CN109663598B - PtNiAu nano hollow sphere material and preparation method and application thereof - Google Patents

PtNiAu nano hollow sphere material and preparation method and application thereof Download PDF

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CN109663598B
CN109663598B CN201710964096.7A CN201710964096A CN109663598B CN 109663598 B CN109663598 B CN 109663598B CN 201710964096 A CN201710964096 A CN 201710964096A CN 109663598 B CN109663598 B CN 109663598B
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邓意达
刘畅
张金凤
胡文彬
何宇
钟澄
韩晓鹏
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Tianjin University
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Abstract

The invention provides a PtNiAu nano hollow sphere material and a preparation method and application thereof, wherein a nickel salt solution and a citric acid solution are mixed according to a certain proportion; secondly, adding a sodium borohydride solution under the protection of nitrogen, and continuously magnetically stirring at room temperature to obtain a brown solution, namely a nickel nanoparticle template; dripping chloroplatinic acid solution with certain concentration to obtain black solution, namely the PtNi nano hollow sphere; and (3) continuing to magnetically stir at room temperature for a certain time, then dripping a certain amount of chloroauric acid solution, reacting for a period of time, and then carrying out centrifugal cleaning on the obtained black mixed solution to obtain the PtNiAu hollow nanospheres. The method has the advantages of simple and convenient operation, controllable appearance, lower energy consumption, safety and environmental protection.

