CN108404989B - Preparation method of gold cluster/graphene composite catalytic membrane - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000010931 gold Substances 0.000 title claims abstract description 51
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 4
- 150000003573 thiols Chemical class 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 239000000523 sample Substances 0.000 claims description 7
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 3
- CMNQZZPAVNBESS-UHFFFAOYSA-N 6-sulfanylhexanoic acid Chemical compound OC(=O)CCCCCS CMNQZZPAVNBESS-UHFFFAOYSA-N 0.000 claims description 3
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 claims description 3
- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 claims description 2
- FYEMIKRWWMYBFG-UHFFFAOYSA-N 8-sulfanyloctanoic acid Chemical compound OC(=O)CCCCCCCS FYEMIKRWWMYBFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 11
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 150000002343 gold Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
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- 238000005303 weighing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000409 membrane extraction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
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- 238000005054 agglomeration Methods 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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Abstract
The invention relates to a preparation method of a gold cluster/graphene composite catalytic film, which comprises the following steps: (1) adding deionized water into graphene oxide, uniformly dispersing, and performing ultrasonic dispersion to obtain a dispersion liquid; reducing graphene oxide into reduced graphene oxide rGO by adopting a hydrothermal reduction method, and freeze-drying to obtain rGO powder; (2) adding rGO powder into a gold cluster solution protected by a thiol ligand, adding ultrapure water, and performing ultrasonic dispersion to obtain a mixed solution; and loading the mixed solution on the base membrane by vacuum filtration, and washing to obtain the finished product. The method has the advantages of simple and convenient operation, large gold cluster loading capacity, high catalytic activity and easy recycling, realizes the construction of a high-efficiency catalytic membrane, and has good application prospect.
Description
Technical Field
The invention belongs to the field of catalytic membranes, and particularly relates to a preparation method of a gold cluster/graphene composite catalytic membrane.
Background
Recent researches show that a catalytic separation membrane system integrates a catalytic process and a membrane separation process into the same processing unit, and has the advantages of fast mass transfer, easy amplification, controllable process, recoverable catalyst and the like. In addition, some catalytic separation membranes also have the functions of selectively providing reactants, selectively removing reaction products, and accelerating reaction kinetics. High-efficiency membrane materials having a decisive role in catalytic and separation performance are naturally attracting high attention in the field of catalytic separation membranes as the core of this system. However, preparing a catalytic membrane with high catalytic activity, reproducibility, low cost, high selectivity, high stability, and green and non-toxic properties at present is still a challenge in the membrane technology field.
On one hand, the preparation of the high-efficiency stable catalytic membrane needs to consider the influence of properties such as microscopic morphology and surface characteristics of the material in addition to the catalytic performance. The carbon nano material has the characteristics of excellent conductivity, high mechanical stability, large specific surface area and the like, so the carbon nano material is considered to be a very promising catalytic separation membrane construction material. The graphene which is widely concerned has the characteristics of large specific surface area and planar two-dimensional structure, and is an ideal catalyst loading material. However, graphene has strong hydrophobicity, and can be uniformly dispersed in an aqueous solution by virtue of a surfactant. In addition, graphene materials have very limited catalytic activity themselves, but can achieve catalytic functions by doping or supporting other catalysts with heteroatoms.
On the other hand, the 'size effect' of the noble metal nano material provides an important opportunity for the development of the catalytic separation membrane. Gold nanocluster materials have an ultra small size <2nm, showing a completely different "anomalous size effect" than slightly larger sized nanocrystals and bulk materials. However, the gold clusters are difficult to recover from the reaction solution because of their extremely small size. Therefore, improving the stability of gold clusters and developing reusable gold cluster materials are also challenges in the current field of catalysis.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a gold cluster/graphene composite catalytic membrane, which is simple and convenient in technical operation, large in gold cluster loading capacity, high in catalytic activity, easy to recycle, capable of realizing construction of a high-efficiency catalytic membrane and good in application prospect.
