CN112547094A - Preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres - Google Patents
Preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres Download PDFInfo
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 67
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002077 nanosphere Substances 0.000 title claims abstract description 41
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical class [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 24
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 13
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
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- 238000005119 centrifugation Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
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- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910017816 Cu—Co Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 108010048233 Procalcitonin Proteins 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- CWCXERYKLSEGEZ-KDKHKZEGSA-N procalcitonin Chemical compound C([C@@H](C(=O)N1CCC[C@H]1C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H]([C@@H](C)CC)C(=O)NCC(=O)N[C@@H](C(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1[C@@H](CCC1)C(=O)NCC(O)=O)[C@@H](C)O)NC(=O)[C@@H](NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](NC(=O)[C@H](CC=1C=CC(O)=CC=1)NC(=O)[C@@H](NC(=O)CNC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCSC)NC(=O)[C@H]1NC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CO)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(N)=O)NC(=O)CNC(=O)[C@@H](N)CSSC1)[C@@H](C)O)[C@@H](C)O)[C@@H](C)O)C1=CC=CC=C1 CWCXERYKLSEGEZ-KDKHKZEGSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/33—
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- B01J35/40—
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- B01J35/51—
-
- 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
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres, belonging to the technical field of nano material preparation. In the process, a solvent thermal method is utilized, glycol is used as a solvent, and a copper-cobalt double-doped spherical cerium dioxide nanosphere is obtained through a high-temperature high-pressure reaction; modifying the palladium element in the sodium chloropalladate in situ to the surface of the copper-cobalt double-doped cerium dioxide nanospheres by a chemical reduction method to obtain the palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres. The palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres are regular in morphology and uniform in size, have good dispersibility in an organic solvent, and have a better microstructure, so that the catalytic activity of the cerium dioxide is improved, the copper-cobalt doped cerium dioxide nanospheres have important significance in the construction of an electrochemical biosensor, and the copper-cobalt doped cerium dioxide nanospheres have great potential in improving the sensitivity of the electrochemical biosensor.
Description
Technical Field
The invention relates to a nano material which takes spherical cerium dioxide nano particles as a template, dopes two elements of copper and cobalt on the surface of the spherical cerium dioxide and modifies palladium element in situ, belongs to the technical field of nano material preparation, and particularly relates to a preparation method of copper and cobalt doped cerium dioxide nanospheres modified by palladium in situ.
Background
Among metal oxides, ceria has attracted considerable attention due to its excellent physicochemical properties, including its high optical properties, mechanical strength, oxygen ion conductivity, and high thermal stability. The ceria is in a fluorite-like cubic structure, each tetravalent cerium ion being surrounded by eight divalent oxyanions in a face-centered cubic (fcc) arrangement, and each divalent oxyanion being tetrahedrally surrounded by four tetravalent cerium ions. Internal oxygen vacancy defects can rapidly form and annihilate the ceria lattice, facilitating the mediation of lattice expansion and strain, and thus contribute significantly to a stable grain boundary structure. Thus, ceria has been successfully applied to various applications such as energy and magnetic data storage, photocatalytic and nitrophenol sensors, ultraviolet blockers, solar fuel synthesis, water oxidation, oxygen transfer, fuel cells, metal gates, oxide semiconductor devices, promoters in three-way catalysts, and auto-exhaust to eliminate pollution from vehicles, and the like. Such as Hyunwoo Ha, Sinmyung Yoon, Kwangjin An, and Hyun You Kim. ACS catalysis, 2018, 8 (12), pp 11491-; the copper-manganese double-doped spherical cerium dioxide material for detecting procalcitonin is successfully synthesized by ZHENHAN Yang, Shirong Ren, Ying Zhuo, Ruo Yuan, YaQin Chai, Analytical Chemistry, 2017, 89, 13349 and 13356. However, due to the structural limitation of cerium dioxide, the requirement of constructing a high-sensitivity and high-selectivity electrochemical biosensor for the signaling probe cannot be completely met.
