CN112264067A - Non-noble metal transition metal-based carbon dioxide electroreduction catalyst and preparation method thereof - Google Patents
Non-noble metal transition metal-based carbon dioxide electroreduction catalyst and preparation method thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 18
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 11
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- XZWVIKHJBNXWAT-UHFFFAOYSA-N argon;azane Chemical compound N.[Ar] XZWVIKHJBNXWAT-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 5
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Abstract
The invention discloses a non-noble metal transition metal-based carbon dioxide electro-reduction catalyst and a preparation method thereof. The interface of the copper-nickel alloy and the anti-perovskite structure is the active site of the catalyst, the catalyst is at-0.856V vs RHE, the Faraday efficiency of CO can reach 94.4%, and the exchange current density can reach 5.322mA/cm2The stability at the potential can reach 10 hours, and the CO Faraday efficiency of more than 85 percent can still be maintained.
Description
Technical Field
The present invention belongs to the field of electrocatalytic reduction of CO2The technical field of materials, in particular to a non-noble metal transition metal-based carbon dioxide electroreduction catalyst and a preparation method thereof.
Background
With the large-scale development and use of traditional energy sources, the carbon dioxide content in the atmosphere is increased sharply, and a series of environmental and energy problems follow. Researchers have studied and developed new energy technologies, such as clean and renewable energy sources like wind energy, nuclear energy, solar energy, etc., in various fields in order to reduce carbon emissions in the air. There are two broad categories of ways of fixing carbon dioxide that are currently being investigated: one is to collect and store carbon dioxide in the earth crust, and the other is to chemically convert carbon dioxide molecules into reusable carbon-based energy substances. Obviously, the latter mode takes effect more quickly and has stronger sustainable development. The current methods for treating carbon dioxide by the latter method specifically include electrocatalytic reduction, photocatalytic reduction, thermal reduction, biological reduction, and the like. The electrocatalytic reduction method can convert carbon dioxide into chemical products for reuse, such as carbon monoxide, formic acid, methane and the like, under mild conditions, and simultaneously realize the storage of clean electric energy. In addition, the electrocatalytic reduction of carbon dioxide has the advantages of controllable reaction, simple equipment and the like. Carbon dioxide, however, is a thermodynamically extremely stable gas (C ═ O, 806kJ/mol), coupled with a vigorous hydrogen evolution competing reaction, making this conversion process still currently a significant challenge. Therefore, designing and developing a high-efficiency carbon dioxide electro-reduction catalyst is a task to be completed urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a non-noble metal transition metal-based carbon dioxide electroreduction catalyst.
The invention also aims to provide a preparation method of the non-noble metal transition metal-based carbon dioxide electro-reduction catalyst.
The technical scheme of the invention is as follows:
a non-noble metal transition metal-based carbon dioxide electro-reduction catalyst comprises a porous hollow nano carbon sphere, wherein a copper-nickel alloy is loaded on the porous hollow nano carbon sphere and uniformly dispersed, and the outer layer of the copper-nickel alloy is coated with an anti-perovskite material.
In a preferred embodiment of the invention, the molar ratio of copper to nickel is 1: 3 and the molar ratio of copper, nitrogen and nickel is 1: 3.
The preparation method of the non-noble metal transition metal-based carbon dioxide electro-reduction catalyst comprises the following steps:
(1) weighing nickel acetate tetrahydrate, copper acetate and polyether F127, adding acetone and diethylene glycol, slowly adding nitric acid, sealing with a sealing film, and uniformly mixing with an ultrasonic machine at the temperature of ultrasonic treatment not higher than 30 ℃;
(2) magnetically stirring the material obtained in the step (1);
(3) putting the material obtained in the step (2) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8-12h at the temperature of 110-;
(4) centrifugally washing the material obtained in the step (3), wherein the detergent is absolute ethyl alcohol;
(5) drying the centrifuged precipitate, and grinding the dried precipitate to obtain yellow-green uniform fine solid powder;
(6) putting the solid powder into a porcelain boat, ablating in a pure argon atmosphere, heating to 340-;
(7) heating the material obtained in the step (6) to 340-fold-material 360 ℃ at the speed of 4-6 ℃/min in an ammonia-argon mixed atmosphere, preserving heat for 1h, heating to 490-fold-material 510 ℃ at the speed of 0.5-1.5 ℃/min, preserving heat for 2.5-3.5h, finally heating to 690-fold-material 710 ℃ at the speed of 0.5-1.5 ℃/min, preserving heat for 2.5-3.5h, and cooling to room temperature to obtain the non-noble-metal transition metal-based carbon dioxide electro-reduction catalyst, wherein the volume ratio of argon to ammonia in the ammonia-argon mixed atmosphere is 80-90: 10-20.
