CN114016074B - Preparation method and application of high-load transition metal single-atom carbon-based catalyst - Google Patents
Preparation method and application of high-load transition metal single-atom carbon-based catalyst Download PDFInfo
- Publication number
- CN114016074B CN114016074B CN202111252727.5A CN202111252727A CN114016074B CN 114016074 B CN114016074 B CN 114016074B CN 202111252727 A CN202111252727 A CN 202111252727A CN 114016074 B CN114016074 B CN 114016074B
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- carbon
- transition metal
- based catalyst
- hydrothermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
Abstract
The invention discloses a preparation method and application of a high-load transition metal single-atom carbon-based catalyst, and belongs to the field of new materials. Taking iron loading as an example, zinc oxide with exposed special crystal faces is synthesized by a hydrothermal synthesis method, and then the zinc oxide and ferric nitrate solution with certain concentration are subjected to dipping treatment to obtain the iron-containing zinc oxide template. The template and 2-methylimidazole react at high temperature according to a certain proportion to obtain the carbon-based catalyst. The carbon-based catalyst can be applied to preparing carbon monoxide by electrocatalytic reduction of carbon dioxide. The invention controls the exposed special crystal face of the zinc oxide template by adjusting the hydrothermal condition, which not only can effectively control the dispersion of iron atoms in the dipping process, but also can promote the reaction rate of zinc oxide and 2-methylimidazole at high temperature, and is beneficial to the monoatomic state dispersion of iron atoms on carbon bases. The obtained carbon-based catalyst can realize the directional catalytic reduction of carbon dioxide under low voltage, and shows excellent selectivity and stability.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a preparation method of a transition metal single-atom carbon-based catalyst and application of the transition metal single-atom carbon-based catalyst in directional catalytic reduction of carbon dioxide.
Background
The development of the 21 st century industry and the increase of population have led to the massive use of fossil fuels such as coal, oil and natural gas and related industrial products, resulting in the continuous accumulation of carbon dioxide in the atmosphere, and further, serious problems in terms of environment and climate, called "global warming effect". Rich, cheap and easily available CO 2 The conversion into other directly usable energy becomes a widely discussed solution [1-2] . The electrochemical carbon dioxide reduction reaction not only effectively utilizes clean energy such as solar energy, wind energy and the like, but also can directly convert carbon dioxide into industrial raw materials, and the electrochemical carbon dioxide reduction reaction is becoming a key technology for solving the problem of human carbon cycle in the human society as a clean and controllable energy conversion technology. The key to the electrochemical carbon dioxide reduction reaction is the catalyst, which is due to: on one hand, products of carbon dioxide reduction are various, and in order to ensure the industrial value of the products, the catalyst needs to have excellent selectivity; on the other hand, since the reaction system is often used in an electrolyte solution, the presence of water molecules causes a hydrogen evolution reaction and further lowers the energy utilization efficiency of the system, and therefore, it is necessary to design a catalyst while suppressing the reaction. In addition, in consideration of industrial use value, the catalyst design also needs to consider aspects such as service life, cost, process feasibility and the like.
In recent years, a monatomic catalyst material (SACS) having good catalytic activity has been successively reported as a catalyst for high-efficiency carbon dioxide electrocatalytic reduction, such as a monatomic ruthenium-based/palladium-based catalyst [3-4] . Although current research has made relevant progress, most research has focused on precious metal SACs. Due to the shortage of precious metals and high cost, which limits their large-scale application, in economic terms, non-precious metal SACs have recently received wide attention as catalysts with high activity and good stability in electrocatalytic systems, such as carbon nanospheres (E) supported by monoatomic cobalt 1/2 Electrochemical oxygen reduction activity of = 0.838V) close to commercial Pt/C (E) 1/2 = 0.834 V） [5] The water splitting potential of the monoatomic iron and nickel loaded monolayer graphene is 10 mA cm -2 Reaches 1.51V, which is comparable to commercial IrO 2 Much lower catalyst [6] . The development of non-noble metal SACs offers a potential approach to designing cost-effective catalysts with activity comparable to the noble metal SACs benchmark.
Although non-noble metal SACs are promising electrocatalysts, maintaining the unique structure of the monatomic active sites, which are closely associated with the metal center, and increasing the current density, which is closely associated with the support, remains a challenge. Fe. Transition metals such as Co, ni and the like are common choices of monatomic active sites, and are used in various catalytic systems, for a carbon dioxide electrocatalytic reduction system, the high-activity potential platform of the Co monatomic active site is the widest, the selectivity of the Ni monatomic active site is the highest, the characteristics of the Fe monatomic active site are between the Co monatomic active site and the Ni monatomic active site, and the Co monatomic active site, the Ni monatomic active site and the Fe monatomic active site are all potential optimal choices. In order to maintain the monoatomic state at high temperature and avoid agglomeration, metal atoms are usually fixed in advance by means of template confinement, such as a metal organic framework, a polymer network, and the like. With CeO 2 [7] ，MoC [8] 、MoS 2 [9] And TiO 2 2 [10] Compared with metal compound carriers, carriers such as carbon-rich materials attract extensive attention due to their special stability, modifiable surface chemistry and high electrical conductivity [11] Including carbon nanospheres, carbon nanofibers, graphene, metal organic framework derived carbon, covalent triazine framework, carbon nitride, phthalocyanine derived carbon, and the like. The carbon material is used as the carrier of the electrocatalyst, so that the catalytic activity of the active sites can be fully exerted. However, the existing monatomic active site preparation still has the defects of complex process and high cost. Therefore, the development of the high-load transition metal single-atom carbon-based catalyst for the high-efficiency carbon dioxide electrocatalytic reduction system is of great significance.
Reference documents:
[1] D. D. Zhu; J. L. Liu; S. Z. Qiao, Adv. Mater. 2016, 28, 3423-3452.
[2] Y. Wang; J. Liu; Y. Wang; A. M. Al-Enizi; G. Zheng, Small 2017, 13, 1701809.
[3] Y. Wang; S. L. Marquard; D. Wang; C. Dares; T. J. Meyer, ACS Energy Letters 2017, 2, 1395-1399.
[4] S. Back; Y. Jung, ACS Energy Letters 2017, 2, 969-975.
[5] A. Han; W. Chen; S. Zhang; M. Zhang; Y. Han; J. Zhang; S. Ji; L. Zheng; Y. Wang; L. Gu; C. Chen; Q. Peng; D. Wang; Y. Li, Adv. Mater. 2018, 30, e1706508.
[6] X. Cui; P. Ren; D. Deng; J. Deng; X. Bao, Energy & Environmental Science 2016, 9, 123-129.
[7] Y. Wang; Z. Chen; P. Han; Y. Du; Z. Gu; X. Xu; G. Zheng, ACS Catalysis 2018, 8, 7113-7119.
