CN115121244B - Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite - Google Patents
Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite Download PDFInfo
- Publication number
- CN115121244B CN115121244B CN202210690903.1A CN202210690903A CN115121244B CN 115121244 B CN115121244 B CN 115121244B CN 202210690903 A CN202210690903 A CN 202210690903A CN 115121244 B CN115121244 B CN 115121244B
- Authority
- CN
- China
- Prior art keywords
- graphene
- nanocomposite
- sodium borohydride
- gold cluster
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 84
- 239000010931 gold Substances 0.000 title claims abstract description 82
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 39
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 39
- 230000009467 reduction Effects 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 150000002343 gold Chemical class 0.000 claims abstract description 28
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 15
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000987 azo dye Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 16
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 16
- ZFMRLFXUPVQYAU-UHFFFAOYSA-N sodium 5-[[4-[4-[(7-amino-1-hydroxy-3-sulfonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-2-hydroxybenzoic acid Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3O)N)S(=O)(=O)O)N=NC5=CC(=C(C=C5)O)C(=O)O.[Na+] ZFMRLFXUPVQYAU-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- BWBQXMAXLAHHTK-YFKPBYRVSA-N (2r)-2-(2-methylpropanoylamino)-3-sulfanylpropanoic acid Chemical compound CC(C)C(=O)N[C@@H](CS)C(O)=O BWBQXMAXLAHHTK-YFKPBYRVSA-N 0.000 claims description 14
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000013507 mapping Methods 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011066 ex-situ storage Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 108010024636 Glutathione Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000002626 targeted therapy Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application thereof, comprising the following steps: graphene pretreatment: activating carboxyl on graphene by EDC and NHS; graphene-supported gold clusters: and (3) carrying out reduction reaction on chloroauric acid by using NIBC and TCEP, adding graphene after activating carboxyl for continuous reaction after full reaction, adding sodium borohydride for reduction reaction after full reaction, and purifying after reaction is finished to obtain the graphene loaded gold cluster nanocomposite. The method adopts a sodium borohydride in-situ reduction method to prepare the graphene loaded gold cluster nanocomposite with small particle size distribution and uniformity. The graphene loaded gold cluster nanocomposite prepared by the method has high efficiency on the catalytic degradation of the azo dye, and the catalytic degradation capability of the material is not reduced by multiple times of catalysis, so that the graphene loaded gold cluster nanocomposite has circulation stability.
Description
Technical Field
The invention belongs to the field of preparation of synthetic functional nano materials, and particularly relates to a method for preparing a graphene-loaded gold cluster nano composite material by in-situ reduction of sodium borohydride and application thereof.
Background
Gold clusters are composed of several to hundreds of gold atoms, and their size is usually 1-3nm. The size of the nano-interface is equivalent to the Fermi wavelength of electrons, so that the nano-interface has the property of a semiconductor, and meanwhile, the optical property, the catalytic activity and the like are greatly different from those of bulk gold, has a high electron density, is easy to functionalize, and has good biocompatibility, and is widely applied to the aspects of catalysis, fluorescence imaging, targeted therapy, drug carriers and the like at present. However, the specific surface area is large, spontaneous aggregation is extremely easy to occur in a solution system, and although the ligand modification technology which is mature at present is used for stabilizing the ligand modification technology, the ligand modification technology still cannot achieve good effect.
The loading of gold clusters onto a two-dimensional lamellar structure is an effective way to solve the problem, and graphene has the advantages of large specific surface area, high mechanical strength and large thermal conductivity, so that the graphene is widely studied in various fields. Meanwhile, graphene has an important property of containing boundary groups and plane defects. This enables the graphene surface to be functionalized, thereby loading the gold clusters.
There is also much work currently being explored the preparation of graphene-supported gold cluster nanocomposite materials, by Song et al (Song et al, journal of Materials Chemistry A,2017,5 (1): 230) using glutathione as the ligand for gold clusters, which are supported onto graphene sheets by in situ hydrothermal reduction. The graphene loaded gold cluster nanocomposite prepared in this way has small and uniform particle size. The hydrothermal reduction method is used as a mild and slow method, which can prepare nano materials with uniform particle size, but is not suitable for mass production because the required conditions are severe and the crystal growth process and principle cannot be monitored. For the synthesis of gold clusters, however, brust et al (Mathias Brust et al, journal of the Chemical Society, chemical Communications,1994, 7:801) prepared gold clusters of uniform particle size using sodium borohydride as a reducing agent. Yu et al (Yu et al, chemical Engineering Journal,2018,335 (1): 176) prepared gold clusters with uniform particle size distribution using the Brust method, and then attached the gold clusters to graphene using EDC-NHS. The method belongs to an ex-situ method, and the preparation steps are complicated.
