CN116675443A - Method for directly depositing metal palladium by utilizing solar energy - Google Patents
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- CN116675443A CN116675443A CN202310781412.2A CN202310781412A CN116675443A CN 116675443 A CN116675443 A CN 116675443A CN 202310781412 A CN202310781412 A CN 202310781412A CN 116675443 A CN116675443 A CN 116675443A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000000151 deposition Methods 0.000 title claims abstract description 27
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 76
- 239000011787 zinc oxide Substances 0.000 description 38
- 239000011701 zinc Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3607—Coatings of the type glass/inorganic compound/metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3655—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing at least one conducting layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
- C03C2217/241—Doped oxides with halides
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method for depositing and recovering noble metal palladium on a cathode conductive substrate by utilizing a solar catalytic photo-anode, which adopts the following technical scheme: dividing a cylindrical electrolyzer into an anode chamber and a cathode chamber, adding Na into the anode chamber 2 SO 4 Solution, pd (NO) is added into the cathode chamber 3 ) 2 Solution, the solution and the solution are isolated by a proton exchange membrane; putting a ZnO photoelectrode as an anode into an anode chamber, putting a conductive substrate as a cathode into a cathode chamber, and connecting the anode with the cathode by using an external lead; the ZnO photoelectrode is directly irradiated with sunlight for a period of time. In the method of the invention, elemental metal palladium is deposited on the conductive substrate after a period of time by irradiating the photoelectrode with light. The method for depositing and recovering the noble metal palladium by using solar irradiation without applying voltage can provide a new thought for solar energy storage conversion and traditional metal recovery.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a method for directly depositing metallic palladium by utilizing solar energy.
Background
With excessive consumption of resources, environmental problems are increasingly prominent, with precious metals as a precious non-renewable resource, with less reserves. At present, the methods for recovering rare and noble metals in China comprise an electrolytic method, a chemical reduction method, a fire gun soot blowing method and the like, the procedures of the methods are complex, the recovery cost is high, and a virtuous circle system for recycling is not established. The rare and noble metals in the waste are effectively recycled, so that not only can the consumption of metal resources in China be reduced, but also the harm to the environment can be reduced, and the method has remarkable economic and environmental benefits. Solar energy is clean, efficient and sustainable green energy, is inexhaustible, and is a novel energy source capable of relieving energy shortage and protecting environment. Meanwhile, semiconductor materials with photocatalysis function are common in photoelectric conversion. Zinc oxide has the advantages of low cost, easy availability, good controllability, high stability and the like, and can exert better catalytic performance under acidic or alkaline conditions, so that the zinc oxide has wider application in photocatalysis. When the ZnO photo-anode is excited by photons with energy larger than or equal to the band gap, electrons in the valence band are excited to the conduction band to form photo-generated holes and photo-generated electrons, the photo-generated holes participate in OER of the anode, and the photo-generated electrons reach the cathode through an external circuit to perform reduction reaction of metal ions. The method for collecting the noble metal palladium by the cathode deposition without applying external voltage through illumination of the anode further widens the utilization of renewable energy sources, has the advantages of simple flow and environmental friendliness while reducing the recovery cost through a photo-induced deposition method, and has a large-scale industrial application prospect in the future.
Disclosure of Invention
In order to solve the problems, the invention provides a method for realizing pollution-free recovery of noble metal palladium by utilizing a photo-anode to receive solar energy and simultaneously depositing noble metal palladium on a cathode. The solar energy recycling system is a novel solar energy utilization form, and provides a novel idea for solar energy storage conversion and traditional metal recovery.
The invention adopts the technical scheme that:
a method for directly depositing metallic palladium by solar energy, comprising the following steps:
1) In column type electrolytic tanksNa is added into the anode chamber of (a) 2 SO 4 Adding Pd (NO) into the cathode chamber of column type electrolyzer 3 ) 2 A proton membrane is arranged in a connecting pipeline between the anode chamber and the cathode chamber;
2) Placing a ZnO photoelectrode as an anode in an anode chamber of a column-type electrolytic cell, placing a conductive substrate as a cathode in a cathode chamber of the column-type electrolytic cell, and connecting the ZnO photoelectrode with the conductive substrate by using a wire;
3) The ZnO photoelectrode is directly irradiated by sunlight for 20-120 minutes, and elemental metal palladium is deposited on the conductive substrate of the cathode.
