CN105552388A - Preparation method of gold mercury amalgam nano particle with high catalytic activity and application thereof - Google Patents

Preparation method of gold mercury amalgam nano particle with high catalytic activity and application thereof Download PDF

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CN105552388A
CN105552388A CN201610040340.6A CN201610040340A CN105552388A CN 105552388 A CN105552388 A CN 105552388A CN 201610040340 A CN201610040340 A CN 201610040340A CN 105552388 A CN105552388 A CN 105552388A
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nanometer particle
golden nanometer
golden
particle
nano particle
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CN105552388B (en
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向娟
秦云
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Central South University
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a preparation method of a gold mercury amalgam nano particle with a high catalytic activity and an application thereof. The preparation of the gold mercury amalgam nano particle comprises the following steps: taking sodium citrate as a reducing agent, and synthesizing a gold nano particle by reducing chloroauric acid step by step; physically loading the gold nano particle to a surface of a glassy carbon electrode surface, then taking the glassy carbon electrode as a working electrode, placing the glassy carbon electrode into a mercury nitrate solution, obtaining a glassy carbon electrode of the surface modified gold mercury amalgam nano particle through a cyclic voltammetry, and performing an ultrasonic treatment, then the gold mercury amalgam nano particle can be obtained. The preparation method is simple, low in cost and simple and convenient in operation; the prepared gold mercury amalgam nano particle shows an obvious electrocatalytic activity for oxygen reduction, and has a better stability and a potential application value in fuel cells, environmental catalysis and other aspects.

Description

A kind of preparation method and application thereof with the golden mercury alloy nano particle of high catalytic activity
Technical field
The present invention relates to a kind of preparation method and the application thereof with the golden mercury alloy nano particle of high catalytic activity, belong to nano electro-catalytic Material Field.
Background technology
Nano material is the noble metal nanometer material such as gold, platinum especially, because it has and the features such as common material difference skin effect, quantum size effect, small-size effect, them are made to occupy very important status (Phys.Chem.Chem.Phys. in catalyst field, 2007,9,2654 – 2675; Phys.Chem.Chem.Phys., 2014,16,13583), in the energy, chemical industry etc., demonstrate huge potential using value.
Golden nanometer particle is subject to extensive research (JSolidStateElectrochem in various catalytic reaction, 2014,18,3299 – 3306), size, form the performance that controlled nano material greatly can improve nano particle, widen its application.Existing document (ChemPhysChem2004,5,1405 – 1410) report synthesizes golden mercury alloy by the method for electro-deposition, at metal cation (Cr iII, Co iI, Cd iI, Cu iI) context of detection has higher sensitivity, but method disclosed in the document is uncontrollable to golden mercury alloy nano particle diameter, cannot reach the requirement of various application.The Polarium nano chain (RSCAdv., 2014,4,52640 – 52646) that reduced graphene is supported shows good oxygen reduction catalytic activity, but cost is higher, is unsuitable for large-scale production.
Summary of the invention
For prior art Problems existing, the object of the invention is to be to provide a kind of simple to operate, efficient, preparation regular appearance, size uniform and size is controlled, and there is the method for the golden mercury alloy nano particle of high oxygen reduction catalytic activity.
Another object of the present invention is the application being to provide a kind of described golden mercury alloy nano particle, it can be used as electrochemical catalyst to show excellent catalytic activity and good catalytic stability to hydrogen reduction.
In order to realize above-mentioned technical purpose, the invention provides a kind of preparation method with the golden mercury alloy nano particle of high catalytic activity, the method is that reducing agent is by step-by-step reduction gold chloride synthesis golden nanometer particle with natrium citricum; By described golden nanometer particle physical load to glassy carbon electrode surface, obtain the glass-carbon electrode of finishing golden nanometer particle; With the glass-carbon electrode of finishing golden nanometer particle for work electrode, be placed in mercuric nitrate solution, obtained the glass-carbon electrode of finishing gold mercury alloy nano particle by cyclic voltammetry; The glass-carbon electrode of finishing gold mercury alloy nano particle is placed in solution and carries out ultrasonic stripping, obtain golden mercury alloy nano particle.