In addition, gold clusters, due to their size comparable to the fermi wavelength of electrons, have discrete electronic states and molecular-like structural properties, which unique physicochemical properties lead to their extremely high potential in the catalytic field. However, the specific surface area is large, spontaneous aggregation is extremely easy to occur in a solution system, and although the ligand modification technology which is mature is used for stabilizing the ligand modification technology at present. And in the catalytic process, as the catalytic active site is positioned on the surface of the gold atom, the aggregation of the gold atom can be accelerated, so that the cycling stability of the catalyst is reduced. Therefore, the development of a dye degradation catalyst with high activity and high stability is the focus of attention of the current academy.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide sodium borohydride (NaBH 4 ) The method adopts a brust method to prepare the graphene-loaded gold cluster nanocomposite with small particle size distribution and uniform graphene loading gold cluster nanocomposite in situ.
Another object of the invention is to provide a use of the graphene-supported gold cluster nanocomposite.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
in one aspect, the invention provides a method for preparing a graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride, comprising the following steps:
graphene pretreatment:
activating carboxyl on graphene by adopting 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide;
graphene-supported gold clusters:
N-isobutyryl-L-cysteine and tri (2-carboxyethyl) phosphine are adopted to carry out reduction reaction on chloroauric acid, graphene after carboxyl activation is added for continuous reaction after full reaction, sodium borohydride is added for reduction reaction after full reaction, and the graphene loaded gold cluster nanocomposite is obtained after purification after reaction.
Preferably, the specific steps of graphene pretreatment are as follows: preparing graphene aqueous slurry by adopting a dispersing agent, dissolving the graphene aqueous slurry in methanol, weighing 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, adding the 1-ethyl- (3-dimethylaminopropyl) carbodiimide and the N-hydroxysuccinimide into the mixture, performing ultrasonic dispersion together, and preserving the mixture at a low temperature. Because the dispersibility of graphene in water is not very good, a dispersing agent is adopted to obtain the graphene material with good dispersibility in water, so that the subsequent synthesis and application are facilitated. Wherein the dispersing agent is selected by the routine in the field.
Further preferably, the graphene content in the graphene aqueous slurry is 1-1.5wt%.
It is further preferred that the molar ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide to N-hydroxysuccinimide is 1:1.
Preferably, the specific steps of the graphene-supported gold cluster are as follows: weighing N-isobutyryl-L-cysteine and tris (2-carboxyethyl) phosphine, dissolving in methanol, adding chloroauric acid solution and acetic acid into the mixture, stirring the mixture at low temperature and normal pressure for reaction, adding pretreated graphene solution into the solution system after full reaction, continuing to react at low temperature and normal pressure, adding sodium borohydride solution into the solution system after full reaction, stirring the solution at low temperature and normal pressure for reaction, and obtaining solid powder after the reaction is finished, settling, centrifuging, dialyzing and freeze-drying to obtain the graphene loaded gold cluster nanocomposite.
It is further preferred that the mass ratio of N-isobutyryl-L-cysteine to tris (2-carboxyethyl) phosphine is 19:1.
It is further preferred that the molar ratio of chloroauric acid to N-isobutyryl-L-cysteine is 1 (2-4).
It is further preferred that the molar ratio of chloroauric acid to sodium borohydride is 1 (10-30).
On the other hand, the invention provides application of the graphene-supported gold cluster nanocomposite in catalytic degradation of azo dyes.
Preferably, the azo dye comprises congo red, direct deep brown M.