Further, in the above method for directly depositing metallic palladium by solar energy, in step 1), the Na 2 SO 4 The concentration of the solution is 0.1-2mol/L.
Further, in the above method for directly depositing metallic palladium by solar energy, in step 1), the Pd (NO 3 ) 2 The mass concentration of the solution is 0.005-5%.
Further, in the method for directly depositing metallic palladium by solar energy, in the step 2), the conductive substrate is a pure FTO conductive glass substrate.
Further, in the method for directly depositing metallic palladium by using solar energy, in the step 3), the direct irradiation intensity of sunlight is 50-200 mW.cm -2 。
Further, in the above method for directly depositing palladium metal by solar energy, in the step 2), the preparation method of the ZnO photoelectrode includes the following steps:
1) Zn (NO) 3 ) 2 ·2H 2 O ethanol solution is dripped on the conductive side of the FTO conductive glass, the conductive glass is put into a baking oven to be dried after dripping is finished, and the steps are repeated for three times; putting the obtained FTO conductive glass containing Zn element into a muffle furnace, annealing for 10-25min at 300-650 ℃ to form ZnO crystals, and cooling to room temperature;
2) Will contain Zn (NO) 3 ) 2 ·2H 2 Pouring the mixed solution of O and hexamethylenetetramine into a reaction kettle with the FTO conductive glass substrate obtained in the step 1)And (3) placing the reaction kettle in an oven, reacting for 3-6 hours at 90-120 ℃, cooling to room temperature, washing and drying to obtain the ZnO photoelectrode.
Further, in the above method for directly depositing metallic palladium using solar energy, in step 1), the Zn (NO 3 ) 2 ·2H 2 The concentration of the O ethanol solution was 0.005mol/L.
Further, in the above method for directly depositing metallic palladium using solar energy, in step 2), the Zn (NO 3 ) 2 ·2H 2 The molar concentration ratio of O and hexamethylenetetramine is 0.05-0.3:0.1-0.6.
Preferably, a method for directly depositing metallic palladium using solar energy as described above, the Zn (NO 3 ) 2 ·2H 2 The molar concentration ratio of O and hexamethylenetetramine is 1:2.
The beneficial effects of the invention are as follows:
1. the method utilizes clean pollution-free solar energy, avoids the use of extra electric energy, and reduces the environmental pressure caused by thermal power generation.
2. The method directly converts solar energy into chemical energy, and provides a new idea for the storage and conversion of solar energy.
3. The method of the invention deposits noble metal palladium on the cathode, which can alleviate the problem of energy shortage to a certain extent.
Drawings
Fig. 1 is an electron microscope scan of a ZnO film (a) on a ZnO photo-electrode and elemental palladium (b) deposited on a cathode conductive substrate.
Fig. 2 is an XRD pattern of FTO conductive glass substrate and elemental palladium deposited.
Fig. 3 is an XRD pattern of a ZnO thin film on a ZnO photo-electrode.
FIG. 4 is an ultraviolet-visible diffuse reflectance spectrum of a ZnO film on a ZnO photo electrode.
FIG. 5 is a graph of I-t characteristics measured when a ZnO photoelectrode is used to deposit metallic palladium in simulated sunlight.
Fig. 6 is a graph of a comparison of cathode conductive substrates before and after photochemical cell performance testing.
Fig. 7 is a schematic structural diagram of a photochemical cell, wherein 1: column type electrolyzer, 1-1: anode chamber, 1-2: cathode chamber, 2: proton membrane, 3: znO photoelectrode, 4: pure FTO conductive glass substrate, 5: and (5) conducting wires.
Fig. 8 is a schematic diagram of a photochemical cell.
