CN105107499A - Preparation method of doped nanoporous gold (NPG) with small pore diameter and large specific surface area - Google Patents
Preparation method of doped nanoporous gold (NPG) with small pore diameter and large specific surface area Download PDFInfo
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Abstract
The invention provides a preparation method of doped nanoporous gold (NPG) with a small pore diameter and a large specific surface area. The preparation method comprises the following steps: 1, cleaning gold alloy foils thoroughly, and drying for standby application; 2, mixing lauryl sodium sulfate or sodium dodecyl benzene sulfonate (SDBS) with corrosive mineral acid uniformly to obtain a corrosive medium solution; 3, placing the gold alloy foils in the corrosive medium solution for dealloying treatment; 4, boiling, washing and soaking the gold alloy foils subjected to dealloying treatment by adopting absolute ethyl alcohol as a solvent, drying to obtain the doped nanoporous gold (NPG) with a small pore diameter and a large specific surface area. According to the preparation method of the doped nanoporous gold (NPG) with a small pore diameter and a large specific surface area, provided by the invention, nanoporous gold (NPG) with high toughness, a small pore diameter and a large specific surface area is prepared by adopting the surface active agent-induced electrochemical corrosion dealloying technology, therefore the advantages that the process is simple, the cost is quite low, the structure is easy to control and the toughness is higher are achieved.
Description
Technical field
The invention belongs to catalysis porous metal material technical field, be specifically related to a kind of preparation method with the doped nano porous gold of small-bore bigger serface.
Background technology
Nano-porous gold receives much concern as a kind of novel catalyst.There is very excellent normal temperature even low-temperature catalytic activity, selective, humidity enhancement effect and fabulous anti-H in CO catalytic oxidation
2s poisoning capability.Very high sensitivity is demonstrated when DNA molecular being detected for biology sensor.Nano-porous gold or a kind of reusable edible SERS matrix material with high activity, stability, adjustability and biocompatibility.
Along with deepening continuously of research, scientific research personnel more and more recognizes that nano-porous structure and pattern have important impact to catalytic reaction.The aperture of nano-pore is less, specific area is larger, more favourable to catalytic reaction.The preparation of the nano-porous gold of small-bore has become the hot issue of nanoporous Au catalyst development.The aperture of the nanoporous Au catalyst reported in current document mainly about 20nm ~ 40nm and the report that regarding pore size is not more than the nano-porous gold of 10nm is little.
In addition, the nano-porous gold ubiquity micro-crack reported in document and blemish, make the toughness of perforated membrane very poor, easily intercrystalline fracture occurs, this seriously inhibits the practical application of nano-porous gold as electrocatalysis material, biology sensor, brake, Raman reinforcing material.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides the preparation method of the doped nano porous gold with small-bore bigger serface.The method adopts lauryl sodium sulfate or neopelex to be surfactant, and the method that the electrochemical corrosion of being induced by surfactant takes off alloy prepares the nano-porous gold of high tenacity, small-bore, bigger serface.Because surfactant can be adsorbed on the surface of gold atom, surfactant is introduced in the preparation of nano-porous gold, the diffusion rate of gold atom can not only be suppressed, other atom can also be made to dissolve and its rate of dissolution can be controlled simultaneously, thus while realizing reducing aperture and skeleton line size, toughness is largely increased.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method with the doped nano porous gold of small-bore bigger serface, and it is characterized in that, the method comprises the following steps:
Step one, that gold alloy foil is cleaned up post-drying is stand-by; Described gold alloy foil is Au-x bianry alloy foil or Au-x-y ternary alloy three-partalloy foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd;
Step 2, by lauryl sodium sulfate and corrosive inorganic acids in mass ratio (0.01 ~ 2.0): 100 mix, and obtain Korrosionsmedium solution; Or, by neopelex and corrosive inorganic acids in mass ratio (0.01 ~ 0.8): 100 mix, and obtain Korrosionsmedium solution;
Step 3, by step one dry after gold alloy foil put into the solution of Korrosionsmedium described in step 2, be 20 DEG C ~ 60 DEG C in temperature, voltage is that under the condition of 0.1V ~ 4V, electrochemical corrosion 0.5h ~ 50h carries out de-alloy treatment;
Step 4, employing absolute ethyl alcohol are that solvent boiling boiling successively through the gold alloy foil taken off after alloy treatment in step 3, rinsing and immersion treatment, obtain the doped nano porous gold with small-bore bigger serface after drying, the specific area of this nano-porous gold is 50m
2/ g ~ 200m
2/ g, aperture is not more than 10nm.
