CN107774269A - Co deposited synthesis copper ceria catalyst, preparation method and application - Google Patents
Co deposited synthesis copper ceria catalyst, preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of Co deposited synthesis copper ceria catalyst preparation method, and mainly including first Hydrothermal Synthesiss carrier ceria, mantoquita is co-precipitated on ceria, and then the catalyst for adhering to mantoquita is calcined:Muffle furnace is calcined 300~800 degree, 3~7 hours, the wherein degrees second of programming rate 5~20, finally carries out reducing annealing:Hydrogen-argon-mixed (H2:Ar=3~19, V:V), anneal 400~600 degree, 3~6 hours, the wherein degrees second of programming rate 5~20.The copper ceria catalyst prepared using the above method and application are also disclosed.The copper ceria catalyst for obtaining doped forms is used in conjunction by low temperature liquid phase coprecipitation and high-temperature roasting annealing method by the present invention, effective stabilized copper ion, make copper ion that the positive monovalence with high catalytic activity be presented in catalytic reduction process, realize high catalytic reduction activity and selectivity.
Description
Technical field
The present invention relates to being co-precipitated mantoquita on ceric oxide nanorod, by high annealing obtain the copper of doped forms-
Ceria catalyst is as efficient oxygen reduction reaction catalyst, and in particular to a kind of Co deposited synthesis copper-ceria
Catalyst, preparation method and application.
Background technology
Currently, environmental problem caused by fossil fuel and energy crisis getting worse.The burning of one side fossil fuel
The discharge of great amount of carbon dioxide is caused, greenhouse effects trigger many climatic environment anomalies, threaten the existence of the mankind;The opposing party
Face, fossil fuel resource are also extremely urgent in exhaustion, the utilization of regenerative resource increasingly.By catalyzed conversion it is unnecessary two
Carbonoxide be hydrocarbon as a kind of resolving ideas turned waste into wealth, its key be solve seek it is a kind of high-efficient and honest
Catalyst.The metal of rich reserves on the copper earth a kind of, should be potential with very big.Copper catalyst it is verified that
Catalytic activity with catalysis reduction carbon dioxide, and produce carbon monoxide, formic acid, hydrocarbonization such as hydro carbons and alcohols with recall
The potential of compound.
Copper electro-catalysis reduction study of carbon dioxide is that Hori is carried out in the 1980s first, and he has found copper electrode dioxy
Hydrocarbon and alcohol can be produced by changing carbon catalysis reduction carbon dioxide, and caused by reduction process among carbon monoxide conduct
Product.Referring to Y.Hori, A.Murata, R.Takahashi.J.Chem.Soc., Faraday Trans.85,2309-2312
(1889).There are many reports as catalyst electroreduction carbon dioxide on copper in recent years, including reductive copper oxide, copper are received
Bianry alloy of rice pin, copper metal complex compound, copper-carbon material composite catalyst, foam copper, copper and other metals etc..
At present, the activated centre for being catalyzed reduction is widely regarded as univalent copper ion, and univalent copper ion is usually with Asia
Existing for stable state, so more highdensity catalytic active center how is obtained, and stabilized univalent copper ion is the key of research
And focus.Dan Ren et al. show catalysis well also by the film of one layer of cuprous oxide of electrochemical deposition on copper sheet
Former activity, referring to Ren D, Deng Y, Handoko A D.ACS Catal.2015,5,2814-2821 (2015).Kas R etc.
Have a significant impact it was found that cuprous oxide film thickness selects to produce ethene to catalysis, referring to Kas R, Kortlever R,
Milbrat A, et al.Physical Chemistry Chemical Physics Pccp, 16 (24):12194-2019
(2014).Metal-metallic oxide structure is applied to carbon dioxide electroreduction first and obtains high catalytic activity by Qing Li et al.
And selectivity, product are carbon monoxide, referring to Qing Li, Jiaju Fu, Wenlei Zhu, et
al.J.Am.Chem.Soc.139(12),4290–4293(2017).But metal-metal and metal oxide system can be effective
Stabilized univalent copper ion, catalyst application prospect has a high potential, but has height for producing ethene etc. under this system
There is presently no report for the catalyst of energy density and Application in Chemical Engineering prospect.