[8] S. Yao; X. Zhang; W. Zhou; R. Gao; W. Xu; Y. Ye; L. Lin; X. Wen; P. Liu; B. Chen; E. Crumlin; J. Guo; Z. Zuo; W. Li; J. Xie; L. Lu; C. J. Kiely; L. Gu; C. Shi; J. A. Rodriguez; D. Ma, Science 2017, 357, 389-393.
[9] R. K. Biroju; D. Das; R. Sharma; S. Pal; L. P. L. Mawlong; K. Bhorkar; P. K. Giri; A. K. Singh;T. N. Narayanan, ACS Energy Lett. 2017, 2, 1355-1361.
[10] J. Wan; W. Chen; C. Jia; L. Zheng; J. Dong; X. Zheng; Y. Wang; W. Yan; C. Chen; Q. Peng; D. Wang; Y. Li, Adv. Mater. 2018, 30, 1705369.
[11] B. Bayatsarmadi; Y. Zheng; A. Vasileff; S.-Z. Qiao, Small 2017, 13, 1700191。
disclosure of Invention
In order to solve the defects of the prior art, the invention provides a preparation method of a high-load transition metal single-atom loaded carbon-based catalyst, and the preparation method is applied to electrocatalytic reduction of carbon dioxide into carbon monoxide. The catalyst is obtained by sweeping and burning zinc oxide loaded by a transition metal monatomic and 2-methylimidazole at high temperature, the zinc oxide loaded by the transition metal monatomic is obtained by dipping the zinc oxide in a transition metal salt solution, and the zinc oxide is hydrothermally synthesized under a specific condition and has a special crystal face exposure. The active site of the catalyst is metal-N coordinated monoatomic transition metal, and the catalyst has the characteristics of high selectivity and wide potential window. The carbon dioxide in the electrolyte solution is subjected to processes of adsorption-reduction reaction-desorption and the like at active sites, and the desorption of the carbon monoxide in the process is the fastest due to the regulation and control of the coordination environment, so that the high selectivity is realized. The zinc oxide plays an important role as a template in the formation process of the transition metal monoatomic atom, in the dipping process, the transition metal atom in the solution replaces the zinc atom on the nonpolar surface of the zinc oxide, and then the zinc atom is embedded into the zinc oxide crystal lattice, and in the process that the zinc oxide loaded by the transition metal monoatomic atom reacts with 2-methylimidazole at high temperature to form ZIF-8, the transition metal atom is limited at the corresponding zinc atom position, so that the zinc atom in the ZIF-8 is replaced, and a metal-N coordinated monoatomic site with catalytic activity is formed.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a preparation method of a high-load transition metal single-atom-loaded carbon-based catalyst, which comprises the following steps:
1) Preparing a zinc oxide template with a special exposed crystal face by a hydrothermal synthesis method;
adding concentrated ammonia water into the zinc ion aqueous solution and carrying out hydrothermal reaction to obtain a zinc oxide template with exposed special crystal faces; wherein the volume of the concentrated ammonia water accounts for 15-18% of the total volume of the hydrothermal solution, the molar concentration of zinc ions in the hydrothermal solution is 0.5-0.6 mol/L, the volume of the hydrothermal solution accounts for 30-50% of the volume of the hydrothermal kettle, the hydrothermal time is 4 h-24 h, and the hydrothermal temperature is 85-115 ℃;
2) Mixing zinc oxide with exposed special crystal faces with deionized water, stirring to a uniform suspension state, then slowly dropwise adding an aqueous solution of transition metal salt into the mixed system, wherein the molar ratio of the zinc oxide to the transition metal salt is 99.5-97, dipping 0.5 h-2 h when the dropwise adding is started, and then filtering, washing and drying to obtain the transition metal monatomic supported zinc oxide.
3) The transition metal monatomic supported zinc oxide and 2-methylimidazole are placed in a tubular furnace to react for 0.25 h-2 h at the temperature of 600-1000 ℃ according to the molar ratio of 1.8-1.
In a preferred embodiment of the present invention, the transition metal is one or a combination of iron, cobalt and nickel. The salt can be water-soluble salts such as ferric nitrate, cobalt nitrate, nickel nitrate and the like.
Preferably, when the hydrothermal synthesis method is used for preparing the zinc oxide with the exposed special crystal face, the volume of the concentrated ammonia water accounts for 17.5% of the volume of the hydrothermal solution, and the molar concentration of zinc ions in the hydrothermal solution is 0.57 mol/L.
Preferably, in the step 2), the molar ratio of the zinc oxide to the transition metal ions is 99.
Preferably, the molar ratio of the transition metal monatomic supported zinc oxide to the 2-methylimidazole reaction is 1.
The invention also provides a transition metal single atom supported carbon-based catalyst prepared by the method.
The invention also provides application of the transition metal single-atom loaded carbon-based catalyst in electrocatalytic reduction of carbon dioxide into carbon monoxide.
Preferably, the application is to use an Ag/AgCl electrode as a reference electrode, a Pt column as a counter electrode and the transition metal monatomic supported carbon-based catalyst of claim 6 as a raw material to manufacture a working electrode, wherein the electrolyte solution is 0.1M-0.5M KHCO 3 The solution is in a carbon dioxide dissolved saturated state; constant voltage electrocatalytic reduction was performed in the range of 0.84V-1.44V.
Preferably, the working electrode made of the transition metal monatomic supported carbon-based catalyst is applied to the electrocatalytic reduction after the CV activation.
Preferably, the prepared carbon-based catalyst is mixed with 0.5 percent Nafion and absolute ethyl alcohol according to the proportion of 10 mg, 100 mu L and 900 mu L, 2 h is subjected to ultrasonic treatment, 12 h is stirred until the mixture is uniformly dispersed to obtain ink, and 100 mu L ink is uniformly coated on 1 cm x 1 cm carbon paper to obtain the cathode of the electrolytic cell. The cathode was placed at 0.5M and saturated KHCO was dissolved in carbon dioxide 3 CV activation in solutionAnd then used as a working electrode for a three-electrode system. The selectivity of carbon monoxide can reach 95 percent at normal temperature and normal pressure.
Compared with the prior art, the invention has the beneficial effects that:
(1) The transition metal monoatomic-supported carbon-based catalyst prepared by the invention maintains transition metal monoatomic active sites in a zinc oxide template confinement mode. The reported confinement modes for maintaining the monoatomic active site include metal organic frameworks, polymers and the like, generally adopt a mode of firstly coordinating an organic precursor and metal ions and then calcining at high temperature, and the metal organic frameworks or the polymers cannot bear overhigh temperature and are easy to generate structural change or even collapse under the high-temperature condition. On one hand, the effective limit of metal ions cannot be realized, the regulation and control of active sites are influenced, the agglomeration is increased, and on the other hand, part of metal ions are lost. The zinc oxide as a template can bear very high temperature without structural change or loss of metal ions, and can well maintain the transition metal monoatomic active sites.