Description

PtNiAu nano hollow sphere material and preparation method and application thereof
Technical Field
The invention relates to the field of new energy functional materials, and relates to a preparation method of a PtNiAu nano hollow sphere material, which is simple and convenient to operate, controllable in shape, low in energy consumption, safe and environment-friendly.
Background
The noble metal nano-catalyst has higher conductivity, catalytic activity and stability, and is widely used as a fuel cell catalyst. However, as the resource and energy crisis and other problems become more severe, the noble metal resources are increasingly scarce, and the noble metal catalysts prepared by using non-noble metals as templates have become hot research in recent years due to the expensive price. Due to the limitation of a binary structure regulation space, a third metal is introduced to develop a ternary metal catalyst with controllable morphology, a hollow structure, a large specific surface area and high activity, and the method has important significance. At present, further optimization of the catalytic performance of the material is one of the problems still faced by the hollow structure noble metal catalyst. Based on a sacrificial template method commonly adopted for preparing the hollow structure at present, the PtNiAu hollow nanosphere material is prepared by combining a chemical reduction method at room temperature, and the controllable preparation of the product morphology is realized by regulating and controlling process parameters.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides the PtNiAu hollow nanosphere material which is simple and convenient to operate, controllable in shape, low in energy consumption, safe and environment-friendly.
The purpose of the invention is realized by the following technical scheme.
The PtNiAu nano hollow sphere material and the preparation method thereof are carried out according to the following steps:
step 1, adding a sodium borohydride solution into a mixed solution of a nickel salt solution and a citric acid solution under an anaerobic condition, adding a chloroplatinic acid solution into the mixed solution, and magnetically stirring the mixed solution at room temperature of 20-25 ℃ for 1-2 hours to obtain a black mixed solution, wherein the concentration of the nickel salt solution is 0.1-0.3mol/L, the concentration of the citric acid solution is 0.3-0.5mmol/L, the concentration of the sodium borohydride solution is 0.02-0.04mol/L, the concentration of the chloroplatinic acid solution is 8-12mmol/L, and the volume ratio of the nickel salt solution to the citric acid solution to the sodium borohydride solution to the chloroplatinic acid solution is (1-3): (400-600): (40-60): (20-30);
and 2, dripping a chloroauric acid solution into the black mixed solution prepared in the step 1, reacting for 0-40min, centrifuging, and cleaning to obtain the PtNiAu hollow nanosphere material, wherein the concentration of the chloroauric acid solution is 0.5-12mmol/L, and the addition amount is 0.05-1.5 mL.
In step 1, an inert shielding gas is used to provide oxygen-free conditions for the reaction system, such as nitrogen, helium or argon.
In the step 1, the concentration of the nickel salt solution is 0.2mol/L, the concentration of the citric acid solution is 0.4mmol/L, the concentration of the sodium borohydride solution is 0.03mol/L, and the concentration of the chloroplatinic acid solution is 10 mmol/L; the nickel salt is nickel sulfate.
In the step 1, the volume ratio of the nickel salt solution to the citric acid solution to the sodium borohydride solution to the chloroplatinic acid solution is 1:500:50: 25; magnetically stirring at room temperature of 20-25 deg.C for 1.5 h.
In the step 2, the chloroauric acid solution is dripped into the black mixed solution for reaction for 0-30 min.
In step 2, after the centrifugal speed is 16000-20000rpm and the centrifugal time is 8-12min, washing with deionized water for 3-5 times.
In step 2, the concentration of the chloroauric acid solution is 1-10mmol/L, and the addition amount is 0.1-1 mL.
The application of the PtNiAu nano hollow sphere material in electrocatalysis methanol oxidation, and the preparation method of the working electrode comprises the following steps: mixing the PdNiAu nano hollow sphere material with an organic solvent, deionized water and a binder, performing ultrasonic dispersion to obtain slurry, uniformly dripping the slurry on a glassy carbon electrode, and drying to obtain the working electrode.
The volume ratio of the organic solvent to the deionized water is (1-3) to 1, preferably 2 to 1, the adding amount of the PtNiAu nano hollow sphere material is 8-12 parts by weight, and the binder is Nafion solution with the mass fraction of 0.1-0.3 wt%.
The invention has the beneficial effects that: the PtNiAu hollow nanosphere methanol oxidation catalyst with high platinum utilization rate is prepared by a simple and easy process method, and controllable preparation of morphological components of a product is realized by regulating and controlling few process parameters.
Drawings
FIG. 1 is an X-ray diffraction diagram of a PtNiAu nano hollow sphere prepared in example 3 of the present invention;
FIG. 2 is a transmission electron microscope image of PtNiAu hollow nanospheres prepared in example 3 of the present invention;
FIG. 3 is a transmission electron microscope image of PtNiAu hollow nanospheres prepared by the method of embodiment 4 of the invention;
fig. 4 is a transmission electron microscope image of the PtNiAu hollow nanosphere prepared by the method of embodiment 5 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated by the following specific examples, wherein the solution is an aqueous solution unless otherwise specified.
Example 1
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) 0.1mL of 10mmol/L chloroauric acid solution prepared in advance is dropped into the black solution, the mixture is not stirred and centrifuged at 18000rpm, and is washed by deionized water and repeated for a plurality of times, so that the incompletely-grown PtNiAu nano hollow sphere material is obtained.
5) Mixing the 10ug PtNiAu nano material obtained in the step 4) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
This example finally resulted in incompletely grown PtNiAu hollow nanosphere material.
Example 2
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) dripping 1mL of pre-prepared 1mmol/L chloroauric acid solution into the black solution, and magnetically stirring at room temperature for 30 min;
5) and centrifuging the obtained mixed solution at 18000rpm, washing with deionized water, and repeating for several times to obtain the PtNiAu hollow nanospheres.
