CN110773196A - Method for preparing recyclable Au-Cu porous filler with catalytic function - Google Patents
Method for preparing recyclable Au-Cu porous filler with catalytic function Download PDFInfo
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- CN110773196A CN110773196A CN201911111567.5A CN201911111567A CN110773196A CN 110773196 A CN110773196 A CN 110773196A CN 201911111567 A CN201911111567 A CN 201911111567A CN 110773196 A CN110773196 A CN 110773196A
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- 239000000945 filler Substances 0.000 title claims abstract description 48
- 229910002708 Au–Cu Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000000053 physical method Methods 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000520 microinjection Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysis, in particular to a method for preparing recyclable Au-Cu porous filler with a catalytic function. The method comprises the following steps: (1) mixing chloroauric acid water solution with the concentration of 0.1mol/L and water, and pouring the mixture into a container; the amount of the chloroauric acid aqueous solution is 0.05-0.25 mL; (2) folding the copper wire for 2 times and putting the copper wire into the container; standing at normal temperature, and setting the replacement time to be 2-4 h; (3) and after the replacement is finished, removing residual liquid, washing and drying a reaction product to obtain the Au-Cu porous filler. The method has the advantages of low cost, environmental protection, simple process and the like, and the prepared Au-Cu porous filler has the advantages of stable performance, high catalytic efficiency, good repeatability and the like.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a method for preparing recyclable Au-Cu porous filler with a catalytic function.
Background
With the continuous improvement of the industrialization degree of various countries, organic pollutants, especially 4-nitrophenol, are discharged into rivers and lakes in large quantity. 4-nitrophenol has high toxicity, stability and an accumulative effect, and the harm caused by the 4-nitrophenol poses a potential threat to the environment and the health of human beings.
At present, people mainly adopt a physical method and a chemical method to treat 4-nitrophenol in a water body. The physical method mainly separates and removes pollutants in the wastewater through physical adsorption, but the treatment period is long and the subsequent treatment is needed. Compared to physical methods, chemical methods are widely used because of their high efficiency and low cost for treating organic pollutants. Among chemical methods, the photocatalytic method has become a research hotspot due to the characteristic of green and pollution-free. In the photocatalytic reaction, most of the catalyst is granular, but the granular catalyst is difficult to recover and the loss of the catalyst is serious. In recent years, thin film catalysts have gradually replaced particulate catalysts. The preparation method of the thin film catalyst mainly comprises a physical method and a chemical method. (1) The physical method is a magnetron sputtering method, but the magnetron sputtering method has strong dependence on equipment and high production cost, and the large granularity of the surface film is not beneficial to the application of the surface film in the photocatalytic reaction. (2) The chemical method is usually an electrostatic self-assembly-seed growth method, and the nano particles are plated on the etched channels by the electrostatic self-assembly-seed growth method to form the catalyst film. The film catalyst and carrier prepared by the method can be used as filler in a filler type reactor to degrade 4-nitrophenol. Compared with the physical and chemical methods, the chemical method has higher quality and better effect. However, in the channel processing, in order to ensure the coating quality of the catalyst, a large amount of toxic and expensive organic reagent is used, which may cause serious environmental pollution.
Disclosure of Invention
The invention provides a method for preparing recyclable Au-Cu porous filler with a catalytic function, which solves the problems that in the prior art, a particle catalyst is difficult to recover, the physical method is expensive in membrane preparation cost, the granularity of a thin membrane is large, and the membrane preparation in a chemical method can cause environmental pollution. Compared with a seed growth method, the preparation method of the filler has the advantages of low cost, environmental protection, simple process and the like, and the prepared Au-Cu porous filler has the advantages of stable performance, high catalytic efficiency and reusability. Therefore, the filler prepared in the way has huge application potential and practical value in the technical field of catalysis.
Specifically, the technical scheme of the invention is as follows:
the invention discloses a method for preparing recyclable Au-Cu porous filler with catalytic function, which comprises the following steps:
(1) mixing chloroauric acid water solution with the concentration of 0.1mol/L and water, and pouring the mixture into a container; the amount of the chloroauric acid aqueous solution is 0.05-0.25mL, and the volume of the water is 7 mL;
(2) folding the copper wire for 2 times and putting the copper wire into the container; standing at normal temperature, and setting the replacement time to be 2-4 h;
(3) and after the replacement is finished, removing residual liquid, washing and drying a reaction product to obtain the Au-Cu porous filler.