The invention provides a preparation method of a gold cluster/graphene composite catalytic membrane, which comprises the following steps:
(1) adding deionized water into graphene oxide, uniformly dispersing, and performing ultrasonic dispersion to obtain a dispersion liquid; reducing graphene oxide into reduced graphene oxide rGO by adopting a hydrothermal reduction method, and freeze-drying to obtain rGO powder;
(2) adding the rGO powder in the step (1) into a gold cluster solution protected by a thiol ligand, adding ultrapure water, and performing ultrasonic dispersion to obtain a mixed solution; loading the mixed solution on a base membrane by adopting vacuum filtration, and washing to obtain a gold cluster/graphene composite catalytic membrane; wherein the dosage ratio of the rGO to the gold cluster is 5-10mg:5-20 mu mol.
The hydrothermal reduction reaction temperature in the step (1) is 120-200 ℃, and the hydrothermal reduction reaction time is 3-20 h. The hydrothermal reduction reaction time is preferably 5 hours.
The concentration of the dispersion liquid in the step (1) is 1g/L-5 g/L.
The thiol ligand in the step (2) is 6-Mercaptohexanoic acid (MHA), 4-Mercaptobenzoic acid (4-Mercaptobenzoic acid, MBA), 8-Mercaptooctanoic acid (8-Mercaptocontanoic acid, MOA) or 11-Mercaptoundecanoic acid (11-Mercaptotonnanoic acid, MUA).
The concentration of the gold cluster solution protected by the thiol ligand in the step (2) is 1 mM.
And (3) performing ultrasonic dispersion in the steps (1) and (2) by using a probe, wherein the ultrasonic power is 50-500W, and the ultrasonic time is 20-60 min.
And (3) washing in the step (2) by using deionized water.
The gold carbon atomic ratio of the gold cluster/graphene composite catalytic film obtained in the step (2) is 1% -6%, and the thickness is 5-20 μm.
The principle of the invention is as follows:
the gold nanoclusters protected by the thiol ligand can stably exist in an aqueous solution, and the thiol ligand of the gold nanoclusters can be combined with the hydrophobic group of graphene through hydrophobic interaction to promote uniform dispersion of the graphene in the aqueous solution. The mercaptan ligand of the gold cluster plays a role of a surfactant, the gold atoms of the gold cluster play a role of catalytic active sites, and the graphene can be used as an excellent carrier material to realize effective carrying of the gold cluster and is beneficial to separation and recovery of the cluster material. The functions are expected to jointly realize the construction of the high-efficiency catalytic membrane.
The reduced graphene has large surface area and folds, is easy to modify chemical functions, and can realize the effective load of the gold clusters. The gold nano-catalyst is favored by researchers due to the high-efficiency catalytic activity of the gold nano-catalyst, and a series of gold-carbon composite catalytic materials are developed successively. The gold cluster can promote the dispersion of the graphene in water, the graphene can provide an attached active site for the gold cluster, and the interaction of the gold cluster and the graphene provides a good foundation for the preparation of the composite membrane. The invention shows that the catalytic performance of the composite membrane has close relation with the reduction degree of graphene, the loading capacity of gold clusters and the like.
Advantageous effects
The method has the advantages of simple and convenient technical operation, large gold cluster loading capacity, high catalytic activity and easy recycling; the gold cluster protected by the mercaptan ligand can avoid agglomeration, the mercaptan ligand of the gold cluster is combined with the hydrophobic group of the graphene to promote the graphene to be uniformly dispersed in the aqueous solution, the gold cluster is carried by the graphene in a vacuum filtration mode, and the gold atoms of the gold cluster play a role in catalyzing active sites, so that the construction of a high-efficiency catalytic membrane is realized, and the gold cluster has a good application prospect.
