CN107930623B - Gold-urea complex nanosphere and preparation method thereof, and preparation method and application of porous nanogold - Google Patents
Gold-urea complex nanosphere and preparation method thereof, and preparation method and application of porous nanogold Download PDFInfo
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- CQVNZICBXZRFTM-UHFFFAOYSA-N gold;urea Chemical compound [Au].NC(N)=O CQVNZICBXZRFTM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002077 nanosphere Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000010931 gold Substances 0.000 claims abstract description 58
- 229910052737 gold Inorganic materials 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000010894 electron beam technology Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 description 46
- 239000007787 solid Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
The invention provides a gold-urea complex nanosphere and a preparation method thereof, and a preparation method and application of porous nanogold. The used time is short, the experimental efficiency is improved compared with the prior method, an amplification experiment is carried out, the gold-urea complex nanospheres are obtained in the first step of reaction in the same proportion, and the uniformity of the particles is still found through characterization. The used raw materials are simple and clean, only the chloroauric acid and the urea react in the aqueous solution, and no surfactant and other substances are added. The prepared gold-urea complex is calcined, heated in a dark place or bombarded by electron beams to obtain the porous nano-gold material with good catalytic performance.
Description
Technical Field
The invention belongs to the field of synthesis, and particularly relates to a gold-urea complex nanosphere and a preparation method thereof, and a preparation method and application of porous nanogold.
Background
The noble metal nano particles have good stability and biocompatibility and unique catalytic property. Gold nanomaterials are of great interest due to their excellent catalytic properties. Among them, the porous/hollow gold nano material becomes one of the hot points of research. The material has photocatalysis, electrocatalysis and organic catalysis performances related to morphology, and is expected to play an important role as an active catalytic component or a high-sensitivity probe in the field of energy, key reaction and detection. The porous/hollow gold nano material has wide application prospect in the aspects of organic catalysis, oxygen reduction and biomacromolecule detection and has huge potential value.
The current synthesis methods, including metal replacement, seed method, template method, etc., all have some defects:
metal replacement method: the steps need to obtain the nano structure with the corresponding size of another metal firstly, which is the first step (the cost is at least doubled), and then the step of modification is omitted, and the replacement conditions need to be strictly controlled in the second step to synthesize the final hollow gold nanosphere.
A seed method: the synthesis requirement is high, the chloroauric acid is mostly reduced into small gold nanoparticles by adopting a method for reducing chloroauric acid, a surfactant is utilized to further assemble porous and hollow gold nanoparticles, and the synthesis process can be completed only by three steps of reduction, modification and assembly growth; moreover, the storage time is short, a certain amount of large size (>100nm) exists, and although the large size is definitely small in quantity, the large size occupies considerable mass in terms of mass ratio, and various performance parameters under unit mass are greatly influenced. The conditions of the metal displacement process are also very harsh and difficult to control.
Template method: the method is a process of taking a substance with a nano structure and an easily controlled shape as a template, depositing related materials into holes or surfaces of the template by a physical or chemical method, and then removing the template to obtain the nano material with the standard shape and size of the template; i.e., templates need to be prepared or purchased to reduce chloroauric acid onto the nano-template particles and then removed using other special treatments.
It can be seen that these synthetic methods have the disadvantages: the size and the morphology of the prepared initial gold nanoparticles cannot be well controlled, and the uniformity of the finally obtained material is poor; in addition, the method has the defects of complex experimental steps, harsh conditions and very high cost.
All in all, the above factors greatly influence the application of porous/hollow materials. In order to overcome the above disadvantages, it is necessary to improve controllability of preparing the porous/hollow gold nanomaterial and efficiency of the process of preparing the porous/hollow gold nanomaterial.
Disclosure of Invention
The invention aims to provide a gold-urea complex nanosphere and a preparation method thereof, and a gold-urea complex with uniform size is prepared in one step through a hydrothermal synthesis reaction.
The invention also provides a preparation method of the porous nanogold, which is characterized in that solid porous nanogold materials are prepared by heating in a dark place or irradiating by an ultraviolet lamp, and hollow nanogold materials are obtained by high-temperature calcination or TEM electron beam bombardment.
The invention also provides an application of the porous nanogold as a catalyst.
The invention provides a preparation method of a gold-urea complex nanosphere, which comprises the following steps:
and (3) dispersing urea and chloroauric acid solution in pure water at room temperature, then heating and carrying out reflux reaction, and washing a product to obtain the gold-urea complex nanosphere with a clean surface.