The above-mentioned preparation method with the doped nano porous gold of small-bore bigger serface, is characterized in that, the thickness of gold alloy foil described in step one is 0.1 μm ~ 100 μm.
The above-mentioned preparation method with the doped nano porous gold of small-bore bigger serface, it is characterized in that, corrosive inorganic acids described in step 2 is perchloric acid, nitric acid or sulfuric acid.
The above-mentioned preparation method with the doped nano porous gold of small-bore bigger serface, it is characterized in that, the concentration of perchloric acid described in step 2 is 0.05mol/L ~ 2mol/L, and the concentration of described nitric acid is 0.1mol/L ~ 5mol/L, and the concentration of described sulfuric acid is 0.5mol/L ~ 10mol/L.
The above-mentioned preparation method with the doped nano porous gold of small-bore bigger serface, is characterized in that, described in step 3, the voltage of de-alloy treatment is 0.5V ~ 3V, and the time of described de-alloy treatment is 0.5h ~ 25h.
The above-mentioned preparation method with the doped nano porous gold of small-bore bigger serface, is characterized in that, temperature dry described in step 4 is 20 DEG C ~ 60 DEG C, and the time of described drying is 5h ~ 10h.
The present invention compared with prior art has the following advantages:
1, the present invention has prepared a kind of doping type auri material with nano-porous structure, and this material has the distinguishing features such as high tenacity, small-bore, bigger serface; The present invention adopts lauryl sodium sulfate or neopelex to be surfactant, carries out electrochemical corrosion to remove other element in alloy except gold, effectively reduces aperture, improve product intensity and toughness by surfactant induction billon.
2, the present invention carries out de-alloy treatment by introducing surfactant in Korrosionsmedium solution, thus prepares the nano-porous gold of high tenacity, small-bore, bigger serface.Nano-porous gold prepared by the present invention is the uniform three-dimensional spongy nano-porous structure of class continuously of pattern.
3, the nano-porous gold prepared by the present invention is metal-doped shaped material, but not simple metal; Its aperture and skeleton phase linear dimension are not more than 10nm, and porosity is 60% ~ 80%, and specific area is 10m
2/ g ~ 200m
2/ g, has very high catalytic activity, and tensile yield strength is 80MPa, and product strength is high, and toughness is high.
4, with existing document in record add as the 3rd element the method preparing ultra-fine aperture nano-porous gold in initial alloy using noble metal to, and the electrochemistry reducing voltage raised temperature takes off alloy approach and compares, the present invention has the advantage that process is simple, cost is very low, structure easily controls, toughness is higher, and made nano-porous gold has the toughness of larger specific area, less aperture and Geng Gao.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the surface topography SEM photo of nano-porous gold prepared by the embodiment of the present invention 1.
Fig. 2 is the BHJ aperture size distribution curve of nano-porous gold prepared by the embodiment of the present invention 1.
Fig. 3 is the N of nano-porous gold prepared by the embodiment of the present invention 1
2adsorption-desorption isothermal.
Fig. 4 is the surface topography SEM photo of the nano-porous gold of comparative example 1 of the present invention preparation.
Fig. 5 is the BHJ aperture size distribution curve of the nano-porous gold of comparative example 1 of the present invention preparation.
Fig. 6 is the N of the nano-porous gold of comparative example 1 of the present invention preparation
2adsorption-desorption isothermal.
Fig. 7 is the surface topography SEM photo of nano-porous gold prepared by the embodiment of the present invention 2.
Fig. 8 is the BHJ aperture size distribution curve of superfine nano porous gold prepared by the embodiment of the present invention 2.
Fig. 9 is the N of nano-porous gold prepared by the embodiment of the present invention 2
2adsorption-desorption isothermal.
Figure 10 is the surface topography SEM photo of the nano-porous gold of comparative example 2 of the present invention preparation.
Figure 11 is the BHJ aperture size distribution curve of the nano-porous gold of comparative example 2 of the present invention preparation.
Figure 12 is the N of the nano-porous gold of comparative example 2 of the present invention preparation
2adsorption-desorption isothermal.