Preferred scheme, the process of natrium citricum step-by-step reduction gold chloride synthesis golden nanometer particle is: gold chloride is added in water by (1), is heated to boiling, then adds sodium citrate solution, stirring reaction, obtain golden nanometer particle seed; (2) described golden nanometer particle seed is joined in the water boiled, then add gold chloride and sodium citrate solution successively, stirring reaction, obtain golden nanometer particle A1; (3) grain size of target setting golden nanometer particle, repeats (2) process several times by described golden nanometer particle A1, making the particle size growth of golden nanometer particle A1 to setting grain size, obtaining final product.
More preferably scheme, be that gold chloride 350 ~ 370 μ L of 22 ~ 28mmol/L is added to after in 27 ~ 29mL water by concentration, be heated to boiling, add sodium citrate solution 180 ~ 220 μ L that concentration is 165 ~ 175mmol/L more fast, stirring reaction to solution is ruby red, stops heating, continues stirring reaction 25 ~ 35min, add water again and make overall solution volume be 30mL, obtain golden nanometer particle seeded dispersion liquid; Getting 4 ~ 6mL golden nanometer particle seeded dispersion liquid joins in the water that 85 ~ 92mL boils, add gold chloride 530 ~ 550 μ L that concentration is 22 ~ 28mmol/L again and concentration is 165 ~ 175mmol/L sodium citrate solution 850 ~ 950 μ L, stop heating, continue stirring reaction 55 ~ 65min, add water and make overall solution volume be 100mL, obtain golden nanometer particle A1 dispersion liquid; Getting 18 ~ 22mL golden nanometer particle A1 dispersion liquid joins in the water boiled, add sodium citrate solution 750 ~ 850 μ L that gold chloride 470 ~ 490 μ L that concentration is 22 ~ 28mmol/L and concentration are 165 ~ 175mmol/L again, stop heating, continue stirring 55 ~ 65min, add water and make overall solution volume be 100mL, obtain golden nanometer particle A2 dispersion liquid; Getting 48 ~ 52mL golden nanometer particle A2 dispersion liquid joins in the water boiled, add sodium citrate solution 480 ~ 520 μ L that gold chloride 290 ~ 310 μ L that concentration is 22 ~ 28mmol/L and concentration are 165 ~ 175mmol/L, stop heating, continue stirring 55 ~ 65min, add water and make overall solution volume be 100mL, obtain golden nanometer particle A3 dispersion liquid; Repeat the building-up process twice of golden nanometer particle A3 dispersion liquid, obtain golden nanometer particle A4 dispersion liquid and golden nanometer particle A5 dispersion liquid successively.
Preferred scheme further, golden nanometer particle A1 grain size is 36 ~ 46nm.
Preferred scheme further, golden nanometer particle A2 grain size is 57 ~ 67nm.
Preferred scheme further, golden nanometer particle A3 grain size is 72 ~ 82nm.
Preferred scheme further, golden nanometer particle A4 grain size is 86 ~ 96nm.
Golden nanometer particle A5 grain size is 100 ~ 110nm.
Preferred scheme, golden nanometer particle drips glassy carbon electrode surface by physical absorption in glassy carbon electrode surface with solation.By the high speed centrifugation washing at least twice under 5000 ~ 7000rpm rotating speed of golden nanometer particle dispersion liquid, each washing 8min, obtains golden nanometer particle colloidal sol, then golden nanometer particle colloidal sol is added drop-wise to glassy carbon electrode surface, dry under infrared lamp, realize golden nanometer particle and be modified at glassy carbon electrode surface.
Preferred scheme, cyclic voltammetry condition is: take-off potential 0.8V, stops current potential 0.2V, sweep speed 300mVs -1, circulate 6 weeks.
More preferably scheme, cyclic voltammetry is to electrode with platinum filament, and Ag/AgCl is reference electrode, and the concentration of mercuric nitrate solution is 0.45 ~ 0.65mmol/L.
The water that the present invention adopts is preferably ultra-pure water, as redistilled water; The solvent that gold chloride and sodium citrate solution adopt preferably also uses ultra-pure water.Gold chloride needs to keep in Dark Place before using.
Present invention also offers the described application with the golden mercury alloy nano particle of high catalytic activity, this application is that golden mercury alloy nano particle is applied to catalytic oxidation-reduction as electrochemical catalyst.
Hinge structure, the Advantageous Effects that technical scheme of the present invention is brought:
1, golden nanometer particle of the present invention is prepared by step-by-step reduction method, and it has regular appearance, the uniform feature of size, and for golden mercury alloy nano particle provides good template, and the particle diameter of golden nanometer particle can regulate and control arbitrarily.