The content of the invention
The purpose of the present invention is low for existing existing copper catalyst activity, the problems such as selectivity of product difference, there is provided
Co deposited synthesis copper-ceria catalyst is applied to carbon dioxide electro-reduction reaction, molten by mantoquita by coprecipitation
Liquid concentration controls the doping of copper in cerium oxide nano-rod, by controlling sintering temperature and time to control cerium oxide nano-rod
The existence form of middle salt, the annealing of later stage reducibility gas are active to improve the reduction catalystses of copper.The invented technology is simple, green is clear
It is clean, ingenious in design, safely controllable, cost is cheap.
First technical scheme of the present invention:Co deposited synthesis copper-ceria catalyst preparation method, this method bag
Include following steps:
(1), Hydrothermal Synthesiss carrier ceria:
A, 0.5~1.0g cerous nitrates are weighed and is dissolved in ultra-pure water, configure sodium hydroxide solution
The cerous nitrate aqueous solution is added dropwise to the sodium hydroxide solution being stirred continuously B,;
C, immigration reactor, 100~200 DEG C, 12~24 hours reaction time;
D, reaction product, centrifugation are taken out, deionization is washed more than three times;
E, freeze drier freezes;
(2) mantoquita, is co-precipitated on ceria:
A, claim the above-mentioned reaction products of 0.3~1.0g to be dissolved in ultra-pure water, equably suspension is stirred by ultrasonic into;
The copper nitrate for weighing different content is dissolved in 10~30mL ultra-pure waters;
B, ceria suspension pH is adjusted to 8~11 with 0.5mol/L sodium carbonate liquors, and by 10~30mL copper nitrates
The aqueous solution is added dropwise, while sodium carbonate liquor is added dropwise, and adjusts pH=8~11;
C, after above-mentioned remaining copper nitrate solution is added completely into, 1~3h is persistently stirred;
D, move into centrifuge tube, centrifuge washing three times more than;
E, freeze drier freezes;
(3), the catalyst for adhering to mantoquita is calcined:300~800 degree of Muffle furnace roasting, 3~7 hours, wherein heating up
The degrees second of speed 5~20;
(4), reducing annealing:Hydrogen-argon-mixed (H2:Ar=3~19, V:V), anneal 400~600 degree, 3~6 is small
When, the wherein degrees second of programming rate 5~20.
Second technical scheme of the present invention is the copper-ceria catalyst prepared using the above method, and copper ion exists
The positive monovalence with high catalytic activity is presented in catalytic reduction process.
The 3rd technical scheme of the present invention is copper-ceria catalyst application, for carbon dioxide electro-reduction reaction.
Beneficial effects of the present invention:
Copper-the titanium dioxide for obtaining doped forms is used in conjunction by low temperature liquid phase coprecipitation and high-temperature roasting annealing method by the present invention
Cerium catalyst, effective stabilized copper ion, makes copper ion that the positive monovalence with high catalytic activity be presented in catalytic reduction process,
Realize high catalytic reduction activity and selectivity.
In addition, synthetic method craft of the present invention is simple and convenient to operate, is easily controllable, and it is not used poisonous anti-
Raw material is answered, is a kind of environment-friendly green synthesis process.
Brief description of the drawings
The XRD of copper-ceria catalyst of Fig. 1 different Cu dopings.
The Raman figures of copper-ceria catalyst of Fig. 2 different Cu dopings.
The low power and high power TEM photos of Fig. 3 copper-ceria catalyst:
A. low power;B. high power;
Fig. 4 copper-ceria catalyst X-ray photoelectron spectroscopic analysis figure:
A, copper X-ray photoelectron spectroscopic analysis figure b, Ce elements X-ray photoelectron spectroscopic analysis figure
C, oxygen element X-ray photoelectron spectroscopic analysis figure;
The faradic efficiency of Fig. 5 copper-ceria catalyst and copper foil contrast production ethene;
Fig. 6 copper-ceria catalyst stability test.
Embodiment
Below by accompanying drawing, the present invention is further illustrated.Embodiments of the invention are to preferably make this area
Technical staff more fully understand the present invention, not to the present invention make any limitation.