It should be understood that the steps of the present invention are not limited to the above steps, and other additional steps may be included before step (1), between steps (1) and (2), between steps (2) and (3), and after step (3), and all are within the scope of the present invention.
Preferably, the concentration of the chloroauric acid aqueous solution is 0.1mol/L, and the volume of the water is 7 mL.
Preferably, the diameter of the copper wire is 0.18-0.3mm, and the length of the copper wire is 20 cm.
It should be understood that the size of the wire in the present invention is not limited to a diameter of 0.18-0.3mm and a length of 20cm, and the wire is not limited to the substitution of copper wire, but may include the substitution of other wires such as silver, tungsten, aluminum, etc.
Preferably, in step (3), after the completion of the replacement, the residual liquid is removed, and the reaction product is washed with 20mL of deionized water each time and washed 3 times continuously.
Preferably, in step (3), the reaction product is dried in air for 1 h.
The second aspect of the invention discloses the Au-Cu porous filler prepared by the method.
The third aspect of the invention discloses a small-sized packed reactor, which comprises the Au-Cu porous packing.
Preferably, the small-sized packed reactor further comprises a glass tube, the folded Au-Cu porous packing is placed in the glass tube, and two ends of the glass tube are sealed by rubber plugs.
Preferably, the length of the glass tube is 5cm, the outer diameter is 4mm, and the inner diameter is 2 mm.
Preferably, the container is a centrifuge tube.
The fourth aspect of the invention discloses the application of the method, the Au-Cu porous filler or the small-sized filler type reactor in the technical field of catalysis.
On the basis of the common general knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily without departing from the concept and the protection scope of the invention.
Compared with the prior art, the invention has the following remarkable advantages and effects:
compared with the prior art, the invention has the following beneficial effects:
(1) compared with the electrostatic self-assembly-seed growth method, the method has the advantages of high catalytic efficiency, environmental protection, large-scale production and the like.
(2) Compared with granular fillers, the prepared Au-Cu porous filler has the advantages of stable performance, low cost and reusability.
Drawings
FIG. 1 is an SEM image of the surface of an Au-Cu porous filler in an example of the present invention;
FIG. 2 is a UV-Vis spectrum of 4-NP subjected to photocatalytic degradation in example of the present invention;
FIG. 3 is a bar graph of degradation rate for 5 replicates in an example of the invention;
FIG. 4 is a SEM image of the surface of an Au-Cu porous filler in an embodiment of the invention;
FIG. 5 is a UV-Vis spectrum of 4-NP subjected to photocatalytic degradation in example of the present invention;
FIG. 6 is a bar graph of the degradation rate for 5 replicates in an example of the invention.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the drawings and the embodiments, but the present invention is not limited to the scope of the embodiments.
The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The reagents and starting materials used in the present invention are commercially available.
The invention mainly comprises the following technical scheme, and firstly discloses a preparation method of an Au-Cu porous filler, which comprises the following steps:
(1) mixing chloroauric acid water solution (0.05-0.25mL, concentration 0.1mol/L) and 7mL of water, and pouring into a container;
(2) folding copper wire (diameter 0.18-0.3mm, length 20cm) for 2 times, and placing into the container; standing at normal temperature, and setting the replacement time to be 2-4 h;
(3) after the replacement is finished, removing residual liquid, washing the reaction product with 20mL of deionized water each time, and continuously washing for 3 times;
(4) after washing, placing the mixture in air to dry for 1 hour to obtain Au-Cu porous filler; the surface topography can be observed by SEM images.
(5) Placing Au-Cu porous filler in a glass tube (with length of 5cm, outer diameter of 4mm and inner diameter of 2mm), sealing two ends of the glass tube with rubber plugs, and making into a small-sized filler type reactor.