2, the present invention is that template passes through electrochemical production gold mercury alloy nano particle with golden nanometer particle, and process conditions gentleness is controlled, convenient and swift, environmental friendliness, and golden mercury alloy nano particle good stability, the regular appearance of preparation.
3, the preparation technology of golden mercury alloy nano particle of the present invention is simple to operate, cheap, efficient.
4, the golden mercury alloy nanoparticle properties that prepared by the present invention is stablized, and all significant catalytic capability is had to the electrochemical reduction of oxygen in the solution of different pH, showing excellent catalytic activity and good stability as during electrochemical catalyst to hydrogen reduction, there is good application prospect at fuel-cell catalyst and field of energy utilization.
Accompanying drawing explanation
The grain size distribution of the AuNPs (A3 and A5) that [Fig. 1] is prepared for the embodiment of the present invention 1;
Scanning electron microscopy (SEM) figure of the Au-Hg alloy nano particle that [Fig. 2] is prepared for the embodiment of the present invention 1;
X-ray photoelectron spectroscopic analysis (XPS) figure of the Au-Hg alloy nano particle that [Fig. 3] is prepared for the embodiment of the present invention 1;
In the solution that [Fig. 4] is different pH, catalytic activity figure: the A of hydrogen reduction is the H of 0.5mol/L 2sO 4solution, B is the NaOH solution of 0.5mol/L, and C is the Na of 0.5mol/L 2sO 4solution, the 1 linear sweep voltammetry curve that is Au-Hg alloy nano particle (prepared by embodiment 1) in the saturated solution of nitrogen, 2 is that in the solution that oxygen is saturated, AuNPs is to the catalytic activity figure of hydrogen reduction, and 3 is Au-Hg alloy nano particle (prepared by embodiment 1) the catalytic activity figure to hydrogen reduction.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe meticulously more comprehensively to the present invention in conjunction with Figure of description and specific embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Embodiment 1
(1) preparation method of AuNPs, step is as follows:
360 μ L25mmol/LHAuCl are added in the there-necked flask of 50mL 4and 28mL ultra-pure water, after being heated to boil under the effect of stirring (1500rpm), condensing reflux, add 200 μ L170mmol/LNa 3c 6h 5o 7, after a few second, solution colour becomes ruby red and stable, stops heating, and continue to stir 30min, add ultra-pure water and make overall solution volume be 30mL, gained nm of gold is S.Under stirring, 5mLS is joined in the ultra-pure water of 90mL boiling, add 540 μ L25mmol/LHAuCl 4, add 900 μ L170mmol/LNa immediately 3c 6h 5o 7, stop heating and continue to stir 60min, add water and make cumulative volume be 100mL, obtaining nm of gold is A1.Under stirring, 20mLA1 is joined in the ultra-pure water of 75mL boiling, add 480 μ L25mmol/LHAuCl 4, add 800 μ L170mmol/LNa immediately 3c 6h 5o 7, stop heating and continue to stir 60min, add water and make cumulative volume be 100mL, obtaining nm of gold is A2.Under stirring, 50mLA2 is joined in the ultra-pure water of 45mL boiling, add 300 μ L25mmol/LHAuCl 4, add 500 μ L170mmol/LNa immediately 3c 6h 5o 7, stop heating and continue to stir 60min, add water and make cumulative volume be 100mL, obtaining nm of gold is A3.Repeat the operation twice of A3 synthesis, obtain A4 and A5 nano Au particle respectively.A1 average-size is about 41nm, A1 average-size be about 62nm, A3 average-size is about 77nm (as shown in Figure 1), A4 average-size is about 91nm, A5 average-size is about 105nm (as shown in Figure 1), and domain size distribution is very narrow, within the scope of 10nm; Reduce compared with the obtained nm of gold of gold chloride with sodium borohydride under room temperature one step, particle diameter is more homogeneous.
(2) preparation method of Au-Hg alloy nano particle, step is as follows:
Get 1500 μ LA5 centrifugal, after siphoning away supernatant, add ultra-pure water, ultrasonic disperse.Centrifugal repetition twice, adds ultra-pure water in the most backward centrifuge tube, make cumulative volume be 500 μ L.
Successively glass-carbon electrode to be polished extremely smooth minute surface with the alumina powder of 0.3 μm with 1.0 μm, then rinse well with redistilled water, then ultrasonic 5min in alcohol and redistilled water respectively, finally dried up with nitrogen.