In a preferred embodiment of the present invention, the hydrothermal reaction is carried out at a temperature of 120 ℃ for a time of 10 hours.
In a preferred embodiment of the present invention, the rotation speed of the centrifugal washing in the step (4) is 8000-10000 rpm.
In a preferred embodiment of the present invention, the temperature of the drying in the step (5) is 65 to 75 ℃.
In a preferred embodiment of the present invention, the step (6) is: putting the solid powder into a porcelain boat, ablating in a pure argon atmosphere, heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3h, finally heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and cooling to room temperature.
In a preferred embodiment of the present invention, the step (7) is: and (3) heating the material obtained in the step (6) to 350 ℃ at the speed of 5 ℃/min in an ammonia-argon mixed atmosphere, preserving heat for 1h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3h, heating to 700 ℃ at the speed of 1 ℃/min, preserving heat for 3h, and cooling to room temperature to obtain the non-noble metal transition metal-based carbon dioxide electro-reduction catalyst.
Further preferably, the volume ratio of argon gas to ammonia gas in the ammonia-argon mixed atmosphere is 90: 10.
In a preferred embodiment of the present invention, the ratio of nickel acetate tetrahydrate, copper acetate, polyether F127, acetone, diethylene glycol and nitric acid is 0.3733 g: 0.0998 g: 3 g: 60 mL: 2 mL: 0.2 mL.
The invention has the beneficial effects that:
1. the interface of the copper-nickel alloy and the anti-perovskite structure is the active site of the catalyst, the catalyst is at-0.856V vs RHE, the Faraday efficiency of CO can reach 94.4%, and the exchange current density can reach 5.322mA/cm2The stability at the potential can reach 10 hours, and the CO Faraday efficiency of more than 85 percent can still be maintained.
2. Compared with noble metal catalysts, carbon-based catalysts and non-noble metal catalysts, the catalyst has excellent selectivity and stability.
3. According to the preparation method, nickel acetate and copper acetate are used as metal sources, polyether F127 is used as a pore-forming agent, acetone is used as a solvent, the dissolution of acetate is promoted by nitric acid, the acetate is coordinated with a diethylene glycol organic ligand and then hydrothermally synthesized into a precursor, the precursor has a uniform spherical structure, a sphere has an ordered mesoporous structure after pure argon is ablated, and a copper-nickel alloy is loaded on the sphere; then the alloy is ablated by ammonia-argon mixed atmosphere or directly ablated by ammonia-argon mixed atmosphere without pure argon, wherein the alloy can be prepared by the inverse perovskite CuNNi3Coated copper nickel alloy CuNi3The small particles with the structure, the specific technological process is simple and convenient to operate, raw materials are easy to obtain, the method has important significance for converting synthesis gas and reducing carbon emission, and has wide application prospects in the fields of clean and green energy sustainable development and environment.
Drawings
FIG. 1 is a LSV spectrum of the catalyst prepared in example 2 of the present invention after stabilization by cyclic voltammetry CV scanning.
Figure 2 is a graph of the faradaic efficiency and current density of the catalyst prepared in example 2 of the present invention, as measured by a multi-step potential test.
FIG. 3 is an XRD spectrum of the feedstock obtained in example 1 of the present invention and the catalyst obtained in example 2.
FIG. 4 is a SEM photograph of the material obtained in step (4) of example 1 of the present invention.
FIG. 5 is a scanning electron micrograph of a catalyst prepared in example 2 of the present invention.
Figure 6 is a graph of the stability of the catalyst prepared in example 2 of the present invention for 10h (SCE ═ 1.5V).
FIG. 7 is a graph of BET results of tests on the catalyst prepared in example 2 of the present invention.
FIG. 8 is a graph showing the results of catalyst test xps made in example 2 of the present invention.
Figure 9 is a graph of the faradaic efficiency of the catalyst of comparative example 1 of the present invention as measured by a multi-step potential test.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Weighing 0.3733g of nickel acetate tetrahydrate, 0.0998g of copper acetate and 3g of polyether F127, adding 60mL of acetone and 2mL of diethylene glycol, slowly adding 0.2mL of nitric acid, sealing with a sealing film, and uniformly mixing by using an ultrasonic machine, wherein the temperature in ultrasonic treatment cannot exceed 30 ℃, and the ultrasonic treatment time is 30 min;
(2) magnetically stirring the material obtained in the step (1) at 600rpm for 20 min;
(3) putting the material obtained in the step (2) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 10 hours at 120 ℃;
(4) carrying out centrifugal washing on the material obtained in the step (3) at a rotating speed of 9000rpm, wherein a detergent is absolute ethyl alcohol, and repeatedly carrying out centrifugal washing for three times;
(5) drying the precipitate after the last centrifugation in a 70 ℃ oven, and grinding the dried precipitate to obtain yellow-green uniform fine solid powder;
(6) putting the solid powder into a porcelain boat, ablating in pure argon (100%) atmosphere, heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3h, heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and cooling to room temperature.
