CN111215111B - Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof - Google Patents
Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application 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 156
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 90
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 230000009467 reduction Effects 0.000 title claims abstract description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001301 oxygen Substances 0.000 title claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 31
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 9
- 238000001338 self-assembly Methods 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test 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
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
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Abstract
The invention relates to a carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies, a preparation method and application thereof. The technical scheme is as follows: a carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle loaded on nitrogen-doped graphene, which is prepared by performing adsorption and hydrothermal self-assembly on one or more metal salt precursors and graphene oxide through two-step chemical vapor deposition, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the catalyst comprises the following components in parts by mass: 2-10 parts of C: 80-92 parts, N: 2-6 parts, O: 3-8 parts. The preparation method is simple, the preparation period is short, and the adopted precursor non-noble metal salt has the characteristic of low cost. The carbon dioxide electrochemical reduction catalyst prepared by the invention has excellent carbon dioxide electrochemical reduction performance, the prepared nano particles are stably dispersed on a carbon substrate, and oxygen vacancies as active sites show excellent CO2RR performance.
Description
Technical Field
The invention belongs to the field of electrochemical reduction catalysts, and particularly relates to an oxygen vacancy-rich carbon dioxide electrochemical reduction catalyst, and a preparation method and application thereof.
Background
Carbon dioxide is a common greenhouse gas and an abundant carbon source, and how to utilize the carbon dioxide in a resource manner is one of the great challenges for maintaining sustainable development. Electrochemical reduction of carbon dioxide (CO)2RR) is an important process of carbon dioxide conversion, and can convert carbon dioxide into high-value-added fuels and chemicals such as carbon monoxide, formic acid and alcohols in one step under mild reaction conditions, so that the high-efficiency conversion of carbon dioxide is realized. However, carbon dioxide is a relatively stable small molecule, and the electrocatalytic reduction reaction requires a high negative potential to drive. Meanwhile, the transfer process of several protons accompanied by multiple electrons also requires similar potential, resulting in that the product selectivity control becomes very difficult. And the application of electrocatalytic carbon dioxide reduction is seriously hindered by using noble metals such as gold, silver or platinum and the like in the traditional catalyst. Therefore, there is a need to develop a non-noble metal catalyst with high efficiency, high selectivity and low price, among which nickel, iron, zinc, etc. are widely spotlighted.
The nano metal material is a metal material with the grain size less than 100nm, has the characteristics of large specific surface area, high surface atom number, large surface energy and surface binding energy and the like, and has superiority different from common materials. But it also has some defects in itself, such as small size, large surface energy, easy agglomeration and deactivation. The nanometer metal is attached to carriers with special structural functions, such as activated carbon, graphene oxide and organic polymer carriers, so that the inherent characteristics of the nanometer metal material can be maintained, the stability of the nanometer metal material is enhanced, and the activity of the material is greatly improved.
Under standard conditions, CO2Activation of molecules to CO in aqueous solution2 -The standard electrode potential required for anions is-1.9V (vs RHE) versus standard hydrogen. Promotion of CO2Has been CO activated2The difficulty of research in electrocatalytic reduction reactions, generally thought to be electron to CO2The efficient transfer of molecules is CO2The key step of activation. This can be achieved by constructing the surface of the catalyst rich in electrons. And the electron enrichment state caused by the surface oxygen vacancy defect can effectively activate CO2Molecules, thereby enhancingCO2Electrocatalytic reduction reaction activity. Therefore, a simple and effective method is selected to prepare the oxygen vacancy-rich supported metal nano-catalyst for CO2RR is very promising.
Disclosure of Invention
The invention aims to provide an oxygen vacancy-rich carbon dioxide electrochemical reduction catalyst, and a preparation method and application thereof2RR catalysts with high electrocatalytic activity.
