the reducing agent is a borane tert-butylamine complex solution.
7. The method of claim 6, wherein the volume ratio of the reducing agent to the precursor suspension is 1:10.
8. the method according to claim 1, wherein the temperature of the reduction reaction is room temperature and the time of the reduction reaction is 2 to 10 minutes.
9. The gold-silver nano alloy prepared by the ultra-clean preparation method of any one of claims 1 to 8 is granular.
10. The use of the gold and silver nanoalloy of claim 9 for reduction of p-nitrophenol.
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