Detailed description of the invention
Embodiment 1
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 50 μm by thickness, width is 10mm, and it is stand-by that length is that the gold alloy foil of 30mm cleans up post-drying; Described gold alloy foil is Au-x bianry alloy foil or Au-x-y ternary alloy three-partalloy foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The present embodiment is preferably Au-Ag bianry alloy foil (nominal composition is Au-75Ag);
Step 2, lauryl sodium sulfate and corrosive inorganic acids to be mixed in mass ratio at 0.05: 100, obtain Korrosionsmedium solution; The perchloric acid of described corrosive inorganic acids to be concentration be 0.1mol/L;
Step 3, by step one dry after gold alloy foil put into the solution of Korrosionsmedium described in step 2, take gold alloy foil as anode, taking platinized platinum as negative electrode, is 40 DEG C in temperature, and voltage is that under the condition of 0.8V, electrochemical corrosion 20h carries out de-alloy treatment;
Step 4, the gold alloy foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 6h in the drying box of 40 DEG C in temperature, obtain the nano-porous gold with ultra-fine aperture.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Ag atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Ag doping.The surface topography SEM photo of nano-porous gold prepared by the present embodiment for shown in Fig. 1, BHJ aperture size distribution curve as shown in Figure 2, N
2adsorption-desorption isothermal as shown in Figure 3.Composition graphs 1, Fig. 2 and Fig. 3 can find out, the aperture of nano-porous gold prepared by the present embodiment is little (being mainly distributed within the scope of 2nm ~ 8nm, average pore size 5nm), and specific area is large, and (specific area is 190m
2/ g).
Comparative example 1
This comparative example is only with the difference of embodiment 1: do not add lauryl sodium sulfate in the solution of Korrosionsmedium described in step 2.
The surface topography SEM photo of nano-porous gold prepared by this comparative example for shown in Fig. 4, BHJ aperture size distribution curve as shown in Figure 5, N
2adsorption-desorption isothermal as shown in Figure 6.Composition graphs 4, Fig. 5 and Fig. 6 can find out, the aperture large (being mainly distributed within the scope of 20nm ~ 80nm, average pore size 40nm) of nano-porous gold prepared by the present embodiment, specific area is little, and (specific area is 17m
2/ g).
In addition, by carrying out comparative analysis discovery in kind to embodiment 1 and the made nano-porous gold of comparative example 1, the surperficial zero defect of the made nano-porous gold of embodiment 1, obviously there is intergranular corrosion cracks in the surface of the made nano-porous gold of comparative example 1, it can thus be appreciated that the toughness of the made nano-porous gold of embodiment 1 is far above comparative example 1.
Embodiment 2
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 90 μm by thickness, width is 10mm, and it is stand-by that length is that the gold alloy foil of 20mm cleans up post-drying; Described gold alloy foil is Au-x bianry alloy foil or Au-x-y ternary alloy three-partalloy foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The preferred gold alloy foil of the present embodiment is Au-Cu bianry alloy foil (nominal composition is Au-75Cu);
Step 2, neopelex and corrosive inorganic acids to be mixed in mass ratio at 0.5: 100, obtain Korrosionsmedium solution; The nitric acid of described corrosive inorganic acids to be concentration be 3mol/L;
Step 3, by step one dry after gold alloy foil put into the solution of Korrosionsmedium described in step 2, take gold alloy foil as anode, taking platinized platinum as negative electrode, is 60 DEG C in temperature, and voltage is that under the condition of 1.2V, electrochemical corrosion 15h carries out de-alloy treatment;
Step 4, the gold alloy foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 9h in the drying box of 30 DEG C in temperature, obtain the nano-porous gold with ultra-fine aperture.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Cu atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Cu doping.The surface topography SEM photo of nano-porous gold prepared by the present embodiment for shown in Fig. 7, BHJ aperture size distribution curve as shown in Figure 8, N
2adsorption-desorption isothermal as shown in Figure 9.Composition graphs 7, Fig. 8 and Fig. 9 can find out, the aperture of nano-porous gold prepared by the present embodiment is little (being mainly distributed within the scope of 2nm ~ 8nm), and specific area is large, and (specific area is 80m
2/ g).
Comparative example 2
This comparative example is only with the difference of embodiment 2: do not add neopelex in the solution of Korrosionsmedium shown in step 2.