Disclosure of Invention
The invention aims to prepare the copper-cobalt doped cerium dioxide nanosphere modified in situ by palladium. Specifically, by utilizing a solvothermal method and a chemical reduction method, two elements, namely copper and cobalt, are doped into spherical cerium dioxide by the solvothermal method, then a palladium element is doped on the surface of the copper and cobalt double-doped spherical cerium dioxide in situ by the chemical reduction method, the framework structure of the spherical cerium dioxide is maintained, and finally the palladium in situ modified copper and cobalt doped cerium dioxide nanosphere with the average particle size of about 200 nm is obtained. The method has the advantages of cheap and easily-obtained reagents and equipment, simple material preparation method and mild reaction conditions, and is a green and environment-friendly nano material preparation method.
The technical scheme of the invention is as follows:
a palladium in-situ modified copper-cobalt doped cerium dioxide nanosphere takes spherical cerium dioxide nanoparticles as a template, copper and cobalt elements are doped on the surface of the spherical cerium dioxide nanoparticles through a solvothermal method, and palladium elements are doped through a further chemical reduction method to jointly form a copper-cobalt-palladium triple-doped spherical cerium dioxide structure. The cerium dioxide nano particles are spherical, have a large specific surface area, and have a large number of oxygen cavity structures on the surface, so that a carrier environment is provided for doping copper, cobalt and palladium elements; the copper-cobalt-palladium element has good dispersibility and size uniformity on the surface of spherical cerium dioxide, and the size of the copper-cobalt-palladium element is about 200 nm. The three elements of copper, cobalt and palladium doped on the surface of the spherical cerium dioxide can improve the catalytic activity of the material, and simultaneously, the good chemical properties of the cerium dioxide material are kept, so that the palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres are formed.
A preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres is characterized by comprising the following steps:
(1) preparation of copper-cobalt double-doped cerium dioxide nanospheres: weighing 500-600 mg of cerium nitrate and 200-300 mg of polyvinylpyrrolidone, dissolving in 10-15 mL of ethylene glycol solution, stirring at room temperature for 30 min at constant speed, respectively weighing 100-200 mg of copper chloride and 200-300 mg of cobalt chloride, dissolving in 5-10 mL of ultrapure water, stirring to fully dissolve, respectively transferring 0.5-1.0 mL of copper chloride and cobalt chloride solutions into the ethylene glycol solution of cerium nitrate by using a liquid transfer gun, continuing to stir, transferring the reaction solution into a high-pressure reaction kettle with a dried capacity of 20 mL of polytetrafluoroethylene lining after uniformly stirring the mixed solution, placing the reaction kettle into a drying box for high-temperature reaction at 160 ℃ for 8 h to ensure complete reaction, naturally cooling to room temperature, centrifugally separating the solution at the rotation speed of 10000 r/min for 10 min, respectively washing the finally obtained product with ultrapure water and absolute ethyl alcohol for three times, rotating speed is 10000 r/min, centrifuging time is 5 min, transferring the obtained product into a porcelain ark, putting the porcelain ark into an oven, drying at 60 ℃ overnight, putting the dried powder into a muffle furnace, calcining at 300 ℃ for 1 h at a heating rate of 1 ℃/min, and obtaining white powder, namely the copper-cobalt double-doped cerium dioxide nanospheres;
(2) preparing copper-cobalt doped cerium dioxide nanospheres modified by palladium in situ: firstly, 50-100 mg of prepared copper-cobalt double-doped cerium dioxide nanosphere and 0.5-1.0 mg of sodium chloropalladate are dissolved in 10 mL of ultrapure water, and are stirred for 30 min in a dark light resistant container, then 0.5-1.0 mL of 17.6 mg/mL ascorbic acid solution is dripped into the solution and reacts for 14 h at room temperature, then a product is collected by centrifugation, the rotation speed is 10000 r/min, the centrifugation time is 10 min, the solution is washed by ultrapure water for several times, the rotation speed is 10000 r/min, the centrifugation time is 5 min, and finally the obtained product is dried in a vacuum oven at 40 ℃ overnight to obtain the palladium in-situ modified copper-cobalt doped cerium dioxide nanosphere, and the scanning electron microscope, the transmission electron microscope and the X-ray energy spectrum characterization of the palladium in-situ modified copper-cobalt doped cerium dioxide nanosphere are respectively shown as the attached figure 1, As shown in fig. 2 and 3.