Further, the molar ratio between chloroauric acid and urea is 0.0001-0.002: 1.
the concentration of the chloroauric acid solution is 0.001-0.01 mol/L. The concentration of chloroauric acid after dispersion in pure water was 1 x 10-5–1*10-4mol/L。
The heating reflux reaction is carried out for 10-20 min at the temperature of 90-120 ℃.
The gold-urea complex nanosphere provided by the invention is prepared by adopting the method.
The invention provides a preparation method of porous nanogold, which comprises the following steps:
and heating the prepared gold-urea complex nanosphere at 160 ℃ for 30-50 minutes in a dark place to obtain the solid porous gold nanomaterial.
Or irradiating the prepared gold-urea complex nanosphere for 20-30 minutes by using a 300W ultraviolet lamp at room temperature to obtain the solid porous gold nanomaterial.
Or heating the prepared gold-urea complex nanosphere for 40-50 minutes at 190 ℃ in a dark place to obtain the hollow porous gold nanomaterial.
Or bombarding the prepared gold-urea complex nanosphere by a TEM electron beam of a transmission electron microscope, wherein the accelerating voltage of the TEM electron beam is 200kV, and the current is 10mA to obtain the hollow porous gold nanomaterial.
Or placing the prepared ethanol dispersion liquid of the gold-urea complex nanosphere in a porcelain boat, placing the porcelain boat in a tube furnace, heating to 800 ℃, keeping the temperature at 10 ℃/min for 20 minutes at 800 ℃, and cooling to room temperature to obtain the porcelain boat coated with a layer of black substance, namely the hollow nano gold wires.
The invention provides an application of porous nanogold as a catalyst. For the catalytic reduction of nitrophenols to p-aminophenols.
Compared with the prior art, the gold-urea complex nanosphere prepared by the method has the advantages that the gold-urea complex nanosphere with uniform size is prepared in one step through simple hydrothermal synthesis reaction, any surfactant is added, the pH value is not required to be adjusted, the method is simple, and the conditions are controllable. The used time is short, the experimental efficiency is improved compared with the prior method, an amplification experiment is carried out, the gold-urea complex nanospheres are obtained in the first step of reaction in the same proportion, and the uniformity of the particles is still found through characterization. The used raw materials are simple and clean, only the chloroauric acid and the urea react in the aqueous solution, and no surfactant and other substances are added. In a word, the invention reduces the cost on the existing method for preparing the porous gold, is easy to prepare and has high yield, and finally the porous nano-gold material with clean surface can be obtained. The prepared gold-urea complex is calcined, heated in a dark place or bombarded by electron beams to obtain the porous nano-gold material with good catalytic performance. Different treatment methods and different temperatures affect the gold-urea complex nanosphere, thereby affecting the morphology and the catalytic performance of the nanosphere.
Drawings
FIG. 1 is an infrared spectrum of a gold urea complex nanosphere converted to a gold nanomaterial by heating;
FIG. 2 is an XRD pattern of gold urea complex nanospheres converted to gold nanomaterials by heating;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the gold urea complex nanomaterial obtained in example 1;
FIG. 4 is a Transmission Electron Microscope (TEM) image of the porous solid gold nanomaterial prepared in example 2;
FIG. 5 is a Transmission Electron Microscope (TEM) image of the porous hollow gold nanomaterial prepared in example 3;
FIG. 6 is a transition log of the gold-urea complex nanospheres prepared in example 5 under TEM electron beam bombardment for different times;
FIG. 7 is a SEM image of calcined gold-urea complex nanospheres of example 6 at high temperature of 800 ℃;
FIG. 8 is a TEM image of the calcined gold-urea complex nanospheres of example 6 at high temperature of 800 ℃;
FIG. 9 is a graph showing the change of ultraviolet absorption peak of p-nitrophenol catalysis with time after the hollow porous gold nano-material prepared in example 3; the time is 0, 45, 90, 135, 180, 225, 270, 315 and 360s from top to bottom;
FIG. 10 is a graph comparing the catalytic speed of the hollow porous gold nanomaterial prepared in example 3 with that of a common solid gold sphere having a diameter of 50 nm.
Detailed Description
Example 1
A preparation method of a gold-urea complex nanosphere comprises the following steps:
dispersing 2g of urea and 6mL of chloroauric acid solution with the concentration of 0.009mol/L in 100mL of pure water at room temperature, fully stirring, heating to 100 ℃ for refluxing for 15 minutes, adding water into the obtained product, performing ultrasonic centrifugal washing once for 5 minutes, and adding ethanol, performing ultrasonic centrifugal washing twice for 5 minutes each time; and obtaining the gold-urea complex nanosphere with clean surface.