(6) Respectively putting 4mL of 4-nitrophenol solution (0.003mol/L) and 4mL of sodium borohydride solution (0.15mol/L) into two injectors, controlling two streams of liquid by using a micro-injection pump so that the flow rate of sodium borohydride is consistent with that of 4-nitrophenol, injecting the solution into a small-sized filler type reactor, starting a photocatalytic degradation experiment after injection is finished, and stopping reaction after 5 min. The degradation rate of 4-nitrophenol is analyzed by using a UV-Vis absorption spectrogram. And then taking out the Au-Cu porous filler, washing the Au-Cu porous filler by using 20mL of deionized water, and repeating the photocatalytic degradation experiment for 5 times according to the steps after the Au-Cu porous filler is dried in the air.
Example 1
The invention provides a method for preparing recyclable Au-Cu porous filler with a catalytic function, which comprises the following steps:
(1)0.05mL of an aqueous chloroauric acid solution (0.1mol/L) and 7mL of water were mixed and poured into a container.
(2) Folding copper wire (diameter 0.18mm, total length 20cm) for 2 times, and placing into the container; standing at normal temperature, and setting the replacement time to be 2 h.
(3) After the replacement is finished, removing residual liquid, washing the reaction product with 20mL of deionized water each time, and continuously washing for 3 times; (4) after washing, placing the mixture in air to dry for 1 hour to obtain Au-Cu porous filler; the surface topography can be observed by SEM images, as shown in figure 1.
(5) Placing Au-Cu porous filler in a glass tube (with length of 5cm, outer diameter of 4mm and inner diameter of 2mm), sealing two ends of the glass tube with rubber plugs, and making into a small-sized filler type reactor.
(6) 4mL of 4-nitrophenol solution (0.003mol/L) and 4mL of sodium borohydride solution (0.15mol/L) are respectively put into two injectors, a microinjection pump is used for controlling two streams of liquid, so that the flow rate of the sodium borohydride is consistent with that of the 4-nitrophenol, and the solution is injected into a small-sized filler type reactor to start a photocatalytic degradation experiment. The reaction was stopped after 5 min. The degradation rate is 90.8%, and the UV-Vis spectrum is shown in figure 2. And then taking out the Au-Cu porous filler, washing the Au-Cu porous filler by using 20mL of deionized water, and repeating the photocatalytic degradation experiment for 5 times according to the steps after the Au-Cu porous filler is dried in the air. The degradation rates were all 90.8% + -2% with no significant change, as shown in fig. 3.
Example 2
The embodiment provides a method for preparing an Au-Cu porous filler which can be recycled and has a catalytic function, which comprises the following specific steps:
(1)0.25mL of an aqueous chloroauric acid solution (0.1mol/L) and 7mL of water were mixed and poured into a container.
(2) Folding copper wire (diameter 0.3mm, total length 20cm) for 2 times, and placing into the container; standing at normal temperature, and setting the replacement time to be 4 h.
(3) After the replacement is finished, removing residual liquid, washing the reaction product with 20mL of deionized water each time, and continuously washing for 3 times; (4) after washing, placing the mixture in air to dry for 1 hour to obtain Au-Cu porous filler; the surface topography was observed by SEM images, as shown in fig. 4.
(5) Placing Au-Cu porous filler in a glass tube (with length of 5cm, outer diameter of 4mm and inner diameter of 2mm), sealing two ends of the glass tube with rubber plugs, and making into a small-sized filler type reactor.
(6) 4mL of 4-nitrophenol solution (0.003mol/L) and 4mL of sodium borohydride solution (0.15mol/L) are respectively put into two injectors, a microinjection pump is used for controlling two streams of liquid, so that the flow rate of the sodium borohydride is consistent with that of the 4-nitrophenol, and the solution is injected into a small-sized filler type reactor to start a photocatalytic degradation experiment. The reaction was stopped after 5 min. The degradation rate is 91.7%, and the UV-Vis spectrum is shown in figure 5. And then taking out the Au-Cu porous filler, washing the Au-Cu porous filler by using 20mL of deionized water, and repeating the photocatalytic degradation experiment for 5 times according to the steps after the Au-Cu porous filler is dried in the air. The degradation rates were all 91.7% + -2% with no significant change, as shown in fig. 6.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for preparing recyclable Au-Cu porous filler with catalytic function is characterized by comprising the following steps:
(1) mixing chloroauric acid water solution with the concentration of 0.1mol/L and water, and pouring the mixture into a container; the amount of the chloroauric acid aqueous solution is 0.05-0.25mL, and the volume of the water is 7 mL;
(2) folding the copper wire for 2 times and putting the copper wire into the container; standing at normal temperature, and setting the replacement time to be 2-4 h;
(3) and after the replacement is finished, removing residual liquid, washing and drying a reaction product to obtain the Au-Cu porous filler.