Compared with the prior art, the invention has the following beneficial effects:
existing techniques for preparing graphene-supported gold clusters are mainly divided into two categories: ex situ and in situ hydrothermal reduction. The main idea of the ex-situ method is to prepare gold clusters first, and then connect the gold clusters to graphene sheets by EDC-NHS method, so as to obtain the graphene-loaded gold cluster nanocomposite. The method needs two steps for synthesis, which is troublesome. And gold clusters are more sterically hindered and are more difficult to attach to graphene sheets. The main thought of the in-situ hydrothermal reduction method is as follows: firstly, connecting a ligand to a graphene sheet layer through a chemical bond method, then adding chloroauric acid as a gold source, and carrying out hydrothermal reduction for a long time under a high temperature condition to obtain the graphene-loaded gold cluster nanocomposite. Although the method is mild, the process is too energy-consuming and time-consuming. According to the invention, the graphene-loaded gold cluster nanocomposite with uniform particle size distribution can be rapidly prepared by adopting an in-situ sodium borohydride reduction method. The main idea is as follows: the ligand is first blended with chloroauric acid and trivalent gold is reduced to a monovalent gold complex (Au-SR) via a thiol group on the ligand. And then adding graphene sheets subjected to carboxyl activation into the mixed system, so that Au-SR connects gold to the graphene sheets through the chemical bond action between the ligand and the graphene. Inspired by the brust method, finally sodium borohydride is added to rapidly reduce the monovalent gold complex into Jin Tuancu, so that the graphene-loaded gold cluster nanocomposite is prepared.
According to the preparation method disclosed by the invention, the monovalent gold complex is connected with the graphene to form an amide bond, so that the defect of overlarge steric hindrance of gold clusters can be avoided compared with an ex-situ method, and the effective collision between chloroauric acid and the ligand can be effectively improved, and the reaction efficiency is improved compared with a method for connecting the ligand to the graphene in advance. Compared with a hydrothermal method, the sodium borohydride reduction method is simple and convenient to operate and simple in process, and the obtained graphene-loaded gold cluster nanocomposite is small and uniform in particle size.
The graphene loaded gold cluster nanocomposite prepared by the method has high efficiency on the catalytic degradation of the azo dye, and the catalytic degradation capability of the material is not reduced by multiple times of catalysis, so that the graphene loaded gold cluster nanocomposite has circulation stability.
Drawings
Fig. 1 is a STEM image of a graphene-supported gold cluster nanocomposite of example 1 of the present invention.
Fig. 2 is EDS mapping of sulfur of the graphene-supported gold-cluster nanocomposite of example 1 of the present invention.
Fig. 3 is EDS mapping of gold of the graphene-supported gold-cluster nanocomposite of example 1 of the present invention.
Fig. 4 is EDS mapping of gold and sulfur of the graphene-supported gold-cluster nanocomposite of example 1 of the present invention.
Fig. 5 is a large scale Transmission Electron Microscope (TEM) image of the graphene-supported gold-cluster nanocomposite of example 1 of the present invention.
Fig. 6 is a small scale Transmission Electron Microscope (TEM) image of the graphene-supported gold-cluster nanocomposite of example 1 of the present invention.
Fig. 7 is a statistical chart of particle size distribution of the graphene-supported gold cluster nanocomposite according to example 1 of the present invention.
Fig. 8 is an X-ray photoelectron spectroscopy (XPS) total spectrum of the graphene-supported gold-cluster nanocomposite of example 1 of the present invention.
Fig. 9 is a gold subdivision spectrum of X-ray photoelectron spectroscopy (XPS) of the graphene-supported gold cluster nanocomposite of example 1 of the present invention.
Fig. 10 is a graph showing the conversion rate of congo red catalyzed by graphene-supported gold clusters according to experimental example 1 of the present invention with time.
Fig. 11 is a graph showing the cycle performance of the graphene-supported gold cluster-catalyzed congo red according to experimental example 1 of the present invention.
Fig. 12 is a graph showing the conversion rate of graphene-supported gold cluster catalyzed direct deep brown M according to experimental example 2 of the present invention with time.
Fig. 13 is a graph showing the cycle performance of graphene-supported gold cluster catalyzed direct deep brown M according to experimental example 2 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, preferred embodiments of the present invention will be described below with reference to specific examples, but the present invention should not be construed as being limited thereto, but only by way of example.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are obtained from conventional commercial sources or prepared in conventional manner.