(2) The transition metal monatomic supported carbon-based catalyst prepared by the invention limits the transition metal atom by adopting a zinc oxide impregnation mode with a special crystal face exposed, and effectively forms a large amount of supported transition metal monatomics. The zinc oxide generally has a hexagonal crystal form, oxygen ions and zinc ions are stacked in layers in the crystal, two ions on the side surface of the stack are uniformly distributed, and only one atom is on the top surface and the bottom surface, so that different exposed crystal faces have different surface chemical properties. This difference in chemical properties is also reflected in the adsorption of transition metal ions during impregnation. The polar crystal face has the strongest reaction activity, and is quickly adsorbed with transition metal ions, so that agglomeration is easily formed. According to the invention, the zinc oxide with the exposed nonpolar surface is prepared, the exposure of a polar crystal face is greatly reduced, the adsorption of transition metal ions is slowed down, and the agglomeration is inhibited, and on the other hand, the adsorption of transition metal atoms is further inhibited by the sites which have adsorbed the transition metal atoms, and finally a large amount of loaded transition metal single atoms are formed on the nonpolar surface.
(3) The transition metal single atom loaded carbon-based catalyst prepared by the invention has the characteristics of high active site exposure and high atom utilization rate. Because transition metal atoms only exist on the surface of the zinc oxide in the dipping process, the reaction of the zinc oxide and the 2-methylimidazole is also only on the surface of the zinc oxide under the high-temperature condition, the surface of the zinc oxide is used as a reaction interface, and the single-atom active sites of the transition metal formed by the reaction are completely exposed on the surface of the catalyst after carbonization, the catalyst has the characteristics of high active site exposure ratio and high atom utilization ratio.
(4) The transition metal single-atom loaded carbon-based catalyst prepared by the invention has low cost and simple preparation process. The raw materials used in the invention mainly comprise zinc acetate dihydrate, strong ammonia water, transition metal nitrate and 2-methylimidazole, the solvent is water, the cost of the raw materials is low, and the ammonia, the zinc and the like can be recycled in the process industry. The preparation process comprises three steps of hydrothermal, dipping and high-temperature reaction, the conditions are mild and easy to control, and the industrial production is easy to realize.
Drawings
Fig. 1 is XRD spectra of commercial zinc oxide, zinc oxide (a) with non-polar crystal faces exposed in example 1, zinc oxide (b) with non-polar crystal faces exposed before and after iron monatomic loading in example 1, and carbon-based catalyst (c) with iron monatomic loading in example 1.
Fig. 2 is a graph of the appearance of zinc oxide with an exposed non-polar crystal face, zinc oxide supported by an iron monoatomic atom, and a carbon-based catalyst supported by an iron monoatomic face, and an element distribution diagram of the zinc oxide supported by an iron monoatomic face and the carbon-based catalyst supported by an iron monoatomic face in example 1 of the present invention.
Fig. 3 is an XPS chart of nitrogen and iron in the carbon-based catalyst supported by an iron single atom in example 1 of the present invention.
Fig. 4 is LSV curves of an iron supported catalyst prepared using non-polar surface exposed zinc oxide as a template according to example 1 of the present invention, an iron supported catalyst prepared using commercial zinc oxide as a raw material according to comparative example 1, and a catalyst prepared using polar surface exposed zinc oxide as a template according to comparative example 2.
Fig. 5 is a graph showing faradaic efficiency curves of an iron supported catalyst prepared using non-polar surface-exposed zinc oxide as a template according to example 1 of the present invention, an iron supported catalyst prepared using commercial zinc oxide as a raw material according to comparative example 1, and a catalyst prepared using polar surface-exposed zinc oxide as a template according to comparative example 2.
Fig. 6 is a carbon monoxide partial current curve of an iron supported catalyst prepared using non-polar surface exposed zinc oxide as a template according to example 1 of the present invention, an iron supported catalyst prepared using commercial zinc oxide of comparative example 1 as a starting material, and a catalyst prepared using polar surface exposed zinc oxide of comparative example 2 as a template.
FIG. 7 is a schematic diagram of the preparation principle of the iron monatomic supported carbon-based catalyst of the present invention.
Detailed Description
In order to effectively understand the present invention, the present invention will be further described with reference to the following examples and drawings, it should be noted that the present invention is not limited to these examples, and those skilled in the art can make insubstantial modifications and adjustments under the core theory of the present invention, and still fall within the scope of the present invention. Wherein the mass concentration of the concentrated ammonia water used in each embodiment and comparative example is 25-28%.
Example 1:
1. preparation of iron monatomic supported carbon-based catalyst: on the basis of synthesizing the zinc oxide exposed on a special crystal face (a nonpolar face (1010)) loaded by monatomic iron, the monatomic iron and 2-methylimidazole react at high temperature in a tubular furnace in an argon atmosphere to obtain the final catalyst in one step. The method specifically comprises the following steps:
(1) Weighing 0.407 g iron-loaded zinc oxide and 0.977 g 2-methylimidazole, and placing the iron-loaded zinc oxide and the 2-methylimidazole in a corundum boat with a cover of 2 cm x 10 cm, wherein the iron-loaded zinc oxide is placed in the middle of the corundum boat and corresponds to the downwind direction of carrier gas; the 2-methylimidazole is arranged at the head of the corundum boat and corresponds to the upward wind direction of the carrier gas.
(2) And (3) placing the corundum boat in the middle of a 4 cm-3 mm-60cm quartz tube, then placing the quartz tube in a tube furnace quartz tube, and placing corundum furnace plugs at two ends of the quartz tube so that the corundum boat corresponds to the thermocouple position of the tube furnace.
(3) And (3) vacuumizing the tube furnace by using a vacuum pump, opening an argon flowmeter valve after vacuumizing to be vacuum, inflating the tube furnace until gauge pressure is zero, and repeating for three times to ensure that air is completely discharged out of the tube furnace. Finally, the flow of argon is adjusted to 10 mL/min, and the tail end of the tube furnace is communicated with the atmosphere.
(4) Setting a temperature raising program, continuously raising the temperature from the normal temperature to 900 ℃ at a temperature raising rate of 5 ℃/min, maintaining 0.5 h, and then freely lowering the temperature to the room temperature. Zinc oxide completely reacts with 2-methylimidazole in the high-temperature process to generate ZIF-8, the ZIF-8 is further carbonized and graphitized at high temperature, iron atoms replace partial zinc atom positions, fe-N active sites are formed at high temperature, and zinc atoms volatilize along with the carbonization of the ZIF-8 at high temperature.