Drawings
Fig. 1 is a schematic view of a gold cluster/graphene composite catalytic film according to the present invention;
FIG. 2 is a diagram of a gold cluster/graphene composite catalytic membrane according to the present invention;
fig. 3 is an electron Scanning Electron Microscope (SEM) image of the gold cluster/graphene composite catalytic film according to the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Weighing 50mg of graphene oxide in a beaker by using an analytical balance, adding 25mL of deionized water, performing ultrasonic treatment for 15min by using a probe to uniformly disperse the graphene oxide to obtain a mixed solution A, pouring the A into a polytetrafluoroethylene reaction kettle, performing hydrothermal treatment for 5h at 180 ℃ to obtain rGO which is rod-shaped, performing freeze drying, adding 10mL of thiol ligand-protected gold cluster solution (1mM) and 10mL of ultrapure water to the 5mg of rGO, performing ultrasonic treatment for 45min to obtain a uniformly dispersed mixed solution B, performing membrane extraction on the B, and washing redundant substances by using 150mL of deionized water to form a homogeneous composite catalytic membrane. The solution of 0.2mM p-nitrophenol (4-NP) is used for passing through a membrane for 2 hours under the condition of the flow rate of 1mL/min to reach the adsorption saturation, and then the solution of 0.5mM p-nitrophenol (4-NP) is respectively degraded in sequence, wherein the degradation effects are respectively 100%, 100% and 100%.
Example 2
Weighing 50mg of graphene oxide in a beaker by using an analytical balance, adding 25mL of deionized water, performing ultrasonic treatment for 15min by using a probe to uniformly disperse the graphene oxide to obtain a mixed solution A, pouring the A into a polytetrafluoroethylene reaction kettle, performing hydrothermal treatment for 5h at 180 ℃ to obtain rGO which is rod-shaped, performing freeze drying, adding 5mL of rGO into 5mL of thiol ligand protected gold cluster solution (1mM) and 15mL of ultrapure water, performing ultrasonic treatment for 45min to obtain uniformly dispersed mixed solution B, performing membrane extraction on the B, and washing redundant substances by using 150mL of deionized water to form a homogeneous composite catalytic membrane. The degradation effect is respectively 100%, 96.1% and 62.1% after the membrane is passed through a 0.2mM p-nitrophenol (4-NP) solution for 2h under the condition of flow rate of 1mL/min to reach adsorption saturation, and the degradation effect is respectively 0.5mM,1.0mM and 1.5mM 4-NP.
Example 3
Weighing 50mg of graphene oxide in a beaker by using an analytical balance, adding 25mL of deionized water, performing ultrasonic treatment for 15min by using a probe to uniformly disperse the graphene oxide to obtain a mixed solution A, pouring the A into a polytetrafluoroethylene reaction kettle, performing hydrothermal treatment for 5h at 180 ℃ to obtain rGO which is rod-shaped, performing freeze drying, adding 20mL of thiol ligand-protected gold cluster solution (1mM) into 5mg of rGO, performing ultrasonic treatment for 45min to obtain a uniformly dispersed mixed solution B, performing membrane extraction on the mixed solution B, and washing redundant substances by using 150mL of deionized water to form a homogeneous composite catalytic membrane. The solution of 0.2mM p-nitrophenol (4-NP) is used for passing through the membrane for 2 hours under the condition of the flow rate of 1mL/min to reach the adsorption saturation, and then the 0.5mM,1.0mM and 1.5mM 4-NP are respectively degraded in sequence, wherein the degradation effects are respectively 100%, 100% and 100%.
Comparative example 1
Weighing 50mg of graphene oxide in a beaker by using an analytical balance, adding 25mL of deionized water, performing ultrasonic treatment for 15min by using a probe to uniformly disperse the graphene oxide, pouring the mixed solution into a polytetrafluoroethylene reaction kettle, performing hydrothermal treatment for 3h at 180 ℃, obtaining rGO as a suspension, adding 10mL of thiol ligand-protected gold cluster solution (1mM) and 10mL of ultrapure water into one tenth of the suspension, performing ultrasonic treatment for 45min, and then drawing a membrane, wherein the membrane is too compact and the water flux is too small.