Embodiment 1
(1), Hydrothermal Synthesiss carrier ceria, such as copper-ceria catalyst building-up process figure:
A, 0.65g cerous nitrates are weighed and is dissolved in 10ml ultra-pure waters, 7.20g sodium hydroxides are dissolved in 20ml ultra-pure waters, are made into respectively
The solution of clear;
The cerous nitrate aqueous solution is added dropwise to the sodium hydroxide solution being stirred continuously with 30ml/h, mixing speed is B,
600r/min, stir 30 minutes;
C, immigration 45ml reactors, 100 DEG C, 24 hours reaction time;
D, reaction product ceria rod, centrifugation are taken out, deionization is washed three times;
E, freeze drier freezes.
(2) mantoquita, is co-precipitated on ceria:
A, claim the above-mentioned reaction product ceria rods of 0.5g to be dissolved in 25ml ultra-pure waters, equably suspension is stirred by ultrasonic into;
Weigh copper nitrate and be dissolved in 12.5ml ultra-pure waters;
B, with 0.5mol/L sodium carbonate liquors adjust ceria suspension pH to 9, and by 10ml copper nitrate aqueous solutions by
It is added dropwise to, while adds sodium carbonate liquor, adjusts pH=9;
C, after remaining copper nitrate solution is added completely into, 1h is persistently stirred;
D, centrifuge tube is moved into, centrifuge washing is three times;
E, freeze drier freezes.
(3), the catalyst for adhering to mantoquita is calcined:Muffle furnace is calcined 500 degree, and (10 degree of programming rate is every within 4 hours
Second).
(4), reducing annealing:Hydrogen-argon-mixed (H2:Ar=19, V:V), 500 degree of 3 hours (programming rates 10 of annealing
Degree per second).
Embodiment 2
(1), Hydrothermal Synthesiss carrier ceria, such as copper-ceria catalyst building-up process figure:
A, 0.5g cerous nitrates are weighed and is dissolved in 8ml ultra-pure waters, 7.20g sodium hydroxides are dissolved in 20ml ultra-pure waters, are made into respectively clear
Clear bright solution;
The cerous nitrate aqueous solution is added dropwise to the sodium hydroxide solution being stirred continuously with 60ml/h, mixing speed is B,
700r/min, stir 30 minutes;
C, immigration 45ml reactors, 200 DEG C, 12 hours reaction time;
D, reaction product ceria rod, centrifugation are taken out, deionization is washed 4 times;
E, freeze drier freezes.
(2) mantoquita, is co-precipitated on ceria:
A, claim the above-mentioned reaction product ceria rods of 0.3g to be dissolved in 20ml ultra-pure waters, equably suspension is stirred by ultrasonic into;
Weigh copper nitrate and be dissolved in 10ml ultra-pure waters;
B, with 0.5mol/L sodium carbonate liquors adjust ceria suspension pH to 8, and by 10ml copper nitrate aqueous solutions by
It is added dropwise to, while adds sodium carbonate liquor, adjusts pH=8;
C, after remaining copper nitrate solution is added completely into, 1h is persistently stirred;
D, centrifuge tube, centrifuge washing 5 times are moved into;
E, freeze drier freezes.
(3), the catalyst for adhering to mantoquita is calcined:Muffle furnace is calcined 300 degree, and (5 degree of programming rate is every within 7 hours
Second).
(4), reducing annealing:Hydrogen-argon-mixed (H2:Ar=3, V:V), 400 degree of 3 hours (5 degree of programming rates of annealing
It is per second).
Embodiment 3
(1), Hydrothermal Synthesiss carrier ceria:
A, 1.0g cerous nitrates are weighed and is dissolved in 20ml ultra-pure waters, 7.20g sodium hydroxides are dissolved in 20ml ultra-pure waters, are made into respectively clear
Clear bright solution;
The cerous nitrate aqueous solution is added dropwise to the sodium hydroxide solution being stirred continuously with 40ml/h, mixing speed is B,
600r/min, stir 30 minutes;
C, immigration 45ml reactors, 150 DEG C, 18 hours reaction time;
D, reaction product ceria rod, centrifugation are taken out, deionization is washed 4 times;
E, freeze drier freezes.