A gold-urea complex nanosphere is prepared by adopting the method.
The infrared spectrum detection is carried out on the gold-urea complex nano material obtained in the example 1, and the test result is shown in figure 1.
FIG. 1 is the IR spectrum of the nanosphere of gold-urea complex and urea, and it can be seen that the formed gold-urea complex still maintains the absorption peak pattern of urea in IR spectrum, but the absorption peak is shifted, which indicates that the gold-urea complex is formed.
The gold-urea complex nano material obtained in example 1 is subjected to X-ray diffraction pattern (XRD) detection, the test angle is 20-70 degrees, and the test result is shown in figure 2
Fig. 2 is an XRD pattern of gold-urea complex nanospheres transformed into gold nanomaterials by heating, wherein the corresponding peaks of gold (111), (200), (200) crystallographic planes are from absent to evident, such a transformation process from gold-urea complex nanospheres to gold nanomaterials.
Scanning Electron Microscope (SEM) scanning was performed on the gold-urea complex nanomaterial obtained in example 1, and the specific results are shown in fig. 3.
The results of fig. 3 show that: the gold-urea complex nanosphere obtained by the method has good dispersibility and uniformity.
Example 2
A solid porous gold nano-material is prepared by the following steps: and heating the gold-urea complex nanosphere prepared in the example 1 at 160 ℃ for 50 minutes in a dark place to obtain the solid porous gold nanomaterial.
The porous/solid gold nanomaterial prepared in example 2 was photographed by a Transmission Electron Microscope (TEM), and the results are shown in fig. 4.
The results in figure 4 show that the sample is a clear solid porous gold nanomaterial,
example 3
A hollow porous gold nano material is prepared by the following steps:
and heating the gold-urea complex nanosphere prepared in the example 1 at 190 ℃ in a dark place for 50 minutes to obtain the hollow porous gold nanomaterial.
The porous/hollow gold nanomaterial prepared in example 3 was photographed by a Transmission Electron Microscope (TEM), and the results are shown in fig. 5.
The results of fig. 5 indicate that the sample is a clear hollow porous gold nanomaterial.
Example 4
A solid porous gold nano-material is prepared by the following steps:
and (3) irradiating the gold-urea complex nanosphere prepared in the example 1 for 20 minutes by using a 300W ultraviolet lamp at room temperature to obtain the solid porous gold nanomaterial.
The TEM microtopography effect of example 4 is the same as example 2.
Example 5
A hollow porous gold nano material is prepared by the following steps:
the gold-urea complex nanospheres prepared in example 1 were bombarded with TEM electron beams of a transmission electron microscope (model Tecnai G220S-TWIN), wherein the TEM electron beam acceleration voltage is 200kV, the current is about 10mA, and the gold-urea complex nanospheres are transformed into hollow porous gold nanomaterials after being bombarded by the TEM electron beams.
The transformation of the hollow porous gold nanomaterial of example 5 under TEM electron beam bombardment was recorded and the specific results are shown in fig. 7. As can be seen from FIG. 7, when a TEM electron beam with an acceleration voltage of 200kv was used, the gold-urea complex nanospheres rapidly transformed into a porous structure under an observation field of a small scale of 200 nm.
Example 6
A hollow nano gold wire material is prepared by the following steps:
the ethanol dispersion liquid of the gold-urea complex nanosphere prepared in the example 1 is placed in a porcelain boat and is placed in a tube furnace to be heated to 800 ℃, the heating rate is 10 ℃/min, the porcelain boat is kept at 800 ℃ for 20 minutes, then the porcelain boat is slowly cooled to room temperature, a layer of black substances is coated on the porcelain boat, and at the moment, the hollow nano gold wire is generated.
The calcination results of the gold-urea complex nanosphere in example 6 at high temperature of 800 ℃ are characterized, and the specific results are shown in fig. 7 and 8. As can be seen from fig. 7, the left side is the SEM image of the large area nanowires, and it can be seen that the size is uniform and the width of the nanowires is about 100 nm. On the left is an SEM image of a single nanowire, which can be seen to be up to 7um in length. In the TEM of fig. 8, the void in the middle of the nanowire can be clearly seen, indicating that the nanowire is a hollow structure.