The technical scheme adopted by the invention is as follows:
a carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by performing adsorption and hydrothermal self-assembly on one or more metal salt precursors and graphene oxide through two-step chemical vapor deposition and loaded on nitrogen-doped graphene, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the catalyst comprises the following components in parts by mass: 2-10 parts of C: 80-92 parts, N: 2-6 parts, O: 3-8 parts.
Further, the metal salt precursor is any one or a mixture of more of nickel chloride hexahydrate, ferric nitrate nonahydrate and zinc nitrate hexahydrate in any proportion.
The preparation method of the oxygen vacancy-rich carbon dioxide electrochemical reduction catalyst comprises the following steps:
(1) ultrasonically dispersing graphene oxide in deionized water, and ultrasonically treating for 2-8h to prepare a uniform suspension with the concentration of 1-5mg/mL, which is marked as a dispersion liquid A;
(2) adding a metal salt solution of one or more of nickel chloride hexahydrate, ferric nitrate nonahydrate and zinc nitrate hexahydrate into the dispersion liquid A, ultrasonically dispersing for 1-4h, placing the dispersion liquid A into a hydrothermal kettle for heating reaction at the reaction temperature of 140-;
(3) the first step of chemical vapor deposition:
setting the furnace temperature at 700-1100 ℃, the gas flow rate at Ar of 100 +/-50 sccm and NH 350 +/-20 sccm, putting the dried compound prepared in the step (2) into the center of a tubular furnace, and performing high-temperature heat treatment reaction for 0.5-3h to obtain metal nanoparticles loaded on nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100 plus or minus 50sccm and H 210 plus or minus 5sccm, and performing high-temperature heat treatment reaction for 10-60min to obtain the oxygen vacancy-rich carbon dioxide electrochemical reduction catalyst.
Further, in the step (2), a metal salt solution of one or more of nickel chloride hexahydrate, ferric nitrate nonahydrate and zinc nitrate hexahydrate is added into the dispersion liquid A, and the amount of the added metal salt solution is 1-10% of the mass percentage of the metal in the graphene oxide.
Further, the hydrogen in the step (4) is hydrogen which is firstly passed through primary water to carry water vapor.
The application of the oxygen vacancy-rich carbon dioxide electrochemical reduction catalyst in electrochemical reduction reaction.
The preparation method comprises the steps of taking nitrogen-doped graphene as a carrier, forming a stable structure through interaction of rich oxygen-containing functional groups and one or more metal ions, firstly synthesizing metal nano particles loaded on the nitrogen-doped graphene through a Chemical Vapor Deposition (CVD) method, then introducing hydrogen containing water vapor, forming a metal oxide phase at a high temperature, and simultaneously obtaining a nano metal electrocatalyst rich in oxygen vacancies through high-temperature reduction and hydrogen reduction, wherein the prepared nano particles are stably dispersed on a carbon substrate, and the oxygen vacancies as active sites represent excellent CO2RR performance. Compared with the prior art, the invention has the following advantages:
1. the preparation method is simple and short in preparation period, one or more metal precursors are uniformly mixed in the graphene aqueous solution, and the graphene oxide film can be prepared by hydrothermal and twice chemical vapor deposition, and the adopted precursor is non-noble metal salt, so that the preparation method has the characteristic of low cost.
2. The graphene oxide used in the invention contains abundant oxygen-containing functional groups, provides a large number of anchoring sites for metal nanoparticles, can maintain the inherent characteristics of the nano metal material, enhances the stability of the nano metal material, and greatly improves the activity of the material.
3. The preparation method of the oxygen vacancy of the catalyst is simple, the catalyst is firstly adsorbed on graphene through metal salt, graphene-loaded metal nanoparticles are obtained through chemical vapor deposition, and the preparation of metal oxidation and oxygen vacancy defects is completed in one step through introducing hydrogen/water vapor, so that the electrocatalyst rich in the oxygen vacancy is obtained.
4. The electron-rich state resulting from oxygen vacancy defects of the catalyst of the present invention promotes electrons to CO2Efficient transfer of molecules, thereby efficiently activating CO2Molecule, enhanced CO2Electrocatalytic reduction reaction activity.