The preparation process of the iron-loaded zinc oxide with the exposed non-polar surface in this example is as follows:
(1) 2.502 g zinc acetate dihydrate is weighed into a 50 mL polytetrafluoroethylene hydrothermal kettle, then 16.5 mL deionized water is added, and stirring is carried out on an electromagnetic stirring table for 10 min until complete dissolution. Then 3.5 mL strong ammonia water is mixed with the solution and stirred for 10 min, at this time, a clear solution is obtained.
(2) And (3) transferring the hydrothermal kettle to a 95 ℃ oven, maintaining the temperature at 8 h, and then freely cooling to room temperature. And taking out the hydrothermal kettle, and filtering, washing and drying the reaction product to obtain the zinc oxide with the non-polar surface (1010) exposed.
When preparing the zinc oxide with the non-polar surface (1010) exposed, the inventor finds that the zinc oxide with the non-polar surface exposed can be obtained when the volume ratio of the concentrated ammonia water in the clear solution in the step 1) is 15 to 18 percent.
(3) 0.407 g of the zinc oxide and 50 mL deionized water are mixed and stirred to be uniform, then 0.5 mL of 0.1M ferric nitrate solution is slowly added into the mixed solution in a dropwise manner, and the stirring is continued until 1 h is reached. Filtering, washing and drying to obtain the zinc oxide with the exposed non-polar surface (1010) loaded with iron.
2. Preparation and activation treatment of electrode
(1) Using a three-electrode system, mixing the prepared catalyst with 0.5 percent Nafion and absolute ethyl alcohol according to the proportion of 10 mg, 100 uL and 900 uL, carrying out ultrasonic treatment on the mixture to obtain 2 h, and stirring 12 h until the mixture is uniformly dispersed to obtain the catalystTo ink, 100 uL ink is evenly coated on 1 cm x 1 cm carbon paper in four times to be used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt column electrode is used as a counter electrode, an H-type double-chamber electrolytic cell is used, and 0.5M KHCO saturated in carbon dioxide solution is used 3 The solution is an electrolyte.
(2) The Shanghai Chenghua CHI 660E electrochemical workstation is used, a CV program is adopted, the test interval is 0.84V-1.64V vs. Ag/AgCl, the sweep rate is 50 mV/s, and the cycle is 50 circles until the electrode reaches a stable state.
3. Linear Sweep Voltammetry (LSV) testing
After the electrode is activated, the switching program is an LSV program, the test interval is 0.84V-1.64V vs. Ag/AgCl, and the sweep rate is 25 mV/s.
4. Gas Analysis Chromatography (GAC) test
After LSV testing, the switching program is an I-t program, the voltage is from 0.84V vs. Ag/AgCl to 1.44 vs Ag/AgCl, and a test point is taken every 0.1V. And communicating the gas outlet of the electrolytic cell with a gas chromatograph. The gas chromatography sample introduction is carried out once every 15 min, and the test voltage is changed once every 15 min.
Example 2:
1. preparation of a cobalt monoatomic supported carbon-based catalyst: on the basis of synthesizing the zinc oxide with the exposed non-polar surface loaded by the monatomic cobalt, the zinc oxide and 2-methylimidazole react at high temperature in a tubular furnace in the argon atmosphere to obtain the final catalyst in one step. The method specifically comprises the following steps:
(1) Weighing 0.407 g cobalt-loaded zinc oxide and 0.977 g 2-methylimidazole, and placing the cobalt-loaded zinc oxide and the 2-methylimidazole in a corundum boat with a cover of 2 cm x 10 cm, wherein the cobalt-loaded zinc oxide is placed in the middle of the corundum boat and corresponds to the downwind direction of carrier gas; the 2-methylimidazole is arranged at the head of the corundum boat and corresponds to the upward wind direction of the carrier gas.
(2) And (3) placing the corundum boat in the middle of a 4 cm-3 mm-60cm quartz tube, then placing the quartz tube in a tube furnace quartz tube, and placing corundum furnace plugs at two ends of the quartz tube so that the corundum boat corresponds to the thermocouple position of the tube furnace.
(3) And (3) vacuumizing the tube furnace by using a vacuum pump, opening an argon flowmeter valve after vacuumizing to be vacuum, inflating the tube furnace until gauge pressure is zero, and repeating for three times to ensure that air is completely discharged out of the tube furnace. Finally, the flow of argon is adjusted to 10 mL/min, and the tail end of the tube furnace is communicated with the atmosphere.
(4) Setting a temperature raising program, continuously raising the temperature from the normal temperature to 900 ℃ at a temperature raising rate of 5 ℃/min, maintaining 0.5 h, and then freely lowering the temperature to the room temperature. Zinc oxide completely reacts with 2-methylimidazole in the high-temperature process to generate ZIF-8, the ZIF-8 is further carbonized and graphitized at high temperature, cobalt atoms replace partial zinc atom positions, a Co-N active site is formed at high temperature, and zinc atoms volatilize along with the carbonization of the ZIF-8 at high temperature.
The preparation process of the cobalt-loaded zinc oxide with the exposed nonpolar surface in the embodiment is as follows:
(1) 2.502 g zinc acetate dihydrate is weighed into a 50 mL polytetrafluoroethylene hydrothermal kettle, then 16.5 mL deionized water is added, and stirring is carried out on an electromagnetic stirring table for 10 min until complete dissolution. Then 3.5 mL strong ammonia water is mixed with the solution and stirred for 10 min, at this time, a clear solution is obtained.
(2) And (3) transferring the hydrothermal kettle to a 95 ℃ oven, maintaining the temperature at 8 h, and then freely cooling to room temperature. And taking out the hydrothermal kettle, and filtering, washing and drying the reaction product to obtain the zinc oxide with the non-polar surface (1010) exposed.
(3) 0.407 g of the zinc oxide is mixed with 50 mL deionized water and stirred to be uniform, then 0.5 mL of 0.1M cobalt nitrate solution is slowly added dropwise into the mixed solution, and stirring is continued until 1 h. Filtering, washing and drying to obtain the zinc oxide with the exposed cobalt-loaded non-polar face (1010).
2. Preparation and activation treatment of electrode
(1) Mixing the prepared catalyst with 0.5 percent Nafion and absolute ethyl alcohol according to the proportion of 10 mg, 100 uL and 900 uL by using a three-electrode system, carrying out ultrasonic treatment on the mixture to obtain 2H and stirring the mixture to obtain 12H until the mixture is uniformly dispersed to obtain ink, taking 100 uL ink for four times to uniformly coat the ink on 1 cm and 1 cm of carbon paper to serve as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt column electrode as a counter electrode, using an H-type double-chamber electrolytic cell, and taking 0.5M and KHCO which is saturated by dissolving carbon dioxide in the H-type double-chamber electrolytic cell 3 The solution being electrolysisAnd (4) quality.
(2) The electrochemical workstation of Shanghai Chenghua CHI 660E is used, CV program is adopted, the test interval is 0.84V-1.64V vs. Ag/AgCl, the sweep rate is 50 mV/s, and the cycle is 50 circles until the electrode reaches the stable state.
3. Linear Sweep Voltammetry (LSV) testing
After the electrode is activated, the switching program is an LSV program, the test interval is 0.84V-1.64V vs. Ag/AgCl, and the sweep rate is 25 mV/s.
4. Gas Analysis Chromatography (GAC) test
After LSV testing, the switching program is an I-t program, the voltage is from 0.84V vs. Ag/AgCl to 1.44 vs Ag/AgCl, and a test point is taken every 0.1V. And communicating the gas outlet of the electrolytic cell with a gas chromatograph. The gas chromatography sample introduction is carried out once every 15 min, and the test voltage is changed once every 15 min.
Comparative example 1:
1. preparation of iron-supported carbon-based catalyst: on the basis of commercial iron-impregnated zinc oxide, the catalyst is reacted with 2-methylimidazole in a tubular furnace at high temperature in an argon atmosphere to obtain the final catalyst in one step. The method specifically comprises the following steps:
(1) Weighing 0.407 g iron-impregnated commercial zinc oxide and 0.977 g 2-methylimidazole, and placing the weighed commercial zinc oxide and the 2-methylimidazole in a corundum boat with a cover of 2 cm x 10 cm, wherein the iron-impregnated commercial zinc oxide is placed in the middle of the corundum boat and corresponds to the downwind direction of a carrier gas; the 2-methylimidazole is arranged at the head of the corundum boat and corresponds to the upward wind direction of the carrier gas.
(2) And (3) placing the corundum boat in the middle of a 4 cm-3 mm-60cm quartz tube, then placing the quartz tube in a tube furnace quartz tube, and placing corundum furnace plugs at two ends of the quartz tube so that the corundum boat corresponds to the thermocouple position of the tube furnace.
(3) And (3) vacuumizing the tube furnace by using a vacuum pump, opening an argon flowmeter valve after vacuumizing to be vacuum, inflating the tube furnace until gauge pressure is zero, and repeating for three times to ensure that air is completely discharged out of the tube furnace. Finally, the flow rate of argon is adjusted to 10 mL/min, and the tail end of the tubular furnace is communicated with the atmosphere.
(4) Setting a temperature rise program, continuously raising the temperature from the normal temperature to 900 ℃ at a temperature rise rate of 5 ℃/min, maintaining the temperature for 0.5 h, and then freely cooling to the room temperature.
The procedure used in this example to prepare iron impregnated commercial zinc oxide was:
0.407 g of commercial zinc oxide was mixed with 50 mL deionized water and stirred until homogeneous, then 0.5 mL of 0.1m ferric nitrate solution was slowly added dropwise to the mixture and stirring continued until 1 h. Filtered, washed and dried to obtain iron impregnated commercial zinc oxide. 2. Preparation and activation treatment of electrode
(1) Mixing the prepared catalyst with 0.5 percent Nafion and absolute ethyl alcohol according to the proportion of 10 mg, 100 uL and 900 uL by using a three-electrode system, carrying out ultrasonic treatment on the mixture to obtain 2H and stirring the mixture to obtain 12H until the mixture is uniformly dispersed to obtain ink, taking 100 uL ink for four times to uniformly coat the ink on 1 cm and 1 cm of carbon paper to serve as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt column electrode as a counter electrode, using an H-type double-chamber electrolytic cell, and taking 0.5M and KHCO which is saturated by dissolving carbon dioxide in the H-type double-chamber electrolytic cell 3 The solution is an electrolyte.
(2) The electrochemical workstation of Shanghai Chenghua CHI 660E is used, CV program is adopted, the test interval is 0.84V-1.64V vs. Ag/AgCl, the sweep rate is 50 mV/s, and the cycle is 50 circles until the electrode reaches the stable state.
3. Linear Sweep Voltammetry (LSV) testing
After the electrode is activated, the switching program is an LSV program, the test interval is 0.84V-1.64V vs. Ag/AgCl, the sweep rate is 25 mV/s, and the result shows that the current is far smaller than that of an example sample.
4. Gas Analysis Chromatography (GAC) test
After LSV testing, the switching program is an I-t program, the voltage is from 0.84V vs. Ag/AgCl to 1.44 vs Ag/AgCl, and a test point is taken every 0.1V. The gas outlet of the electrolytic cell is communicated with the gas chromatograph. The gas chromatography samples once every 15 min, and the test voltage was changed once every 15 min, and the results show that the selectivity of carbon monoxide is obviously inferior to that of the sample in the working interval.
Comparative example 2:
1. preparation of a catalyst using zinc oxide with a polar face (0001) exposed as a template: on the basis of zinc oxide with an iron-loaded polar surface exposed, carrying out high-temperature reaction with 2-methylimidazole in a tubular furnace in an argon atmosphere to obtain the final catalyst in one step. The method comprises the following specific steps:
(1) Weighing 0.407 g zinc oxide exposed on the iron-loaded polar surface and 0.977 g 2-methylimidazole, and placing the zinc oxide and the 2-methylimidazole in a corundum boat with a cover, wherein the zinc oxide exposed on the iron-loaded polar surface is placed in the middle of the corundum boat and corresponds to the downwind direction of carrier gas; the 2-methylimidazole is arranged at the head of the corundum boat and corresponds to the upward wind direction of the carrier gas.
(2) And (3) placing the corundum boat in the middle of a 4 cm-3 mm-60cm quartz tube, then placing the quartz tube in a tube furnace quartz tube, and placing corundum furnace plugs at two ends of the quartz tube so that the corundum boat corresponds to the thermocouple position of the tube furnace.
(3) And (3) vacuumizing the tube furnace by using a vacuum pump, opening an argon flowmeter valve after vacuumizing to be vacuum, inflating the tube furnace until gauge pressure is zero, and repeating for three times to ensure that air is completely discharged out of the tube furnace. Finally, the flow of argon is adjusted to 10 mL/min, and the tail end of the tube furnace is communicated with the atmosphere.
(4) Setting a temperature rise program, continuously raising the temperature from the normal temperature to 900 ℃ at a temperature rise rate of 5 ℃/min, maintaining the temperature for 0.5 h, and then freely cooling to the room temperature.
The preparation process of the zinc oxide with the iron-loaded polar surface exposed in the comparative example is as follows:
(1) 2.502 g zinc acetate dihydrate is weighed into a 50 mL polytetrafluoroethylene hydrothermal kettle, then 16.5 mL deionized water is added, and stirring is carried out on an electromagnetic stirring table for 10 min until complete dissolution. Then 1 mL strong ammonia water is mixed with the solution and stirred for 10 min, at this time, a clear solution is obtained.
(2) And (3) transferring the hydrothermal kettle to a 95 ℃ oven, maintaining the temperature at 8 h, and then freely cooling to room temperature. And (3) taking out the hydrothermal kettle, filtering, washing and drying the reaction product to obtain the zinc oxide with the exposed polar surface (0001).
(3) 0.407 g of the zinc oxide is mixed with 50 mL deionized water and stirred to be uniform, then 0.5 mL of 0.1M ferric nitrate solution is slowly added into the mixed solution dropwise, and stirring is continued until 1 h. And filtering, washing and drying to obtain the zinc oxide with the exposed iron-loaded polar face (0001).
2. Preparation and activation treatment of electrode
(1) Mixing the prepared catalyst with 0.5 percent Nafion and absolute ethyl alcohol according to the proportion of 10 mg, 100 uL and 900 uL by using a three-electrode system, carrying out ultrasonic treatment on 2H and stirring 12H until the mixture is uniformly dispersed to obtain ink, uniformly coating 100 uL ink on 1 cm x 1 cm carbon paper in four times to be used as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt column electrode as a counter electrode, using an H-shaped double-chamber electrolytic cell, and taking 0.5M and KHCO saturated by carbon dioxide solution 3 The solution is an electrolyte.
(2) The electrochemical workstation of Shanghai Chenghua CHI 660E is used, CV program is adopted, the test interval is 0.84V-1.64V vs. Ag/AgCl, the sweep rate is 50 mV/s, and the cycle is 50 circles until the electrode reaches the stable state.
3. Linear Sweep Voltammetry (LSV) testing
After the electrode is activated, the switching program is an LSV program, the test interval is 0.84V-1.64V vs. Ag/AgCl, the sweep rate is 25 mV/s, and the result shows that the current is far smaller than that of an example sample.
4. Gas Analysis Chromatography (GAC) test
After LSV testing, the switching program is an I-t program, the voltage is from 0.84V vs. Ag/AgCl to 1.44 vs Ag/AgCl, and a test point is taken every 0.1V. And communicating the gas outlet of the electrolytic cell with a gas chromatograph. The gas chromatography samples once every 15 min, and the test voltage was changed once every 15 min, and the results show that the selectivity of carbon monoxide is obviously inferior to that of the sample in the working interval.
FIG. 1 shows XRD spectra of Commercial zinc oxide ("ZnO-Commercial" in the figure), nonpolar crystal surface exposed zinc oxide ("ZnO-1010" in the figure) (a), nonpolar crystal surface exposed zinc oxide before iron monoatomic loading ("ZnO-1010" in the figure), after (Fe doped ZnO-1010 "in the figure) (b), and iron monoatomic loading carbon-based catalyst Fe-N-C (C). It can be seen that the corresponding non-polar crystal plane peaks are more prominent compared to commercial zinc oxide, non-polar face exposed zinc oxide; for zinc oxide loaded by iron monoatomic atoms, the characteristic peak completely corresponds to a zinc oxide standard spectrogram, no extra peak related to iron is generated, and the atomic-scale distribution of iron elements is proved; for the iron monatomic supported carbon-based catalyst, a distinct graphite carbon peak can be seen, which is the result of the high temperature treatment.
Fig. 2 shows the topography of the non-polar crystal face-exposed zinc oxide (a), the iron monoatomic zinc oxide (b), and the iron monoatomic carbon-based catalyst (c) and the elemental distribution of the iron monoatomic zinc oxide (d) and the iron monoatomic carbon-based catalyst (e) in example 1, respectively. The zinc oxide exposed on the non-polar surface is in a rod shape, and the side surface of the rod shape corresponds to the polar surface of the zinc oxide and is matched with the XRD result; the shape of the zinc oxide loaded by the iron monoatomic atom is consistent with that of the zinc oxide exposed from the nonpolar surface, and iron elements are uniformly distributed on the surface of the zinc oxide; the shape of the iron monoatomic supported carbon-based catalyst also corresponds to the rod shape of the zinc oxide, and the wrapping relation between carbon and the zinc oxide rod can be seen.
Fig. 3 is an XPS graph of nitrogen and iron in the carbon-based catalyst supported on an iron single atom in example 1. The main forms of nitrogen are graphite nitrogen and metal nitrogen, which indicates that the nitrogen exists in the carrier in the catalyst to form nitrogen-doped graphene and coordinates with metal atoms to form a catalytic active site. The valence state of the iron element is +3, which is related to the coordination environment of the iron element.
FIG. 4 shows LSV curves of a catalyst prepared using non-polar face-exposed zinc oxide as a template ("ZnO-1010" in the figure) of example 1, a catalyst prepared using commercial zinc oxide as a raw material ("ZnO-commercial" in the figure) of comparative example 1, and a catalyst prepared using polar face-exposed zinc oxide as a template ("ZnO-0001" in the figure) of comparative example 2, respectively. It can be seen that the catalyst prepared by using the non-polar surface exposed zinc oxide as the template has higher current under the same voltage, on one hand, more active sites provide more current related to the reaction, and on the other hand, less iron agglomeration reduces the loss of the carbon-based carrier, which is beneficial to providing higher current for the carrier. The catalyst prepared by taking the non-polar surface exposed zinc oxide as a template has smaller over potential, which also indicates that the catalyst has more active sites and is more favorable for the target reaction.
FIG. 5 is a graph showing Faraday efficiency curves of a catalyst prepared using the nonpolar face exposed zinc oxide of example 1 as a template ("ZnO-1010" in the figure), a catalyst prepared using the commercial zinc oxide of comparative example 1 as a raw material ("ZnO-commercial" in the figure), and a catalyst prepared using the polar face exposed zinc oxide of comparative example 2 as a template ("ZnO-0001" in the figure). The catalyst prepared by taking the non-polar surface exposed zinc oxide as a template has higher Faraday efficiency which can reach 95 percent at most and can keep more than 90 percent of Faraday efficiency in a wider potential range. This shows that the catalyst has high selectivity of carbon monoxide, and can well inhibit hydrogen evolution reaction.
FIG. 6 is a carbon monoxide partial current curve of a catalyst prepared using non-polar surface-exposed zinc oxide as a template ("ZnO-1010" in the figure) of example 1, a catalyst prepared using commercial zinc oxide as a raw material ("ZnO-commercial" in the figure) of comparative example 1, and a catalyst prepared using polar surface-exposed zinc oxide as a template ("ZnO-0001" in the figure) of comparative example 2. The catalyst prepared by using the non-polar surface exposed zinc oxide as a template has higher carbon monoxide partial current, which indicates that the catalyst has more active sites.
Based on the above analysis results, and in combination with the preparation process of the examples, a schematic diagram of the preparation principle of the iron monatomic supported carbon-based catalyst in example 1 of the present invention can be visually shown in fig. 7, in which "ZnO-1010" refers to the non-polar surface (1010) exposed zinc oxide prepared after completion of step 2) in the preparation process of the iron supported non-polar surface exposed zinc oxide in example 1; in the figure, "Fe-dopedZnO-1010" means the iron-supported non-polar face (1010) exposed zinc oxide obtained after completion of step 3) in the preparation of the iron-supported non-polar face exposed zinc oxide in example 1; in the figure, "Fe-N-C" refers to the iron monatomic supported carbon-based catalyst obtained in the end of example 1.
It can be intuitively understood from fig. 7 that the transition metal monatomic supported carbon-based catalyst prepared by the present invention has the characteristics of high active site exposure and high atom utilization. Because the nonpolar Surface (1010) of the zinc oxide is exposed on the Surface, transition metal atoms are limited on the Surface of the zinc oxide in the dipping process (in the figure, "Impregnation"), the reaction of the zinc oxide and 2-methylimidazole (in the figure, "Surface reaction") under high temperature condition is only on the Surface of the zinc oxide, the Surface of the zinc oxide is used as a reaction interface, and the single atom active sites of the transition metal formed by the reaction are completely exposed on the Surface of the catalyst after Carbonization (in the figure, "Carbonization"), so the zinc oxide has the characteristics of high active site exposure ratio and high atom utilization rate.
It should be noted that the above-mentioned specific implementation method describes the technical solution and application result of the present invention in detail, and the reader should understand that the above-mentioned embodiment is only the most preferable embodiment and is not used to limit the present invention, and modifications or equivalent substitutions made by the related technicians within the core theory scope of the present invention should fall into the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-load transition metal single-atom carbon-based catalyst is characterized by comprising the following steps:
1) Preparing a zinc oxide template with exposed special crystal faces by a hydrothermal synthesis method, adding concentrated ammonia water into a zinc ion aqueous solution, and carrying out hydrothermal reaction, wherein the volume of the concentrated ammonia water accounts for 15-18% of the total volume of the hydrothermal solution, the mass concentration of the concentrated ammonia water is 25-28%, the molar concentration of zinc ions in the hydrothermal solution is 0.5-0.6 mol/L, the volume of the hydrothermal solution accounts for 30-50% of the volume of a hydrothermal kettle, the hydrothermal time is 4 h-24 h, and the hydrothermal temperature is 85-115 ℃;
2) Mixing zinc oxide with exposed special crystal faces with deionized water, stirring to a uniform suspension state, then slowly dropwise adding an aqueous solution of transition metal salt into the mixed system, wherein the molar ratio of the zinc oxide to the transition metal salt is 99.5-97, dipping 0.5 h-2 h when dropwise adding is started, and then filtering, washing and drying to obtain the transition metal monatomic-loaded zinc oxide; wherein the special crystal face exposed in the special crystal face is a nonpolar crystal face;
3) Reacting 0.25 h-2 h with transition metal monatomic supported zinc oxide and 2-methylimidazole in a molar ratio of 1.8-1;
the transition metal is one or the combination of iron and cobalt.
2. The method for preparing the transition metal monatomic carbon-based catalyst with high load capacity according to claim 1, wherein when the hydrothermal synthesis method is used for preparing the zinc oxide with the exposed special crystal face, the volume of the concentrated ammonia water accounts for 17.5% of the volume of the hydrothermal solution, and the molar concentration of zinc ions in the hydrothermal solution is 0.57 mol/L.
3. The method for preparing the high-load transition metal single-atom carbon-based catalyst according to claim 1, wherein in the step 2), the molar ratio of zinc oxide to transition metal ions is 99 to 1, and the impregnation time is 1 h.
4. The method for preparing the high-load transition metal monatomic carbon-based catalyst according to claim 1, characterized in that the molar ratio of the transition metal monatomic-loaded zinc oxide to the 2-methylimidazole is 1.
5. The method for preparing the high-load transition metal monatomic carbon-based catalyst according to claim 1, wherein the specific crystal plane in the specific crystal plane exposure is a nonpolar crystal plane (1010).
6. A transition metal monatomic supported carbon-based catalyst prepared by the method according to any one of claims 1 to 5.
7. Use of a transition metal monatomic supported carbon-based catalyst according to claim 6 for the electrocatalytic reduction of carbon dioxide to carbon monoxide.
8. The method of claim 7The application is characterized in that an Ag/AgCl electrode is used as a reference electrode, a Pt column is used as a counter electrode, the transition metal monoatomic supported carbon-based catalyst of claim 6 is used as a raw material to manufacture a working electrode, and the electrolyte solution is 0.1M-0.5M KHCO 3 The solution is in a state of carbon dioxide dissolved saturation; the constant voltage electrocatalytic reduction is carried out in the range of 0.84V-1.44 zxft 3262.
9. The use of claim 8, wherein the working electrode made of carbon-based catalyst supported by transition metal monoatomic atoms is applied to electrocatalytic reduction after CV activation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252727.5A CN114016074B (en) | 2021-10-27 | 2021-10-27 | Preparation method and application of high-load transition metal single-atom carbon-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252727.5A CN114016074B (en) | 2021-10-27 | 2021-10-27 | Preparation method and application of high-load transition metal single-atom carbon-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114016074A CN114016074A (en) | 2022-02-08 |
| CN114016074B true CN114016074B (en) | 2022-10-21 |
Family
ID=80057885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111252727.5A Active CN114016074B (en) | 2021-10-27 | 2021-10-27 | Preparation method and application of high-load transition metal single-atom carbon-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114016074B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609460A (en) * | 2015-01-29 | 2015-05-13 | 武汉大学 | Nano-zinc oxide with controllable length and preparation method thereof |
| CN104649312A (en) * | 2013-11-20 | 2015-05-27 | 上海工程技术大学 | Synthetic method of zinc oxide/zinc silicate core-shell super structure assembled by nanorods |
| CN106215942A (en) * | 2016-07-12 | 2016-12-14 | 华南理工大学 | A kind of controllable synthesis method of the new discotic zinc oxide being doped with transition metal or rare earth metal |
| CN108899556A (en) * | 2018-06-29 | 2018-11-27 | 首都师范大学 | A kind of method that ball milling auxiliary prepares the monatomic iron catalyst of carbon nitrogen base |
| CN109301221A (en) * | 2018-10-12 | 2019-02-01 | 台州学院 | A kind of compound micron bar electrode material of zinc oxide/nickel and preparation method thereof |
| CN109589917A (en) * | 2018-12-07 | 2019-04-09 | 南京理工大学 | Based on double layer hollow zinc oxide/carbon material solid-phase micro-extraction fibre and preparation method thereof |
| CN109647529A (en) * | 2018-12-21 | 2019-04-19 | 福州大学 | A method of ZnO/ZIF-CN/Ag nanocomposite is synthesized based on ZIF-8 |
| CN111313040A (en) * | 2018-12-12 | 2020-06-19 | 中国科学院大连化学物理研究所 | Fe-N-C catalyst and preparation and application thereof |
| CN111584889A (en) * | 2020-05-29 | 2020-08-25 | 深圳大学 | Zinc-containing monatomic catalyst and preparation method and application thereof |
| CN112909272A (en) * | 2021-03-19 | 2021-06-04 | 哈尔滨工业大学 | Preparation method of non-noble metal oxygen reduction reaction catalyst for constructing bimetallic active sites |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8747804B2 (en) * | 2008-07-18 | 2014-06-10 | Basf Se | Modified zinc oxide particles |
| SG11201805804SA (en) * | 2016-01-14 | 2018-08-30 | Agency Science Tech & Res | Free-standing mof-derived hybrid porous carbon nanofiber mats |
-
2021
- 2021-10-27 CN CN202111252727.5A patent/CN114016074B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649312A (en) * | 2013-11-20 | 2015-05-27 | 上海工程技术大学 | Synthetic method of zinc oxide/zinc silicate core-shell super structure assembled by nanorods |
| CN104609460A (en) * | 2015-01-29 | 2015-05-13 | 武汉大学 | Nano-zinc oxide with controllable length and preparation method thereof |
| CN106215942A (en) * | 2016-07-12 | 2016-12-14 | 华南理工大学 | A kind of controllable synthesis method of the new discotic zinc oxide being doped with transition metal or rare earth metal |
| CN108899556A (en) * | 2018-06-29 | 2018-11-27 | 首都师范大学 | A kind of method that ball milling auxiliary prepares the monatomic iron catalyst of carbon nitrogen base |
| CN109301221A (en) * | 2018-10-12 | 2019-02-01 | 台州学院 | A kind of compound micron bar electrode material of zinc oxide/nickel and preparation method thereof |
| CN109589917A (en) * | 2018-12-07 | 2019-04-09 | 南京理工大学 | Based on double layer hollow zinc oxide/carbon material solid-phase micro-extraction fibre and preparation method thereof |
| CN111313040A (en) * | 2018-12-12 | 2020-06-19 | 中国科学院大连化学物理研究所 | Fe-N-C catalyst and preparation and application thereof |
| CN109647529A (en) * | 2018-12-21 | 2019-04-19 | 福州大学 | A method of ZnO/ZIF-CN/Ag nanocomposite is synthesized based on ZIF-8 |
| CN111584889A (en) * | 2020-05-29 | 2020-08-25 | 深圳大学 | Zinc-containing monatomic catalyst and preparation method and application thereof |
| CN112909272A (en) * | 2021-03-19 | 2021-06-04 | 哈尔滨工业大学 | Preparation method of non-noble metal oxygen reduction reaction catalyst for constructing bimetallic active sites |
Non-Patent Citations (4)
| Title |
|---|
| Highly efficient and selective CO2 electro-reduction with atomic Fe-C-N hybrid coordination on porous carbon nematosphere;Haixia Zhong等;《纳米研究(英文版)》;20191231;第12卷(第9期);第2318-2323页 * |
| Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells;Eric Proietti等;《Nature Communications》;20111231;第2卷;第416页 * |
| M(M=Fe，Co，Mn)-N-C催化剂用于燃料电池的氧化还原反应;刘扬;《电池工业》;20211231;第25卷(第6期);第308-316页 * |
| Promoting Electrochemical CO2 Reduction via Boosting Activation of Adsorbed Intermediates on Iron Single-Atom Catalyst;Jiayi Chen等;《Advanced Functional Materials》;20220220;第1-9页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114016074A (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Amination strategy to boost the CO 2 electroreduction current density of M–N/C single-atom catalysts to the industrial application level | |
| Chen et al. | Mn-doped RuO2 nanocrystals as highly active electrocatalysts for enhanced oxygen evolution in acidic media | |
| Zhang et al. | Boosting overall water splitting via FeOOH nanoflake-decorated PrBa0. 5Sr0. 5Co2O5+ δ nanorods | |
| Sanetuntikul et al. | Cobalt and nitrogen co-doped hierarchically porous carbon nanostructure: a bifunctional electrocatalyst for oxygen reduction and evolution reactions | |
| Santori et al. | High performance FeNC and Mn-oxide/FeNC layers for AEMFC cathodes | |
| Wan et al. | Oxygen-evolution catalysts based on iron-mediated nickel metal–organic frameworks | |
| Wang et al. | Efficient oxygen evolution reaction from iron-molybdenum nitride/molybdenum oxide heterostructured composites | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| Wang et al. | Facile synthesis of ZnCo-ZIFs-derived ZnxCo3− xO4 hollow polyhedron for efficient oxygen evolution reduction | |
| CN110433839B (en) | Preparation method of cobalt carbon nitrogen material loaded with cerium dioxide | |
| KR102436831B1 (en) | Method for producing a catalyst electrode for water splitting reaction comprising a nickel iron selenide nanohybrid structure | |
| CN114150340B (en) | Method for preparing high-load type single-atom carbon-based catalyst based on one-step gas-solid reaction and application | |
| Huang et al. | Ultrathin nitrogenated carbon nanosheets with single-atom nickel as an efficient catalyst for electrochemical CO2 reduction | |
| CN108579718B (en) | Preparation method and application of indium-doped nano porous carbon material | |
| KR20150036350A (en) | Carbendazim-based catalytic materials | |
| Meng et al. | An electrochemically reconstructed WC/WO 2–WO 3 heterostructure as a highly efficient hydrogen oxidation electrocatalyst | |
| Song et al. | Progress and perspective of single‐atom catalysts for membrane electrode assembly of fuel cells | |
| Li et al. | Rational design of self-supported WC/Co3W3N/Co@ NC yolk/shell nitrogen-doped porous carbon catalyst for highly efficient overall water splitting | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| Zhang et al. | Few-atom-layer metallene quantum dots toward CO2 electroreduction at ampere-level current density and Zn-CO2 battery | |
| Ren et al. | Single-atom catalysts for electrochemical applications | |
| Gong et al. | Heterogeneous single-atom catalysts for energy process: recent progress, applications and challenges | |
| Lee et al. | Deciphering mass transport behavior in membrane electrode assembly by manipulating porous structures of atomically dispersed Metal-Nx catalysts for High-Efficiency electrochemical CO2 conversion | |
| CN114016074B (en) | Preparation method and application of high-load transition metal single-atom carbon-based catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |