CN114210339B - Porous silver loaded on copper-based carrier in situ and preparation method and application thereof - Google Patents
Porous silver loaded on copper-based carrier in situ and preparation method and application thereof Download PDFInfo
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- CN114210339B CN114210339B CN202111501032.6A CN202111501032A CN114210339B CN 114210339 B CN114210339 B CN 114210339B CN 202111501032 A CN202111501032 A CN 202111501032A CN 114210339 B CN114210339 B CN 114210339B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 146
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 141
- 239000004332 silver Substances 0.000 title claims abstract description 141
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 132
- 239000010949 copper Substances 0.000 title claims abstract description 132
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 54
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011889 copper foil Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 210000003041 ligament Anatomy 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 238000012876 topography Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 description 2
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
-
- B01J35/60—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Abstract
The invention provides porous silver loaded on a copper-based carrier in situ, and a preparation method and application thereof. The preparation method of the porous silver loaded on the copper-based carrier in situ comprises the following steps: dissolving silver nitrate and chlorobenzoic acid in water to prepare a mixed solution; immersing the pretreated copper-based carrier into the mixed solution, and obtaining the porous silver loaded on the copper-based carrier in situ through reaction, washing and drying. The method can rapidly and efficiently prepare the porous silver, does not need complex operation steps and reaction equipment, and can be used for mass production. The method can realize that the porous silver is loaded on copper-based carriers with different structures in situ, so that the loss of the porous silver is reduced; and the porous silver in-situ loaded on the copper-based carrier has excellent catalytic performance and SERS performance.
Description
Technical Field
The invention relates to porous silver loaded on a copper-based carrier in situ, and a preparation method and application thereof, and belongs to the technical field of metal materials.
Background
Porous silver has excellent physicochemical properties, large specific surface area, low density, high porosity, excellent electrical and thermal conductivity, and is not easily oxidized, and has been widely used in the fields of catalysis, sensing, surface-enhanced raman scattering, biomedical and the like. At present, the common preparation methods of the porous silver mainly comprise a template method, a dealloying method and a physical sputtering method, but the methods have certain problems, such as complicated steps, complicated equipment and difficulty in realizing the mass production of the porous silver.
Chinese patent document CN104525937a discloses a porous silver micro-nano structure and a preparation method with controllable morphology and size. The overall appearance of the porous silver micro-nano structure prepared by the method is hexagonal sandwich appearance, quadrilateral appearance or strip appearance, and is formed by stacking silver basic constituent units of 30-50 nanometers, and the porous silver micro-nano structure is formed by stacking silver basic constituent units. The preparation method comprises the steps of dissolving sodium citrate, sodium carbonate and citric acid in deionized water, sequentially adding a silver nitrate solution and a D-glucose solution, stirring, precipitating, centrifuging and drying to obtain a precursor; and carrying out heat treatment on the precursor to obtain the porous silver micro-nano structure. However, the preparation process of the method is complex, a long-time synthesis process is required, and the prepared silver nanometer basic units are easy to aggregate, so that the catalytic performance of the silver nanometer basic units is reduced to a certain extent.
In the process of porous silver application, porous silver is often required to be secondarily supported on a carrier to realize the catalytic performance thereof; however, the loading process is complex and the performance loss of the catalyst is easy to cause; therefore, there is a need to develop a synthesis method which can load porous silver in situ, is simple to operate and easy to implement, reduces catalyst loss, and improves application performance of the porous silver.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides porous silver loaded on a copper-based carrier in situ, and a preparation method and application thereof. The method can rapidly and efficiently prepare the porous silver, does not need complex operation steps and reaction equipment, and can be used for mass production. The method can realize that the porous silver is loaded on copper-based carriers with different structures in situ, so that the loss of the porous silver is reduced; and the porous silver in-situ loaded on the copper-based carrier has excellent catalytic performance and SERS performance.
In order to achieve the technical purpose, the invention is realized by the following technical scheme:
porous silver loaded on a copper-based carrier in situ, wherein the porous silver is uniformly loaded on the surface of the copper-based carrier in the form of curled porous silver nano-sheets; the pore structure is in a three-dimensional open pore form, and the pore ligament size is 20-30nm.
The preparation method of the porous silver loaded on the copper-based carrier in situ comprises the following steps:
(1) Dissolving silver nitrate and chlorobenzoic acid in water to prepare a mixed solution;
(2) Immersing the pretreated copper-based carrier into the mixed solution, and obtaining the porous silver loaded on the copper-based carrier in situ through reaction, washing and drying.
According to the invention, the concentration of silver nitrate in the mixed solution in the step (1) is 15-30mmol/L; preferably, the concentration of silver nitrate is 20-25mmol/L, most preferably 20mmol/L.
According to a preferred embodiment of the present invention, in the step (1), the chlorobenzoic acid is one of 2-chlorobenzoic acid, 3-chlorobenzoic acid and 4-chlorobenzoic acid.
According to the invention, in step (1), the molar ratio of silver nitrate to chlorobenzoic acid is preferably from 1.5 to 4:1, most preferably 2:1.
According to the invention, in the step (2), the copper-based carrier is copper foil, copper foam, copper mesh or copper wire.
According to a preferred embodiment of the present invention, in the step (2), the pretreatment method of the copper-based carrier is as follows: soaking the copper-based carrier in an acidic solution to remove oxides on the surface, and then washing and drying the copper-based carrier by water to obtain a pretreated copper-based carrier; the acidic solution is an aqueous solution of fluoroboric acid, a dilute aqueous solution of hydrochloric acid or a dilute aqueous solution of sulfuric acid, and the mass concentration of the acidic solution is 40-60%.
Preferably, the soaking time is 3-10 minutes, and the soaking temperature is room temperature; the acidic solution is an aqueous solution of fluoroboric acid.
According to the invention, in the step (2), the ratio of the mass of the pretreated copper-based carrier to the volume of the mixed solution is 10:0.5-1.5g/L.
Preferably, in step (2), the reaction temperature is 15-25 ℃ and the reaction time is 1-15 minutes; preferably, the reaction temperature is 15-20 ℃ and the reaction time is 2-10 minutes.
According to a preferred embodiment of the present invention, in step (2), the washing method is washing with ethanol and deionized water in sequence.
According to a preferred embodiment of the present invention, the method for preparing porous silver supported on a copper-based carrier in situ comprises the steps of:
(1) Soaking copper foil in 50% fluoboric acid water solution at room temperature for 10 min to remove oxide on the surface of the copper foil, washing with water, and drying to obtain pretreated copper-based carrier.
(2) Dissolving silver nitrate and 2-chlorobenzoic acid in water to prepare 100ml of mixed solution of silver nitrate and 2-chlorobenzoic acid; in the mixed solution, the concentration of silver nitrate is 20mmol/L, and the concentration of 2-chlorobenzoic acid is 10mmol/L;
(3) 20mg of the pretreated copper-based carrier is immersed in 2ml of mixed solution, reacted for 5 minutes at 20 ℃, and then washed and dried by ethanol and deionized water in sequence, so as to obtain the porous silver loaded on the copper-based carrier in situ.
Application of porous silver in situ loaded on copper-based carrier as catalyst for catalyzing NaBH 4 And 4-nitrophenol (4-NP).
According to the invention, the following method is preferred: adding porous silver loaded on copper-based carrier in situ into NaBH 4 And 4-nitrophenol, and carrying out catalytic reduction reaction for 30s-5min at room temperature.
Preferably, the concentration of 4-nitrophenol in the mixed solution is 0.05-0.5mmol/L, preferably 0.1mmol/L; naBH 4 And molar ratio of 4-nitrophenol40-60:1, preferably 50:1.
Preferably, the mass of the porous silver supported in situ on the copper-based carrier is equal to that of NaBH 4 The volume ratio of the mixed solution of the 4-nitrophenol and the water is 1-3:1g/L.
The application of the porous silver in-situ loaded on the copper-based carrier is used as a SERS substrate to detect the p-mercaptoaniline (PATP).
The invention has the technical characteristics and beneficial effects that:
1. according to the invention, chlorobenzoic acid molecules are used as a regulating agent to regulate the current displacement reaction between copper and silver nitrate, so that porous silver can be loaded on a copper-based carrier in situ, and the performance loss in the secondary loading process of the porous silver is avoided. The synthesized porous silver is uniformly loaded on the surface of a copper-based carrier in the form of curled porous silver nano-sheets, the porosity is high, the pore structure is in a three-dimensional open pore form, and the porous silver is uniformly distributed on the carrier.
2. Compared with other types of molecular regulators (such as 2-nitrobenzoic acid, hydroxybenzoic acid and the like), the chlorobenzoic acid used in the method has more obvious morphology regulation and control effect, and is mainly based on that the adsorption of the chlorobenzoic acid to different crystal faces of the nano silver crystal influences the surface free energy of the crystal faces, thereby influencing the growth process of a silver structure, and finally the porous silver with morphology, structure and performance can be successfully prepared.
3. Compared with other silver nanostructures, the porous silver nanostructure has larger specific surface area, can provide more active sites, and has wide application prospects in catalysis and SERS.
4. The method has the advantages of rapid reaction process, simple operation, no need of complex equipment and easy realization of large-scale production. The method can realize that the porous silver is loaded on copper-based carriers with different structures in situ, can realize the change of the macrostructure of the porous silver by customizing the structure of copper based on the plasticity of the copper carrier, and can be applied to different scenes.
5. The porous silver in-situ loaded on the copper-based carrier obtained by the method has excellent catalytic performance and SERS performance; in the catalysis of NaBH 4 Reduction reaction of p-4-nitrophenol (4-NP)Exhibit excellent catalytic activity in the reaction; as a SERS substrate, the signal of the PATP can be sufficiently detected, the PATP can be applied to detection of the PATP, and the uniformity is good. .
6. The preparation method of the invention is that the porous silver loaded on the copper-based carrier in situ can be prepared under specific conditions and specific proportion as a whole.
Drawings
Fig. 1 is an SEM morphology of porous silver loaded in situ on a copper-based carrier synthesized in example 1 at 3 ten thousand magnification.
Fig. 2 is an SEM morphology of porous silver loaded in situ on a copper-based carrier synthesized in example 1 at 2 ten thousand magnification.
Fig. 3 is an SEM topography at 1 ten thousand magnification of porous silver in situ supported on a copper-based carrier synthesized in example 1.
Fig. 4 is an SEM topography at 5 thousand magnification of porous silver loaded in situ on a copper-based support synthesized in example 1.
Fig. 5 is an SEM topography of porous silver in situ supported on a copper-based support synthesized with copper foam as a support in example 2.
FIG. 6 is a SEM topography of the in situ supported silver on a copper-based support synthesized with 2-nitrobenzoic acid as a regulatory molecule in comparative example 1.
Fig. 7 is an SEM morphology of in-situ supported silver on a copper-based support synthesized with 2-hydroxybenzoic acid as a regulatory molecule in comparative example 2.
Fig. 8 is an SEM topography of in situ supported silver on a copper-based support synthesized in comparative example 3.
Fig. 9 is an SEM topography of in situ silver loading on the copper-based support synthesized in comparative example 4.
FIG. 10 is a schematic diagram of an in situ supported porous silver-catalyzed NaBH of application example 1 on a copper-based support synthesized in example 1 4 Ultraviolet absorption spectrum of reduced p-nitrophenol.
Fig. 11 is a raman spectrum of a SERS substrate using porous silver in situ supported on the copper-based carrier synthesized in example 1 in application example 2.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.
The methods described in the examples are conventional, unless otherwise specified; the materials or reagents used are commercially available unless otherwise indicated.
Example 1
A method for preparing porous silver loaded on a copper-based carrier in situ, which comprises the following steps:
1) The copper foil is soaked in 50% fluoboric acid water solution at room temperature for 10 min to remove oxide on the surface, and then the pretreated copper-based carrier is obtained through water washing and drying.
2) A mixed solution of 100mL of silver nitrate (20 mmol/L) and 2-chlorobenzoic acid (10 mmol/L) was prepared.
3) 20mg of the pretreated copper foil was immersed in 2mL of the mixed solution at 20℃and reacted for 5 minutes.
4) And washing the obtained copper foil loaded with the porous silver with ethanol and deionized water in sequence, and drying to obtain the porous silver loaded on the copper-based carrier in situ.
The SEM images of the porous silver in situ supported on the copper-based carrier prepared in this example are shown in fig. 1-4, the porous structure exists in the form of three-dimensional open pores, the pore ligament size is about 20-30nm (the ligament size refers to the size of the porous structure at the hole and the hole connection), and a plurality of uniformly distributed curled porous silver nano-sheets are formed on the surface of the copper material.
Example 2
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: copper foam was used instead of copper foil.
The SEM morphology graph of the porous silver in-situ loaded on the copper-based carrier obtained in this example is shown in fig. 5, and it can be seen from the graph that when the copper-based material is changed to copper foam, a curled porous silver nano-sheet structure with uniform distribution and high porosity can still be grown on the surface of the copper-based material.
Example 3
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: copper foil is replaced by copper mesh.
Example 4
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: copper wires are used instead of copper foil.
Example 5
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 1), the fluoroboric acid was replaced with a dilute aqueous hydrochloric acid solution having a mass concentration of 40%.
Example 6
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 1), the fluoroboric acid was replaced with a dilute aqueous sulfuric acid solution having a mass concentration of 40%.
Example 7
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (5 mmol/L) and 2-chlorobenzoic acid (10 mmol/L) was prepared.
Example 8
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (10 mmol/L) and 2-chlorobenzoic acid (10 mmol/L) was prepared.
Example 9
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (15 mmol/L) and 2-chlorobenzoic acid (10 mmol/L) was prepared.
Example 10
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (25 mmol/L) and 2-chlorobenzoic acid (10 mmol/L) was prepared.
Example 11
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (20 mmol/L) and 2-chlorobenzoic acid (5 mmol/L) was prepared.
Example 12
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (20 mmol/L) and 2-chlorobenzoic acid (7.5 mmol/L) was prepared.
Example 13
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 2 minutes.
Example 14
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 3 minutes.
Example 15
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 4 minutes.
Example 16
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 6 minutes.
Example 17
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 7 minutes.
Example 18
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 8 minutes.
Example 19
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 9 minutes.
Example 20
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction time was 10 minutes.
Example 21
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction temperature was 18 ℃.
Example 22
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction temperature was 19 ℃.
Example 23
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 3), the reaction temperature was 20 ℃.
Example 24
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 3-chlorobenzoic acid is used instead of 2-chlorobenzoic acid.
Example 25
A method for preparing porous silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 4-chlorobenzoic acid is used instead of 2-chlorobenzoic acid.
Comparative example 1
A method for preparing silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 2-chlorobenzoic acid is replaced by 2-nitrobenzoic acid; other steps and conditions were consistent with example 1.
The SEM morphology graph of in-situ silver loading on the copper-based carrier obtained in the comparative example is shown in fig. 6, and it can be seen from the graph that the silver nano structure prepared under the condition is irregular silver nano blocks, and part of the silver nano blocks are aggregated into silver nano spheres; therefore, the regulator chlorobenzoic acid plays an important role in the morphology of the porous silver.
Comparative example 2
A method for preparing silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 2-chlorobenzoic acid is replaced by 2-hydroxybenzoic acid; other steps and conditions were consistent with example 1.
The SEM morphology graph of the in-situ silver loaded on the copper-based carrier obtained in the comparative example is shown in fig. 7, and as can be seen from the graph, the silver nano structure prepared by the condition is irregular silver nano particles, and the size and the shape are not uniform; therefore, the regulator chlorobenzoic acid plays an important role in the morphology of the porous silver.
Comparative example 3
A method for preparing silver supported in situ on a copper-based carrier, as described in example 1, except that: no 2-chlorobenzoic acid was added, namely: step 2), 100mL of an aqueous solution of silver nitrate (20 mmol/L) was prepared.
FIG. 8 is an SEM morphology of in-situ supported silver on a copper-based support obtained in this comparative example, where silver nanostructures were found to be dendritic silver; therefore, the regulator chlorobenzoic acid plays an important role in the morphology of the porous silver.
Comparative example 4
A method for preparing silver supported in situ on a copper-based carrier, as described in example 1, except that: in step 2), 100mL of a mixed solution of silver nitrate (20 mmol/L) and 2-chlorobenzoic acid (2.5 mmol/L) was prepared.
Fig. 9 is an SEM micrograph of in situ silver loading on a copper-based support synthesized in this comparative example. It can be found that when the dosage of the 2-chlorobenzoic acid is low, the porous silver with the morphology of the invention can not be obtained, and the obtained porous structure is less; it follows that the importance of a suitable amount of chlorobenzoic acid is high.
Application example 1
Application of porous silver in situ supported on copper-based carrier:
25mg of porous silver supported in situ on the copper-based carrier prepared in example 1 was added to 15ml of NaBH 4 And 4-nitrophenol, wherein the concentration of 4-nitrophenol is 0.1mmol/L, naBH 4 The concentration of (2) is 5mmol/L, the supernatant (namely the catalyzed solution) is taken after the catalytic reaction is carried out for 1 minute at room temperature, and is added into a cuvette, and the catalytic reduction degree is monitored by an ultraviolet-visible spectrophotometer.
Copper-based carrier precursors of the inventionBit-supported porous silver-catalyzed NaBH 4 The ultraviolet absorption spectrum of the reduced p-nitrophenol is shown in fig. 10, and the peak of 4-nitrophenol at 400nm wavelength can disappear under the condition of catalyzing the porous silver for 1 minute, which proves that the porous silver has good catalytic capability. In the figure, the initial solution is NaBH 4 And 4-nitrophenol.
Application example 2
SERS application of porous silver supported in situ on a copper-based support:
25mg of porous silver supported in situ on the copper-based carrier prepared in example 1 was placed at 10 -5 Soaking in a mol/L p-mercaptoaniline (PATP) solution for 4h; and then randomly selecting 16 points on the porous silver surface in-situ loaded on the soaked copper-based carrier by using a Raman spectrometer to detect PATP signals so as to test the uniformity of the PATP signals serving as a SERS substrate.