The invention has the beneficial effects that:
(1) the preparation method of the palladium in-situ modified copper-cobalt doped cerium dioxide nanosphere is simple to operate, has mild reaction conditions, and is a green and environment-friendly nano material synthesis method.
(2) The doping of copper, cobalt and palladium elements changes the surface/interface structure of cerium dioxide crystal lattice, can obviously optimize the morphology of cerium dioxide and improve the electrocatalytic activity of the cerium dioxide.
(3) The doped cerium dioxide nano material has excellent biocompatibility and redox characteristics, so that the doped cerium dioxide nano material has more important significance in the construction of an electrochemical biosensor and has great potential for improving the sensitivity of the electrochemical biosensor.
Description of the drawings:
the invention is described in further detail below with reference to the following figures and detailed description:
FIG. 1 is a Scanning Electron Microscope (SEM) image of palladium in-situ modified Cu-Co doped ceria nanospheres;
FIG. 2 is a Transmission Electron Microscope (TEM) of palladium in-situ modified Cu-Co doped ceria nanospheres;
figure 3 is an X-ray energy spectrum (EDS) of palladium in-situ modified copper cobalt doped cerium dioxide nanospheres.
Detailed Description
A preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres is characterized by comprising the following steps:
(1) preparation of copper-cobalt double-doped cerium dioxide nanospheres: weighing 500 mg of cerium nitrate and 200 mg of polyvinylpyrrolidone, dissolving in 14 mL of ethylene glycol solution, uniformly stirring for 30 min at room temperature, respectively weighing 160 mg of copper chloride and 229.44 mg of cobalt chloride, dissolving in 8 mL of ultrapure water, stirring to fully dissolve the copper chloride and the cobalt chloride, respectively transferring 0.5 mL of copper chloride and cobalt chloride solution into the ethylene glycol solution of cerium nitrate by using a liquid transfer gun, continuously stirring, transferring the reaction solution into a high-pressure reaction kettle which is cleaned and dried and has a capacity of 20 mL of polytetrafluoroethylene lining after the mixed solution is uniformly stirred, placing the reaction solution into a drying box, reacting at a high temperature of 160 ℃ for 8 h to ensure complete reaction, naturally cooling to room temperature, centrifugally separating the solution at a rotation speed of 10000 r/min for 10 min, washing the finally obtained product with ultrapure water and absolute ethyl alcohol for three times respectively at a rotation speed of 10000 r/min, centrifuging for 5 min, transferring the obtained product into a porcelain ark, putting the porcelain ark into an oven, drying at 60 ℃ overnight, putting the dried powder into a muffle furnace, calcining at 300 ℃ for 1 h at the heating rate of 1 ℃/min to obtain white powder, namely the copper-cobalt double-doped cerium dioxide nanospheres;
(2) preparing copper-cobalt doped cerium dioxide nanospheres modified by palladium in situ: firstly, 50 mg of prepared copper-cobalt double-doped cerium dioxide nanosphere and 0.6 mg of sodium chloropalladate are dissolved in 10 mL of ultrapure water, and are stirred for 30 min in a dark light resistant container, then 0.2 mL of 17.6 mg/mL ascorbic acid solution is dripped into the solution and reacts for 14 h at room temperature, then a product is collected by centrifugation, the rotation speed is 10000 r/min, the centrifugation time is 10 min, the product is washed by ultrapure water for several times, the rotation speed is 10000 r/min, the centrifugation time is 5 min, and finally the obtained product is dried in a vacuum oven at 40 ℃ overnight, so that the palladium in-situ modified copper-cobalt doped cerium dioxide nanosphere can be obtained.