Detailed Description
Example 1 method for direct deposition of metallic palladium Using solar energy
The method (one) is as follows
1. Preparation of ZnO photoelectrodes:
1) 0.005mol/L Zn (NO) 3 ) 2 ·2H 2 O ethanol solution is dripped on the conductive side of the FTO conductive glass, the conductive glass is put into a baking oven after dripping, the temperature is 60 ℃ until baking is carried out, and the steps are repeated for three times; putting the obtained FTO conductive glass containing Zn element into a muffle furnace, annealing for 15min at 450 ℃ to form ZnO crystals, and cooling to room temperature;
2) Will contain 0.1mol/L Zn (NO) 3 ) 2 ·2H 2 Pouring the mixed solution of O and 0.2mol/L Hexamethylenetetramine (HMT) into a reaction kettle provided with the FTO conductive glass substrate obtained in the step 1), placing the reaction kettle into an oven, reacting for 4 hours at 95 ℃, cooling to room temperature, washing, and drying to obtain the ZnO photoelectrode with the ZnO film coated on the surface.
2. Preparation of photochemical cell:
the structure of the photochemical cell is shown in fig. 7, and the physical diagram is shown in fig. 8.
1) 50mL of Na having a concentration of 0.5mol/L is added to the anode chamber (1-1) of the column-type electrolytic cell (1) 2 SO 4 A solution; 50mL of Pd (NO) having a mass concentration of 0.01% was added to the cathode chamber (1-2) of the column-type electrolytic cell (1) 3 ) 2 A solution; a proton membrane (2) is arranged in a connecting pipeline between the anode chamber (1-1) and the cathode chamber (1-2);
2) Placing a ZnO photoelectrode (3) as an anode in an anode chamber (1-1) of a column-type electrolytic cell, placing a pure FTO conductive glass substrate (4) as a cathode in a cathode chamber (1-2) of the column-type electrolytic cell, and connecting the ZnO photoelectrode with the pure FTO conductive glass substrate (4) by using a lead (5);
3) The light intensity was 120mW cm -2 The ZnO photoelectrode is irradiated by the simulated solar light for 60 minutes, and simple substance metal palladium is deposited on the pure FTO conductive glass substrate (4) of the cathode.
(II) Performance detection
1) Scanning by electron microscope
The prepared ZnO photoelectrode and the elementary palladium deposited on the cathode conductive substrate are scanned by an electron microscope respectively, and the morphology of the ZnO film and the elementary palladium on the ZnO photoelectrode is characterized, and the result is shown in figure 1. As can be seen from fig. 1a, the prepared ZnO photoelectrode, it can be seen that the ZnO nanoarray is formed of nanorods perpendicular to the FTO substrate, the surface of which has a regular hexagonal edge structure. As can be seen in fig. 1b, the elemental palladium deposited is in particulate form and is closely disposed on the FTO substrate.
2) XRD testing
FTO conductive glass substrates and deposits were characterized and the results are shown in fig. 2. FTO conductive glass substrates were characterized as having six diffraction peaks at 2θ=26.6 °, 33.8 °, 37.8 °, 51.8 °, 61.7 °, 65.7 °, corresponding to (110), (101), (200), (211), (310), (301) diffraction planes of tin dioxide (JCPDS-No. 46-1088), respectively. The deposited material was characterized as having 3 diffraction peaks at 2θ=40.1°, 46.7 ° and 68.1 °, corresponding to (111), (200) and (220) diffraction planes of palladium (JCPDS-No. 05-0681), respectively.
The ZnO photoelectrode was characterized and the result is shown in FIG. 3. The ZnO photoelectrode was characterized as having 8 diffraction peaks at 2θ=31.8 °, 34.4 °, 36.3 °, 47.5 °, 56.6 °, 62.9 °, 68.0 °, 69.1 °, corresponding to (100), (002), (101), (102), (110), (103), (112), (201) diffraction planes of zinc oxide (JCPDS-No. 36-1451), respectively.
