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CN114433158B - 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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CN114433158B
CN114433158B CN202011127124.8A CN202011127124A CN114433158B CN 114433158 B CN114433158 B CN 114433158B CN 202011127124 A CN202011127124 A CN 202011127124A CN 114433158 B CN114433158 B CN 114433158B
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nitrogen
based catalyst
hierarchical pore
carbon
doped hierarchical
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CN114433158A (en
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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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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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 the content of zinc-nitrogen; wherein the contents of the graphite nitrogen and the zinc-nitrogen are calculated by nitrogen element. 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 each type of N element and excellent CO 2 The 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, and belongs to the technical field of electrochemical reduction of carbon dioxide.
Background
At present, the economy and society of China are in a high-speed development stage, and the demand for energy is increasing, so that the serious problem of carbon dioxide emission is caused. Global CO in 2017 was estimated from the latest reports of International Energy Agency (IEA) 2 The discharge amount reaches 410 hundred million tons, and is increased by 2% compared with 2016. Therefore, how to reduce CO 2 Is effective in utilizing CO 2 Become a hot spot of research in recent years.
CO 2 The conversion and utilization of (a) mainly comprises four types of biochemical conversion, chemical conversion, electrochemical conversion and photochemical conversion. With other CO 2 Electrochemical reduction of CO compared to conversion techniques 2 The (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 pressure 2 Is capable of storing electric energy in the form of chemical energy and balancing the intermittent generation of wind energy, solar energy and the likeAnd (5) sexual power resources.
Electrochemical reduction of CO 2 The technology is to utilize the electric energy generated by renewable energy sources to convert CO 2 Reduction to chemical, realization of CO 2 An effective technique for resource utilization. Electrochemical CO production 2 Directly with H 2 O reacts to generate high added value compounds 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 can realize the storage of renewable energy sources and form a carbon and energy conversion cycle. Currently, the main factors restricting ERC technology development include: (1) higher reaction overpotential; (2) lower reactivity of the reaction; (3) poor product selectivity. Thus, the search for suitable catalysts to reduce the reaction overpotential, to increase the product selectivity and the activity of the reaction is key to current research. At present, the research on the catalyst is mainly focused on noble metal catalysts such as gold and silver, and the like, and the selectivity on CO is high, but the price is high, so that the catalyst is not suitable for large-scale commercial production. However, there is relatively little research on nonmetallic nitrogen-doped carbon-based catalysts, where nitrogen-doped porous carbon has received extensive attention due to its high specific surface area, adjustable pore structure, high conductivity, and low price. ZIF8 is a porous nitrogen-doped carbon precursor rich in microporous structures, and is directly carbonized to obtain the catalyst, so that the following problems generally exist: the microporous structure is unfavorable for the transmission of carbon dioxide; high zinc-nitrogen content is prone to induce hydrogen evolution side reactions; low conductivity.
Disclosure of Invention
According to one aspect of the present application, there is provided a nitrogen-doped hierarchical pore carbon-based catalyst having the characteristics of hierarchical pore structure, high conductivity and adjustable composition, and having a reasonable content of each type of N element and excellent CO 2 The 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 the content 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 the zinc-nitrogen content.
Optionally, the total content of nitrogen elements in the nitrogen-doped hierarchical pore carbon-based catalyst is 4% -7%.
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.2 to 1 percent higher than the content of pyridine nitrogen
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.6-1% higher than the content of pyridine nitrogen
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.3% -0.9% higher than the content of pyrrole nitrogen.
Optionally, the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 0.3% -0.51% higher than the content of pyrrole nitrogen.
Optionally, the graphite nitrogen of the nitrogen-doped hierarchical pore carbon-based catalyst accounts for 30% -50% of the total content of nitrogen elements.
Optionally, the graphite nitrogen of the nitrogen-doped hierarchical pore carbon-based catalyst accounts for 35% -50% of the total content of nitrogen elements.
Optionally, the zinc-nitrogen of the nitrogen doped hierarchical pore carbon-based catalyst accounts for 8% -20% of the total content of nitrogen elements.
Optionally, the zinc-nitrogen of the nitrogen doped hierarchical pore carbon-based catalyst accounts for 8% -13% of the total content of nitrogen elements.
Optionally, the pyridine nitrogen of the nitrogen doped hierarchical pore carbon-based catalyst accounts for 15% -30% of the total nitrogen element content.
Optionally, the pyridine nitrogen of the nitrogen doped hierarchical pore carbon-based catalyst accounts for 15% -25% of the total nitrogen element content.
Optionally, pyrrole nitrogen of the nitrogen-doped hierarchical pore carbon-based catalyst accounts for 20% -35% of the total content of nitrogen elements.
Optionally, pyrrole nitrogen of the nitrogen-doped hierarchical pore 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 calculated by nitrogen element.
The graphite nitrogen is nitrogen connected with three carbon atoms in a graphite carbon structure and forms a six-membered ring structure;
the zinc-nitrogen is a bond structure of 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 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 pore carbon-based catalyst is 0.6-1.2 cm 3 Per gram, the micropore volume is 0.18-0.45 cm 3 Per g, mesoporous volume of 0.5-0.8 cm 3 /g。
Alternatively, the upper limit of the total volume is selected from 0.82cm 3 /g、0.88cm 3 /g、0.95cm 3 /g、1cm 3 /g、1.2cm 3 /g; the lower limit is selected from 0.6cm 3 /g、0.65cm 3 /g、0.75cm 3 /g、0.82cm 3 /g。
Optionally, the upper limit of the micropore volume is selected from 0.24cm 3 /g、0.28cm 3 /g、0.45cm 3 /g; the lower limit is selected from 0.18cm 3 /g、0.2cm 3 /g、0.24cm 3 /g。
Optionally, the total surface area of the nitrogen-doped hierarchical pore carbon-based catalyst is 700 to 1000m 2 Per gram, the micropore surface area is 400-800 m 2 /g。
Alternatively, the upper limit of the total surface area is selected from 785m 2 /g、800m 2 /g、850m 2 /g、900m 2 /g、1000m 2 /g; the lower limit is selected from 700m 2 /g、750m 2 /g、785m 2 /g。
Optionally, the upper limit of the micropore surface area is 437m 2 /g、500m 2 /g、550m 2 /g、800m 2 /g; the lower limit is selected from 400m 2 /g、420m 2 /g、437m 2 /g。
Optionally, the mesoporous volume has an upper limit selected from 0.58m 2 /g、0.65m 2 /g、0.7m 2 /g、0.8m 2 /g; the lower limit is selected from 0.5m 2 /g、0.55m 2 /g、0.58m 2 /g。
Optionally, the surface of the nitrogen-doped hierarchical pore carbon-based catalyst has graphitized stripes with long range order.
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: immersing ZIF8 in bismuth salt solution to obtain solution I, and separating to obtain a product I; calcining the product I at 900-1050 ℃ to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
According to the application, ZIF8 is used as a carbon precursor, and bismuth salt is used for regulating and controlling the ZIF8, 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 ℃, 920 ℃ and 950 ℃.
Optionally, the calcining is: under the condition of inactive gas, the calcination 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 and neon.
Optionally, the upper calcination time limit is selected from 2h, 2.5h, 3h; the lower limit is selected from 1h, 1.5h and 2h.
Optionally, the temperature rising 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 ℃/min and 3 ℃/min.
Optionally, the bismuth salt is at least one selected from 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 the solution I is selected from 5g/L, 6g/L, 7g/L, 8g/L and 10g/L; the lower limit is selected from 1g/L, 2g/L, 3g/L and 5g/L.
Optionally, the concentration of bismuth salt in the solution I is 2-4 g/L.
Optionally, the upper concentration limit of bismuth salt in the solution I is selected from 2.4g/L, 2.8g/L, 3.5g/L and 4g/L; the lower limit is selected from 2.2g/L and 2.4g/L.
Optionally, the impregnating is specifically: the mixture of ZIF8 and bismuth salt solution is stirred for 12 to 24 hours.
Optionally, the separation is specifically: and (3) freeze drying or drying at 60-90 ℃ for 12-24 h after centrifugation.
Optionally, the preparation method of the ZIF8 comprises the following steps: stirring the solution II containing the dimethylimidazole and zinc nitrate to obtain the ZIF8.
Optionally, the solvent of the solution II is selected from at least one of methanol, ethanol and propanol.
Optionally, the concentration of the dimethylimidazole in the solution II is 15-30 g/L.
Optionally, the upper limit of the concentration of the dimethylimidazole in the solution II is selected from 23g/L, 25g/L, 28g/L and 30g/L; the lower limit is selected from 15g/L, 18g/L, 20g/L and 13g/L.
Optionally, the concentration of zinc nitrate in the solution II is 5-15 g/L.
Optionally, the upper concentration limit of zinc nitrate in the solution II is selected from 11.7g/L, 13g/L and 15g/L; the lower limit is selected from 5g/L, 7g/L, 9g/L and 11.7g/L.
Optionally, after the stirring step II is finished, a separation step is further included, where the separation step is: and (3) freeze drying or drying at 60-90 ℃ for 12-24 h after centrifugation.
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 as described in any one of the preceding claims, the nitrogen-doped hierarchical pore carbon-based catalyst prepared according to the method as described in any one of the preceding claims.
Optionally, the carbon dioxide electrochemical reduction catalyst is a carbon dioxide electrochemical reduction cathode catalyst.
As one embodiment of the present application, the present application adopts the following technical scheme:
a preparation method of a nitrogen-doped hierarchical pore carbon-based catalyst comprises the following steps:
1) Preparing a solution A: 30-60 g/L dimethyl imidazole methanol solution; preparing a solution B: 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 in a volume ratio of 1:0.5-3, and stirring for 12-24 h;
2) Centrifuging and drying the obtained product to obtain ZIF8;
3) Adding ZIF8 into saturated ethanol solution of bismuth salt, stirring for 12-24 h, and centrifuging and 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 calcination condition is that the temperature is raised from room temperature to 900-1050 ℃ at a heating rate of 2-5 ℃/min, and then the temperature is kept for 1-3 h.
Optionally, the step 2) is performed after centrifugation and then is performed for 12-24 hours at 60-90 ℃ or is performed after freeze drying.
Optionally, the bismuth salt in the 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 the application of the cathode of the electrochemical reduction reaction of carbon dioxide.
Optionally, the cathode is prepared by adding a catalyst and 2-8wt% of Nafion solution into ethanol solution, wherein the content of the nitrogen-doped graded pore carbon-based catalyst is 4-10 mg/ml, the content of Nafion is 40-100 ul/ml, and the prepared catalyst dispersion is coated on the surface of the glassy carbon electrode in a liquid drop manner by ultrasonic for 0.5-1.5 h.
The application utilizes bismuth salt to regulate and control the pore structure, the surface area, the conductivity and the components of ZIF8, thereby obtaining the nitrogen-doped hierarchical pore carbon-based catalyst with hierarchical pore structure, high conductivity and low zinc-nitrogen content. At lower overpotential, similar CO faraday efficiency as noble metals is achieved.
The application has the beneficial effects that:
(1) The nitrogen-doped hierarchical pore carbon-based catalyst provided by the application has the characteristics of hierarchical pore structure, high conductivity and adjustable components, and has reasonable content of each type of N element and excellent CO 2 The 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, bismuth salt is firstly introduced into the microporous structure and the surface of the ZIF8, then bismuth metal with a low boiling point is removed through a high-temperature calcination process, so that the nitrogen-doped hierarchical pore carbon material is obtained, and the nitrogen-doped carbon-based catalyst with a hierarchical pore structure is obtained by controlling the mass ratio of the bismuth salt to the ZIF8 and the regulation and control of calcination conditions. Bismuth salt in and on ZIF8 pores undergoes the whole processes of melting, generation of metallic bismuth nano particles and sublimation of bismuth along with the rise of temperature in the whole calcination process, so that the hierarchical pore structure carbon material is realized, and the mesoporous volume is larger. The surface of the catalyst is rich in micro-mesoporous structures, and micropores are beneficial to adsorption of carbon dioxide and promote enrichment of the carbon dioxide at a reaction interface; the mesoporous structure effectively promotes mass transport.
(3) According to the preparation method of the nitrogen-doped hierarchical pore carbon-based catalyst, the whole change process of bismuth salt further regulates and controls the pore surface structure and composition, and graphitization of carbon is effectively promoted. In addition, the type of N element is effectively changed by introducing bismuth salt, compared with a ZIF8 carbon material which is not modified by bismuth salt, the percentage of graphite nitrogen in the nitrogen-containing carbon material is obviously increased, the Zn-N content is obviously reduced, and the electrocatalytic performance of the catalyst is further improved.
(4) Bismuth chloride is a low-boiling-point metal salt, firstly, bismuth chloride is adsorbed into a microporous structure of ZIF8 through a simple liquid-phase impregnation process, and in the later calcination process, bismuth chloride is in a molten state, so that the Zn-N structure of nearby ZIF8 is seriously damaged, and the aggregation and volatilization of zinc atoms are promoted. In addition, bismuth chloride itself is reduced by carbon at high temperature to bismuth nanoparticles and further volatilizes to produce a series of mesoporous structures. Bismuth metal is effective in promoting graphitization of nearby carbon at high temperatures. Thus, a nitrogen doped hierarchical pore carbon-based catalyst is obtained which has a hierarchical pore structure, high conductivity, and low zinc-nitrogen content. Realize the CO Faraday efficiency (90%) similar to noble metals in a wider potential range and have high catalytic activity.
(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 post-complex treatment process (removing bismuth salt template). The preparation method is simple, the production equipment is conventional, and the method is suitable for large-scale production.
(6) The nitrogen doped graded pore carbon-based catalyst provided by the application is used as a cathode for electrochemical reduction reaction of carbon dioxide, which is beneficial to exposing more active sites, so that the electrode has higher catalytic activity.
Drawings
FIG. 1 is a TEM image of the nitrogen-doped hierarchical pore carbon-based catalyst prepared in example 1, comparative examples 4 to 8 of the present application, wherein a is a TEM image (100 nm) of comparative example 5; b is the TEM image (100 nm) of comparative example 6, c is the TEM image (100 nm) of comparative example 7; d is the TEM image (100 nm) of comparative example 8; e is the TEM image (100 nm) of comparative example 4; f is the TEM image (100 nm) of example 1.
FIG. 2 is an SEM image and a TEM image of an electrode prepared according to example 1 of the application, where a is the SEM image (100 nm) of example 1; b is the TEM image (100 nm) of example 1; c is the TEM image (10 nm) of example 1.
FIG. 3 is an SEM image and a TEM image of an electrode prepared according to comparative example 1, wherein a is an SEM image (100 nm) of comparative example 1; b is a TEM image (50 nm) of comparative example 1; c is a TEM image (10 nm) of comparative example 1.
FIG. 4 is an SEM and TEM image of an electrode prepared according to comparative example 2, where a is the SEM image (100 nm) of comparative example 2; b is the TEM image (50 nm) of comparative example 2; c is a TEM image (10 nm) of comparative example 2.
FIG. 5 is an SEM image and a TEM image of an electrode prepared according to comparative example 3, where a is an SEM image (100 nm) of comparative example 3; b is the TEM image (50 nm) of comparative example 3; c is a TEM image (10 nm) of comparative example 3.
FIG. 6 is a graph showing the electrochemical performance of the electrodes prepared in example 1 and comparative examples 1 to 3 according to the present application, wherein a is a graph showing the comparison of Faraday efficiency of CO generation; b is a graph comparing the current density of the generated CO.
FIG. 7 is a graph showing the results of nitrogen adsorption specific surface test of the catalysts prepared in example 1 and comparative examples 1 to 3 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparing a solution A: 7.0g of dimethyl imidazole was added to 150ml of methanol and stirred; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Pouring the solution B into the solution A rapidly, and stirring for 12h;
2) And centrifuging the obtained product, and then drying at 75 ℃ to obtain ZIF8.
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 heating the dried sample from room temperature to 950 ℃ at a speed of 3 ℃/min under an argon environment, and then preserving heat for 2 hours to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
Adding the prepared nitrogen-doped hierarchical pore carbon-based catalyst and 5wt% Nafion solution into 300ul of 99% ethanol solution, wherein the content of the nitrogen-doped hierarchical pore carbon-based catalyst is 2mg, the content of the Nafion is 20ul, carrying out ultrasonic treatment for 0.5h, and then coating the prepared catalyst on a film of 1.5X2.0 cm 2 And drying the surface of the glassy carbon electrode to obtain the electrode.
Examples 2 to 3
The preparation methods of examples 2 to 3 were the same as in example 1, except for the raw materials/conditions listed in table 1.
Table 1, examples 2 to 3 differ from example 1 in the raw materials/conditions
Raw materials/conditions Example 1 Example 2 Example 3
Bismuth salt species 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) Preparing a solution A: 7.0g of dimethyl imidazole was added to 150ml of methanol and stirred; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Pouring the solution B into the solution A rapidly, and stirring for 12h;
2) And centrifuging the obtained product, and then drying at 75 ℃ to obtain ZIF8.
3) Adding 0.2g ZIF8 into 40ml ethanol solution, stirring for 12h, centrifuging with distilled water, and drying at 75deg.C for 12h;
4) Calcining the dried sample ZIF8 at 950 ℃ for 2 hours under argon, and obtaining the nitrogen-doped hierarchical pore carbon-based catalyst at a heating rate of 3 ℃/min.
(2) Preparation of cathode for carbon dioxide reduction
The prepared nitrogen-doped hierarchical pore carbon-based catalyst and 5wt% Nafion solution were added to 300ul of 99% ethanol solution, the nitrogen-doped hierarchical pore carbon-based catalyst content was 2mg, the Nafion content was 20ul, and the mixture was sonicated for 0.5h, and then coated to 1.5X2.0 cm 2 And drying the surface of the glassy carbon electrode to obtain the electrode.
Comparative example 2
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparing a solution A: 7.0g of dimethyl imidazole was added to 150ml of methanol and stirred; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Pouring the solution B into the solution A rapidly, and stirring for 12h;
2) And centrifuging the obtained product, and then drying at 75 ℃ to obtain ZIF8.
3) Adding 24mg 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 heating the dried sample from room temperature to 950 ℃ at a speed of 3 ℃/min under an argon environment, and then preserving heat for 2 hours to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
The prepared nitrogen-doped hierarchical pore carbon-based catalyst and 5wt% Nafion solution were added to 300ul of 99% ethanol solution, the nitrogen-doped hierarchical pore carbon-based catalyst content was 2mg, the Nafion content was 20ul, and the mixture was sonicated for 0.5h, and then coated to 1.5X2.0 cm 2 And drying the surface of the glassy carbon electrode to obtain the electrode.
Comparative example 3
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparing a solution A: 7.0g of dimethyl imidazole was added to 150ml of methanol and stirred; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Pouring the solution B into the solution A rapidly, and stirring for 12h;
2) And centrifuging the obtained product, and then drying at 75 ℃ to obtain ZIF8.
3) 48mg of bismuth chloride is added into 40ml of ethanol solution, 0.2g of ZIF8 is added into the solution and stirred for 12 hours, and then the obtained product is centrifuged, and then dried for 12 hours at 75 ℃;
4) And heating the dried sample from room temperature to 950 ℃ at a speed of 3 ℃/min under an argon environment, and then preserving heat for 2 hours to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
The prepared nitrogen-doped hierarchical pore carbon-based catalyst and 5wt% Nafion solution were added to 300ul of 99% ethanol solution, the nitrogen-doped hierarchical pore carbon-based catalyst content was 2mg, the Nafion content was 20ul, and the mixture was sonicated for 0.5h, and then coated to 1.5X2.0 cm 2 And drying the surface of the glassy carbon electrode to obtain the electrode.
Comparative example 4
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
1) Preparing a solution A: 7.0g of dimethyl imidazole was added to 150ml of methanol and stirred; preparing a solution B: 3.5g of zinc nitrate was added to 150ml of methanol and stirred. Pouring the solution B into the solution A rapidly, and stirring for 12h;
2) And centrifuging the obtained product, and then drying at 75 ℃ to obtain ZIF8.
3) 96mg of bismuth chloride is added into 40ml of ethanol solution, 0.2g of ZIF8 is added into the solution and stirred for 12 hours, and then the obtained product is centrifuged, and then dried for 12 hours at 75 ℃;
4) And heating the dried sample from room temperature to 750 ℃ at a speed of 3 ℃/min under an argon environment, and then preserving heat for 2 hours to obtain the nitrogen-doped hierarchical pore carbon-based catalyst.
(2) Preparation of cathode for carbon dioxide reduction
The prepared nitrogen-doped hierarchical pore carbon-based catalyst and 5wt% Nafion solution were added to 300ul of 99% ethanol solution, the nitrogen-doped hierarchical pore carbon-based catalyst content was 2mg, the Nafion content was 20ul, and the mixture was sonicated for 0.5h, and then coated to 1.5X2.0 cm 2 And drying the surface of the glassy carbon electrode to obtain the electrode.
Comparative examples 5 to 8
(1) Preparation of nitrogen-doped hierarchical pore carbon-based catalyst
The same procedure as in comparative example 4 is distinguished only by the calcination temperature in step 4). Wherein the calcination temperature of comparative example 5 was 25 ℃, the calcination temperature of comparative example 6 was 250 ℃, the calcination temperature of comparative example 7 was 350 ℃, and the calcination temperature of comparative example 8 was 550 ℃.
(2) Preparation of cathode for carbon dioxide reduction
The same procedure as in comparative example 4.
Determination of total Nitrogen content and various types of Nitrogen content of the Nitrogen-doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 1 to 3
The measurement was performed by using an X-ray photoelectron spectroscopy technique, and the results are shown in table 2.
TABLE 2 Total Nitrogen content and various types of Nitrogen contents of the Nitrogen doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 1 to 3
Determination of surface area and volume of Nitrogen-doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 1 to 3
The results of the measurement using a nitrogen adsorption specific surface area meter are shown in Table 3 and FIG. 7.
TABLE 3 surface area and volume of Nitrogen doped staged pore carbon-based catalysts prepared in example 1, comparative examples 1-3
It can also be seen from FIG. 7 that example 1 has a wider hysteresis loop in the relative medium pressure section (0.4-0.8) and thus example 1 contains a larger mesoporous volume, as can be seen more clearly from Table III, the comparative example has a higher mesoporous volume. The regulation and control of bismuth salt can effectively increase the mesoporous structure of the catalyst material and the graphitization degree of catalytic carbon, thereby being beneficial to improving the conductivity and the material transmission capacity of the catalyst.
Morphology characterization of the Nitrogen doped hierarchical pore carbon-based catalysts prepared in example 1 and comparative examples 4 to 8
The method comprises the following steps: scanning electron microscope and transmission electron microscope
As can be seen from a-e in FIG. 1, a large amount of metal bismuth particles remain on the surface of the material under the calcination treatment at 25-750 ℃, a mesoporous structure cannot be effectively formed, and 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, the bismuth salt in and on the ZIF8 pores in example 1 underwent the whole process of melting, generation of metallic bismuth nanoparticles, and sublimation of bismuth with the increase of temperature during the whole calcination process, thereby realizing a hierarchical pore structure of carbon material. The surface of the catalyst is rich in micro-mesoporous structures, and micropores are beneficial to adsorption of carbon dioxide and promote enrichment of the carbon dioxide at a reaction interface; the mesoporous structure effectively promotes mass transport.
Characterization of morphology of the electrodes prepared in example 1, comparative examples 1 to 3
The method comprises the following steps: scanning electron microscope and transmission electron microscope.
The results are shown in fig. 2 to 5, wherein:
FIG. 2 is an SEM image and a TEM image of an electrode prepared according to example 1 of the application, where a is the SEM image (100 nm) of example 1; b is the TEM image (100 nm) of example 1; c is the TEM image (10 nm) of example 1.
FIG. 3 is an SEM image and a TEM image of an electrode prepared according to comparative example 1, wherein a is an SEM image (100 nm) of comparative example 1; b is a TEM image (50 nm) of comparative example 1; c is a TEM image (10 nm) of comparative example 1.
FIG. 4 is an SEM and TEM image of an electrode prepared according to comparative example 2, where a is the SEM image (100 nm) of comparative example 2; b is the TEM image (50 nm) of comparative example 2; c is a TEM image (10 nm) of comparative example 2.
FIG. 5 is an SEM image and a TEM image of an electrode prepared according to comparative example 3, where a is an SEM image (100 nm) of comparative example 3; b is the TEM image (50 nm) of comparative example 3; c is a TEM image (10 nm) 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 graphitized stripes with long range order, and as can also 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 regulation and control of bismuth salt can effectively increase the mesoporous structure of the catalyst material and the graphitization degree of catalytic carbon, thereby being beneficial to improving the conductivity and the material transmission capacity of the catalyst.
Electrochemical performance measurement of the 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 electrochemical test is carried out through a three-electrode system, and the determination method comprises the following steps:
the working electrode was the electrode prepared in example 1, comparative examples 1 to 3;
the counter electrode is a Pt sheet, and the reference electrode is Ag/AgCl. The distance between WE (working electrode) and RE (reference electrode) is 0.5cm, and the liquid junction potential is reduced by adopting a salt bridge. The cathode and anode electrolyte is 0.5M KHCO 3 Sol, catholyte volume 160ml and anolyte volume 80ml. CO 2 The flow rate is controlled by a mass flowmeter, and the flow rate is 20ml/min; constant potential electrolysis is carried out under the potential of-0.3V to-1.0V. The results are shown in FIG. 6.
From FIGS. 6 a-b, it can be seen that the Faraday efficiency of CO of the catalyst prepared in example 1 reaches 90% at a potential of-0.5V to-0.7V; comparative example 1 CO at-0.5V potential 2 Reduction to CO Faraday efficiency of 50%; comparative example 2 CO at-0.5V potential 2 Reduction to a CO faraday efficiency of 78%; comparative example 3 CO at-0.5V potential 2 The reduction to CO faradaic efficiency was 80%. The faraday efficiency of example 1 was increased by 40% compared to comparative example 1 without doping with bismuth salt, the current density was increased by 5 times compared to comparative example 1, the faraday efficiency of example 1 was increased by 10% compared to comparative examples 2 and 3, and the current density was increased by 2 times compared to comparative example 1.
As can be seen from the analysis, the preparation method of the nitrogen-doped hierarchical pore carbon-based catalyst provided by the application is simple/easy to control, and the obtained nitrogen-doped hierarchical pore carbon-based catalyst has excellent CO 2 Selectivity for CO production by electrochemical reduction, electrodes produced with the obtained nitrogen-doped hierarchical pore carbon-based catalysts have excellent ERC (electrochemical reduction of CO 2 ) Stability. According to the application, the ZIF8 is regulated and controlled by calcining the bismuth salt 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, and the higher graphite nitrogen content indicates that the catalyst has higher conductivity, and the lower zinc-nitrogen content is favorable for inhibiting hydrogen evolution reaction, so that the catalyst has high catalytic activity and selectivity. The catalyst material can be effectively prepared by properly regulating the mass ratio of the metal bismuth salt to ZIF8The nitrogen type on the surface of the material is regulated and controlled, so that higher catalytic performance is realized.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (16)

1. A preparation method of a nitrogen-doped hierarchical pore carbon-based catalyst is characterized in that,
the preparation method comprises the following steps: immersing ZIF8 in bismuth salt solution to obtain solution I, and separating to obtain a product I; calcining the product I at 900-1050 ℃ to obtain the nitrogen-doped hierarchical pore carbon-based catalyst;
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 the content of zinc-nitrogen;
wherein the contents of the graphite nitrogen and the zinc-nitrogen are calculated by nitrogen element;
the content of graphite nitrogen in the nitrogen-doped hierarchical pore carbon-based catalyst is 1.40% -2% higher than that of zinc-nitrogen;
the bismuth salt is at least one selected from bismuth sulfate, bismuth chloride and bismuth nitrate;
the concentration of bismuth salt in the solution I is 2-4 g/L;
the surface of the nitrogen-doped hierarchical pore carbon-based catalyst is provided with graphitized stripes with long-range order.
2. The method for preparing a nitrogen-doped hierarchical pore carbon-based catalyst according to claim 1, wherein the total content of nitrogen elements in the nitrogen-doped hierarchical pore carbon-based catalyst is 4% -7%.
3. The method for preparing a 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 0.2% -1% higher than the content of pyridine nitrogen.
4. The method for preparing a 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 0.3% -0.9% higher than the content of pyrrole nitrogen.
5. The method for preparing a nitrogen-doped hierarchical porous carbon-based catalyst according to claim 1, wherein the proportion of micropores is 30% -50%, and the proportion of mesopores is 50% -70%.
6. The method for preparing a nitrogen-doped hierarchical pore carbon-based catalyst according to claim 1, wherein the pore diameter of the micropores is 0.7-1.1 nm, and the pore diameter of the mesopores is 3-10 nm.
7. The method for preparing a nitrogen-doped hierarchical pore carbon-based catalyst according to claim 1, wherein the total volume of the nitrogen-doped hierarchical pore carbon-based catalyst is 0.6-1.2 cm 3 Per gram, the micropore volume is 0.18-0.45 cm 3 Per g, mesoporous volume of 0.5-0.8 cm 3 /g。
8. The method for preparing a nitrogen-doped hierarchical pore carbon-based catalyst according to claim 1, wherein the total surface area of the nitrogen-doped hierarchical pore carbon-based catalyst is 700 to 1000m 2 Per gram, the micropore surface area is 400-800 m 2 /g。
9. The method of claim 1, wherein the calcining is: under the condition of inactive gas, the calcination time is 1-3 h.
10. The method according to claim 1, wherein the temperature rise rate of the calcination is 2 to 5 ℃/min.
11. The preparation method according to claim 1, wherein the solvent of the solution I is at least one selected from the group consisting of ethanol solution, propanol solution and methanol solution.
12. The method according to claim 1, wherein the concentration of ZIF8 in the solution I is 1 to 10g/L.
13. The preparation method according to claim 1, characterized in that the impregnation is in particular: the mixture of ZIF8 and bismuth salt solution is stirred for 12 to 24 hours.
14. The preparation method according to claim 1, wherein the separation is specifically: and (3) freeze drying or drying at 60-90 ℃ for 12-24 h after centrifugation.
15. A carbon dioxide electrochemical reduction catalyst comprising at least one of the nitrogen-doped hierarchical pore carbon-based catalysts prepared by the method of any one of claims 1-14.
16. The carbon dioxide electrochemical reduction catalyst of claim 15, wherein the carbon dioxide electrochemical reduction catalyst is a carbon dioxide electrochemical reduction cathode catalyst.
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