CN114433158A - Nitrogen-doped hierarchical pore carbon-based catalyst and preparation method and application thereof - Google Patents

Nitrogen-doped hierarchical pore carbon-based catalyst and preparation method and application thereof Download PDF

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CN114433158A
CN114433158A CN202011127124.8A CN202011127124A CN114433158A CN 114433158 A CN114433158 A CN 114433158A CN 202011127124 A CN202011127124 A CN 202011127124A CN 114433158 A CN114433158 A CN 114433158A
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李先锋
姚鹏飞
邱艳玲
郑琼
张华民
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Dalian Institute of Chemical Physics of CAS
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Abstract

The application discloses a nitrogen-doped hierarchical pore carbon-based catalyst, and a preparation method and application thereof. The nitrogen-doped hierarchical pore carbon-based catalyst has a micropore and mesopore structure; the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is higher than that of zinc-nitrogen; wherein the contents of the graphite nitrogen and the zinc-nitrogen are calculated by nitrogen element. The nitrogen is dopedThe mixed hierarchical pore carbon-based catalyst has the characteristics of hierarchical pore structure, high conductivity and adjustable components, and has reasonable content of various N elements and excellent CO2The Faraday efficiency of preparing CO by electrochemical reduction is suitable for catalyzing the electrochemical reduction reaction of carbon dioxide.

Description

Nitrogen-doped hierarchical pore carbon-based catalyst and preparation method and application thereof
Technical Field
The application relates to a nitrogen-doped hierarchical pore carbon-based catalyst and a preparation method and application thereof, belonging to the technical field of carbon dioxide electrochemical reduction.
Background
Currently, the economy and society of China are in a high-speed development stage, the demand for energy is increasing day by day, and a serious problem of carbon dioxide emission is brought. According to the latest report of International Energy Agency (IEA), the worldwide CO was estimated in 20172The emission reaches 410 hundred million tons, which is increased by 2 percent compared with 2016. Therefore, how to reduce CO2Effective utilization of CO2Has become a hot spot of research in recent years.
CO2The transformation and utilization of (1) mainly include four types, i.e., biochemical transformation, chemical transformation, electrochemical transformation and photochemical transformation. With other CO2Compared with the conversion technology, the electrochemical reduction of CO2The (ERC) technology has the outstanding advantages that water can be used as a hydrogen source for reaction, and CO can be realized at normal temperature and normal pressure2The high-efficiency conversion of the energy storage device is realized, electric energy is stored in a chemical energy form, and intermittent power resources generated by wind energy, solar energy and the like can be balanced.
Electrochemical reduction of CO2The technology is to utilize the electric energy generated by renewable energy sources to convert CO2Reduction to chemicals to effect CO2An effective technique for resource utilization. CO generation by electrochemical techniques2Directly with H2And O reacts to generate compounds with high added values, such as ethanol, methane, hydrocarbon compounds and the like, so that the conversion between electric energy and chemical energy is realized. Not only makes the ERC technology more economical, but also realizes the storage of renewable energy sources and forms a carbon and energy conversion cycle. Currently, the main factors restricting the development of ERC technology include: (1) the reaction overpotential is higher; (2) the activity of the reaction is low; (3) the product selectivity is poor. Therefore, the key to the current research is to find suitable catalysts to reduce the overpotential of the reaction, improve the product selectivity and the activity of the reaction. At present, the research on the catalyst mainly focuses on noble metal catalysts such as gold and silver, and although the selectivity of the catalyst on CO is high, the catalyst is expensive and is not suitable for large-scale commercial production. However, the research on the non-metal nitrogen-doped carbon-based catalyst is relatively few, and the nitrogen-doped porous carbon has attracted extensive attention due to the advantages of high specific surface area, adjustable pore structure, high conductivity, low price and the like. ZIF8 is a microporous structure rich polypeptideThe catalyst obtained by directly carbonizing a porous nitrogen-doped carbon precursor has the following common problems: the microporous structure is not beneficial to the transmission of carbon dioxide; high zinc-nitrogen content is easy to induce hydrogen evolution side reaction; low electrical conductivity.
Disclosure of Invention
According to one aspect of the application, the nitrogen-doped hierarchical pore carbon-based catalyst has the characteristics of hierarchical pore structure, high conductivity and adjustable components, and the content of each type of N element is reasonable, so that the nitrogen-doped hierarchical pore carbon-based catalyst has excellent CO2The Faraday efficiency of preparing CO by electrochemical reduction is suitable for catalyzing the electrochemical reduction reaction of carbon dioxide.
A nitrogen-doped hierarchical pore carbon-based catalyst having a microporous and mesoporous structure;
the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is higher than that of zinc-nitrogen;
wherein the contents of the graphite nitrogen and the zinc-nitrogen are calculated by nitrogen element.
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 1.4-2% higher than that of zinc-nitrogen.
Optionally, the total content of nitrogen elements in the nitrogen-doped hierarchical pore carbon-based catalyst is 4% to 7%.
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.2 to 1 percent higher than that of pyridine nitrogen
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.6 to 1 percent higher than that of pyridine nitrogen
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.3% to 0.9% higher than that of pyrrole nitrogen.
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.3% to 0.51% higher than that of pyrrole nitrogen.
Optionally, the graphite nitrogen of the nitrogen-doped hierarchical porous carbon-based catalyst accounts for 30-50% of the total content of nitrogen elements.
Optionally, the graphite nitrogen of the nitrogen-doped hierarchical porous carbon-based catalyst accounts for 35% to 50% of the total content of nitrogen elements.
Optionally, the zinc-nitrogen content of the nitrogen-doped hierarchical porous carbon-based catalyst accounts for 8% -20% of the total content of nitrogen elements.
Optionally, the zinc-nitrogen content of the nitrogen-doped hierarchical porous carbon-based catalyst accounts for 8% -13% of the total content of nitrogen elements.
Optionally, pyridine nitrogen of the nitrogen-doped graded pore carbon-based catalyst accounts for 15% -30% of the total content of nitrogen elements.
Optionally, pyridine nitrogen of the nitrogen-doped graded pore carbon-based catalyst accounts for 15% -25% of the total content of nitrogen elements.
Optionally, pyrrole nitrogen of the nitrogen-doped hierarchical porous carbon-based catalyst accounts for 20% -35% of the total content of nitrogen elements.
Optionally, pyrrole nitrogen of the nitrogen-doped hierarchical porous carbon-based catalyst accounts for 27% -35% of the total content of nitrogen elements.
The contents of graphite nitrogen, zinc-nitrogen, pyridine nitrogen and pyrrole nitrogen are all calculated by nitrogen element.
The graphitic nitrogen is nitrogen that is attached to three carbon atoms in a graphitic carbon structure and forms a six-membered ring structure;
the zinc-nitrogen is a bond structure formed by zinc atoms and nitrogen atoms in a graphite carbon structure;
the pyridine nitrogen is nitrogen connected with two carbon atoms in the graphite carbon structure and forms a six-membered ring structure;
the pyrrole nitrogen is nitrogen which is connected with two carbon atoms in the graphite carbon structure and forms a five-membered ring structure;
optionally, the proportion of the micropores is 30% -50%, and the proportion of the mesopores is 50% -70%.
Optionally, the pore diameter of the micropores is 0.7-1.1 nm, and the pore diameter of the mesopores is 3-10 nm.
Optionally, the total volume of the nitrogen-doped hierarchical porous carbon-based catalyst is 0.6-1.2 cm3The volume of the micro pores is 0.18-0.45 cm3The mesoporous volume is 0.5-0.8 cm3/g。
Optionally, the upper total volume limit is selected from 0.82cm3/g、0.88cm3/g、0.95cm3/g、1cm3/g、1.2cm3(ii)/g; the lower limit is selected from 0.6cm3/g、0.65cm3/g、0.75cm3/g、0.82cm3/g。
Optionally, the upper micropore volume limit is selected from 0.24cm3/g、0.28cm3/g、0.45cm3(ii)/g; the lower limit is selected from 0.18cm3/g、0.2cm3/g、0.24cm3/g。
Optionally, the total surface area of the nitrogen-doped hierarchical pore carbon-based catalyst is 700-1000 m2The surface area of the micropores is 400-800 m2/g。
Optionally, the upper total surface area limit is selected from 785m2/g、800m2/g、850m2/g、900m2/g、1000m2(ii)/g; the lower limit is selected from 700m2/g、750m2/g、785m2/g。
Optionally, the upper micropore surface area limit is selected from 437m2/g、500m2/g、550m2/g、800m2(ii)/g; the lower limit is selected from 400m2/g、420m2/g、437m2/g。
Optionally, the mesopore volume is up to an upper limit selected from 0.58m2/g、0.65m2/g、0.7m2/g、0.8m2(ii)/g; the lower limit is selected from 0.5m2/g、0.55m2/g、0.58m2/g。
Optionally, the surface of the nitrogen-doped hierarchical pore carbon-based catalyst has long-range ordered graphitized stripes.