The surface topography SEM photo of nano-porous gold prepared by this comparative example for shown in Figure 10, BHJ aperture size distribution curve as shown in figure 11, N
2adsorption-desorption isothermal as shown in figure 12.Can find out in conjunction with Figure 10, Figure 11 and Figure 12, the aperture large (being mainly distributed within the scope of 20nm ~ 80nm) of nano-porous gold prepared by the present embodiment, specific area is little, and (specific area is 9m
2/ g).
In addition, by carrying out comparative analysis discovery in kind to embodiment 2 and the made nano-porous gold of comparative example 2, the surperficial zero defect of the made nano-porous gold of embodiment 2, obviously there is intergranular corrosion cracks in the surface of the made nano-porous gold of comparative example 2, it can thus be appreciated that the toughness of the made nano-porous gold of embodiment 2 is far above comparative example 2.
Embodiment 3
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 40 μm by thickness, width is 8mm, and it is stand-by that length is that the billon paillon foil of 20mm cleans up post-drying; Described billon paillon foil is Au-x bianry alloy paillon foil or Au-x-y ternary alloy three-partalloy paillon foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The preferred billon paillon foil of the present embodiment is Au-Al-Pt ternary alloy three-partalloy paillon foil (nominal composition is Au-65Cu-5Pt);
Step 2, neopelex and corrosive inorganic acids to be mixed in mass ratio at 0.05: 100, obtain Korrosionsmedium solution; The sulfuric acid of described corrosive inorganic acids to be concentration be 10mol/L;
Step 3, by step one dry after billon paillon foil put into the solution of Korrosionsmedium described in step 2, with billon paillon foil for anode, taking platinized platinum as negative electrode, is 60 DEG C in temperature, and voltage is that under the condition of 4V, electrochemical corrosion 0.5h carries out de-alloy treatment;
Step 4, the billon paillon foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 10h in the drying box of 20 DEG C in temperature, obtain the doped nano porous gold with high-specific surface area.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Al, Pt atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Al, Pt doping.Surface topography sem analysis, the distributional analysis of BHJ aperture size, N is carried out by the doped nano porous gold prepared the present embodiment
2adsorption-desorption is analyzed known, and the present embodiment products made thereby has nano-porous structure, and the aperture of made nano-porous gold is little (being mainly distributed within the scope of 3nm ~ 9nm), and specific area is large, and (specific area is 50m
2/ g).
Embodiment 4
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 10 μm by thickness, width is 10mm, and it is stand-by that length is that the billon paillon foil of 10mm cleans up post-drying; Described billon paillon foil is Au-x bianry alloy paillon foil or Au-x-y ternary alloy three-partalloy paillon foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The preferred billon paillon foil of the present embodiment is Au-Zn bianry alloy paillon foil (nominal composition is Au-65Zn);
Step 2, neopelex and corrosive inorganic acids to be mixed in mass ratio at 0.01: 100, obtain Korrosionsmedium solution; The sulfuric acid of described corrosive inorganic acids to be concentration be 10mol/L;
Step 3, by step one dry after billon paillon foil put into the solution of Korrosionsmedium described in step 2, with billon paillon foil for anode, taking platinized platinum as negative electrode, is 60 DEG C in temperature, and voltage is that under the condition of 0.1V, electrochemical corrosion 25h carries out de-alloy treatment;
Step 4, the billon paillon foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 7h in the drying box of 25 DEG C in temperature, obtain the doped nano porous gold with high-specific surface area.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Zn atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Zn doping.Surface topography sem analysis, the distributional analysis of BHJ aperture size, N is carried out by the doped nano porous gold prepared the present embodiment
2adsorption-desorption is analyzed known, and the present embodiment products made thereby has nano-porous structure, and the aperture of made nano-porous gold is little (being mainly distributed within the scope of 4nm ~ 9nm), and specific area is large, and (specific area is 100m
2/ g).
Embodiment 5
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 0.1 μm by thickness, width is 10mm, and it is stand-by that length is that the billon paillon foil of 30mm cleans up post-drying; Described billon paillon foil is Au-x bianry alloy paillon foil or Au-x-y ternary alloy three-partalloy paillon foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The preferred billon paillon foil of the present embodiment is Au-Ni-Pd ternary alloy three-partalloy paillon foil (nominal composition is Au-70Ni-4Pd);
Step 2, neopelex and corrosive inorganic acids to be mixed in mass ratio at 0.8: 100, obtain Korrosionsmedium solution; The perchloric acid of described corrosive inorganic acids to be concentration be 0.05mol/L;
Step 3, by step one dry after billon paillon foil put into the solution of Korrosionsmedium described in step 2, with billon paillon foil for anode, taking platinized platinum as negative electrode, is 40 DEG C in temperature, and voltage is that under the condition of 3V, electrochemical corrosion 10h carries out de-alloy treatment;
Step 4, the billon paillon foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 7h in the drying box of 30 DEG C in temperature, obtain the doped nano porous gold with high-specific surface area.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Ni, Pd atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Ni, Pd doping.Surface topography sem analysis, the distributional analysis of BHJ aperture size, N is carried out by the doped nano porous gold prepared the present embodiment
2adsorption-desorption is analyzed known, and the present embodiment products made thereby has nano-porous structure, and the aperture of made nano-porous gold is little (being mainly distributed within the scope of 3nm ~ 8nm), and specific area is large, and (specific area is 150m
2/ g).
Embodiment 6
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 50 μm by thickness, width is 10mm, and it is stand-by that length is that the billon paillon foil of 50mm cleans up post-drying; Described billon paillon foil is Au-x bianry alloy paillon foil or Au-x-y ternary alloy three-partalloy paillon foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The preferred billon paillon foil of the present embodiment is Au-Ag-Pt ternary alloy three-partalloy paillon foil (nominal composition is Au-70Ag-8Pt);
Step 2, lauryl sodium sulfate and corrosive inorganic acids to be mixed in mass ratio at 2: 100, obtain Korrosionsmedium solution; The perchloric acid of described corrosive inorganic acids to be concentration be 2mol/L;
Step 3, by step one dry after billon paillon foil put into the solution of Korrosionsmedium described in step 2, with billon paillon foil for anode, taking platinized platinum as negative electrode, is 60 DEG C in temperature, and voltage is that under the condition of 4V, electrochemical corrosion 0.5h carries out de-alloy treatment;
Step 4, the billon paillon foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 5h in the drying box of 60 DEG C in temperature, obtain the doped nano porous gold with high-specific surface area.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Ag, Pt atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Ag, Pt doping.Surface topography sem analysis, the distributional analysis of BHJ aperture size, N is carried out by the doped nano porous gold prepared the present embodiment
2adsorption-desorption is analyzed known, and the present embodiment products made thereby has nano-porous structure, and the aperture of made nano-porous gold is little (being mainly distributed within the scope of 1nm ~ 5nm), and specific area is large, and (specific area is 180m
2/ g).
Embodiment 7
The preparation method that the present embodiment has the doped nano porous gold of small-bore bigger serface comprises the following steps:
Step one, be 20 μm by thickness, width is 10mm, and it is stand-by that length is that the billon paillon foil of 40mm cleans up post-drying; Described billon paillon foil is Au-x bianry alloy paillon foil or Au-x-y ternary alloy three-partalloy paillon foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd; The preferred billon paillon foil of the present embodiment is Au-Al bianry alloy paillon foil (nominal composition is Au-85Al);
Step 2, neopelex and corrosive inorganic acids to be mixed in mass ratio at 0.8: 100, obtain Korrosionsmedium solution; The nitric acid of described corrosive inorganic acids to be concentration be 5mol/L;
Step 3, by step one dry after billon paillon foil put into the solution of Korrosionsmedium described in step 2, with billon paillon foil for anode, taking platinized platinum as negative electrode, is 50 DEG C in temperature, and voltage is that under the condition of 3V, electrochemical corrosion 0.5h carries out de-alloy treatment;
Step 4, the billon paillon foil in step 3 after de-alloy treatment boiled successively and boils, rinse and immersion treatment, the solvent boiling, rinse and adopt in immersion treatment process that boils is absolute ethyl alcohol, time of boiling of boiling is 30min, washing time is 2 ~ 3 times, soak time is 15h, then be dry 10h in the drying box of 20 DEG C in temperature, obtain the doped nano porous gold with high-specific surface area.
Carry out XPS analysis by the doped nano porous gold prepared the present embodiment known, also containing Al atom in the made nano-porous gold of the present embodiment, institute's prepared material is the nano-porous gold of Al doping.Surface topography sem analysis, the distributional analysis of BHJ aperture size, N is carried out by the doped nano porous gold prepared the present embodiment
2adsorption-desorption is analyzed known, and the present embodiment products made thereby has nano-porous structure, and the aperture of made nano-porous gold is little (being mainly distributed within the scope of 1nm ~ 4nm), and specific area is large, and (specific area is 200m
2/ g).