2. The method according to claim 1, characterized in that the copper wire has a diameter of 0.18-0.3mm and a length of 20 cm.
3. The method according to claim 1, wherein in the step (3), after completion of the substitution, the residual liquid is removed, and the reaction product is washed with 20mL of deionized water each time and washed 3 times in succession.
4. The method of claim 1, wherein the container is a centrifuge tube.
5. The method of claim 1, wherein in step (3), the reaction product is dried in air for 1 hour.
6. An Au-Cu porous filler prepared according to the method of any one of claims 1 to 5.
7. A compact packed reactor comprising the Au-Cu porous packing of claim 6.
8. The compact packed reactor according to claim 7, further comprising a glass tube in which the folded Au-Cu porous packing is placed, both ends of the glass tube being sealed with rubber stoppers.
9. Use of the process according to any one of claims 1 to 5, the Au-Cu porous packing according to claim 6 or the compact packed reactor according to any one of claims 7 to 8 in the field of catalytic technology.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911111567.5A CN110773196A (en) | 2019-11-13 | 2019-11-13 | Method for preparing recyclable Au-Cu porous filler with catalytic function |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911111567.5A CN110773196A (en) | 2019-11-13 | 2019-11-13 | Method for preparing recyclable Au-Cu porous filler with catalytic function |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11347411A (en) * | 1998-06-02 | 1999-12-21 | Dalian Chem Ind Co Ltd | Production of catalyst and production of acetic alkenyl ester |
| CN1483539A (en) * | 2003-07-29 | 2004-03-24 | 中国科学院上海光学精密机械研究所 | Method for preparing metal nano material by using metal replacement reaction |
| CN103983628A (en) * | 2013-12-13 | 2014-08-13 | 江南大学 | Preparation method of copper net base foliated gold SERS active substrate |
| CN106215827A (en) * | 2016-09-10 | 2016-12-14 | 天津大学 | The small liquid-solid fluid bed reactor of photocatalysis |
| CN107639235A (en) * | 2017-09-07 | 2018-01-30 | 浙江工业大学 | A kind of preparation method and applications of golden copper nano-wire material |
-
2019
- 2019-11-13 CN CN201911111567.5A patent/CN110773196A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11347411A (en) * | 1998-06-02 | 1999-12-21 | Dalian Chem Ind Co Ltd | Production of catalyst and production of acetic alkenyl ester |
| CN1483539A (en) * | 2003-07-29 | 2004-03-24 | 中国科学院上海光学精密机械研究所 | Method for preparing metal nano material by using metal replacement reaction |
| CN103983628A (en) * | 2013-12-13 | 2014-08-13 | 江南大学 | Preparation method of copper net base foliated gold SERS active substrate |
| CN106215827A (en) * | 2016-09-10 | 2016-12-14 | 天津大学 | The small liquid-solid fluid bed reactor of photocatalysis |
| CN107639235A (en) * | 2017-09-07 | 2018-01-30 | 浙江工业大学 | A kind of preparation method and applications of golden copper nano-wire material |
Non-Patent Citations (3)
| Title |
|---|
| R.皮尔斯等: "《催化及化学过程》", 30 November 1989, 成都科技大学出版社 * |
| 中国化工装备总公司: "《塔填料产品及技术手册》", 31 May 1995, 化学工业出版社 * |
| 陆标等: "一维Cu-Au纳米异质结构制备及催化性能研究", 《浙江理工大学学报（自然科学版）》 * |
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