According to another aspect of the present application, there is provided a method for preparing a nitrogen-doped hierarchical pore carbon-based catalyst, the method comprising the steps of: soaking ZIF8 in a bismuth salt solution to obtain a solution I, and separating to obtain a product I; and calcining the product I at the temperature of 900-1050 ℃ to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
According to the method, ZIF8 is used as a carbon precursor, and bismuth salt is used for regulating and controlling the carbon precursor, so that the nitrogen-doped hierarchical pore carbon-based catalyst is obtained.
In the preparation method of the nitrogen-doped hierarchical pore carbon-based catalyst provided by the application, a reducing agent is not required to be added into the solution I.
Optionally, the upper temperature condition limit is selected from 950 ℃, 980 ℃, 1000 ℃, 1050 ℃; the lower limit is selected from 900 deg.C, 920 deg.C, 950 deg.C.
Alternatively, the calcining is: and under the condition of inactive gas, the calcining time is 1-3 h.
Optionally, the inert gas is selected from at least one of nitrogen or an inert gas.
Optionally, the inert gas is selected from at least one of argon, helium, neon.
Alternatively, the upper calcination time limit is selected from 2h, 2.5h, 3 h; the lower limit is selected from 1h, 1.5h and 2 h.
Optionally, the temperature rise speed of the calcination is 2-5 ℃/min.
Optionally, the heating rate is selected from 3 ℃/min, 4 ℃/min, 5 ℃/min; the lower limit is selected from 2 deg.C/min and 3 deg.C/min.
Optionally, the bismuth salt is selected from at least one of bismuth sulfate, bismuth chloride and bismuth nitrate.
Optionally, the solvent of the solution I is at least one selected from ethanol solution, methanol solution and propanol solution.
Optionally, the concentration of the ethanol solution is 90-99%.
Optionally, the concentration of ZIF8 in the solution I is 1-10 g/L.
Optionally, the upper concentration limit of ZIF8 in solution I is selected from 5g/L, 6g/L, 7g/L, 8g/L, 10 g/L; the lower limit is selected from 1g/L, 2g/L, 3g/L, 5 g/L.
Optionally, the concentration of the bismuth salt in the solution I is 2-4 g/L.
Optionally, the upper limit of the concentration of the bismuth salt in the solution I is selected from 2.4g/L, 2.8g/L, 3.5g/L and 4 g/L; the lower limit is selected from 2.2g/L and 2.4 g/L.
Optionally, the impregnation is specifically: and stirring the mixture of ZIF8 and the bismuth salt solution for 12-24 h.
Optionally, the separating is specifically: and (4) after centrifugation, carrying out freeze drying or drying at 60-90 ℃ for 12-24 h.
Optionally, the preparation method of ZIF8 comprises the following steps: and stirring the solution II containing dimethylimidazole and zinc nitrate to obtain the ZIF 8.
Optionally, the solvent of the solution II is selected from at least one of methanol, ethanol, propanol.
Optionally, the concentration of the dimethyl imidazole in the solution II is 15-30 g/L.
Optionally, the upper limit of the concentration of the dimethyl imidazole in the solution II is selected from 23g/L, 25g/L, 28g/L and 30 g/L; the lower limit is selected from 15g/L, 18g/L, 20g/L, 13 g/L.
Optionally, the concentration of zinc nitrate in the solution II is 5-15 g/L.
Optionally, the upper limit of the concentration of the zinc nitrate in the solution II is selected from 11.7g/L, 13g/L and 15 g/L; the lower limit is selected from 5g/L, 7g/L, 9g/L, 11.7 g/L.
Optionally, after the step of stirring II is finished, the method further comprises a separation step, where the separation step is: and (4) after centrifugation, carrying out freeze drying or drying at 60-90 ℃ for 12-24 h.
According to another aspect of the present application, there is provided a carbon dioxide electrochemical reduction catalyst comprising at least one of the nitrogen-doped hierarchical pore carbon-based catalyst of any of the above, the nitrogen-doped hierarchical pore carbon-based catalyst prepared according to the method of any of the above.
Optionally, the carbon dioxide electrochemical reduction catalyst is a carbon dioxide electrochemical reduction cathode catalyst.