(2) mantoquita, is co-precipitated on ceria:
A, claim the above-mentioned reaction product ceria rods of 1.0g to be dissolved in 25ml ultra-pure waters, equably suspension is stirred by ultrasonic into;
Weigh copper nitrate and be dissolved in 30ml ultra-pure waters;
B, with 0.5mol/L sodium carbonate liquors adjust ceria suspension pH to 11, and by 30ml copper nitrate aqueous solutions by
It is added dropwise to, while adds sodium carbonate liquor, adjusts pH=11;
C, after above-mentioned remaining copper nitrate solution is added completely into, 3h is persistently stirred;
D, centrifuge tube is moved into, centrifuge washing is three times;
E, freeze drier freezes.
(3), the catalyst for adhering to mantoquita is calcined:Muffle furnace is calcined 800 degree, and (20 degree of programming rate is every within 3 hours
Second).
(4), reducing annealing:Hydrogen-argon-mixed (H2:Ar=15, V:V), 600 degree of 6 hours (programming rates 20 of annealing
Degree per second).
Embodiment 4
(1), Hydrothermal Synthesiss carrier ceria, building-up process are shown in Fig. 1:
A, 0.75g cerous nitrates are weighed and is dissolved in 10ml ultra-pure waters, 7.20g sodium hydroxides are dissolved in 20ml ultra-pure waters, are made into respectively
The solution of clear;
The cerous nitrate aqueous solution is added dropwise to the sodium hydroxide solution being stirred continuously with 50ml/h, mixing speed is B,
650r/min, stir 30 minutes;
C, immigration 45ml reactors, 100 DEG C, 24 hours reaction time;
D, reaction product ceria rod, centrifugation are taken out, deionization is washed three times;
E, freeze drier freezes.
(2) mantoquita, is co-precipitated on ceria:
A, claim the above-mentioned reaction product ceria rods of 0.5g to be dissolved in 25ml ultra-pure waters, equably suspension is stirred by ultrasonic into;
Weigh copper nitrate and be dissolved in 12.5ml ultra-pure waters;
B, added dropwise to 9, and by copper nitrate aqueous solution with 0.5mol/L sodium carbonate liquors regulation ceria suspension pH
Enter, while add sodium carbonate liquor, adjust pH=9;
C, after copper nitrate solution is added completely into, 1h is persistently stirred;
D, centrifuge tube is moved into, centrifuge washing is three times;
E, freeze drier freezes.
(3), the catalyst for adhering to mantoquita is calcined:Muffle furnace is calcined 500 degree, and (10 degree of programming rate is every within 4 hours
Second).
(4), reducing annealing:Hydrogen-argon-mixed (H2:Ar=19 volume fractions), 500 degree of 3 hours (heating speed of annealing
Spend 10 degree per seconds).
The copper nitrate amount of weighing in the step of above-described embodiment 1 to 4 (2) A is as shown in table 1 below:
The copper nitrate addition of the different Cu content copper of table 1-ceria catalyst
Embodiment | A=(Cu/CeO2) wt% | Cu/g | Cu(NO3)2·3H2O/g |
1 | 5 | 0.025 | 0.095 |
2 | 7 | 0.0375 | 0.133 |
3 | 10 | 0.075 | 0.190 |
4 | 15 | 0.100 | 0.285 |
Above-mentioned product is characterized, the XRD and Raman of copper-ceria catalyst of different Cu doping figure (Fig. 1,
Do not occur the peak of copper and copper oxides Fig. 2), illustrate that the incorporation cerium of copper does not separate out completely, offset and illustrated by peak position, formed
Copper atom substitutes the structure of cerium atom
Bar-shaped knot is presented in the low power and high power TEM photos of Fig. 3 copper-ceria catalyst, low power TEM photos catalyst
Structure, 50~150nm of length, 5~15nm of diameter.Show to exist obvious lattice fringe in high power TEM photo rods, present good
Crystallinity, and there is not particulate material, further proved the explanation of Fig. 1 and Fig. 2 on structure.
Fig. 4 copper-ceria catalyst X-ray photoelectron spectroscopic analysis figure:
A copper X-ray photoelectron spectroscopic analysis figures, illustrate that the valence state of copper is presented monovalence divalence and coexisted, b Ce elements X is penetrated
Photoelectron spectra analysis chart, because the incorporation of copper, Ce elements are presented is changed into tetravalence by trivalent entity.C oxygen element X ray light
Electron spectroscopy analysis figure, illustrate that copper doped causes a certain amount of Lacking oxygen.
The faradic efficiency of Fig. 5 copper-ceria catalyst and copper foil contrast production ethene, contrasts copper foil, in -1.1V current potentials
Under, ethene faradic yield is up to 47%.