Getting the above-mentioned solution of 10 μ L drops on the glass-carbon electrode that carries out processing in prior surface, irradiates, obtain the glass-carbon electrode that golden nanometer particle covers, i.e. AuNPs/GC electrode through infrared lamp.The golden nanometer particle of AuNPs/GC electrode as substrate, by the method for electrochemical redox at 0.65mmol/LHg (NO 3) 2solution in carry out cyclic voltammetry scan, sweep speed for 300mVs -1, circulation 6 circle, potential range is 0.8 ~ 0.2V.Obtain the glass-carbon electrode of Au-Hg alloy nanoparticle subcovering, i.e. Au-Hg/GC electrode.Ultrasonic Au-Hg/GC electrode, obtains Au-Hg alloy nano particle.
The Au-Hg alloy nano particle pattern prepared as can be seen from Figure 2 is regular subsphaeroidal particle, and even particle size.
Nano particle is made up of Au and the Hg element of simple substance as can be seen from Figure 3.
(3) sign of Au-Hg/GC electrode and oxygen reduction catalytic activity thereof, step is as follows:
(1) AuNPs/GC is at the H of 0.5mol/L 2sO 4cyclic voltammetry is carried out in solution;
(2) H of the AuNPs/GC 0.5mol/L that, oxygen saturated at nitrogen is saturated respectively 2sO 4solution, the NaOH solution of 0.5mol/L, the Na of 0.5mol/L 2sO 4carry out linear sweep voltammetry test in solution, sweep speed is 50mVs -1;
(3) AuNPs/GC electrode is at 0.65mmol/LHg (NO 3) 2solution in carry out cyclic voltammetry, sweep speed is 50mVs -1;
(4) H of the Au-Hg/GC 0.5mol/L that, oxygen saturated at nitrogen is saturated respectively 2sO 4solution, the NaOH solution of 0.5mol/L, the Na of 0.5mol/L 2sO 4carry out linear sweep voltammetry test in solution, sweep speed is 50mVs -1;
(5) XPS sample: Au-Hg/GC dries naturally.
(6) SEM sample: Au-Hg/GC dries naturally.
In the solution of different pH as can be seen from Figure 4, Au-Hg alloy nano particle is to the catalytic activity Be very effective of hydrogen reduction, A, B, C figure all can observe obvious hydrogen reduction peak, and Au-Hg alloy nano particle is shuffled to the take-off potential of hydrogen reduction relative to AuNPs in the solution of different pH, under acid condition, hydrogen reduction current potential is shuffled about 120mV, under alkali condition, hydrogen reduction current potential is shuffled about 140mV, and under acid condition, hydrogen reduction current potential is shuffled about 150mV.
With same procedure process A3, catalytic efficiency is about 85% of A5 process gained alloy particle.

Claims (8)

1. there is a preparation method for the golden mercury alloy nano particle of high catalytic activity, it is characterized in that: be that reducing agent is by step-by-step reduction gold chloride synthesis golden nanometer particle with natrium citricum; By described golden nanometer particle physical load to glassy carbon electrode surface, obtain the glass-carbon electrode of finishing golden nanometer particle; With the glass-carbon electrode of finishing golden nanometer particle for work electrode, be placed in mercuric nitrate solution, obtained the glass-carbon electrode of finishing gold mercury alloy nano particle by cyclic voltammetry; The glass-carbon electrode of finishing gold mercury alloy nano particle is placed in solution and carries out ultrasonic stripping, obtain golden mercury alloy nano particle.
2. the preparation method with the golden mercury alloy nano particle of high catalytic activity according to claim 1, it is characterized in that: the process of natrium citricum step-by-step reduction gold chloride synthesis golden nanometer particle is: gold chloride is added in water by (1), be heated to boiling, add sodium citrate solution again, stirring reaction, obtains golden nanometer particle seed; (2) described golden nanometer particle seed is joined in the water boiled, then add gold chloride and sodium citrate solution successively, stirring reaction, obtain golden nanometer particle A1; (3) grain size of target setting golden nanometer particle, repeats (2) process several times by described golden nanometer particle A1, making the particle size growth of golden nanometer particle A1 to setting grain size, obtaining final product.