As one embodiment of the present application, the technical solution adopted by the present application is as follows:
a preparation method of a nitrogen-doped hierarchical pore carbon-based catalyst comprises the following steps:
1) preparing a solution A: a methanol solution of dimethylimidazole with the mass concentration of 30-60 g/L; preparing a solution B: a methanol solution of zinc nitrate with the mass concentration of 10-30 g/L; mixing a methanol solution of dimethyl imidazole and a methanol solution of zinc nitrate according to a volume ratio of 1: 0.5-3, and stirring for 12-24 hours;
2) carrying out centrifugal drying treatment on the obtained product to obtain ZIF 8;
3) adding ZIF8 into a saturated ethanol solution of bismuth salt, stirring for 12-24 h, and then centrifugally drying for 12-24 h; the mass concentration of ZIF8 in the solution is 1-10 g/L, and the mass concentration of bismuth salt in the ethanol solution is 2-4 g/L;
4) calcining the dried sample at high temperature under the argon condition to obtain a catalyst; the calcining condition is that the temperature is raised from the room temperature to 900-1050 ℃ at the temperature raising speed of 2-5 ℃/min, and then the temperature is kept for 1-3 h.
Optionally, the drying after centrifugation in the step 2) is freeze drying or drying at 60-90 ℃ for 12-24 h.
Optionally, the bismuth salt in step 3) is one or more of bismuth sulfate, bismuth chloride and bismuth nitrate.
The nitrogen-doped hierarchical pore carbon-based catalyst prepared by the preparation method is applied to a cathode of a carbon dioxide electrochemical reduction reaction.
Optionally, the preparation of the cathode is that a catalyst and 2 wt% -8 wt% of Nafion solution are added into an ethanol solution, the content of the nitrogen-doped hierarchical porous carbon-based catalyst is 4-10 mg/ml, the content of Nafion is 40-100 ul/ml, ultrasonic treatment is carried out for 0.5-1.5 h, and the prepared catalyst dispersion liquid is dripped on the surface of the glassy carbon electrode.
According to the preparation method, the pore structure, the surface area, the conductivity and the components of the ZIF8 are regulated and controlled by utilizing the bismuth salt, so that the nitrogen-doped hierarchical pore carbon-based catalyst with the hierarchical pore structure, high conductivity and low zinc-nitrogen content is obtained. The similar CO Faraday efficiency as noble metals at lower overpotentials is achieved.
The beneficial effect that this application can produce includes:
(1) the nitrogen-doped hierarchical pore carbon-based catalyst has the characteristics of hierarchical pore structure, high conductivity and adjustable components, and has reasonable content of various N elements and excellent CO2The Faraday efficiency of preparing CO by electrochemical reduction is suitable for catalyzing the electrochemical reduction reaction of carbon dioxide.
(2) According to the preparation method of the nitrogen-doped hierarchical pore carbon-based catalyst, firstly, bismuth salt is introduced into a micro-pore structure and a surface of ZIF8, then low-boiling-point bismuth metal is removed through a high-temperature calcination process, so that a nitrogen-doped hierarchical pore carbon material is obtained, and the nitrogen-doped carbon-based catalyst with the hierarchical pore structure is obtained by controlling the mass ratio of the bismuth salt to ZIF8 and regulating and controlling calcination conditions. During the whole calcining process, bismuth salt in the pores and on the surface of the ZIF8 undergoes the whole processes of melting, generation of metal bismuth nanoparticles and sublimation of bismuth along with the rise of temperature, so that the carbon material with a hierarchical pore structure is realized, and the mesoporous volume is large. The surface of the material is rich in micro-mesoporous structures, and micropores are favorable for the adsorption of carbon dioxide and promote the enrichment of the carbon dioxide on a reaction interface; the mesoporous structure effectively promotes material transport.
(3) According to the preparation method of the nitrogen-doped hierarchical pore carbon-based catalyst, the whole change process of the bismuth salt further regulates and controls the pore surface structure and composition, and the graphitization of carbon is effectively promoted. In addition, the introduction of the bismuth salt effectively changes the type of the N element, compared with a ZIF8 carbon material which is not modified by the bismuth salt, the percentage content of graphite nitrogen in the nitrogen-containing carbon material is obviously increased, the content of Zn-N is obviously reduced, and the electro-catalytic performance of the catalyst is further improved.
(4) Bismuth chloride is a low-boiling-point metal salt, and is firstly adsorbed into a microporous structure of ZIF8 through a simple liquid-phase impregnation process, and is in a molten state in a later calcining process, so that a Zn-N structure of nearby ZIF8 is seriously damaged, and the agglomeration and volatilization of zinc atoms are promoted. In addition, bismuth chloride is reduced into bismuth nanoparticles by carbon at high temperature and further volatilized to generate a series of mesoporous structures. Bismuth metal can effectively promote graphitization of nearby carbon at high temperature. Thereby obtaining the nitrogen-doped hierarchical pore carbon-based catalyst with hierarchical pore structure, high conductivity and low zinc-nitrogen content. Not only CO Faraday efficiency (90%) similar to noble metals but also high catalytic activity over a wide potential range is achieved.