5. The carbon dioxide electrochemical reduction catalyst prepared by the invention has excellent carbon dioxide electrochemical reduction performance, high activity, strong selectivity, stable performance and the like.
Drawings
FIG. 1 is an XRD pattern of a carbon dioxide electrochemical reduction catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the weight percentage content of each element component of the carbon dioxide electrochemical reduction catalyst prepared in example 1 of the present invention measured by XPS;
FIG. 3 is a HRTEM spectrum of a carbon dioxide electrochemical reduction catalyst prepared in example 1 of the present invention;
FIG. 4 is an IR diagram of a carbon dioxide electrochemical reduction catalyst prepared in example 1 of the present invention;
FIG. 5 is an SEM image of a carbon dioxide electrochemical reduction catalyst prepared in example 2 of the present invention;
FIG. 6 is a TEM image of the carbon dioxide electrochemical reduction catalyst prepared in example 2 of the present invention;
FIG. 7 is a graph of the mass percentage content of each element component of the carbon dioxide electrochemical reduction catalyst prepared in example 2 of the present invention by XPS test;
FIG. 8 is an XPS spectrum of a carbon dioxide electrochemical reduction catalyst prepared in example 2 of the present invention;
FIG. 9 is an XPS spectrum of a carbon dioxide electrochemical reduction catalyst prepared in example 3 of the present invention;
FIG. 10 is a graph showing the XPS test results of the elemental compositions of the carbon dioxide electrochemical reduction catalyst prepared in example 3 of the present invention;
FIG. 11 is a graph showing the Faraday efficiency of the product carbon monoxide produced by the electrochemical reduction catalyst for carbon dioxide according to the present invention when applied to the electrochemical reduction reaction for carbon dioxide;
FIG. 12 is a polarization curve diagram of the carbon dioxide electrochemical reduction catalyst prepared by the present invention applied to the carbon dioxide electrochemical reduction reaction;
fig. 13 is a stability test chart of the carbon dioxide electrochemical reduction catalyst prepared by the present invention when applied to electrochemical reduction of carbon dioxide.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Graphene oxide in the following examples was prepared using a modified Hummers method, as follows: dispersing 3.0g of flake graphite into concentrated H with the volume ratio of 9:1 under the condition of ice-water bath at 0 DEG C2SO4/H3PO4(360:40mL), 18g KMnO was added slowly with mechanical stirring4Then, it was stirred well and slowly warmed, and when the temperature rose to 35-40 ℃, the temperature was kept at 50 ℃ and stirring was continued for 12 hours. Cooling the solution, pouring the solution into a prepared 400mL ice cube, and adding H with the mass concentration of 30% under continuous stirring2O2And (3) until the solution is bright yellow, performing centrifugal separation, and repeatedly washing with HCl solution with the mass concentration of 30%, deionized water and diethyl ether in sequence to obtain the graphene oxide.
The nickel chloride solution, a precursor of nickel, in the following examples was prepared: 1.79g (7.5 mmol) of NiCl are taken2·6H2Dissolving the O solid in 50mL deionized water, fully stirring, and fixing the volume in a 100mL volumetric flask.
Iron nitrate precursor in the following examplesThe preparation method of the solution comprises the following steps: 2.99g (7.4 mmol) Fe (NO)3)3·9H2Dissolving the O solid in 50mL of deionized water, fully stirring, and fixing the volume in a 100mL volumetric flask.
The preparation method of the zinc nitrate solution as the precursor of zinc in the following examples is as follows: 2.10g (7.1 mmol) Zn (NO)3)2·6H2The O solid is dissolved in 50mL deionized water, fully stirred and added into a 100mL volumetric flask.
Example 1
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by carrying out adsorption and hydrothermal self-assembly on a nickel chloride solution and graphene oxide through two-step chemical vapor deposition and loaded on nitrogen-doped graphene, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 8 hours to prepare a uniform suspension, which is marked as a dispersion A.