3. the preparation method with the golden mercury alloy nano particle of high catalytic activity according to claim 2, it is characterized in that: be that gold chloride 350 ~ 370 μ L of 22 ~ 28mmol/L is added to after in 27 ~ 29mL water by concentration, be heated to boiling, add sodium citrate solution 180 ~ 220 μ L that concentration is 165 ~ 175mmol/L more fast, stirring reaction to solution is ruby red, stop heating, continue stirring reaction 25 ~ 35min, add water again and make overall solution volume be 30mL, obtain golden nanometer particle seeded dispersion liquid; Getting 4 ~ 6mL golden nanometer particle seeded dispersion liquid joins in the water that 85 ~ 92mL boils, add gold chloride 530 ~ 550 μ L that concentration is 22 ~ 28mmol/L again and concentration is 165 ~ 175mmol/L sodium citrate solution 850 ~ 950 μ L, stop heating, continue stirring reaction 55 ~ 65min, add water and make overall solution volume be 100mL, obtain golden nanometer particle A1 dispersion liquid; Getting 18 ~ 22mL golden nanometer particle A1 dispersion liquid joins in the water boiled, add sodium citrate solution 750 ~ 850 μ L that gold chloride 470 ~ 490 μ L that concentration is 22 ~ 28mmol/L and concentration are 165 ~ 175mmol/L again, stop heating, continue stirring 55 ~ 65min, add water and make overall solution volume be 100mL, obtain golden nanometer particle A2 dispersion liquid; Getting 48 ~ 52mL golden nanometer particle A2 dispersion liquid joins in the water boiled, add sodium citrate solution 480 ~ 520 μ L that gold chloride 290 ~ 310 μ L that concentration is 22 ~ 28mmol/L and concentration are 165 ~ 175mmol/L, stop heating, continue stirring 55 ~ 65min, add water and make overall solution volume be 100mL, obtain golden nanometer particle A3 dispersion liquid; Repeat the building-up process twice of golden nanometer particle A3 dispersion liquid, obtain golden nanometer particle A4 dispersion liquid and golden nanometer particle A5 dispersion liquid successively.
4. the preparation method with the golden mercury alloy nano particle of high catalytic activity according to claim 3, is characterized in that: golden nanometer particle A1 grain size is 36 ~ 46nm; Golden nanometer particle A2 grain size is 57 ~ 67nm; Golden nanometer particle A3 grain size is 72 ~ 82nm; Golden nanometer particle A4 grain size is 86 ~ 96nm; Golden nanometer particle A5 grain size is 100 ~ 110nm.
5. the preparation method with the golden mercury alloy nano particle of high catalytic activity according to claim 1, is characterized in that: described golden nanometer particle drips glassy carbon electrode surface by physical absorption in glassy carbon electrode surface with solation.
6. the preparation method with the golden mercury alloy nano particle of high catalytic activity according to claim 1, is characterized in that: described cyclic voltammetry condition is: take-off potential 0.8V, stops current potential 0.2V, sweep speed 300mVs -1, circulate 6 weeks.
7. the preparation method with the golden mercury alloy nano particle of high catalytic activity according to claim 6, it is characterized in that: described cyclic voltammetry is to electrode with platinum filament, Ag/AgCl is reference electrode, and the concentration of mercuric nitrate solution is 0.45 ~ 0.65mmol/L.
8. the application of prepared by the method described in any one of claim 1 ~ 7 the have golden mercury alloy nano particle of high catalytic activity, is characterized in that: be applied to catalytic oxidation-reduction as electrochemical catalyst.
CN201610040340.6A 2016-01-21 2016-01-21 A kind of preparation method and applications of the golden amalgamation golden nanometer particle with high catalytic activity Expired - Fee Related CN105552388B (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1544702A (en) * 2003-11-21 2004-11-10 ���Ŵ�ѧ Process for preparing carbon supported polymer surface nano-alloy electrocatalytic electrode
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544702A (en) * 2003-11-21 2004-11-10 ���Ŵ�ѧ Process for preparing carbon supported polymer surface nano-alloy electrocatalytic electrode
US20060192182A1 (en) * 2005-02-25 2006-08-31 Fry's Metals, Inc. Preparation of metallic particles for electrokinetic or electrostatic deposition
CN102435649A (en) * 2011-09-09 2012-05-02 天津大学 Manufacturing method and application method of Pt-Ag alloy nanoparticle enzyme-free glucose sensor electrode

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Title
DAVID RIOUX等: ""Seeded Growth Synthesis of Composition and Size-Controlled Gold-Silver Alloy Nanoparticles"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *

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