Example 7
An application of porous nano gold as catalyst in quickly catalytic reduction of nitrophenol to p-aminophenol.
The organic catalytic activity and the electrocatalytic activity of the hollow porous gold nanomaterial prepared in example 3 were tested, and a common nanogold sphere with a diameter of 50nm was used as a reference, and the test conditions of the catalytic activity were as follows: 250uL of p-nitrophenol (the concentration is 100mg/L), 40uL of sodium borohydride solution (the concentration is 0.6M) and 2.7mL of pure water are placed in a standard quartz cuvette, the temperature is controlled at 0 ℃, a sample to be detected, namely 40uL of porous gold nano-material and water dispersion liquid of common nano-gold spheres (the concentration is 11.65mM/L) are added, and the curve of characteristic absorption peaks of the p-nitrophenol changing along with time before and after the gold catalyst is added is measured.
The preparation method of the reference substance nano gold ball comprises the following steps: slowly dripping 1mL of chloroauric acid solution (the concentration is 7.39mM) into 10mL of sodium borohydride solution (the concentration is 0.2mg/mL) in an ice-water bath, stirring and reacting for 1h in the ice-water bath, centrifuging to collect a product, and repeatedly washing with deionized water and ethanol-free water for several times respectively to obtain the product.
FIG. 9 is a graph showing the change of ultraviolet absorption peak of p-nitrophenol catalysis with time after the hollow porous gold nano-material prepared in example 3 is added. The results of fig. 9 show that: the change of the ultraviolet characteristic peak corresponding to 400nm clearly shows that the hollow porous gold nano-material prepared in the example 3 can rapidly catalyze and reduce p-nitrophenol into p-aminophenol.
FIG. 10 is a graph comparing the catalytic speed of the hollow porous gold nanomaterials prepared in example 3 with a control (commercial solid gold spheres) having a diameter of 50 nm. The results of fig. 10 show that: under the same catalysis condition, although the hollow porous gold nano-material has the same size, the catalysis rate of the hollow porous gold nano-material prepared in the embodiment 3 is obviously higher than that of a common solid gold ball, and the catalysis rate of the hollow porous gold nano-material is about 8-10 times that of the common solid gold ball. The catalytic effect of the porous/hollow gold nanomaterials of examples 2, 4 and 5 is comparable to example 3.
Claims (6)
1. A method for preparing porous nanogold by using gold-urea complex nanospheres is characterized by comprising the following steps: putting the ethanol dispersion liquid of the gold-urea complex nanosphere into a magnetic boat, putting the magnetic boat into a tube furnace, heating to 800 ℃, keeping the temperature at 10 ℃/min, keeping the temperature at 800 ℃ for 20 minutes, and cooling to room temperature to obtain a black substance coated on the magnetic boat, namely the generation of hollow nano gold wires; the hollow nano gold wire has uniform size, the nano line width is 100nm, the length is 7 mu m, and the nano wire is of a hollow structure;
the gold-urea complex nanosphere is prepared by the following method:
and (3) dispersing urea and chloroauric acid solution in pure water at room temperature, then heating and carrying out reflux reaction, and washing a product to obtain the gold-urea complex nanosphere with a clean surface.
2. The process according to claim 1, characterized in that the molar ratio between chloroauric acid and urea is between 0.0001 and 0.002: 1.
3. the method according to claim 1 or 2, wherein the concentration of the chloroauric acid solution is 0.001-0.01 mol/L.
4. The method of claim 1 or 2, wherein the heating reflux reaction is carried out at 90-120 ℃ for 10-20 min.
5. Use of porous nanogold prepared by the method of claim 1 as a catalyst.
6. Use according to claim 5 for the catalytic reduction of nitrophenols to p-aminophenols.
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| CN101204655A (en) * | 2006-12-21 | 2008-06-25 | 中国人民解放军63971部队 | Process for preparing nanometer gold catalyst |
| CN101979723A (en) * | 2010-11-23 | 2011-02-23 | 东华大学 | Method for preparing p-type CdS nanowires |
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| CN101979723A (en) * | 2010-11-23 | 2011-02-23 | 东华大学 | Method for preparing p-type CdS nanowires |
| CN104874814A (en) * | 2015-05-15 | 2015-09-02 | 皖南医学院 | Gold hydroxide nano-sphere, porous/hollow gold nano-particle material and preparation methods of gold hydroxide nano-sphere and porous/hollow gold nano-particle material |
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