Example 2
(1) To (6) same as example 1;
(7) and (3) heating the material obtained in the step (6) to 350 ℃ at the speed of 5 ℃/min in an ammonia-argon mixed atmosphere (90% argon and 10% ammonia), preserving heat for 1h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3h, finally heating to 700 ℃ at the speed of 1 ℃/min, preserving heat for 3h, and cooling to room temperature to obtain the non-noble metal transition metal-based carbon dioxide electro-reduction catalyst.
Example 3
The non-noble metal transition metal based carbon dioxide electro-reduction catalyst prepared in example 2 was used for electrochemical performance testing: 5mg of the catalyst was dispersed in a solution containing 700. mu.L of isopropanol, 270. mu.L of deionized water, 30. mu.L of nafion,ultrasonically mixing the mixture evenly; then 100 mu L of catalyst slurry is dripped on the surface of a glassy carbon electrode which is polished and grinded cleanly (the area of the glassy carbon electrode is 1 cm)2) Naturally drying in a fume hood; carrying out electrochemical performance test by taking a saturated calomel electrode as a reference electrode and a graphite electrode as a counter electrode; potential reference Saturated Calomel Electrode (SCE): eRHE＝ESCE+0.242+0.059 × pH (0.1M saturated KHCO)3A solution). 0.1M KHCO saturated in carbon dioxide3In solution at 10mV s-1The catalyst was activated by 3 cycles of cyclic voltammetric CV scan (-0.8V-1.6V), and the LSV polarization curve was obtained after the cyclic voltammetric scan was stabilized, see fig. 1. Then, a multi-step potential test is carried out, one potential is set every 30min, samples are subjected to chromatographic analysis after reaction for 15min, and the test results are shown in a figure 2. All electrode potential data were IR compensated 85%.
A quantity of the material from example 1 and the catalyst from example 2 were weighed to test XRD, see FIG. 3.
A certain amount of the material prepared in the step (4) of example 1 was weighed and observed by a scanning electron microscope, referring to FIG. 4.
A certain amount of the catalyst prepared in example 2 was weighed out by a Scanning Electron Microscope (SEM) and shown in FIG. 5.
The stability of the catalyst prepared in example 2 was tested for 10h (SCE ═ 1.5V), see figure 6.
A certain amount of the catalyst prepared in example 2 was weighed to test BET, see FIG. 7.
An amount of the catalyst prepared in example 2 was weighed out and tested xps, see FIG. 8.
From the above, the non-noble metal transition metal-based carbon dioxide electroreduction catalyst prepared in example 2 includes a porous hollow carbon nanocapsule on which a uniformly dispersed copper-nickel alloy is supported, the outer layer of the copper-nickel alloy is coated with an anti-perovskite material, the molar ratio of copper to nickel is 1: 3, and the molar ratio of copper, nitrogen and nickel is 1: 3. Wherein the interface between the copper-nickel alloy and the anti-perovskite material is the active site of the catalyst, the catalyst is at-0.856V vs RHE, the Faraday efficiency of CO can reach 94.4%, and the exchange current density can reach 5.322mA/cm2The stability under the potential can reach 10 hours, the CO Faraday efficiency of more than 85 percent can be still maintained, and the catalyst has excellent selectivity and stability compared with noble metal catalysts, carbon-based catalysts and other non-noble metal catalysts
Comparative example 1
Synthesis of metal-free carbon and nitrogen compounds (excluding carbon source and carbon and nitrogen compounds in the material from CO)2Influence of electroreduction)
(1) 0.3733g of 3g of polyether F127 is weighed, 60mL of acetone and 2mL of diethylene glycol are added, 0.2mL of nitric acid is slowly added, a sealing film is used for sealing, an ultrasonic machine is used for uniformly mixing, the temperature in ultrasonic treatment can not exceed 30 ℃, and the ultrasonic treatment time is 30 min;
(2) to (7) A comparative catalyst was obtained in the same manner as in example 2.