Fig. 6 copper-ceria catalyst stability test.Under -1.1V current potentials, stability is up to six hours, ethene
Faradic efficiency maintains more than 40%.
It should be appreciated that embodiment and example discussed herein simply to illustrate that, to those skilled in the art
For, it can be improved or be converted, and all these modifications and variations should all belong to the protection of appended claims of the present invention
Scope.
Claims (3)
1. Co deposited synthesis copper-ceria catalyst preparation method, it is characterised in that this method comprises the following steps:
(1), Hydrothermal Synthesiss carrier ceria:
A, 0.5~1.0g cerous nitrates are weighed and is dissolved in ultra-pure water, configure sodium hydroxide solution
The cerous nitrate aqueous solution is added dropwise to the sodium hydroxide solution being stirred continuously B,;
C, immigration reactor, 100~200 DEG C, 12~24 hours reaction time;
D, reaction product, centrifugation are taken out, deionization is washed more than three times;
E, freeze drier freezes;
(2) mantoquita, is co-precipitated on ceria:
A, claim the above-mentioned reaction products of 0.3~1.0g to be dissolved in ultra-pure water, equably suspension is stirred by ultrasonic into;
The copper nitrate for weighing different content is dissolved in 10~30mL ultra-pure waters;
B, ceria suspension pH is adjusted to 8~11 with 0.5mol/L sodium carbonate liquors, and 10~30mL copper nitrates is water-soluble
Liquid is added dropwise, while sodium carbonate liquor is added dropwise, and adjusts pH=8~11;
C, after above-mentioned remaining copper nitrate solution is added completely into, 1~3h is persistently stirred;
D, move into centrifuge tube, centrifuge washing three times more than;
E, freeze drier freezes;
(3), the catalyst for adhering to mantoquita is calcined:Muffle furnace is calcined 300~800 degree, 3~7 hours, wherein programming rate
5~20 degrees seconds;
(4), reducing annealing:Hydrogen-argon-mixed (H2:Ar=3~19, V:V), anneal 400~600 degree, 3~6 hours, wherein
The degrees second of programming rate 5~20.
2. copper-the ceria catalyst prepared using the method described in claim 1, it is characterised in that copper ion is being catalyzed
The positive monovalence with high catalytic activity is presented in reduction process.
3. copper according to claim 2-ceria catalyst application, it is characterised in that for carbon dioxide electroreduction
Reaction.
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CN108514881A (en) * | 2018-04-12 | 2018-09-11 | 大连理工大学 | One kind being used for NH3Cu-Ce catalyst, preparation method and the application of the nano bar-shape structure of catalysis oxidation |
CN114345319A (en) * | 2022-01-11 | 2022-04-15 | 浙江大学衢州研究院 | Modified nano cerium dioxide catalyst, preparation method thereof and application thereof in dimethyl carbonate synthesis |
CN114395769A (en) * | 2022-01-29 | 2022-04-26 | 中国科学技术大学 | Supported copper catalyst and preparation method and application thereof |
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CN108448123A (en) * | 2018-03-23 | 2018-08-24 | 福州大学 | A kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction |
CN108448123B (en) * | 2018-03-23 | 2020-08-11 | 福州大学 | Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof |
CN108514881A (en) * | 2018-04-12 | 2018-09-11 | 大连理工大学 | One kind being used for NH3Cu-Ce catalyst, preparation method and the application of the nano bar-shape structure of catalysis oxidation |
CN108514881B (en) * | 2018-04-12 | 2020-11-03 | 大连理工大学 | For NH3Catalytic oxidation Cu-Ce catalyst with nanorod-shaped structure, preparation method and application |
CN114345319A (en) * | 2022-01-11 | 2022-04-15 | 浙江大学衢州研究院 | Modified nano cerium dioxide catalyst, preparation method thereof and application thereof in dimethyl carbonate synthesis |
CN114345319B (en) * | 2022-01-11 | 2024-05-17 | 浙江大学衢州研究院 | Modified nano cerium oxide catalyst, preparation method thereof and application thereof in dimethyl carbonate synthesis |
CN114395769A (en) * | 2022-01-29 | 2022-04-26 | 中国科学技术大学 | Supported copper catalyst and preparation method and application thereof |
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