(5) Compared with other technologies, the preparation method of the nitrogen-doped hierarchical pore carbon-based catalyst provided by the application does not need a later-stage complex treatment process (bismuth salt template removal). The preparation method is simple, the production equipment is conventional, and the method is suitable for large-scale production.
(6) The nitrogen-doped hierarchical pore carbon-based catalyst provided by the application is used as a cathode of a carbon dioxide electrochemical reduction reaction, and is beneficial to exposing more active sites, so that the electrode has higher catalytic activity.
Drawings
FIG. 1 is a TEM image of nitrogen-doped hierarchical porous carbon-based catalysts prepared in example 1 and comparative examples 4 to 8 of the present application, wherein a is a TEM image (100nm) of comparative example 5; b is a TEM image (100nm) of comparative example 6, c is a TEM image (100nm) of comparative example 7; d is a TEM image (100nm) of comparative example 8; e is a TEM image (100nm) of comparative example 4; f is the TEM image of example 1 (100 nm).
FIG. 2 is an SEM and TEM image of an electrode prepared in example 1 of the present application, wherein a is an SEM image (100nm) of example 1; b is a TEM image of example 1 (100 nm); c is the TEM image of example 1 (10 nm).
FIG. 3 is an SEM image and a TEM image of an electrode prepared in comparative example 1 of the present application, wherein a is an SEM image (100nm) of example 1; b is a TEM image (50nm) of comparative example 1; c is a TEM image (10nm) of comparative example 1.
FIG. 4 SEM and TEM images of an electrode prepared in comparative example 2 of the present application, wherein a is the SEM image (100nm) of comparative example 2; b is a TEM image (50nm) of comparative example 2; c is a TEM image (10nm) of comparative example 2.
FIG. 5 is an SEM and TEM image of an electrode prepared in comparative example 3 of the present application, wherein a is an SEM image (100nm) of comparative example 3; b is a TEM image (50nm) of comparative example 3; c is a TEM image (10nm) of comparative example 3.
FIG. 6 is a graph showing electrochemical properties of electrodes prepared in example 1 and comparative examples 1 to 3, wherein a is a comparison of faradaic efficiencies for CO production; b is a comparative plot for generating CO current density.
FIG. 7 is a graph showing the results of nitrogen adsorption specific surface area tests of catalysts prepared in example 1 and comparative examples 1 to 3 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Example 1
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparation of solution A: adding 7.0g of dimethyl imidazole into 150ml of methanol and stirring; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Quickly pouring the solution B into the solution A, and stirring for 12 hours;
2) and centrifuging the obtained product, and drying at 75 ℃ to obtain ZIF 8.
3) Adding 96mg of bismuth chloride into 40ml of ethanol solution, adding 0.2g of ZIF8 into the solution, stirring for 12 hours, centrifuging the obtained product, and drying at 75 ℃ for 12 hours;
4) and (3) heating the dried sample at the speed of 3 ℃/min under the argon environment, heating the sample from room temperature to 950 ℃, and then preserving the heat for 2h to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
Adding the prepared nitrogen-doped hierarchical porous carbon-based catalyst and 5 wt% Nafion solution into 300ul of 99% ethanol solution, performing ultrasonic treatment for 0.5h, and coating the prepared catalyst to 1.5 multiplied by 2.0cm2And drying the surface of the glassy carbon electrode to finally obtain the electrode.
Examples 2 to 3
Examples 2-3 were prepared in the same manner as example 1, except for the raw materials/conditions listed in table 1.
Table 1, examples 2 to 3 and example 1 differ in the raw materials/conditions
Raw materials/conditions Example 1 Example 2 Example 3
Kinds of bismuth salts Bismuth chloride Bismuth nitrate Bismuth chloride
Calcination temperature 950℃ 950℃ 1000℃
Comparative example 1
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparation of solution A: adding 7.0g of dimethyl imidazole into 150ml of methanol and stirring; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Quickly pouring the solution B into the solution A, and stirring for 12 hours;
2) and centrifuging the obtained product, and drying at 75 ℃ to obtain ZIF 8.
3) Adding 0.2g of ZIF8 into 40ml of ethanol solution, stirring for 12 hours, then centrifugally washing with distilled water, and then carrying out drying treatment at 75 ℃ for 12 hours;
4) and calcining the dried sample ZIF8 in argon at 950 ℃ for 2h, and heating at the speed of 3 ℃/min to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
Adding the prepared nitrogen-doped hierarchical porous carbon-based catalyst and 5 wt% Nafion solution into 300ul of 99% ethanol solution, carrying out ultrasonic treatment for 0.5h, and coating the solution to 1.5 × 2.0cm2Glassy carbon electrodeAnd drying the surface to finally obtain the electrode.
Comparative example 2
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparation of solution A: adding 7.0g of dimethyl imidazole into 150ml of methanol and stirring; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Quickly pouring the solution B into the solution A, and stirring for 12 hours;
2) and centrifuging the obtained product, and drying at 75 ℃ to obtain ZIF 8.
3) Adding 24mg of bismuth chloride into 40ml of ethanol solution, adding 0.2g of ZIF8 into the solution, stirring for 12 hours, then centrifuging the obtained product, and then drying at 75 ℃ for 12 hours;
4) and (3) heating the dried sample at the speed of 3 ℃/min under the argon environment, heating the sample from room temperature to 950 ℃, and then preserving the heat for 2h to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
Adding the prepared nitrogen-doped hierarchical porous carbon-based catalyst and 5 wt% Nafion solution into 300ul of 99% ethanol solution, carrying out ultrasonic treatment for 0.5h, and coating the solution to 1.5 × 2.0cm2And drying the surface of the glassy carbon electrode to finally obtain the electrode.
Comparative example 3
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparation of solution A: adding 7.0g of dimethyl imidazole into 150ml of methanol and stirring; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Quickly pouring the solution B into the solution A, and stirring for 12 hours;
2) and centrifuging the obtained product, and drying at 75 ℃ to obtain ZIF 8.
3) Adding 48mg of bismuth chloride into 40ml of ethanol solution, adding 0.2g of ZIF8 into the solution, stirring for 12 hours, centrifuging the obtained product, and drying at 75 ℃ for 12 hours;
4) and (3) heating the dried sample at the speed of 3 ℃/min under the argon environment, heating the sample from room temperature to 950 ℃, and then preserving the heat for 2h to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
Adding the prepared nitrogen-doped hierarchical porous carbon-based catalyst and 5 wt% Nafion solution into 300ul of 99% ethanol solution, carrying out ultrasonic treatment for 0.5h, and coating the solution to 1.5 × 2.0cm2And drying the surface of the glassy carbon electrode to finally obtain the electrode.
Comparative example 4
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparation of solution A: adding 7.0g of dimethyl imidazole into 150ml of methanol and stirring; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Quickly pouring the solution B into the solution A, and stirring for 12 hours;
2) and centrifuging the obtained product, and drying at 75 ℃ to obtain ZIF 8.
3) Adding 96mg of bismuth chloride into 40ml of ethanol solution, adding 0.2g of ZIF8 into the solution, stirring for 12 hours, centrifuging the obtained product, and drying at 75 ℃ for 12 hours;
4) and (3) heating the dried sample at the speed of 3 ℃/min under the argon environment to the temperature of 750 ℃ from room temperature, and then preserving the heat for 2h to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
Adding the prepared nitrogen-doped hierarchical porous carbon-based catalyst and 5 wt% Nafion solution into 300ul of 99% ethanol solution, carrying out ultrasonic treatment for 0.5h, and coating the solution to 1.5 × 2.0cm2And drying the surface of the glassy carbon electrode to finally obtain the electrode.
Comparative examples 5 to 8
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
The same as in comparative example 4, except for the calcination temperature in step 4). Wherein the calcination temperature of comparative example 5 is 25 deg.c, the calcination temperature of comparative example 6 is 250 deg.c, the calcination temperature of comparative example 7 is 350 deg.c, and the calcination temperature of comparative example 8 is 550 deg.c.
(2) Preparation of cathode for carbon dioxide reduction
Same procedure as in comparative example 4.
Determination of total nitrogen content and various types of nitrogen content of nitrogen-doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 1-3
The results of the measurements using X-ray photoelectron spectroscopy are shown in Table 2.
Table 2 shows the total nitrogen content and the nitrogen contents of various types of nitrogen-doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 1 to 3
Figure BDA0002733976660000121
Determination of surface area and volume of nitrogen-doped hierarchical pore carbon-based catalyst prepared in example 1 and comparative examples 1 to 3
The results of measurement using a nitrogen adsorption specific surface measuring instrument are shown in Table 3 and FIG. 7.
TABLE 3 surface area and volume of the nitrogen-doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 1 to 3
Figure BDA0002733976660000122
Figure BDA0002733976660000131
It can be seen from fig. 7 that example 1 has a wider hysteresis loop in the relative medium-pressure section (0.4-0.8), so that example 1 has a larger mesopore volume, and it is more obvious from table three that the comparative example has a higher mesopore volume. The mesoporous structure of the catalyst material and the graphitization degree of the catalytic carbon can be effectively increased by regulating and controlling the bismuth salt, so that the conductivity and the material transmission capability of the catalyst can be improved.
Morphology characterization of nitrogen-doped hierarchical pore carbon-based catalyst prepared in example 1 and comparative examples 4-8
The determination method comprises the following steps: scanning electron microscope and transmission electron microscope
As can be seen from a to e in FIG. 1, a large amount of metal bismuth particles remain on the surface of the material under the calcination treatment at 25 to 750 ℃, a mesoporous structure cannot be effectively formed, and in addition, the high content of bismuth metal promotes the hydrogen evolution side reaction. Therefore, the catalytic performance of the material treated at the temperature is lower. As can be seen from f in fig. 1, in example 1, the bismuth salt in the pores and on the surface of ZIF8 underwent the entire process of melting, generation of metallic bismuth nanoparticles, and sublimation of bismuth with the increase of temperature during the entire calcination process, thereby realizing a carbon material with a hierarchical pore structure. The surface of the material is rich in micro-mesoporous structures, and micropores are favorable for the adsorption of carbon dioxide and promote the enrichment of the carbon dioxide on a reaction interface; the mesoporous structure effectively promotes material transport.
Morphology characterization of electrodes prepared in example 1 and comparative examples 1-3
The determination method comprises the following steps: scanning electron microscopy and transmission electron microscopy.
The results are shown in FIGS. 2 to 5, in which:
FIG. 2 is an SEM and TEM image of an electrode prepared in example 1 of the present application, wherein a is an SEM image (100nm) of example 1; b is a TEM image of example 1 (100 nm); c is the TEM image of example 1 (10 nm).
FIG. 3 is an SEM image and a TEM image of an electrode prepared in comparative example 1 of the present application, wherein a is an SEM image (100nm) of example 1; b is a TEM image (50nm) of comparative example 1; c is a TEM image (10nm) of comparative example 1.
FIG. 4 SEM and TEM images of an electrode prepared in comparative example 2 of the present application, wherein a is the SEM image (100nm) of comparative example 2; b is a TEM image (50nm) of comparative example 2; c is a TEM image (10nm) of comparative example 2.
FIG. 5 is an SEM and TEM image of an electrode prepared in comparative example 3 of the present application, wherein a is an SEM image (100nm) of comparative example 3; b is a TEM image (50nm) of comparative example 3; c is a TEM image (10nm) of comparative example 3.
As can be seen from the electron micrographs of fig. 2 to 5, the electrode surface of example 1 has a richer mesoporous structure, and the catalyst surface has more long-range ordered graphitized stripes, and as can be seen from fig. 7, example 1 has a wider hysteresis loop in the relative medium-pressure section (0.4 to 0.8), so that example 1 has a larger mesoporous volume, and as can be seen from table three, the comparative example has a higher mesoporous volume. The mesoporous structure of the catalyst material and the graphitization degree of the catalytic carbon can be effectively increased by regulating and controlling the bismuth salt, so that the conductivity and the material transmission capability of the catalyst can be improved.
Electrochemical performance measurement of electrodes prepared in example 1 and comparative examples 1 to 3
The electrodes prepared in example 1 and comparative examples 1 to 3 were used as cathodes for carbon dioxide reduction. And performing electrochemical test through a three-electrode system, wherein the determination method comprises the following steps:
the working electrode was the electrode prepared in example 1 and comparative examples 1 to 3;
the counter electrode is a Pt sheet, and the reference electrode is Ag/AgCl. The distance between the WE (working electrode) and the RE (reference electrode) was 0.5cm, and the liquid junction potential was reduced by using a salt bridge. The electrolyte of the cathode and the anode is 0.5M KHCO3Sol, catholyte volume 160ml, anolyte volume 80 ml. CO 22The flow is controlled by a mass flow meter, and the flow rate is 20 ml/min; constant potential electrolysis is carried out at a potential of-0.3V to-1.0V. The results are shown in FIG. 6.
As can be seen from FIGS. 6 a-b, the catalyst prepared in example 1 has a Faraday efficiency of CO of 90% at a potential of-0.5V to-0.7V; comparative example 1 at-0.5V potential, CO2The faradaic efficiency of reduction to CO is 50%; comparative example 2 CO at a potential of-0.5V2The faradaic efficiency of reduction to CO was 78%; comparative example 3 CO at a potential of-0.5V2The faradaic efficiency for reduction to CO was 80%. The faraday efficiency of example 1 was improved by 40% compared to comparative example 1 without doping bismuth salt, and the current density was improved by 5 times compared to comparative example 1, and the faraday efficiency of example 1 was improved by 10% compared to comparative examples 2 and 3, and the current density was improved by 2 times compared to comparative example 1.
From the above analysis, the present application proposesThe preparation method of the provided nitrogen-doped hierarchical pore carbon-based catalyst is simple and easy to control, and the obtained nitrogen-doped hierarchical pore carbon-based catalyst has excellent CO2The selectivity of CO preparation by electrochemical reduction is high, and the electrode prepared by the obtained nitrogen-doped hierarchical pore carbon-based catalyst has excellent ERC (electrochemical reduction of CO)2) And (4) stability. According to the preparation method, the ZIF8 is regulated and controlled by using a proper amount of bismuth salt and calcining in a proper temperature range, so that the mesoporous structure and the graphitization degree of catalytic carbon are effectively regulated and controlled, and the catalytic performance is greatly improved; meanwhile, the nitrogen-doped hierarchical pore carbon-based catalyst has high graphite nitrogen percentage content and low zinc-nitrogen content, the high graphite nitrogen content indicates that the catalyst has high conductivity, and the low zinc-nitrogen content is beneficial to inhibiting hydrogen evolution reaction, so that the catalyst has high catalytic activity and selectivity. By properly regulating the mass ratio of the metal bismuth salt to the ZIF8, the nitrogen species on the surface of the catalyst material can be effectively regulated, so that higher catalytic performance is realized.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A nitrogen-doped hierarchical pore carbon-based catalyst, characterized in that the nitrogen-doped hierarchical pore carbon-based catalyst has a microporous and mesoporous structure;
the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is higher than that of zinc-nitrogen;
wherein the contents of the graphite nitrogen and the zinc-nitrogen are calculated by nitrogen element.
2. The nitrogen-doped hierarchical pore carbon-based catalyst according to claim 1, wherein the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 1.40% to 2% higher than that of zinc-nitrogen;
preferably, the total content of nitrogen elements in the nitrogen-doped hierarchical pore carbon-based catalyst is 4-7%;
preferably, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.2-1% higher than that of pyridine nitrogen;
preferably, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.3-0.9% higher than that of pyrrole nitrogen.
3. The nitrogen-doped hierarchical pore carbon-based catalyst according to claim 2, wherein the proportion of the micropores is 30-50%, and the proportion of the mesopores is 50-70%;
preferably, the aperture of the micropore is 0.7-1.1 nm, and the aperture of the mesopore is 3-10 nm;
preferably, the total volume of the nitrogen-doped hierarchical porous carbon-based catalyst is 0.6-1.2 cm3The volume of the micro pores is 0.18-0.45 cm3The mesoporous volume is 0.5-0.8 cm3/g；
Preferably, the total surface area of the nitrogen-doped hierarchical pore carbon-based catalyst is 700-1000 m2Per g, the surface area of the micropores is 400-800 m2/g。
4. The nitrogen-doped hierarchical pore carbon-based catalyst of claim 1, wherein the surface of the nitrogen-doped hierarchical pore carbon-based catalyst has long-range ordered graphitized stripes.
5. A preparation method of a nitrogen-doped hierarchical pore carbon-based catalyst is characterized by comprising the following steps: soaking ZIF8 in a bismuth salt solution to obtain a solution I, and separating to obtain a product I; and calcining the product I at the temperature of 900-1050 ℃ to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
6. The method of claim 5, wherein the calcining is: under the condition of inactive gas, the calcining time is 1-3 h;
preferably, the temperature rise speed of the calcination is 2-5 ℃/min.
7. The method according to claim 5, wherein the bismuth salt is at least one selected from the group consisting of bismuth sulfate, bismuth chloride and bismuth nitrate.
8. The method according to claim 11, wherein the solvent of the solution I is at least one selected from the group consisting of an ethanol solution, a propanol solution, and a methanol solution;
preferably, the concentration of ZIF8 in the solution I is 1-10 g/L;
preferably, the concentration of the bismuth salt in the solution I is 2-4 g/L;
preferably, the impregnation is in particular: stirring a mixture of ZIF8 and a bismuth salt solution for 12-24 hours;
preferably, the separation is in particular: and (4) after centrifugation, carrying out freeze drying or drying at 60-90 ℃ for 12-24 h.
9. A carbon dioxide electrochemical reduction catalyst comprising at least one of the nitrogen-doped hierarchical pore carbon-based catalyst according to any one of claims 1 to 4 and the nitrogen-doped hierarchical pore carbon-based catalyst prepared by the method according to any one of claims 5 to 8.
10. The catalyst for electrochemical reduction of carbon dioxide as claimed in claim 9, wherein the catalyst for electrochemical reduction of carbon dioxide is a cathode catalyst for electrochemical reduction of carbon dioxide.
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