(2) Accurately transferring 2.3mL of nickel chloride solution into the dispersion liquid A, enabling the addition amount of nickel to be 2.5% of the mass percentage of graphene oxide, ultrasonically dispersing for 4h, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 180 ℃, keeping reacting for 12h, cooling the hydrothermal kettle after the reaction is finished, taking out a product, and drying the columnar product for 5h by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tubular furnace, setting the furnace temperature at 1000 ℃, and setting the gas flow at 100sccm of Ar and NH350sccm, and carrying out high-temperature heat treatment reaction for 1h to obtain metal nano particles loaded on the nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100sccm and H210sccm, wherein hydrogen passes through the first-stage water and enters a tubular furnace with water vapor, and after the high-temperature heat treatment reaction for 30min, carbon dioxide rich in oxygen vacancies is preparedElectrochemically reducing the catalyst.
As shown in fig. 1, an XRD pattern of the carbon dioxide electrochemical reduction catalyst prepared in example 1 is shown. The figure shows a diffraction peak of metallic nickel, which indicates that the catalyst is nickel nanoparticles supported on graphene sheets.
As shown in fig. 2, the mass percentages of the respective element components in the carbon dioxide electrochemical reduction catalyst prepared in example 1, which were obtained by XPS test, are as follows: 2.0 part, C: 92.0 parts, N: 3.0 part, O: 3.0 parts.
As shown in fig. 3, HRTEM of the electrochemical reduction catalyst for carbon dioxide prepared in example 1 shows the crystal lattice of nickel and the crystal lattice of nickel oxide, which indicates that the nickel nanoparticles prepared in this example have a crystal phase of nickel oxide formed on the surface.
As shown in fig. 4, an IR spectrum of the carbon dioxide electrochemical reduction catalyst prepared in example 1 is shown. The catalyst prepared in this example was shown to have Ni-O bonds formed, demonstrating the presence of nickel oxide crystalline phases in the material.
Example 2
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by carrying out adsorption and hydrothermal self-assembly on a nickel chloride solution and an iron nitrate solution and graphene oxide through two-step chemical vapor deposition and loaded on nitrogen-doped graphene, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 6 hours to prepare a uniform suspension, which is marked as a dispersion liquid A.
(2) Accurately transferring 7.3mL of nickel chloride solution and 2.9mL of ferric nitrate solution into the dispersion liquid A, enabling the addition amount of nickel and iron to be 8.0% and 3.0% of the mass percentage of graphene oxide respectively, ultrasonically dispersing for 4 hours, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 220 ℃, keeping the reaction for 10 hours, cooling the hydrothermal kettle after the reaction is finished, taking out the product, and drying the columnar product for 10 hours by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tube furnace, setting the furnace temperature at 1100 deg.C, gas flow at Ar of 100sccm and NH350sccm, and carrying out high-temperature heat treatment reaction for 2h to obtain metal nano particles loaded on the nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100sccm and H210sccm, wherein hydrogen passes through the first-stage water and enters a tubular furnace with water vapor, and the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is prepared after the high-temperature heat treatment reaction for 15 min.
As shown in fig. 5, an SEM image of the carbon dioxide electrochemical reduction catalyst prepared in example 2 shows that graphene has a pleated structure, and dispersed nanoparticles exist on the graphene sheet.
As shown in fig. 6, a TEM spectrum of the carbon dioxide electrochemical reduction catalyst prepared in example 2 shows that graphene has a layered structure.
As shown in fig. 7, the mass percentages of the respective element components in the carbon dioxide electrochemical reduction catalyst prepared in example 2 obtained by XPS test were shown, where Ni: 7.5 parts, Fe: 2.5 parts, C: 80.0 parts, N: 2.0 part, O: 8.0 part.
As shown in fig. 8, which is an XPS spectrum of the carbon dioxide electrochemical reduction catalyst prepared in example 2, fig. 8a is a C element scan before and after the material is treated with hydrogen/water, showing that the C element does not change much by the present preparation method, and fig. 8b is an N element scan before and after the material is treated with hydrogen/water, showing that the total amount of N elements and the ratio of N species change by the present preparation method.
Example 3
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by carrying out adsorption and hydrothermal self-assembly on a nickel chloride solution and graphene oxide through two-step chemical vapor deposition and loaded on nitrogen-doped graphene, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 8 hours to prepare a uniform suspension, which is marked as a dispersion A.
(2) Accurately transferring 5.9mL of nickel chloride solution into the dispersion liquid A, enabling the addition amount of nickel to be 6.5% of the mass percent of the graphene oxide, performing ultrasonic dispersion for 3 hours, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 180 ℃, keeping the reaction for 12 hours, cooling the hydrothermal kettle after the reaction is finished, taking out the product, and drying the columnar product for 5 hours by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tubular furnace, setting the furnace temperature at 800 ℃, and setting the gas flow at 100sccm of Ar and NH350sccm, and carrying out high-temperature heat treatment reaction for 1h to obtain metal nano particles loaded on the nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100sccm and H25sccm, wherein hydrogen passes through the primary water and enters the tubular furnace with water vapor, and the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is prepared after the high-temperature heat treatment reaction for 50 min.
As shown in fig. 9, in order to show the XPS spectrum of the carbon dioxide electrochemical reduction catalyst prepared in example 3, fig. 9a is a scan of O element before and after the material is treated with hydrogen/water, which shows that nickel oxide is generated on the surface of the metallic nickel nanoparticle and is rich in oxygen vacancies by the preparation method, and fig. 9b is a scan of Ni element before and after the material is treated with hydrogen/water, which shows that the surface of the metallic nickel nanoparticle is oxidized and the valence state is increased by the preparation method.
As shown in fig. 10, the mass percentages of the respective element components in the carbon dioxide electrochemical reduction catalyst prepared in example 3 measured by XPS test were set to values in which Ni: 6.0 part, C: 86.0 parts, N: 5.0 part, O: 3.0 parts.
Example 4
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by two-step chemical vapor deposition and loaded on nitrogen-doped graphene by carrying out adsorption and hydrothermal self-assembly on a ferric nitrate solution and graphene oxide, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 8 hours to prepare a uniform suspension, which is marked as a dispersion liquid A.
(2) Accurately transferring 7.2mL of ferric nitrate solution into the dispersion liquid A, enabling the addition amount of iron to be 7.5% of the mass percentage of graphene oxide, ultrasonically dispersing for 4h, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 180 ℃, keeping reacting for 12h, cooling the hydrothermal kettle after the reaction is finished, taking out the product, and drying the columnar product for 5h by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tubular furnace, setting the furnace temperature at 1000 ℃, and setting the gas flow as Ar:100sccm and NH350sccm, performing high-temperature heat treatment for 1h to obtain metal nanoparticles loaded on the nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100sccm and H210sccm, wherein hydrogen passes through the first-stage water and enters a tubular furnace with water vapor, and the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is prepared after the reaction of high-temperature heat treatment for 30 min.
Example 5
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by carrying out adsorption and hydrothermal self-assembly on zinc nitrate solution and graphene oxide through two-step chemical vapor deposition and loaded on nitrogen-doped graphene, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 8 hours to prepare a uniform suspension, which is marked as a dispersion A.
(2) Accurately transferring 4.33mL of ferric nitrate solution into the dispersion liquid A, enabling the addition amount of iron to be 5.0% of the mass percent of the graphene oxide, ultrasonically dispersing for 2h, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 180 ℃, keeping reacting for 12h, cooling the hydrothermal kettle after the reaction is finished, taking out the product, and drying the columnar product for 5h by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tubular furnace, setting the furnace temperature at 1000 ℃, and setting the gas flow at 100sccm of Ar and NH350sccm, performing high-temperature heat treatment for 1h to obtain metal nanoparticles loaded on the nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100sccm and H210sccm, wherein hydrogen passes through the first-stage water and enters a tubular furnace with water vapor, and the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is prepared after the reaction of high-temperature heat treatment for 30 min.
Example 6
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by two-step chemical vapor deposition and loaded on nitrogen-doped graphene by carrying out adsorption and hydrothermal self-assembly on a ferric nitrate solution and graphene oxide, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 2 hours to prepare a uniform suspension, which is marked as a dispersion liquid A.
(2) Accurately transferring 0.96mL of ferric nitrate solution into the dispersion liquid A, enabling the addition amount of iron to be 1.0% of the mass percentage of graphene oxide, ultrasonically dispersing for 1h, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 140 ℃, keeping reacting for 16h, cooling the hydrothermal kettle after the reaction is finished, taking out the product, and drying the columnar product for 20h by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tubular furnace, setting the furnace temperature at 700 ℃, the gas flow at 150sccm of Ar and NH370sccm, performing high-temperature heat treatment for reaction for 30min to obtain metal nanoparticles loaded on the nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 150sccm and H215sccm, wherein hydrogen passes through primary water and enters a tubular furnace with water vapor, and the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is prepared after the reaction for 10min of high-temperature heat treatment.
Example 7
A carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is a metal nanoparticle which is prepared by carrying out adsorption and hydrothermal self-assembly on zinc nitrate solution and graphene oxide through two-step chemical vapor deposition and loaded on nitrogen-doped graphene, and the surface of the metal nanoparticle is rich in a metal oxide phase with oxygen vacancies; the preparation method comprises the following specific steps:
(1) accurately weighing 0.4g of graphene oxide, placing the graphene oxide in 200mL of deionized water, and performing ultrasonic dispersion for 6 hours to prepare a uniform suspension, which is marked as a dispersion A.
(2) Accurately transferring 8.66mL of zinc nitrate solution into the dispersion liquid A, enabling the addition amount of zinc to be 10.0% of the mass percentage of graphene oxide, ultrasonically dispersing for 4h, then transferring the dispersed mixed solution into a hydrothermal kettle, heating to 220 ℃, keeping reacting for 10h, cooling the hydrothermal kettle after the reaction is finished, taking out the product, and drying the columnar product for 10h by using a freeze dryer to obtain a dry compound.
(3) The first step of chemical vapor deposition:
transferring the dried compound to the center of a tubular furnace, setting the furnace temperature at 900 ℃, and setting the gas flow at Ar of 50sccm and NH330sccm, and carrying out high-temperature heat treatment reaction for 3h to obtain the nitrogen-doped graphene loaded with the nitrogenMetal nanoparticles;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 50sccm and H25sccm, wherein hydrogen passes through primary water and enters a tubular furnace with water vapor, and the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is prepared after high-temperature heat treatment reaction for 60 min.
Application examples
The application of the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies prepared by the invention in the carbon dioxide electrochemical reduction reaction is as follows:
electrochemical measurements were performed on an electrochemical workstation (CHI 660E) using a three electrode system. Dispersing the electrochemical reduction catalyst prepared by the method and a 5 wt% Nafion solution in 1mL of water/ethanol at a v/v 4:1 ratio by mass of 40:8, and then carrying out water bath ultrasonic treatment until a uniform catalyst suspension is formed. Then 125. mu.L of the catalyst suspension was dropped in 1cm2And drying the carbon paper at room temperature for 24 hours. The loading of the catalyst is 0.46mg/cm2。
Electrochemical reduction of carbon dioxide (CO)2RR) test:
in H-type cells, CO20.1M KHCO as a reactant gas introduced into the cathode at a controlled flow rate3CO for electrolyte solution2Saturation, using platinum sheet as counter electrode, Ag/AgCl electrode as reference electrode, electrochemical reduction catalyst prepared by said invention as working electrode to form three-electrode system to test CO2RR performance. Linear Sweep Voltammetry (LSV) at a sweep rate of 20mV s-1The test was performed. All potentials were exchanged for a standard hydrogen electrode (RHE): e (rhe) ═ E (Ag/AgCl) + (0.228+0.059 pH).
The mixed gas of the product gas and the reaction gas is led out from the cathode of the electrolytic cell and enters a Gas Chromatograph (GC) for on-line testing, and the Faraday efficiency FE (%) ((Q), (CO))/Q (tot) (. 100%) of the product carbon monoxide is calculated.
As shown in fig. 11, it is a graph of faradaic efficiency of carbon monoxide, which is a product of the electrochemical reduction reaction of carbon dioxide, in which the carbon dioxide electrochemical reduction catalyst prepared by the present invention is applied. As can be seen from the figure, the product carbon monoxide has extremely high Faraday efficiency, and the carbon dioxide electrochemical reduction catalyst has excellent activity and selectivity.
As shown in FIG. 12, the scan rate is 20mV/s, which is a polarization curve of the carbon dioxide electrochemical reduction catalyst prepared by the present invention when applied to electrochemical reduction of carbon dioxide.
As shown in fig. 13, it is a stability test chart of the carbon dioxide electrochemical reduction catalyst prepared by the present invention when applied to electrochemical reduction of carbon dioxide. The current density of the electrochemically reduced carbon dioxide remains well stable over the 20 hour test.
Claims (4)
1. The preparation method of the carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies is characterized by comprising the following steps:
(1) ultrasonically dispersing graphene oxide in deionized water, and ultrasonically treating for 2-8h to prepare a uniform suspension with the concentration of 1-5mg/mL, and marking as a dispersion liquid A;
(2) adding one or more metal salt solutions of nickel chloride hexahydrate, ferric nitrate nonahydrate and zinc nitrate hexahydrate into the dispersion liquid A, ultrasonically dispersing for 1-4h, placing the dispersion liquid A into a hydrothermal kettle for heating reaction at the reaction temperature of 140 ℃ and 220 ℃ for 10-16h, and drying the obtained reaction product in a freeze dryer for 5-20h to obtain a dry compound;
(3) the first step of chemical vapor deposition:
setting the furnace temperature at 700-1100 deg.C, gas flow at Ar of 100 + -50 sccm and NH350 +/-20 sccm, putting the dried compound prepared in the step (2) into the center of a tubular furnace, and performing high-temperature heat treatment reaction for 0.5-3h to obtain metal nanoparticles loaded on nitrogen-doped graphene;
(4) a second step of chemical vapor deposition:
keeping the furnace temperature unchanged, changing the gas flow into Ar of 100 plus or minus 50sccm and H210 plus or minus 5sccm, and performing high-temperature heat treatment reaction for 10-60min to obtain the oxygen vacancy-rich carbon dioxide electrochemical reduction catalyst; wherein hydrogen gasFirstly, the hydrogen carrying water vapor is passed through the first-stage water.
2. The method of claim 1, wherein: in the step (2), one or more metal salt solutions of nickel chloride hexahydrate, ferric nitrate nonahydrate and zinc nitrate hexahydrate are added into the dispersion liquid A, and the amount of the added metal salt solution is 1-10% of the mass percentage of the metal in the graphene oxide.
3. An oxygen vacancy rich carbon dioxide electrochemical reduction catalyst prepared by the preparation method of claim 1 or 2, wherein: the catalyst is metal nanoparticles loaded on nitrogen-doped graphene, and the surface of the metal nanoparticles is rich in a metal oxide phase with oxygen vacancies.
4. Use of an oxygen vacancy rich carbon dioxide electrochemical reduction catalyst prepared by the preparation method of claim 1 or 2 in an electrochemical reduction reaction.
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