Fig. 11 is a raman spectrum using porous silver in situ supported on a copper-based carrier synthesized in example 1 as a SERS substrate. The graph shows that the porous silver is used as a SERS substrate, can fully detect the signal of PATP, can be applied to detect PATP, randomly selects 16 points on the surface of the PATP for testing, has the relative standard deviation of 6.9%, and proves that the porous silver has good uniformity when used as the SERS substrate to detect the PATP.
Claims (8)
1. The application of the porous silver in-situ loaded on the copper-based carrier is characterized in that the porous silver is used as a catalyst for catalyzing NaBH 4 And 4-nitrophenol;
in the porous silver loaded on the copper-based carrier in situ, the porous silver is uniformly loaded on the surface of the copper-based carrier in the form of curled porous silver nano-sheets; the pore structure is in a three-dimensional open pore form, and the pore ligament size is 20-30nm;
the preparation method of the porous silver loaded on the copper-based carrier in situ comprises the following steps:
(1) Dissolving silver nitrate and chlorobenzoic acid in water to prepare a mixed solution; the chlorobenzoic acid is 2-chlorobenzoic acid; the mol ratio of the silver nitrate to the chlorobenzoic acid is 1.5-4:1;
(2) Immersing the pretreated copper-based carrier into the mixed solution, and obtaining porous silver loaded on the copper-based carrier in situ through reaction, washing and drying; the copper-based carrier is copper foil, foam copper, a copper net or copper wires; the reaction temperature is 15-25 ℃ and the reaction time is 1-15 minutes.
2. The use of porous silver supported in situ on a copper-based carrier according to claim 1, wherein the concentration of silver nitrate in the mixed solution of step (1) is 15-30mmol/L.
3. Use of porous silver supported in situ on a copper-based carrier according to claim 2, characterized in that the concentration of silver nitrate is 20-25mmol/L.
4. The use of porous silver supported in situ on a copper-based carrier according to claim 1, wherein in step (1) the molar ratio of silver nitrate to chlorobenzoic acid is 2:1.
5. Use of porous silver supported in situ on a copper-based carrier according to claim 1, characterized in that in step (2) one or more of the following conditions are included:
i. the pretreatment method of the copper-based carrier comprises the following steps: soaking the copper-based carrier in an acidic solution to remove oxides on the surface, and then washing and drying the copper-based carrier by water to obtain a pretreated copper-based carrier; the mass concentration of the acid solution is 40-60%; the soaking time is 3-10 minutes, and the soaking temperature is room temperature; the acid solution is an aqueous solution of fluoroboric acid;
ii. The volume ratio of the mass of the pretreated copper-based carrier to the mixed solution is 10:0.5-1.5g/L;
and iii, the washing method is to wash with ethanol and deionized water in sequence.
6. The use of porous silver supported in situ on a copper-based carrier according to claim 1, wherein in step (2) the reaction temperature is 18-20 ℃ and the reaction time is 2-10 minutes.
7. The use of porous silver supported in situ on a copper-based carrier according to claim 1, wherein the method for preparing porous silver supported in situ on a copper-based carrier comprises the steps of:
(1) Soaking copper foil in 50% fluoboric acid water solution at room temperature for 10 min to remove oxide on the surface of the copper foil, and then washing and drying the copper foil to obtain a pretreated copper-based carrier;
(2) Dissolving silver nitrate and 2-chlorobenzoic acid in water to prepare 100ml of mixed solution of silver nitrate and 2-chlorobenzoic acid; in the mixed solution, the concentration of silver nitrate is 20mmol/L, and the concentration of 2-chlorobenzoic acid is 10mmol/L;
(3) 20mg of the pretreated copper-based carrier is immersed in 2ml of mixed solution, reacted for 5 minutes at 20 ℃, and then washed and dried by ethanol and deionized water in sequence, so as to obtain the porous silver loaded on the copper-based carrier in situ.
8. The use of porous silver supported in situ on a copper-based carrier according to claim 1, characterized by the following method of application: adding porous silver loaded on copper-based carrier in situ into NaBH 4 And 4-nitrophenol, and carrying out catalytic reduction reaction for 30s-5min at room temperature;
in the mixed solution, the concentration of 4-nitrophenol is 0.05-0.5mmol/L; naBH 4 And 4-nitrophenol in a molar ratio of 40-60:1;
the mass of porous silver in situ loaded on copper-based carrier and NaBH 4 The volume ratio of the mixed solution of the 4-nitrophenol and the water is 1-3:1g/L.
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