Claims (3)
1. A preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres is characterized by comprising the following steps:
(1) preparation of copper-cobalt double-doped cerium dioxide nanospheres: weighing 500 mg of cerium nitrate and 200 mg of polyvinylpyrrolidone, dissolving in 14 mL of ethylene glycol solution, uniformly stirring for 30 min at room temperature, respectively weighing 160 mg of copper chloride and 229.44 mg of cobalt chloride, dissolving in 8 mL of ultrapure water, stirring to fully dissolve the copper chloride and the cobalt chloride, respectively transferring 0.5 mL of copper chloride and cobalt chloride solution into the ethylene glycol solution of cerium nitrate by using a liquid transfer gun, continuously stirring, transferring the reaction solution into a high-pressure reaction kettle which is cleaned and dried and has a capacity of 20 mL of polytetrafluoroethylene lining after the mixed solution is uniformly stirred, placing the reaction solution into a drying box, reacting at a high temperature of 160 ℃ for 8 h to ensure complete reaction, naturally cooling to room temperature, centrifugally separating the solution at a rotation speed of 10000 r/min for 10 min, washing the finally obtained product with ultrapure water and absolute ethyl alcohol for three times respectively at a rotation speed of 10000 r/min, centrifuging for 5 min, transferring the obtained product into a porcelain ark, putting the porcelain ark into an oven, drying at 60 ℃ overnight, putting the dried powder into a muffle furnace, calcining at 300 ℃ for 1 h at the heating rate of 1 ℃/min to obtain white powder, namely the copper-cobalt double-doped cerium dioxide nanospheres;
(2) preparing copper-cobalt doped cerium dioxide nanospheres modified by palladium in situ: firstly, 50 mg of prepared copper-cobalt double-doped cerium dioxide nanosphere and 0.6 mg of sodium chloropalladate are dissolved in 10 mL of ultrapure water, and are stirred for 30 min in a dark light resistant container, then 0.2 mL of 17.6 mg/mL ascorbic acid solution is dripped into the solution and reacts for 14 h at room temperature, then a product is collected by centrifugation, the rotation speed is 10000 r/min, the centrifugation time is 10 min, the product is washed by ultrapure water for several times, the rotation speed is 10000 r/min, the centrifugation time is 5 min, and finally the obtained product is dried in a vacuum oven at 40 ℃ overnight, so that the palladium in-situ modified copper-cobalt doped cerium dioxide nanosphere can be obtained.
2. The method for preparing copper-cobalt doped cerium dioxide nanospheres with in-situ palladium modification function according to claim 1, wherein the copper-cobalt double-doped cerium dioxide nanospheres and sodium chloropalladate in step (2) are dissolved in ultrapure water and then stirred in a dark light resistant container.
3. The method for preparing palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres according to claim 1, wherein in step (1), two elements of copper and cobalt are doped into spherical cerium dioxide by a solvothermal method and a chemical reduction method, and in step (2), palladium element is doped into the surface of copper-cobalt double-doped spherical cerium dioxide in situ by a chemical reduction method, and the framework structure of the spherical cerium dioxide is maintained, so that the palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres are finally obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113262792A (en) * | 2021-05-12 | 2021-08-17 | 广州大学 | CoO-CeO2Photocatalyst and preparation method and application thereof |
| CN113509929A (en) * | 2021-04-14 | 2021-10-19 | 西安交通大学 | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof |
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| CN111732121A (en) * | 2020-07-13 | 2020-10-02 | 济南大学 | CuInS2@CuCo-CeO2Composite nano probe and preparation method thereof |
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| CN113509929A (en) * | 2021-04-14 | 2021-10-19 | 西安交通大学 | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof |
| CN113262792A (en) * | 2021-05-12 | 2021-08-17 | 广州大学 | CoO-CeO2Photocatalyst and preparation method and application thereof |
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