Dispersing 5mg of the comparative catalyst in a nafion solution containing 700 mu L of isopropanol, 270 mu L of deionized water and 30 mu L of water, and uniformly mixing the solution by ultrasonic waves; then dropping 100 mu L of catalyst slurry on the surface of the polished and grinded glassy carbon electrode, and placing the glassy carbon electrode in a fume hood for natural air drying; carrying out electrochemical performance test by taking a saturated calomel electrode as a reference electrode and a graphite electrode as a counter electrode; potential reference Saturated Calomel Electrode (SCE): eRHE＝ESCE+0.242+0.059 × pH (0.1M saturated KHCO)3A solution). At 10mV s-1At a scanning rate of 0.1M KHCO saturated with carbon dioxide3And (3) performing cyclic voltammetry CV scanning (minus 0.8V-1.5V) for 3 circles in the solution, activating the comparative catalyst, and obtaining an LSV polarization curve after the cyclic voltammetry scanning is stable. Then, a multi-step potential test is carried out, one potential is set every 30min, and a sample is subjected to chromatographic analysis after reacting for 15min, and the test result is shown in a figure 9.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A non-noble metal transition metal-based carbon dioxide electro-reduction catalyst is characterized in that: comprises a porous hollow nano carbon ball, wherein copper-nickel alloy is loaded on the porous hollow nano carbon ball and uniformly dispersed, and the outer layer of the copper-nickel alloy is coated with an anti-perovskite material.
2. A non-noble metal transition metal based carbon dioxide electroreduction catalyst as claimed in claim 1 wherein: the molar ratio of copper to nickel is 1: 3, and the molar ratio of copper to nitrogen to nickel is 1: 3.
3. The process for preparing a non-noble metal transition metal-based carbon dioxide electroreduction catalyst as claimed in claim 1 or 2, wherein: the method comprises the following steps:
(1) weighing nickel acetate tetrahydrate, copper acetate and polyether F127, adding acetone and diethylene glycol, slowly adding nitric acid, sealing with a sealing film, and uniformly mixing with an ultrasonic machine at the temperature of ultrasonic treatment not higher than 30 ℃;
(2) magnetically stirring the material obtained in the step (1);
(3) putting the material obtained in the step (2) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8-12h at the temperature of 110-;
(4) centrifugally washing the material obtained in the step (3), wherein the detergent is absolute ethyl alcohol;
(5) drying the centrifuged precipitate, and grinding the dried precipitate to obtain yellow-green uniform fine solid powder;
(6) putting the solid powder into a porcelain boat, ablating in a pure argon atmosphere, heating to 340-;
(7) heating the material obtained in the step (6) to 340-fold-material 360 ℃ at the speed of 4-6 ℃/min in an ammonia-argon mixed atmosphere, preserving heat for 1h, heating to 490-fold-material 510 ℃ at the speed of 0.5-1.5 ℃/min, preserving heat for 2.5-3.5h, finally heating to 690-fold-material 710 ℃ at the speed of 0.5-1.5 ℃/min, preserving heat for 2.5-3.5h, and cooling to room temperature to obtain the non-noble-metal transition metal-based carbon dioxide electro-reduction catalyst, wherein the volume ratio of argon to ammonia in the ammonia-argon mixed atmosphere is 80-90: 10-20.
4. The method of claim 3, wherein: the temperature of the hydrothermal reaction is 120 ℃, and the time is 10 h.
5. The method of claim 3, wherein: the rotation speed of the centrifugal washing in the step (4) is 8000-10000 rpm.
6. The method of claim 3, wherein: the temperature of the drying in the step (5) is 65-75 ℃.
7. The method of claim 3, wherein: the step (6) is as follows: putting the solid powder into a porcelain boat, ablating in a pure argon atmosphere, heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3h, finally heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and cooling to room temperature.
8. The method of claim 3, wherein: the step (7) is as follows: and (3) heating the material obtained in the step (6) to 350 ℃ at the speed of 5 ℃/min in an ammonia-argon mixed atmosphere, preserving heat for 1h, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3h, heating to 700 ℃ at the speed of 1 ℃/min, preserving heat for 3h, and cooling to room temperature to obtain the non-noble metal transition metal-based carbon dioxide electro-reduction catalyst.
9. The method of claim 8, wherein: the volume ratio of argon to ammonia in the ammonia-argon mixed atmosphere is 90: 10.
10. The production method according to any one of claims 3 to 9, characterized in that: the ratio of the nickel acetate tetrahydrate, the copper acetate, the polyether F127, the acetone, the diethylene glycol and the nitric acid is 0.3733g, 0.0998g, 3g, 60mL, 2mL and 0.2 mL.
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