6) Mixing the 10ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
The PtNiAu nano material with irregular shape is finally obtained by the embodiment.
Example 3
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) 0.1mL of 10mmol/L chloroauric acid solution prepared in advance is dropped into the black solution, and magnetic stirring is carried out at room temperature for 10 min;
5) centrifuging the obtained mixed solution at 18000rpm, washing with deionized water, and repeating for several times to obtain PtNiAu hollow nanospheres;
6) mixing the 10ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
As shown in fig. 2, the PtNiAu nanomaterial with a regular morphology is finally obtained in this embodiment, and the small particles outside the hollow sphere grow irregularly.
Example 4
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) dripping 1mL of pre-prepared 1mmol/L chloroauric acid solution into the black solution, and magnetically stirring at room temperature for 10 min;
5) and centrifuging the obtained mixed solution at 18000rpm, washing with deionized water, and repeating for several times to obtain the PtNiAu hollow nanospheres.
6) Mixing the 10ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
As shown in fig. 3, the PtNiAu nanomaterial with a regular morphology is finally obtained in this embodiment, and many small particles grow on the surface of the hollow sphere.
Example 5
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) 0.5mL of pre-prepared 1mmol/L chloroauric acid solution is dropped into the black solution, and magnetic stirring is carried out at room temperature for 10 min;
5) and centrifuging the obtained mixed solution at 18000rpm, washing with deionized water, and repeating for several times to obtain the PtNiAu hollow nanospheres with a plurality of nanoparticles attached to the surface.
6) Mixing the 10ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
The phase and the morphology of the PtNiAu hollow nanospheres are respectively characterized by an X-ray diffractometer (XRD) and a Transmission Electron Microscope (TEM), and the PtNiAu hollow nanospheres with regular morphology are successfully prepared by the method. Fig. 1 is an X-ray diffraction pattern of the PtNiAu hollow nanospheres prepared by the method of example 3. Fig. 2 is a transmission electron microscope image of the PtNiAu hollow nanosphere prepared in example 3, which shows that the PtNiAu hollow nanosphere is formed, and small particles outside the hollow nanosphere grow irregularly. As can be seen from fig. 3, the PtNiAu hollow nanospheres prepared by the method in embodiment 4 have a regular morphology with many small particles distributed on the surface of the hollow nanospheres. From fig. 4, it can be seen that the PtNiAu hollow nanospheres with regular shapes are prepared by the method in example 5, and more small particles grow on the surfaces of the hollow nanospheres than those in example 4, which indicates that the components of the product are changed.
Example 6
1) Uniformly mixing 0.2mL of 0.3mol/L nickel salt solution (nickel sulfate solution) with 80mL of 0.5mmol/L citric acid solution;
2) preparing 0.04mol/L sodium borohydride solution, and under the condition of nitrogen protection, adding 8mL of the sodium borohydride solution into the mixed solution and carrying out magnetic stirring, wherein the solution is brown;
3) 4mL of a 12mmol/L chloroplatinic acid solution is taken, and is dripped into the brown mixed solution to obtain a black solution, and the black solution is magnetically stirred for 1h at room temperature;
4) dripping 0.05mL of pre-prepared 12mmol/L chloroauric acid solution into the black solution, and magnetically stirring at room temperature for 1 min;
5) and centrifuging the obtained mixed solution at 16000rpm for 12min, and washing with deionized water for 3 times to obtain the PtNiAu hollow nanosphere material.
6) Mixing the 8ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 3:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
Example 7
1) Uniformly mixing 0.6mL of 0.1mol/L nickel salt solution (nickel sulfate solution) with 120mL of 0.3mmol/L citric acid solution;
2) preparing 0.02mol/L sodium borohydride solution, and adding 12mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 6mL of 8mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring the solution at room temperature for 2 hours;
4) dripping 1.5mL of pre-prepared 0.5mmol/L chloroauric acid solution into the black solution, and magnetically stirring at room temperature for 10 min;
5) centrifuging the obtained mixed solution at 20000rpm for 8min, and washing with deionized water for 5 times to obtain PtNiAu hollow nanospheres;
6) mixing the 12ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 1:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
Example 8
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) dripping 1mL of pre-prepared 1mmol/L chloroauric acid solution into the black solution, and magnetically stirring at room temperature for 40 min;
5) and centrifuging the obtained mixed solution at 18000rpm, washing with deionized water, and repeating for several times to obtain the PtNiAu hollow nanospheres.
6) Mixing the 9ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
Example 9
1) Uniformly mixing 0.2mL of 0.2mol/L nickel salt solution (nickel sulfate solution) with 100mL of 0.4mmol/L citric acid solution;
2) preparing 0.03mol/L sodium borohydride solution, and adding 10mL of the sodium borohydride solution into the mixed solution under the protection of nitrogen while performing magnetic stirring, wherein the solution is brown;
3) taking 5mL of 10mmol/L chloroplatinic acid solution, dripping the chloroplatinic acid solution into the brown mixed solution to obtain a black solution, and magnetically stirring at room temperature for 1.5 h;
4) 0.5mL of 10mmol/L chloroauric acid solution prepared in advance is dropped into the black solution, and magnetic stirring is carried out at room temperature for 20 min;
5) and centrifuging the obtained mixed solution at 18000rpm, washing with deionized water, and repeating for several times to obtain the PtNiAu hollow nanospheres with a plurality of nanoparticles attached to the surface.
6) Mixing the 11ug PtNiAu nano material obtained in the step 5) with isopropanol, deionized water (the volume ratio of the two is 2:1) and 50uL Nafion, and performing ultrasonic dispersion to obtain slurry; and uniformly dripping the slurry on the pretreated platinum carbon, and drying to obtain the working electrode.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