Comparative example 2
Weighing 50mg of graphene oxide in a beaker by using an analytical balance, adding 25mL of deionized water, performing ultrasonic treatment for 15min by using a probe to uniformly disperse the graphene oxide to obtain a mixed solution A, pouring the A into a polytetrafluoroethylene reaction kettle, performing hydrothermal treatment for 10h at 180 ℃ to obtain rGO which is rod-shaped, performing freeze drying, adding 5mg of rGO into 10mL of thiol ligand protected gold cluster solution (1mM) and 10mL of ultrapure water, and performing ultrasonic treatment for 45min to ensure that the graphene oxide cannot be uniformly dispersed (if the ultrasonic intensity and the ultrasonic time are increased, the graphene oxide can still be dispersed theoretically).
Based on the above example, the reduced graphene oxide after the hydrothermal reduction treatment can fully support the gold clusters, and as can be seen from the template reaction for degrading p-nitrophenol, the prepared gold cluster/graphene composite catalytic film has high catalytic activity, and through further characterization studies (as shown in fig. 3), the gold clusters in the gold cluster/graphene composite catalytic film prepared under the above conditions are uniformly distributed without aggregation. Compared with the traditional sequencing batch type, the catalytic membrane prepared by the preparation method can realize continuous and efficient catalysis, and has the characteristics of simple and rapid preparation method, low energy consumption, no secondary pollution and the like.
Claims (4)
1. A preparation method of a gold cluster/graphene composite catalytic film comprises the following steps:
(1) adding deionized water into graphene oxide, uniformly dispersing, and performing ultrasonic dispersion to obtain a dispersion liquid; reducing graphene oxide into reduced graphene oxide rGO by adopting a hydrothermal reduction method, and freeze-drying to obtain rGO powder; wherein the temperature of the hydrothermal reduction reaction is 120-200 ℃, and the time of the hydrothermal reduction reaction is 3-20 h; the concentration of the dispersion liquid is 1g/L-5 g/L;
(2) adding the rGO powder in the step (1) into a gold cluster solution protected by a thiol ligand, adding ultrapure water, and performing ultrasonic dispersion to obtain a mixed solution; loading the mixed solution on a base membrane by adopting vacuum filtration, and washing to obtain a gold cluster/graphene composite catalytic membrane; wherein the dosage ratio of the rGO to the gold cluster is 5-10mg:5-20 mu mol; the thiol ligand is 6-mercaptohexanoic acid, 4-mercaptobenzoic acid, 8-mercaptooctanoic acid or 11-mercaptoundecanoic acid; the concentration of the thiol ligand-protected gold cluster solution was 1 mM.
2. The method for preparing a gold cluster/graphene composite catalytic film according to claim 1, wherein the method comprises the following steps: and (3) performing ultrasonic dispersion in the steps (1) and (2) by using a probe, wherein the ultrasonic power is 50-500W, and the ultrasonic time is 20-60 min.
3. The method for preparing a gold cluster/graphene composite catalytic film according to claim 1, wherein the method comprises the following steps: and (3) washing in the step (2) by using deionized water.
4. The method for preparing a gold cluster/graphene composite catalytic film according to claim 1, wherein the method comprises the following steps: the gold carbon atomic ratio of the gold cluster/graphene composite catalytic film obtained in the step (2) is 1% -6%, and the thickness is 5-20 μm.
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| CN110261449A (en) * | 2019-05-15 | 2019-09-20 | 嘉兴鸿明传感科技有限公司 | A kind of preparation method and catalysis electrode of gas sensor catalysis electrode |
| CN111408366B (en) * | 2020-03-03 | 2023-02-14 | 合肥枡水新能源科技有限公司 | Preparation method of carbon-supported metal nanocluster catalyst |
| CN112023920A (en) * | 2020-08-03 | 2020-12-04 | 东华大学 | Preparation method and application of gold cluster-carbon nanotube electro-catalytic film |
| CN114210343A (en) * | 2022-01-24 | 2022-03-22 | 桂林电子科技大学 | Reduced graphene oxide loaded Ru-Ni bimetallic nanocluster catalytic material |
| CN115121244B (en) * | 2022-06-17 | 2023-04-25 | 武汉理工大学 | Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite |
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