3) Ultraviolet-visible diffuse reflection spectrum detection
The zinc oxide film was subjected to an ultraviolet-visible diffuse reflection test, and the result is shown in fig. 4.
As can be seen from FIG. 4, the absorption edge of zinc oxide is 420nm, and the light absorption is mainly concentrated in the ultraviolet region.
4) Photochemical cell performance test
The zinc oxide film was tested and the results are shown in fig. 5 and 6. FIG. 5 is a graph showing the I-t characteristic measured when a ZnO photoelectrode is used for depositing metallic palladium under simulated sunlight. As can be seen from FIG. 5, when the ZnO film is irradiated with the simulated solar light, the current density of the ZnO photoelectrode is stabilized at 0.13-0.15mA/cm 2 Between them. Fig. 6 is a front-to-back control image on a cathode conductive substrate under conditions simulating irradiation of ZnO photoelectrodes for 60 minutes. As can be seen from fig. 6, after 60 minutes, elemental palladium is evolved on the conductive substrate of the cathode.
Claims (9)
1. A method for directly depositing metallic palladium by solar energy, which is characterized by comprising the following steps:
1) Na is added into the anode chamber of the column type electrolytic tank 2 SO 4 Adding Pd (NO) into the cathode chamber of column type electrolyzer 3 ) 2 A proton membrane is arranged in a connecting pipeline between the anode chamber and the cathode chamber;
2) Placing a ZnO photoelectrode as an anode in an anode chamber of a column-type electrolytic cell, placing a conductive substrate as a cathode in a cathode chamber of the column-type electrolytic cell, and connecting the ZnO photoelectrode with the conductive substrate by using a wire;
3) The ZnO photoelectrode is directly irradiated by sunlight for 20-120 minutes, and elemental metal palladium is deposited on the conductive substrate of the cathode.
2. The method for directly depositing metallic palladium by solar energy according to claim 1, wherein in step 1), said Na 2 SO 4 The concentration of the solution is 0.1-2mol/L.
3. The method for directly depositing metallic palladium by solar energy according to claim 1, wherein in step 1), said Pd (NO 3 ) 2 The mass concentration of the solution is 0.005-5%.
4. The method of claim 1, wherein in step 2), the conductive substrate is a pure FTO conductive glass substrate.
5. The method for directly depositing metallic palladium by solar energy according to claim 1, wherein in step 3), said direct irradiation intensity of solar light is 50-200 mW.cm -2 。
6. The method for directly depositing metal palladium by solar energy according to claim 1, wherein in the step 2), the preparation method of the ZnO photoelectrode comprises the following steps:
1) Zn (NO) 3 ) 2 ·2H 2 O ethanol solution is dripped on the conductive side of the FTO conductive glass, the conductive glass is put into a baking oven to be dried after dripping is finished, and the steps are repeated for three times; putting the obtained FTO conductive glass containing Zn element into a muffle furnace, annealing for 10-25min at 300-650 ℃ to form ZnO crystals, and cooling to room temperature;
2) Will contain Zn (NO) 3 ) 2 ·2H 2 Pouring the mixed solution of O and hexamethylenetetramine into a reaction kettle provided with the FTO conductive glass substrate obtained in the step 1), placing the reaction kettle into an oven, reacting for 3-6 hours at 90-120 ℃, cooling to room temperature, washing and drying to obtain the ZnO photoelectrode.
7. The method for directly depositing metallic palladium by solar energy according to claim 6 wherein in step 1), said Zn (NO 3 ) 2 ·2H 2 The concentration of the O ethanol solution was 0.005mol/L.
8. The method for directly depositing metallic palladium by solar energy according to claim 6 wherein in step 2), said Zn (NO 3 ) 2 ·2H 2 The molar concentration ratio of O and hexamethylenetetramine is 0.05-0.3:0.1-0.6.
9. The method for directly depositing metallic palladium by solar energy according to claim 8, wherein said Zn (NO 3 ) 2 ·2H 2 The molar concentration ratio of O and hexamethylenetetramine is 1:2.
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