  1. The PtNiAu nano hollow sphere material is characterized in that: the method comprises the following steps:
    step 1, adding a sodium borohydride solution into a mixed solution of a nickel salt solution and a citric acid solution under an anaerobic condition, adding a chloroplatinic acid solution into the mixed solution, and magnetically stirring the mixed solution at room temperature of 20-25 ℃ for 1-2 hours to obtain a black mixed solution, wherein the concentration of the nickel salt solution is 0.1-0.3mol/L, the concentration of the citric acid solution is 0.3-0.5mmol/L, the concentration of the sodium borohydride solution is 0.02-0.04mol/L, the concentration of the chloroplatinic acid solution is 8-12mmol/L, and the volume ratio of the nickel salt solution to the citric acid solution to the sodium borohydride solution to the chloroplatinic acid solution is (1-3): (400-600): (40-60): (20-30);
    and 2, dripping a chloroauric acid solution into the black mixed solution prepared in the step 1, reacting for 0-40min, centrifuging, and cleaning to obtain the PtNiAu hollow nanosphere material, wherein the concentration of the chloroauric acid solution is 0.5-12mmol/L, and the addition amount is 0.05-1.5 mL.
  2. 2. The PtNiAu hollow nanosphere material of claim 1, wherein: in step 1, an inert shielding gas is used to provide oxygen-free conditions for the reaction system.
  3. 3. The PtNiAu hollow nanosphere material of claim 1, wherein: in the step 1, the concentration of the nickel salt solution is 0.2mol/L, the concentration of the citric acid solution is 0.4mmol/L, the concentration of the sodium borohydride solution is 0.03mol/L, and the concentration of the chloroplatinic acid solution is 10 mmol/L; the nickel salt is nickel sulfate; the volume ratio of the nickel salt solution to the citric acid solution to the sodium borohydride solution to the chloroplatinic acid solution is 1:500:50: 25; magnetically stirring at room temperature of 20-25 deg.C for 1.5 h.
  4. 4. The PtNiAu hollow nanosphere material of claim 1, wherein: in the step 2, dripping chloroauric acid solution into the black mixed solution, and reacting for 0-30 min; centrifuging at 16000-20000rpm for 8-12min, and washing with deionized water for 3-5 times; the concentration of the chloroauric acid solution is 1-10mmol/L, and the addition amount is 0.1-1 mL.
  5. The preparation method of the PtNiAu nano hollow sphere material is characterized by comprising the following steps: the method comprises the following steps:
    step 1, adding a sodium borohydride solution into a mixed solution of a nickel salt solution and a citric acid solution under an anaerobic condition, adding a chloroplatinic acid solution into the mixed solution, and magnetically stirring the mixed solution at room temperature of 20-25 ℃ for 1-2 hours to obtain a black mixed solution, wherein the concentration of the nickel salt solution is 0.1-0.3mol/L, the concentration of the citric acid solution is 0.3-0.5mmol/L, the concentration of the sodium borohydride solution is 0.02-0.04mol/L, the concentration of the chloroplatinic acid solution is 8-12mmol/L, and the volume ratio of the nickel salt solution to the citric acid solution to the sodium borohydride solution to the chloroplatinic acid solution is (1-3): (400-600): (40-60): (20-30);
    and 2, dripping a chloroauric acid solution into the black mixed solution prepared in the step 1, reacting for 0-40min, centrifuging, and cleaning to obtain the PtNiAu hollow nanosphere material, wherein the concentration of the chloroauric acid solution is 0.5-12mmol/L, and the addition amount is 0.05-1.5 mL.
  6. 6. The preparation method of the PtNiAu hollow nanosphere material according to claim 5, wherein the PtNiAu hollow nanosphere material comprises the following steps: in step 1, an inert shielding gas is used to provide oxygen-free conditions for the reaction system.
  7. 7. The preparation method of the PtNiAu hollow nanosphere material according to claim 5, wherein the PtNiAu hollow nanosphere material comprises the following steps: in the step 1, the concentration of the nickel salt solution is 0.2mol/L, the concentration of the citric acid solution is 0.4mmol/L, the concentration of the sodium borohydride solution is 0.03mol/L, and the concentration of the chloroplatinic acid solution is 10 mmol/L; the nickel salt is nickel sulfate; the volume ratio of the nickel salt solution to the citric acid solution to the sodium borohydride solution to the chloroplatinic acid solution is 1:500:50: 25; magnetically stirring at room temperature of 20-25 deg.C for 1.5 h.
  8. 8. The preparation method of the PtNiAu hollow nanosphere material according to claim 5, wherein the PtNiAu hollow nanosphere material comprises the following steps: in the step 2, dripping chloroauric acid solution into the black mixed solution, and reacting for 0-30 min; centrifuging at 16000-20000rpm for 8-12min, and washing with deionized water for 3-5 times; the concentration of the chloroauric acid solution is 1-10mmol/L, and the addition amount is 0.1-1 mL.
  9. 9. The use of the PtNiAu hollow nanosphere material of any one of claims 1 to 4 in electrocatalytic methanol oxidation, wherein: mixing the PdNiAu nano hollow sphere material with an organic solvent, deionized water and a binder, performing ultrasonic dispersion to obtain slurry, uniformly dripping the slurry on a glassy carbon electrode, and drying to obtain the working electrode.
  10. 10. Use according to claim 9, characterized in that: the volume ratio of the organic solvent to the deionized water is (1-3):1, the adding amount of the PtNiAu nano hollow sphere material is 8-12 parts by weight, and the adhesive is Nafion solution with the mass fraction of 0.1-0.3 wt%.
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* Cited by examiner, † Cited by third party
Title
Carbon supported trimetallic nickelepalladiumegold hollow nanoparticles with superior catalytic activity for methanol electrooxidation;Changshuai Shang等;《Journal of Power Sources》;20150314;第285卷;第12-15页 *
Sophisticated Construction of Au Islands on Pt−Ni: An Ideal Trimetallic Nanoframe Catalyst;Yuen Wu等;《JACS》;20140805;第136卷;第11594-11597页 *

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