CN115323421A - Preparation and application of nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst - Google Patents
Preparation and application of nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst Download PDFInfo
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 41
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims description 11
- -1 nickel oxide cluster-modified nickel-nitrogen-carbon Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 6
- 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 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005303 weighing Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
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- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
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- 235000015497 potassium bicarbonate Nutrition 0.000 abstract description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 abstract description 4
- 239000011736 potassium bicarbonate Substances 0.000 abstract description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract description 4
- 239000012300 argon atmosphere Substances 0.000 abstract description 3
- 238000004939 coking Methods 0.000 abstract description 3
- 239000010411 electrocatalyst Substances 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- 238000003917 TEM image Methods 0.000 description 1
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- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses preparation and application of a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst, and belongs to the technical field of carbon material preparation. The method takes sodium chloride as a template, coal pitch as a carbon source, nickel chloride as a nickel source and urea as a nitrogen source; grinding coal tar pitch into powder, adding sodium chloride, nickel chloride and urea, uniformly mixing, and then placing in a planetary ball mill for grinding for 2-10h; and (3) placing the ground powder into a carbonization furnace, and heating to prepare the nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst in an argon atmosphere. The specific surface area of the monatomic catalyst can reach 300m 2 More than g, total pore volume of 0.25-2cm 3 Between/g as electrochemical reduction of CO 2 In 0.1mol/L potassium bicarbonate electrolyte, the Faraday efficiency of carbon monoxide can reach more than 96 percent, and the conversion frequency of generating carbon monoxide can reach 10000h at most ‑1 Above, it is highCatalytic performance. The invention takes the coal pitch as a carbon source and simultaneously realizes the high value-added utilization of the coking byproduct coal pitch.
Description
Technical Field
The invention belongs to the technical field of carbon material preparationIn particular to a method for treating CO 2 A preparation method of an electroreduction nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst.
Background
Electrochemical reduction of CO 2 Is an effective way for relieving the greenhouse effect and utilizes the electrocatalyst to realize CO 2 The electro-reduction can obtain chemicals with high added value. Development of high efficiency electrocatalyst for CO 2 The reduction preparation of high value-added chemicals has great research significance. The electrocatalyst is used for overcoming CO 2 Activation kinetic energy barrier and inhibition of competitive hydrogen evolution reaction to achieve efficient CO 2 The key to transformation. Metal catalysts are generally expensive and have limited reserves, greatly limiting their large-scale use. Monatomic catalysts having atomically dispersed metal sites have received wide attention as high-efficiency electrocatalysts because they have a high atom utilization rate, excellent activity and high selectivity for CO. In recent years, some researches show that the nitrogen-doped carbon material loaded with nickel monoatomic sites can be used as an electrochemical reduction catalyst for CO 2 The catalyst is high-efficiency. Coal pitch is a byproduct in the coal tar processing process, is a black massive solid at normal temperature, has no fixed melting point, is softened by heating, and has a density of 1.25-1.35 cm 3 Between/g. The coal tar pitch has complex composition, contains a large amount of polycyclic aromatic hydrocarbon, and has the natural advantage of preparing a carbon material with excellent conductivity; by regulating and controlling the structure and surface properties of the carbon-based electrocatalyst, the high-efficiency carbon-based electrocatalyst can be prepared to obtain highly exposed active sites and good electrical conductivity.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a nickel oxide cluster modified nickel-nitrogen-carbon monatomic catalyst by using sodium chloride as a template, coal pitch as a carbon source, nickel chloride as a nickel source and urea as a nitrogen source, so as to construct electrochemical reduction CO with high Faraday efficiency and current density 2 The reaction catalyst solves the problem of Ni-N in the traditional Ni-based monatomic catalyst 4 The symmetric coordination structure of the catalyst causes poor catalytic performance, and simultaneously realizes high added value utilization of coking byproducts.
In order to solve the above problems, the present invention is realized by the following technical solutions.
The invention provides a method for preparing CO 2 The preparation method of the electrically reduced nickel oxide cluster modified nickel-nitrogen-carbon single atom catalyst comprises the following specific steps:
(1) Pretreatment of reactants: pouring the coal tar pitch into a mortar, grinding the coal tar pitch into powder, adding sodium chloride, nickel chloride hexahydrate and urea, and uniformly mixing the four; and (3) putting the uniformly mixed powder into a planetary ball mill for grinding for 2-10h.
(2) Preparing a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst: placing the reactant obtained in the step (1) in a carbonization furnace, heating to 700-1000 ℃ at the heating rate of 1-5 ℃/min, and keeping the temperature for 1-4h; after the reaction is finished, naturally cooling to room temperature.
(3) Taking out the product obtained in the step (2), and using HCl and HNO 3 And sequentially carrying out acid washing for 4-12h, washing with deionized water to be neutral, filtering, and drying to obtain the nickel oxide cluster modified nickel-nitrogen-carbon monatomic catalyst.
The monatomic catalyst prepared by the invention is a highly porous 3D framework structure formed by mutually connected sheets, and the specific surface area of the monatomic catalyst is 300m 2 More than g, total pore volume of 0.25-2cm 3 Between/g.
As an optimization, in the step (2), the tubular furnace is heated to the final temperature of 800 ℃, and the catalytic performance of the prepared catalyst is optimal.
The nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst prepared by the preparation method can be used in CO 2 The method is applied to electroreduction reaction.
Compared with the prior art, the invention has the following technical effects:
1. the nickel oxide cluster modified nickel-nitrogen-carbon monatomic catalyst is prepared by taking sodium chloride as a template, coal pitch as a carbon source, nickel chloride as a nickel source and urea as a nitrogen source in an argon atmosphere, and high value-added utilization of coking byproduct coal pitch is realized.
2. The nickel oxide cluster modified nickel-nitrogen-carbon monogen prepared by the inventionThe highly dispersed NiO clusters in the sub-catalyst cause electron delocalization of the active sites and reduce CO 2 Electroreduction to energy barrier of CO, and Ni-N X The interaction between the sites and the NiO species allows the monatomic catalyst to have a unique electronic structure.
3. The nickel oxide cluster modified nickel-nitrogen-carbon single atom catalyst prepared by the invention has high specific surface area which can reach 300m 2 More than g.
4. In 0.1mol/L potassium bicarbonate electrolyte, the electrochemical performance of a sample prepared at 800 ℃ is obviously higher than 700 ℃, 900 ℃ and 1000 ℃, the Ni content in the sample prepared at 800 ℃ is highest (0.7019 wt.%) according to an inductively coupled plasma emission spectrum, the Faraday efficiency of the sample prepared at 800 ℃ can be more than 96 percent at most, and the partial current density of CO can be 10mA/cm at most 2 Above, TOF can reach 10000h at most -1 As described above, excellent catalytic performance is exhibited.
5. The invention adopts a one-step method, and has the advantages of simple process, easy industrialization and the like.
Drawings
Fig. 1 is a nitrogen adsorption and desorption isotherm of a nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in example 1 of the present invention;
as can be seen from the figure, the catalyst has a large specific surface area and a rich microporous or mesoporous structure.
Fig. 2 is a scanning electron micrograph of the nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in example 1 of the present invention;
as can be seen, the catalyst consists of a three-dimensionally interconnected lamellar structure.
Fig. 3 is a spherical aberration electron micrograph of the nickel oxide cluster-modified nickel-nitrogen-carbon single atom catalyst prepared in example 1 of the present invention;
as can be seen from the figure, the catalyst contains a large amount of uniformly distributed single atoms and clusters.
Fig. 4 is a transmission electron micrograph of the nickel oxide cluster-modified nickel-nitrogen-carbon single atom catalyst prepared in example 1 of the present invention;
as can be seen from the figure, the catalyst has an ultrathin graphene-like structure.
Fig. 5 shows the synchrotron radiation characterization result of the nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in example 1 of the present invention;
wherein: FIG. 5a is a normalized X-ray absorption near-edge structure spectrum of the sample of example 1 and the standard, showing that the valence of Ni in NiO/Ni-N-C-800 is between 0 and 2 +; FIG. 5b is a Fourier transform X-ray absorption fine structure spectrum of the sample of example 1 and the standard sample, showing that the Ni species of NiO/Ni-N-C-800 exist in the form of atomically dispersed Ni-N/Ni-O coordination states and (sub) nano-oxides; FIG. 5c is the fitting result of the Fourier transform X-ray absorption fine structure spectrum of the sample of example 1, the modeling data and the experimental results are in good agreement, indicating the validity of the fitting result; from the above results, it was found that the catalyst contained a NiO cluster-modified Ni-N-C structure and did not contain Ni particles.
Fig. 6 is a pore size distribution diagram of the nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in example 1 of the present invention;
as can be seen from the figure, the catalyst contained a large amount of micropores and mesopores.
Fig. 7 is an N1 s XPS chart of the nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in example 1 of the present invention;
as can be seen from the figure, this catalyst contains a Ni — N coordination structure, pyridine nitrogen, pyrrole nitrogen, graphite nitrogen, and nitrogen oxide.
Fig. 8 is a Ni 2p XPS graph of the nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in example 1 of the present invention;
as can be seen, the valence of the Ni species in the catalyst is between 0 and + 2.
Fig. 9 is a graph showing the trend of the change of the CO faradaic efficiency of the nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst prepared in examples 1, 2, 3 and 4 of the present invention in the electrolyte of 0.1mol/L potassium bicarbonate under different applied voltages;
as can be seen, the NiO/Ni-N-C-800 catalyst of example 1 exhibited the highest faradaic carbon monoxide efficiency at high overpotentials.
FIG. 10 is a graph showing the variation trend of the current density of CO part at different applied voltages in 0.1mol/L potassium bicarbonate electrolyte of the nickel oxide cluster modified nickel-nitrogen-carbon monatomic catalyst prepared in examples 1, 2, 3 and 4 of the present invention;
as can be seen from the graph, the carbon monoxide fraction of the NiO/Ni-N-C-800 catalyst of example 1 has the highest current density.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the examples described above, and it should be understood that changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention, and all such changes and modifications are included within the scope of the present invention.
Example 1
The specific preparation process of the nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-800 is as follows:
(1) Pretreatment of reactants: weighing 1-2g of coal tar pitch solid, putting the coal tar pitch solid into a mortar, grinding and crushing, adding 5-30g of NaCl,1-10g of urea and 0.1-3g of nickel chloride, and grinding and uniformly mixing all the powder; and putting the powder into a planetary ball mill to operate for 2-10h to obtain a reactant.
(2) Preparing a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst: placing the reactant obtained in the step (1) in a carbonization furnace, heating to 800 ℃ at the heating rate of 1-5 ℃/min under the argon atmosphere, and keeping the temperature for 1-4h; after the reaction is finished, naturally cooling to room temperature. Taking out the obtained product, and adding HCl and HNO 3 And sequentially carrying out acid washing for 4-12h, washing with deionized water to be neutral, filtering, and drying to obtain the nickel oxide cluster modified nickel-nitrogen-carbon monatomic catalyst.
The nickel oxide cluster modifies the performance of the nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-800: the maximum Faraday efficiency of carbon monoxide can reach 96%, and the partial current density of carbon monoxide can reach 16.5mA cm -2 The maximum instantaneous conversion frequency of the generated carbon monoxide can reach 10120h -1 Tafel slope of 167.7mV dec -1 The Ni content was 0.7019wt.%.
Example 2
The specific preparation process of the nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-700 is as follows:
(1) Pretreatment of reactants: as in example 1.
(2) Preparing a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst: the difference from example 1 is that the heating temperature was 700 ℃.
The nickel oxide cluster is used for modifying the performance of the nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-700: the maximum Faraday efficiency of the carbon monoxide is only 59.86 percent, and the partial current density of the carbon monoxide is only 1.18mA cm -2 The Tafel slope is 210.06mV dec -1 The Ni content was 0.6788wt.%.
Example 3
The specific preparation process of the nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-900 is as follows:
(1) Pretreatment of reactants: as in example 1.
(2) Preparing a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst: the difference from example 1 is that the heating temperature was 900 ℃.
The nickel oxide cluster modifies the performance of the nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-900: the maximum Faraday efficiency of carbon monoxide can reach 93%, and the partial current density of carbon monoxide can reach 10.27mA cm -2 The Tafel slope is 179.65mV dec -1 Ni content 0.3129wt.%.
Example 4
The specific preparation process of the nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-1000 is as follows:
(1) Pretreatment of reactants: as in example 1.
(2) Preparing a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst: the difference from example 1 is that the heating temperature was 1000 ℃.
The nickel oxide cluster modifies the performance of the nickel-nitrogen-carbon single-atom catalyst NiO/Ni-N-C-1000: the maximum Faraday efficiency of carbon monoxide can reach 90 percent, and the part of carbon monoxideThe highest current density of the current distribution is 6.19mAcm -2 The Tafel slope is 144.75mV dec -1 Ni content 0.2386wt.%.
Claims (3)
1. A preparation method of a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst is characterized by comprising the following steps:
(1) Pretreatment of reactants: weighing a proper amount of coal tar pitch, sodium chloride, nickel chloride hexahydrate and urea, transferring the coal tar pitch, the sodium chloride, the nickel chloride hexahydrate and the urea into a mortar, grinding and mixing, and then putting mixed powder into a planetary ball mill to grind for 2-10 hours to obtain a reactant;
wherein the mass ratio of the sodium chloride to the coal pitch is 20/1, the mass ratio of the nickel chloride hexahydrate to the coal pitch is 0.357/1, and the mass ratio of the urea to the coal pitch is 3/1;
(2) Preparing a nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst: placing the reactant obtained in the step (1) in a carbonization furnace, heating to 700-1000 ℃ at the heating rate of 1-5 ℃/min, and keeping the temperature for 1-4h; after the reaction is finished, naturally cooling to room temperature;
(3) Taking out the product obtained in the step (2), and using HCl and HNO 3 Sequentially carrying out acid washing for 4-12h, washing to be neutral by deionized water, filtering, and drying to obtain the nickel oxide cluster modified nickel-nitrogen-carbon monatomic catalyst;
the monatomic catalyst is a highly porous 3D framework structure formed by interconnected sheets, and the specific surface area of the monatomic catalyst is 300m 2 More than g, total pore volume of 0.25-2cm 3 Between/g.
2. The method for preparing a nickel oxide cluster-modified nickel-nitrogen-carbon monatomic catalyst according to claim 1, wherein in the step (2), the tube furnace is heated to a final temperature of 800 ℃.
3. The method of claim 1, wherein the catalyst is prepared by reacting the nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst with CO 2 Application in electro-reduction reactions.
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| CN115845860A (en) * | 2022-12-08 | 2023-03-28 | 中钢集团鞍山热能研究院有限公司 | Asphalt-based monatomic catalyst and preparation method and application thereof |
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| CN115845860A (en) * | 2022-12-08 | 2023-03-28 | 中钢集团鞍山热能研究院有限公司 | Asphalt-based monatomic catalyst and preparation method and application thereof |
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