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (6)
1. have a preparation method for the doped nano porous gold of small-bore bigger serface, it is characterized in that, the method comprises the following steps:
Step one, that gold alloy foil is cleaned up post-drying is stand-by; Described gold alloy foil is Au-x bianry alloy foil or Au-x-y ternary alloy three-partalloy foil, and described x is Ag, Cu, Al, Ni or Zn, and described y is Pt or Pd;
Step 2, by lauryl sodium sulfate and corrosive inorganic acids in mass ratio (0.01 ~ 2.0): 100 mix, and obtain Korrosionsmedium solution; Or, by neopelex and corrosive inorganic acids in mass ratio (0.01 ~ 0.8): 100 mix, and obtain Korrosionsmedium solution;
Step 3, by step one dry after gold alloy foil put into the solution of Korrosionsmedium described in step 2, be 20 DEG C ~ 60 DEG C in temperature, voltage is that under the condition of 0.1V ~ 4V, electrochemical corrosion 0.5h ~ 50h carries out de-alloy treatment;
Step 4, employing absolute ethyl alcohol are that solvent boiling boiling successively through the gold alloy foil taken off after alloy treatment in step 3, rinsing and immersion treatment, obtain the doped nano porous gold with small-bore bigger serface after drying, the specific area of this nano-porous gold is 50m
2/ g ~ 200m
2/ g, aperture is not more than 10nm.
2. the preparation method with the doped nano porous gold of small-bore bigger serface according to claim 1, is characterized in that, the thickness of gold alloy foil described in step one is 0.1 μm ~ 100 μm.
3. the preparation method with the doped nano porous gold of small-bore bigger serface according to claim 1, it is characterized in that, corrosive inorganic acids described in step 2 is perchloric acid, nitric acid or sulfuric acid.
4. the preparation method with the doped nano porous gold of small-bore bigger serface according to claim 3, it is characterized in that, the concentration of perchloric acid described in step 2 is 0.05mol/L ~ 2mol/L, the concentration of described nitric acid is 0.1mol/L ~ 5mol/L, and the concentration of described sulfuric acid is 0.5mol/L ~ 10mol/L.
5. the preparation method with the doped nano porous gold of small-bore bigger serface according to claim 1, is characterized in that, described in step 3, the voltage of de-alloy treatment is 0.5V ~ 3V, and the time of described de-alloy treatment is 0.5h ~ 25h.
6. the preparation method with the doped nano porous gold of small-bore bigger serface according to claim 1, is characterized in that, temperature dry described in step 4 is 20 DEG C ~ 60 DEG C, and the time of described drying is 5h ~ 10h.
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| CN106920701A (en) * | 2017-04-26 | 2017-07-04 | 济南大学 | The preparation method of ultracapacitor nano manganese oxide electrode material |
| CN110635103A (en) * | 2019-08-29 | 2019-12-31 | 天津工业大学 | Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof |
| CN112342478A (en) * | 2020-11-06 | 2021-02-09 | 西北有色金属研究院 | Preparation method of nano-porous titanium alloy film |
| CN115896526A (en) * | 2022-11-25 | 2023-04-04 | 国网山东省电力公司电力科学研究院 | Sectional control dealloying method for regulating morphology of nano porous gold, nano porous gold and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106920701A (en) * | 2017-04-26 | 2017-07-04 | 济南大学 | The preparation method of ultracapacitor nano manganese oxide electrode material |
| CN106920701B (en) * | 2017-04-26 | 2019-01-22 | 济南大学 | The preparation method of supercapacitor nano manganese oxide electrode material |
| CN110635103A (en) * | 2019-08-29 | 2019-12-31 | 天津工业大学 | Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof |
| CN112342478A (en) * | 2020-11-06 | 2021-02-09 | 西北有色金属研究院 | Preparation method of nano-porous titanium alloy film |
| CN112342478B (en) * | 2020-11-06 | 2022-02-08 | 西北有色金属研究院 | Preparation method of nano-porous titanium alloy film |
| CN115896526A (en) * | 2022-11-25 | 2023-04-04 | 国网山东省电力公司电力科学研究院 | Sectional control dealloying method for regulating morphology of nano porous gold, nano porous gold and application |
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