Example 1
The embodiment provides a preparation method of a graphene-supported gold cluster nanocomposite, which comprises the following steps:
step one, graphene pretreatment:
0.3-0.7mL of graphene aqueous slurry (1 wt%) is dissolved in 1mL of methanol, 10mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 10mg of N-hydroxysuccinimide (NHS) are weighed and added thereto, and then dispersed together by ultrasonic for 10 minutes, and then placed at 0 ℃ for standby. In the step, EDC is used for activating carboxyl on the graphene sheet, but the carboxyl after EDC activation is easy to hydrolyze, NHS is added to form a stable active ester intermediate, and the stable carboxyl is not hydrolyzed and reacts with imino in the ligand to generate a C-N bond.
Step two, graphene loaded gold clusters:
50.35mg of N-isobutyryl-L-cysteine (NIBC) and 2.65mg of tris (2-carboxyethyl) phosphine (TCEP) were weighed into 1mL of methanol, and 0.62mL of chloroauric acid solution (2% in methanol), 2.31mL of methanol and 0.57mL of acetic acid were added thereto and reacted at 0℃under normal pressure with stirring for 0.5h. And adding the pretreated graphene solution into the solution system after the full reaction, and continuing to react for 0.5h at the normal pressure and the temperature of 0 ℃. After the reaction was completed, 2mL of an ethanol-dispersed sodium borohydride solution (71 mg) was added to the above solution system, and the mixture was stirred at 0℃under normal pressure for 0.5h. After the reaction, acetone is added as a sedimentation agent, the mixture is centrifuged for 5 minutes at a speed of 5000 revolutions per minute, the supernatant is discarded, 10mL of water is added for dissolving the sediment, the sediment is transferred into a dialysis bag with a molecular weight cut-off of 50kDa for dialysis for 2 days, and then a solid powder sample is obtained by freeze-drying by a freeze dryer.
Example 2
The embodiment provides a preparation method of a graphene-supported gold cluster nanocomposite, which comprises the following steps:
0.3-0.7mL of graphene aqueous slurry (1.5 wt%) was dissolved in 1mL of methanol, and then 10mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 10mg of N-hydroxysuccinimide (NHS) were added thereto, followed by co-ultrasonic dispersion for 10 minutes and then placed at 0℃for later use.
Step two, graphene loaded gold clusters:
50.35mg of N-isobutyryl-L-cysteine (NIBC) and 2.65mg of tris (2-carboxyethyl) phosphine (TCEP) were weighed into 1mL of methanol, and 0.93mL of chloroauric acid solution (2% in methanol), 2.31mL of methanol and 0.57mL of acetic acid were added thereto and reacted at 0℃under normal pressure with stirring for 0.5 hours. And adding the pretreated graphene solution into the solution system after the full reaction, and continuing to react for 0.5h at the normal pressure and the temperature of 0 ℃. After the reaction was completed, 3mL of an ethanol-dispersed sodium borohydride solution (106.5 mg) was added to the above solution system, and the mixture was stirred at 0℃under normal pressure for 0.5h. After the reaction, acetone is added as a sedimentation agent, the mixture is centrifuged for 5 minutes at a speed of 5000 revolutions per minute, the supernatant is discarded, 10mL of water is added for dissolving the sediment, the sediment is transferred into a dialysis bag with a molecular weight cut-off of 50kDa for dialysis for 2 days, and then a solid powder sample is obtained by freeze-drying by a freeze dryer.
Example 3
The embodiment provides a preparation method of a graphene-supported gold cluster nanocomposite, which comprises the following steps:
0.3-0.7mL of graphene aqueous slurry (1.5 wt%) was dissolved in 1mL of methanol, and then 10mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 10mg of N-hydroxysuccinimide (NHS) were added thereto, followed by co-ultrasonic dispersion for 10 minutes and then placed at 0℃for later use.
Step two, graphene loaded gold clusters:
50.35mg of N-isobutyryl-L-cysteine (NIBC) and 2.65mg of tris (2-carboxyethyl) phosphine (TCEP) were weighed into 1mL of methanol, and 1.24mL of chloroauric acid solution (2% in methanol), 2.31mL of methanol and 0.57mL of acetic acid were added thereto to react under stirring at 0℃under normal pressure for 0.5h. And adding the pretreated graphene solution into the solution system after the full reaction, and continuing to react for 0.5h at the normal pressure and the temperature of 0 ℃. After the reaction was completed, 4mL of an ethanol-dispersed sodium borohydride solution (142 mg) was added to the above solution system, and the mixture was stirred at 0℃under normal pressure for 0.5h. After the reaction, acetone is added as a sedimentation agent, the mixture is centrifuged for 5 minutes at a speed of 5000 revolutions per minute, the supernatant is discarded, 10mL of water is added for dissolving the sediment, the sediment is transferred into a dialysis bag with a molecular weight cut-off of 50kDa for dialysis for 2 days, and then a solid powder sample is obtained by freeze-drying by a freeze dryer.
The invention takes the graphene loaded gold cluster nanocomposite prepared in the embodiment 1 as an example, and describes the characterization of the synthesis result:
fig. 1 is a STEM image of a graphene-supported gold-cluster nanocomposite. This image demonstrates that the gold clusters are uniformly distributed on the graphene sheets.
Fig. 2 is an EDS mapping image of sulfur of a graphene-supported gold-cluster nanocomposite. This image shows the distribution of elemental sulfur in fig. 1.
Fig. 3 is an EDS mapping image of gold of a graphene-supported gold-cluster nanocomposite. This image shows the distribution of gold elements in fig. 1.
Fig. 4 is an EDS mapping image of sulfur and gold of a graphene-supported gold-cluster nanocomposite. This image shows that gold and sulfur are closely located and substantially located at the high contrast in fig. 1.
Fig. 5 is a large scale TEM image of graphene-supported gold-cluster nanocomposite. The graph proves that the gold clusters with high contrast on the graphene sheet layer are uniformly distributed, and a large amount of aggregation phenomenon does not occur in a submicron scale.
Fig. 6 is a small scale TEM image of graphene-loaded gold-cluster nanocomposite. The graph also proves that the gold clusters with high contrast on the graphene sheet layer are uniformly distributed, the aggregation phenomenon does not occur in the nanoscale, and the particle sizes of the gold clusters are uniform.
Fig. 7 is a statistical graph of particle size distribution of graphene-supported gold cluster nanocomposite. The figure shows a statistical analysis of particle size by selecting 200 gold clusters from fig. 5 and 6. The particle size of the cash cluster is about 1.6nm when analyzed, which accords with Gaussian distribution.
Fig. 8 is an XPS survey spectrum of a graphene-supported gold-cluster nanocomposite. The figure demonstrates that the material contains C, N, O, S, au element.
FIG. 9 is XPS Au 4f subdivision spectrum of the graphene-supported gold cluster nanocomposite. The peak of the spectrogram is divided to find that the material contains 0 price and 1 price gold at the same time, and accords with the structure of gold clusters, which shows that the high-contrast gold clusters in the electron microscope images in fig. 1-6.
In order to more conveniently explain that the graphene-loaded gold cluster nanocomposite can be successfully prepared by adopting the technical scheme of the invention, the preferred embodiment 1 of the invention is illustrated as an example, and both the embodiment 2 and the embodiment 3 are successfully synthesized, and the invention is not repeated.
Experimental example 1
The graphene-loaded gold cluster nanocomposite prepared in the embodiment 1 is adopted in the experimental example, and the application effect of the graphene-loaded gold cluster nanocomposite in congo red is verified:
(1) Catalytic congo red degradation experiment: preparing a Congo red aqueous solution with the concentration of 0.1mmol/L, a sodium borohydride aqueous solution with the concentration of 0.1mol/L and a graphene-supported gold cluster aqueous solution with the concentration of 0.1 mg/mL. 2mL of Congo red solution, 0.2mL of sodium borohydride solution and 0.02mL of graphene-supported gold cluster solution are mixed uniformly, and ultraviolet data (with a test wavelength range of 300-600 nm) are measured every 1 minute. The absorbance of ultraviolet absorption is proportional to the concentration of the substance according to lambert-beer's law, so the absorbance can be used instead of the concentration. Congo red hasbase:Sub>A characteristic absorption wavelength of 503nm and is converted according to the formula "conversion (%) = (base:Sub>A-base:Sub>A) 0 )/A 0 "(A is the current absorbance, A 0 For initial absorbance) a conversion versus time curve can be calculated.
(2) Congo red cycle catalytic experiment: and testing the cycle performance of Congo red by adopting a progressive liquid adding method, firstly uniformly mixing 2mL of Congo red solution with 0.2mL of sodium borohydride solution and 0.02mL of graphene-loaded gold cluster solution, and recording the time required for catalyzing until the conversion rate is more than 90%. 2mL of Congo red solution and 0.2mL of sodium borohydride solution were added to the catalytic residual solution, and the time required for the catalytic to reach a conversion of greater than 90% was recorded. 2mL of Congo red solution and 0.2mL of sodium borohydride solution are then added to the catalytic residual solution, and the time required for the catalytic reaction to reach a conversion of greater than 90% is recorded. The principle of the method is as follows: the reaction substrate and the reducing agent are replenished after the first degradation is finished, which is equivalent to diluting the reaction substrate, the reducing agent and the catalyst by one time at the same time, so that the time required for degradation is theoretically consistent.
Fig. 10 is a graph of conversion rate of graphene-supported gold cluster catalyzed degradation congo red over time. The conversion rate is about 13 minutes, and the catalytic degradation of the material by the azo dye is highly effective. FIG. 11 shows the cycling stability of graphene-supported gold cluster catalyzed degradation Congo red. It was found that 3 times of catalysis did not reduce the catalytic degradation ability of the material.
Experimental example 2
The graphene-loaded gold cluster nanocomposite prepared in the embodiment 1 is adopted in the experimental example, and the application effect of the graphene-loaded gold cluster nanocomposite in the direct deep brown M is verified:
(1) Direct deep brown M degradation experiment: preparing 0.3mmol/L of direct deep brown M aqueous solution, 0.1mol/L of sodium borohydride aqueous solution and 0.1mg/mL of graphene-loaded gold cluster aqueous solution. 2mL of the direct deep brown M solution, 0.2mL of sodium borohydride solution and 0.02mL of graphene-supported gold cluster solution were mixed uniformly, and ultraviolet data (test wavelength range 200-750 nm) were measured every 1 minute. The absorbance of ultraviolet absorption is proportional to the concentration of the substance according to lambert-beer's law, so the absorbance can be used instead of the concentration. The characteristic absorption wavelength of the direct deep brown M is 513nm, according to the formula "conversion (%) = (base:Sub>A-base:Sub>A) 0 )/A 0 "(A is the current absorbance, A 0 For initial absorbance) a conversion versus time curve can be calculated.
(2) Direct deep brown M cycle catalytic experiment: the circulation performance of the direct deep brown M is tested by adopting a progressive liquid adding method, firstly, 2mL of the direct deep brown M solution, 0.2mL of sodium borohydride solution and 0.02mL of graphene-loaded gold cluster solution are uniformly mixed, and the time required for catalyzing until the conversion rate is more than 90% is recorded. The catalytic residual solution was supplemented with 2mL of direct dark brown M solution and 0.2mL of sodium borohydride solution and the time required for the catalytic to reach a conversion of more than 90% was recorded. 2mL of the direct deep brown M solution and 0.2mL of sodium borohydride solution were then added to the catalytic residual solution, and the time required for the catalytic reaction to reach a conversion of greater than 90% was recorded.
Fig. 12 is a graph of the conversion rate of graphene-supported gold cluster catalyzed degradation direct deep brown M over time. The conversion rate is about 13 minutes, and the catalytic degradation of the material by the azo dye is highly effective. Fig. 13 shows the cycling stability of graphene-supported gold cluster catalyzed degradation direct deep brown M. It was found that 3 times of catalysis did not reduce the catalytic degradation ability of the material.
In order to more conveniently explain that the graphene-supported gold cluster nanocomposite prepared by adopting the technical scheme of the invention can catalyze and degrade azo dyes, the preferred embodiment 1 of the invention is exemplified, and the degradation effects of the embodiment 2 and the embodiment 3 are basically the same as those of the embodiment 1, and the invention is not repeated.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (10)
1. The method for preparing the graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride is characterized by comprising the following steps of:
graphene pretreatment:
activating carboxyl on graphene by adopting 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide;
graphene-supported gold clusters:
and (3) carrying out a reduction reaction on chloroauric acid by using N-isobutyryl-L-cysteine and tri (2-carboxyethyl) phosphine, adding graphene after activating carboxyl after full reaction, continuing the reaction, adding sodium borohydride after full reaction, carrying out a reduction reaction, and purifying after the reaction is finished to obtain the graphene loaded gold cluster nanocomposite.
2. The method for preparing the graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 1, wherein the specific steps of graphene pretreatment are as follows: preparing graphene aqueous slurry by adopting a dispersing agent, dissolving the graphene aqueous slurry in methanol, weighing 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, adding the 1-ethyl- (3-dimethylaminopropyl) carbodiimide and the N-hydroxysuccinimide into the mixture, performing ultrasonic dispersion together, and preserving the mixture at a low temperature.
3. The method for preparing the graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 2, wherein the graphene content in the graphene aqueous slurry is 1-1.5wt%.
4. The method for preparing the graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 2, wherein the molar ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide to N-hydroxysuccinimide is 1:1.
5. The method for preparing the graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 1, wherein the specific steps of the graphene-supported gold cluster are as follows: weighing N-isobutyryl-L-cysteine and tris (2-carboxyethyl) phosphine, dissolving in methanol, adding chloroauric acid solution and acetic acid into the mixture, stirring the mixture at low temperature and normal pressure for reaction, adding pretreated graphene solution into the solution system after full reaction, continuing to react at low temperature and normal pressure, adding sodium borohydride solution into the solution system after full reaction, stirring the mixture at low temperature and normal pressure for reaction, and obtaining solid powder after the reaction is finished, and carrying out sedimentation, centrifugation, dialysis and freeze drying to obtain the graphene loaded gold cluster nanocomposite.
6. The method for preparing a graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 5, wherein the mass ratio of N-isobutyryl-L-cysteine to tris (2-carboxyethyl) phosphine is 19:1.
7. The method for preparing a graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 5, wherein the molar ratio of chloroauric acid to N-isobutyryl-L-cysteine is 1 (2-4).
8. The method for preparing the graphene-supported gold cluster nanocomposite by in-situ reduction of sodium borohydride according to claim 5, wherein the molar ratio of chloroauric acid to sodium borohydride is 1 (10-30).
9. Use of the graphene-supported gold cluster nanocomposite prepared by the preparation method according to any one of claims 1 to 8 in catalytic degradation of azo dyes.
10. The use of a graphene-supported gold-cluster nanocomposite in the catalytic degradation of azo dyes according to claim 9, characterized in that the azo dyes comprise congo red, direct deep brown M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210690903.1A CN115121244B (en) | 2022-06-17 | 2022-06-17 | Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210690903.1A CN115121244B (en) | 2022-06-17 | 2022-06-17 | Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115121244A CN115121244A (en) | 2022-09-30 |
| CN115121244B true CN115121244B (en) | 2023-04-25 |
Family
ID=83378306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210690903.1A Active CN115121244B (en) | 2022-06-17 | 2022-06-17 | Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115121244B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684560A (en) * | 2016-08-05 | 2018-02-13 | 深圳深见医药科技有限公司 | Material containing Aurum clusters is preparing the application in preventing and treating alzheimer medicine |
| CN108117130A (en) * | 2017-12-25 | 2018-06-05 | 李雪琴 | A kind for the treatment of process of auri composite photocatalyst for degrading dyeing waste water |
| WO2018106128A1 (en) * | 2016-12-09 | 2018-06-14 | Manufacturing Systems Limited | Apparatus and methods for controlled electrochemical surface modification |
| CN108404989A (en) * | 2018-04-28 | 2018-08-17 | 东华大学 | A kind of preparation method of Aurum clusters/graphene catalytic membrane |
| CN111250081A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Ligand protection and in-situ supported noble metal nanocluster catalyst and preparation method and application thereof |
| CN112337466A (en) * | 2020-11-27 | 2021-02-09 | 辽宁大学 | Nano-carbon-loaded cluster-state copper nanoenzyme and preparation method and application thereof |
| CN114371136A (en) * | 2021-12-17 | 2022-04-19 | 江苏大学 | Gold nanocluster-polypeptide sensor and preparation method and application thereof |
-
2022
- 2022-06-17 CN CN202210690903.1A patent/CN115121244B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684560A (en) * | 2016-08-05 | 2018-02-13 | 深圳深见医药科技有限公司 | Material containing Aurum clusters is preparing the application in preventing and treating alzheimer medicine |
| WO2018106128A1 (en) * | 2016-12-09 | 2018-06-14 | Manufacturing Systems Limited | Apparatus and methods for controlled electrochemical surface modification |
| CN108117130A (en) * | 2017-12-25 | 2018-06-05 | 李雪琴 | A kind for the treatment of process of auri composite photocatalyst for degrading dyeing waste water |
| CN108404989A (en) * | 2018-04-28 | 2018-08-17 | 东华大学 | A kind of preparation method of Aurum clusters/graphene catalytic membrane |
| CN111250081A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Ligand protection and in-situ supported noble metal nanocluster catalyst and preparation method and application thereof |
| CN112337466A (en) * | 2020-11-27 | 2021-02-09 | 辽宁大学 | Nano-carbon-loaded cluster-state copper nanoenzyme and preparation method and application thereof |
| CN114371136A (en) * | 2021-12-17 | 2022-04-19 | 江苏大学 | Gold nanocluster-polypeptide sensor and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115121244A (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Facile fabrication of highly dispersed Pd@ Ag core–shell nanoparticles embedded in spirulina platensis by electroless deposition and their catalytic properties | |
| Huang et al. | One-step synthesis of size-tunable gold nanoparticles immobilized on chitin nanofibrils via green pathway and their potential applications | |
| CN109365001B (en) | Synthesis method of Ag-In-Zn-S/CQDs heterojunction material | |
| Gao et al. | Highly recyclable Ag NPs/alginate composite beads prepared via one-pot encapsulation method for efficient continuous reduction of p-nitrophenol | |
| CN101444730B (en) | Method for preparing carbon nano-fiber/silver nano-particle composite catalyst | |
| CN111185235B (en) | Preparation of gold nanoparticle/metal organic framework compound and application of gold nanoparticle/metal organic framework compound in p-nitrophenol reduction | |
| CN104307512A (en) | Supported palladium catalyst and preparation method and application thereof | |
| CN113042085B (en) | Preparation method and application of nitrogen-phosphorus double-doped graphene-supported nickel-cobalt-palladium nano catalyst | |
| Zhan et al. | Controllable morphology and highly efficient catalytic performances of Pd–Cu bimetallic nanomaterials prepared via seed-mediated co-reduction synthesis | |
| CN106563484B (en) | A kind of preparation method of the hollow nitrating carbon copper-clad nanocatalyst of mesoporous type | |
| CN112337499B (en) | Composite nano material with catalytic property, preparation method and application | |
| CN111141726A (en) | SiO with core-shell structure2@ noble metal nano composite material and preparation method thereof | |
| CN113975390B (en) | Modified natural melanin core-shell nanoparticles and preparation method and application thereof | |
| Mor et al. | Pore architecture evolution and OER catalytic activity of hollow Co/Zn zeolitic imidazolate frameworks | |
| CN115121244B (en) | Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite | |
| CN111905730B (en) | Preparation method and application of 0D/1D/2D composite magnesium-aluminum bimetallic oxide nano catalytic material | |
| CN112588287A (en) | Method for synthesizing carbon material loaded Pt nano-particle material by ultraviolet illumination | |
| CN113244965A (en) | Ruthenium dioxide nano particle mediated and synthesized by bovine serum albumin and peroxide mimic enzyme activity thereof | |
| CN115282290A (en) | pH-responsive Au @ ZIF-8 water phase preparation method | |
| CN112675915B (en) | Preparation method and application of Pd/ZIF-8 cubic composite material | |
| Pandit et al. | Functionalized diatom biosilica decorated with nanoparticles: synthesis, characterization, catalytic oxidation, and dye scavenging applications | |
| CN108993534B (en) | Preparation method of nano gold/silver magnetic catalyst with high modification density and good uniformity | |
| CN111744555B (en) | Paper-based Au-AgInSe2Preparation method of (E) -ZIF-8 nanocomposite | |
| Zolotukhina et al. | One-step and one-pot method for synthesis of hybrid composite palladium-polypyrrole-carbon (Pd/PPy/C) nanomaterials | |
| CN117160450A (en) | Black phosphorus loaded gold nanocluster composite material and in-situ preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |