CN115786945A - Nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst and preparation method and application thereof Download PDFInfo
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Images
Abstract
The invention belongs to the technical field of electrocatalysis carbon dioxide reduction electrodes, and discloses a nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst, a preparation method and application thereof, wherein the catalyst is a nitrogen-doped carbon nanotube surface uniformly loaded with beta-Mo with the particle size of 3-10nm 2 C, particles; the preparation process comprises the steps of firstly treating the carbon nano tube with excessive concentrated nitric acid at a specific temperature and time, uniformly mixing the treated carbon nano tube with excessive nitrogen source, and roasting at a specific temperature and time under an inert atmosphere to obtain a nitrogen-doped carbon nano tube; further using ammonium molybdate and nitrogen-doped carbon nano-tube to obtain Mo through impregnation and calcination 2 C/N-CNT. The invention utilizes sp state participation of the catalystModulating the adsorption strength and adsorption configuration of the intermediate, promoting the reaction intermediate to be adsorbed on the surface of the catalyst in an oxygen bonding manner, and adsorbing the reaction intermediate on CO 2 The application of the catalyst in the reduction of methanol shows excellent performance of the reduction of carbon dioxide to methanol.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic carbon dioxide reduction electrodes, and particularly relates to a preparation method of a nitrogen-doped carbon nanotube-loaded transition metal carbide catalyst and application of the nitrogen-doped carbon nanotube-loaded transition metal carbide catalyst in promoting generation of oxygen-containing products.
Background
In recent years, CO has been used excessively in non-renewable energy sources such as petroleum and coal 2 The emission of (2) is increasing year by year, and the greenhouse effect caused by the emission is also becoming more serious (1). Statistics on CO in the atmosphere since 2000 2 The concentration rises at a rate of 2-3ppm, CO, each year 2 Too much accumulation of (b) also becomes a major cause of current climate change. High selectivity CO driven by renewable electricity 2 Reduction reaction (CO) 2 RR) is a promising technology (2,3). Among the numerous reduction products, methanol is a starting material for the production of industrially important chemicals such as formaldehyde, acetic acid and olefins, in addition to being directly used as a fuel, and is receiving much attention. Thermodynamically, CO is electrochemically converted 2 Reduction to methanol is feasible, but methanol is a kinetically slow reaction as a reduction product of six electron transfer. And due to CO 2 Competitive adsorption between RR reaction intermediates (e.g. OCOH, COOH, CO, etc.) and HER competition reactions, which makes further development of methanol catalysts with high activity and selectivity still a great challenge (4).
In order to improve the selectivity of methanol, various effective and inspiring strategies have been demonstrated, such as catalysts with specific crystal planes or interface sites, molecular catalysts, heteroelement-doped catalysts, and the like. For example, gong et al designed and constructed Cu/Cu with controlled length 2 The O interface sites cooperatively regulate the adsorption strength of H and CO intermediates on the surface of the electrode, and the maximum faradaic efficiency of 53.6 percent methanol is realized (5). Liang et al highly disperse cobalt phthalocyanine molecules on carbon nanotubes with a non-covalent anchoring strategy for electrocatalysis of CO 2 Reduction for preparing methanolThe faradaic efficiency of the methanol produced is higher than 40% (6). Hang et al prepared Ag, S double doped Cu 2 The electro-catalytic material of O/Cu shows that the double doping of Ag and S can promote the formation of CHO intermediate, further promote the selective generation of methanol and realize the faradaic efficiency (7) of the methanol of 67.4 percent.
It can be easily found that although some progress has been made in the corresponding research, the faradaic efficiency of methanol is often still lower than 70%. Notably, CH 3 The selective generation of oxygen-containing compounds such as OH depends particularly on the adsorption energy and configuration of the intermediate; this is because the generation of its corresponding Rate Determining Step (RDS) usually requires the participation of protons (8). If the intermediate is adsorbed on the metal surface with a carbon atom, its oxygen atom will be located away from the surface, making the proton more prone to attack this oxygen atom and thus leading to the loss of the oxygen atom, and the selectivity of the oxygen-containing product is reduced (9).
1.Qian H,Xu S,Cao J,et al.Air Pollution Reduction and Climate Co-benefits in China’s industries.Nat. Sustain.2021,4(5):417-425.
2.De Luna P,Hahn C,Higgins D,et al.What Would It Take for Renewably Powered Electrosynthesis to Displace Petrochemical ProcessesScience 2019,364(6438):eaav3506.
3.Birdja YY,Pérez-Gallent E,Figueiredo MC,et al.Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels.Nat.Energy 2019,4(9):732-745.
4.Xu R,Xu H,Ning S,et al.Coupling of Cu Catalyst and Phosphonated Ru Complex Light Absorber with TiO 2 as Bridge to Achieve Superior Visible Light CO 2 Photoreduction.Trans.Tianjin Univ.2020,26(6): 470-478.
5.Chang X,Wang T,Zhao Z-J,et al.Tuning Cu/Cu 2 O interfaces for the reduction of carbon dioxide to methanol in aqueous solutions.Angew.Chem.Int.Ed.2018,130(47):15641-15645.
6.Wu Y,Jiang Z,Lu X,et al.Domino Electroreduction of CO 2 to Methanol on a Molecular catalyst.Nature 2019,575(7784):639-642.
7.Li P,Bi J,Liu J,et al.In situ Dual Doping for Constructing Efficient CO 2 -to-methanol Electrocatalysts. Nat.Commun.2022,13(1):1-9.
8.Nie X,Esopi MR,Janik MJ,et al.Selectivity of CO 2 Reduction on Copper Electrodes:the Role of the Kinetics of Elementary Steps.Angew.Chem.Int.Ed.2013,52(9):2459-2462.
9.Peterson AA,Abild-Pedersen F,Studt F,Rossmeisl J,et al.How Copper Catalyzes the Electroreduction of Carbon Dioxide into Hydrocarbon Fuels.Energy&Environ.Sci.2010,3(9):1311-1315.
Disclosure of Invention
The invention aims to solve the technical problem of low selectivity of oxygen-containing product methanol caused by the traditional catalyst, and provides a nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst and a preparation method and application thereof 2 The application of the catalyst in the reduction of methanol shows excellent performance of the reduction of carbon dioxide to methanol.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the invention, a nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst is provided, which comprises nitrogen-doped carbon nanotubes, wherein the surface of the nitrogen-doped carbon nanotubes is uniformly loaded with beta-Mo 2 C particles of beta-Mo 2 The particle size of the C particles is 3-10nm.
According to another aspect of the present invention, there is provided a method for preparing a nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst, comprising the steps of:
(1) Adding CNT to excess concentrated HNO 3 In the solution, carrying out ultrasonic dispersion to obtain a suspension; subjecting the suspension to a temperature of 100-120 deg.CRefluxing in oil bath for 6-9 hr; after the sample is cooled to room temperature, separating the solid sample to obtain CNT with defects on the surface;
(2) Uniformly mixing the CNT obtained in the step (1) with an excessive nitrogen source; roasting for 1-2 hours at the temperature of 700-800 ℃ under the protection of inert atmosphere to obtain N-CNT;
(3) Dispersing the N-CNT obtained in the step (2) into deionized water to obtain an N-CNT suspension; under the condition of violent stirring, dropwise adding an ammonium molybdate aqueous solution with the mass percent of ammonium molybdate accounting for 25-50% of the N-CNT; after the dropwise addition is finished, continuously stirring the mixture fully at room temperature, and then collecting a solid sample;
(4) Under the protection of inert atmosphere, roasting the solid sample for 1-2 hours at the temperature of 600-700 ℃; after the sample is cooled to the room temperature, the inert atmosphere is switched to oxygen-nitrogen mixed gas containing trace oxygen, and the sample is kept for 0.5 to 2 hours at the room temperature; to obtain beta-Mo 2 C/N-CNT and storing in inert atmosphere.
Further, in the step (1), the carbon nanotubes and the concentrated HNO 3 The mass ratio of the solution is not more than 1.
Further, in the step (1), the concentrated HNO 3 The mass fraction of the solution is 60-65%.
Further, in the step (2), the nitrogen source is 2-methylimidazole or urea.
Further, in the step (2), the mass ratio of the carbon nanotubes to the nitrogen source is not more than 1:10.
further, in the step (4), the volume percentage of the oxygen in the oxygen-nitrogen mixed gas is not more than 1%.
According to another aspect of the invention, the application of the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst in preparing methanol by electrocatalytic carbon dioxide reduction is provided.
Further, the beta-Mo 2 C/N-CNT is dripped on a glassy carbon electrode to be used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt sheet is used as a counter electrode, and the assembly is carried out in an electrochemical cell; continuously introducing CO into the electrochemical cell 2 Until the gas pressure in the electrochemical cell reaches 2-4MPa, introducingThe electricity carries out electrocatalytic reactions.
Furthermore, 0.1-1mg of beta-Mo is dripped on each square centimeter of glassy carbon electrode 2 C/N-CNT。
The invention has the beneficial effects that:
the nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst provided by the invention can obtain beta-phase molybdenum carbide particles with a more stable structure, and improves the dispersity of the beta-phase molybdenum carbide particles by doping nitrogen, so that the beta-phase molybdenum carbide particles with the particle size of 3-10nm are uniformly loaded on the surface of the nitrogen-doped carbon nanotube, thereby effectively avoiding the agglomeration of the beta-phase molybdenum carbide particles and improving CO 2 And (4) reduction reaction activity.
The preparation method of the nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst comprises the steps of mixing and roasting carbon nanotubes treated by excessive concentrated nitric acid and a nitrogen source to obtain nitrogen-doped carbon nanotubes, and then taking ammonium molybdate as a molybdenum source to obtain the nitrogen-doped carbon nanotube-loaded beta-phase molybdenum carbide catalyst by a method of impregnation and further calcination. The raw materials required in the preparation process are simple, the preparation method is simple and feasible, the batch preparation can be realized, and the method has a certain industrial prospect.
The nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst is used for preparing methanol by electrocatalysis carbon dioxide reduction, and the catalyst Mo generated by hybridization between d state of Mo and s state of C in the catalyst 2 The sp state of C splits. The cleavage makes sp state participate in the bonding change of the intermediate to promote the formation and adsorption of the oxygen-bonded intermediate, breaks through the linear correlation of the adsorption strength of carbon and oxygen determined by the center of d band in the traditional catalyst, simply improves the adsorption energy of oxygen atoms under the condition of not influencing the carbon affinity capacity, promotes the formation and conversion of the oxygen-bonded intermediate, prevents the loss of oxygen caused by proton attack, and establishes a CH taking formate (an oxygen-bonded species) as an important intermediate 3 OH formation path, increased generation of oxygen-containing product methanol to 80.4% CH 3 Faraday efficiency of OH in electrocatalysis of CO 2 The performance in preparing methanol is superior.
Drawings
FIG. 1 shows β -Mo obtained in examples 1 to 3 2 Scanning electron micrograph and particle size statistical chart of C/N-CNT;
FIG. 2 shows β -Mo obtained in example 5 2 XRD diffraction pattern of C/N-CNT;
FIG. 3 shows β -Mo obtained in example 5 2 Scanning electron micrograph and particle size statistical chart of C/N-CNT;
FIG. 4 shows β -Mo obtained in example 5 2 A C/N-CNT overlay;
FIG. 5 shows β -Mo obtained in example 6 2 Scanning electron micrograph of C/raw-CNT;
FIG. 6 is a scanning electron micrograph and a particle size distribution chart of the Mo/N-CNT obtained in example 7;
FIG. 7 shows CO corresponding to example 8 2 Solubility versus pressure, and CO at 0.1MPa, 2MPa and 4MPa 2 pH profile of bulk phase under pressure;
FIG. 8 shows the results of N-CNT and β -Mo alloys obtained in examples 1-7 2 C/N-CNT、β-Mo 2 CO of C/raw-CNT and Mo/N-CNT under the conditions of example 8 2 A reduction performance test chart;
FIG. 9 shows β -Mo obtained in example 8 corresponding to examples 5 and 7 2 In situ infrared test patterns of C/N-CNT and Mo/N-CNT;
FIG. 10 shows oxygen in Mo 2 Comparative plot of binding energy of C and Mo surfaces;
FIG. 11 shows Mo (110) and Mo 2 DOS map of C (101).
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
Preparation of N-CNTs
(1) Accurately weigh 1 gram of Carbon Nanotubes (CNT) dispersed in 200 milliliters of 60 to 65wt.% HNO 3 In solution, sonicate for 60 minutes. Then, the mixture was refluxed in an oil bath at 100 ℃ for 6 hours. After the sample is cooled to room temperature, centrifugally collecting a solid sample, cleaning the solid sample by ultrapure water until the supernatant is neutral, and drying the obtained black solid sample at 60 ℃ to obtain the sample with the surface rich in defectsThe CNT of (1).
(2) The CNTs obtained in (1) were mixed uniformly with urea in a mass ratio of 1 2 The gas stream was heated to 700 ℃ and held for 1 hour to yield the final N-CNTs.
β-Mo 2 Preparation of C/N-CNT
(3) Adding the 0.1g of N-CNT into 100 ml of deionized water, and carrying out ultrasonic treatment for 1 hour to obtain an N-CNT suspension; 10ml of an aqueous ammonium molybdate solution (2.5 mg/ml) were then added dropwise to the N-CNT suspension with vigorous stirring, stirred overnight, and the product was collected by centrifugation and dried at 60 ℃.
(4) The resulting powder was charged to a tube furnace at 80sccm N 2 The gas stream was heated to 600 ℃ and held for 1 hour, after it had cooled to room temperature, N was added 2 The gas flow is switched to oxygen-nitrogen mixed gas with the oxygen volume fraction of 0.5 percent, and is kept for 0.5 hour at room temperature to obtain the final beta-Mo 2 C/N-CNT。
FIG. 1a shows β -Mo prepared in example 1 2 Transmission electron micrograph of C/N-CNT; as can be seen from FIG. 1a, beta-Mo 2 The C particles are uniformly loaded on the surface of the N-CNT.
FIG. 1b shows β -Mo prepared in example 1 2 beta-Mo in C/N-CNT 2 The particle size distribution of C; from FIG. 1b, it can be seen that beta-Mo 2 The particle size distribution of C is 3-6nm.
Example 2
Preparation of N-CNTs
(1) Accurately weigh 1 gram of Carbon Nanotubes (CNT) dispersed in 200 milliliters of 60 to 65wt.% HNO 3 In solution, sonication was carried out for 60 minutes. Then, the mixture was refluxed in an oil bath at 120 ℃ for 9 hours. After it was cooled to room temperature, a solid sample was collected by centrifugation, and washed with ultrapure water until the supernatant was neutral, and the resulting black solid sample was dried at 60 ℃ to obtain CNTs rich in defects on the surface.
(2) The CNTs obtained in (1) were mixed uniformly with urea in a mass ratio of 1 2 Heating the gas stream to 800 deg.C for 2 hr to obtain the final productThe final N-CNT.
β-Mo 2 Preparation of C/N-CNT
(3) Adding the 0.1g of N-CNT into 100 ml of deionized water, and carrying out ultrasonic treatment for 1 hour to obtain an N-CNT suspension; 10ml of an aqueous ammonium molybdate solution (5 mg/ml) were then added dropwise to the N-CNT suspension with vigorous stirring, stirred overnight, and the product was collected by centrifugation and dried at 60 ℃.
(4) The resulting powder was charged to a tube furnace at 80sccm N 2 The gas stream was heated to 700 ℃ and held for 2 hours, after it had cooled to room temperature, N was added 2 The gas flow is switched to oxygen-nitrogen mixed gas with the oxygen volume fraction of 1 percent and is kept for 2 hours at room temperature to obtain the final beta-Mo 2 C/N-CNT。
FIG. 1c shows β -Mo prepared in example 2 2 Transmission electron micrograph of C/N-CNT; as can be seen from FIG. 1c, beta-Mo 2 The C particles are uniformly loaded on the surface of the N-CNT.
FIG. 1d shows β -Mo prepared in example 2 2 beta-Mo in C/N-CNT 2 The particle size distribution of C; from FIG. 1d, it can be seen that beta-Mo 2 The particle size distribution of C is about 7-10 nm.
Example 3
Preparation of N-CNTs
(1) Accurately weigh 1.5 grams of Carbon Nanotubes (CNT) dispersed in 200 milliliters of 60 to 65wt.% HNO 3 In solution, sonication was carried out for 60 minutes. Then, the mixture was refluxed in an oil bath at 110 ℃ for 8 hours. After it was cooled to room temperature, a solid sample was collected by centrifugation, and washed with ultrapure water until the supernatant was neutral, and the resulting black solid sample was dried at 60 ℃ to obtain CNTs with defect-rich surfaces.
(2) The CNTs obtained in (1) were mixed uniformly with 2-methylimidazole in a mass ratio of 1 2 The gas stream was heated to 750 ℃ and held for 1.5 hours, after it had cooled to room temperature, N was added 2 The gas flow was switched to an oxygen-nitrogen mixture containing 1% oxygen by volume and kept at room temperature for 1 hour to obtain the final N-CNTs.
β-Mo 2 Preparation of C/N-CNTPrepare for
(3) Adding the 0.1g of N-CNT into 100 ml of deionized water, and carrying out ultrasonic treatment for 1 hour to obtain an N-CNT suspension; 10ml of an aqueous ammonium molybdate solution (4 mg/ml) were then added dropwise to the N-CNT suspension with vigorous stirring, stirred overnight, and the product was collected by centrifugation and dried at 60 ℃.
(4) The resulting powder was charged to a tube furnace at 80sccm N 2 The gas stream was heated to 650 ℃ and held for 2 hours, after it had cooled to room temperature, N was added 2 The gas flow is switched to oxygen-nitrogen mixed gas with the oxygen volume fraction of 1 percent and is kept for 1 hour at room temperature to obtain the final beta-Mo 2 C/N-CNT。
FIG. 1e shows β -Mo prepared in example 3 2 Transmission electron micrograph of C/N-CNT; as can be seen from FIG. 1e, beta-Mo 2 The C particles are uniformly loaded on the surface of the N-CNT.
FIG. 1f shows β -Mo prepared in example 3 2 beta-Mo in C/N-CNT 2 The particle size distribution of C; from FIG. 1f, it can be seen that beta-Mo 2 The particle size distribution of C is about 5-8 nm.
Example 4
Preparation of N-CNTs
(1) Accurately weigh 2 grams of Carbon Nanotubes (CNT) dispersed in 200 milliliters of 60 to 65wt.% HNO 3 In solution, sonicate for 60 minutes. Then, the mixture was refluxed in an oil bath at 120 ℃ for 9 hours. After it was cooled to room temperature, a solid sample was collected by centrifugation, and washed with ultrapure water until the supernatant was neutral, and the resulting black solid sample was dried at 60 ℃ to obtain CNTs with defect-rich surfaces.
(2) The CNTs obtained in (1) were mixed with urea in a mass ratio of 1 2 The gas stream was heated to 800 ℃ and held for 1 hour to yield the final N-CNTs.
Example 5
β-Mo 2 Preparation of C/N-CNT
Adding 0.1g of N-CNT obtained in the example 4 into 100 ml of deionized water, and carrying out ultrasonic treatment for 1 hour to obtain an N-CNT suspension; 10ml of an aqueous ammonium molybdate solution (2.5 mg/ml) were then added dropwise to the N-CNT suspension with vigorous stirring, stirred overnight, and the product was collected by centrifugation and dried at 60 ℃.
The resulting powder was charged to a tube furnace at 80sccm N 2 The gas stream was heated to 600 ℃ and held for 2 hours, after it had cooled to room temperature, N was added 2 The gas flow is switched to oxygen-nitrogen mixed gas with the oxygen volume fraction of 1 percent, and the gas flow is kept for 1 hour at room temperature to obtain the final beta-Mo 2 C/N-CNT。
FIG. 2 shows β -Mo prepared in example 5 2 XRD of C/N-CNT; as can be seen from FIG. 2, except for 20 °
About (2 Theta) diffraction peak belonging to N-CNT, and the rest diffraction peaks and beta-Mo 2 The standard card of C (PDF # 35-0787) is a perfect match. Shows that the obtained beta-Mo has good crystallinity 2 C。
FIG. 3 shows β -Mo prepared in example 5 2 Transmission electron micrograph and particle size statistical plot of C/N-CNT; as can be seen from FIG. 3, beta-Mo 2 The C particles are uniformly loaded on the surface of the N-CNT, and beta-Mo 2 The particle size distribution of C is about 3-6nm.
FIG. 4 shows Mo obtained in example 5 2 A C/N-CNT overlay; from fig. 4, the successful introduction of the N element and the uniform distribution of the Mo element can be seen.
Example 6
β-Mo 2 Preparation of C/raw-CNT
The only difference from example 5 is the replacement of N-CNT with untreated carbon nanotubes (raw-CNT).
FIG. 5 shows β -Mo obtained in the preparation of example 6 2 Transmission electron micrograph of C/raw-CNT; as can be seen from FIG. 5, β -Mo 2 And C is agglomerated into a block, and is partially coated on the surface of raw-CNT.
Example 7
Preparation of Mo/N-CNT
The only difference from example 6 is that the powder obtained is placed in a tube furnace at 80sccm H 2 The gas stream was heated to 800 ℃ and held for 8 hours to give the final Mo/N-CNT.
FIG. 6 is a transmission electron micrograph and a particle size distribution of Mo/N-CNT obtained in the preparation process of example 7; as can be seen from FIG. 6, mo is uniformly supported on the surface of N-CNT, and the particle size distribution of Mo is about 3-6nm.
Example 8
Electrocatalytic CO treatment of the catalysts prepared in examples 1 to 7 2 And (5) testing the reduction performance.
The catalysts prepared in examples 1-7 were drop-coated onto glassy carbon electrodes as working electrodes (0.1-1 mg β -Mo per square centimeter of glassy carbon electrode drop-coating) 2 C/N-CNT), pt sheet electrode as counter electrode, ag/AgCl as reference electrode, assembling electrochemical cell, and performing electrocatalysis on CO 2 Reduction performance testing and electrode stability testing. 0.1mol/L of CO in the electrolyte 2 Saturated KHCO 3 Solution, working electrode area 1cm 2 . And detecting the gas phase product by using gas chromatography, and detecting the liquid phase product by using a quantitative mode of matching liquid chromatography and nuclear magnetism.
CO at 0.1MPa for 0.1mg of catalyst prepared in examples 4-7 2 Electrolyte solution pH 6.8 under pressure, applied potential CH at-1.1V vs. SHE 3 The OH product selectivity is shown in table 1.
TABLE 1
CO at 0.1MPa for 1mg of catalyst prepared in examples 4-7 2 Electrolyte solution pH 6.8 under pressure, applied potential CH at-1.1V vs. SHE 3 The OH product selectivity is shown in table 2.
TABLE 2
Due to CO 2 Reduction to CH 3 The OH-dependent step is proton dependentLower pH is more favorable for the reaction, and CO is simultaneously carried out under normal pressure 2 Lower solubility also limits the performance of the catalyst. Thus increasing CO 2 Pressure of 2MPa and 4MPa of CO, respectively 2 The activity test was performed under pressure. As shown in FIG. 7, CO 2 The solubility of (a) increases significantly with increasing pressure; at the same time, CO dissolved in water 2 Molecular formation of H 2 CO 3 The proton concentration in the electrolyte can be effectively improved; from FIG. 7 it can be seen that the pH at 2MPa and 4MPa are both much lower than the pH at 0.1MPa.
CO at 2MPa for 1mg of catalyst prepared in examples 4-7 2 Electrolyte solution pH 5.6 under pressure, applied potential CH at-1.1V vs. SHE 3 The OH product selectivity is shown in table 3.
TABLE 3
CO at 4MPa Using 0.1mg of catalyst prepared in examples 4-7 2 The catalytic activity tests were carried out under pressure and at different voltages, and the product distributions are shown in FIG. 8, respectively. It can be seen from Table 3 and FIG. 8 that CH is present at 2MPa and 4MPa 3 The selectivity of OH is obviously better than 0.1MPa.
FIG. 8a is CO of N-CNT prepared in example 4 2 A reduction performance map. The experimental results show that the N-CNT catalyst prepared in example 4 has CH 3 The best selectivity for OH is 1.09%.
FIG. 8b shows β -Mo from example 5 2 CO of C/N-CNT 2 Reduction performance diagram. The experimental results show that Mo prepared in example 5 2 CH of C/N-CNT catalyst 3 The optimum selectivity to OH is 80.4%.
FIG. 8c shows β -Mo obtained in example 6 2 CO of C/raw-CNT 2 A reduction performance map. The experimental results show that Mo prepared in example 6 2 CH of C/raw-CNT catalyst 3 The optimum selectivity to OH was 35.76%.
FIG. 8d is CO of Mo/N-CNT prepared in example 7 2 Reduction performance diagram. The experimental results show that Mo prepared in example 7 2 CH of C/raw-CNT catalyst 3 The best selectivity for OH is 7.82%.
Visible, beta-Mo 2 The formation of C effectively improves the selectivity of methanol, and secondly, the introduction of N improves Mo 2 The dispersibility of the C particles (as shown in FIG. 3, 5) increases the number of active sites. Meanwhile, as shown in FIG. 9, mo/N-CNT obtained in example 7 and β -Mo obtained in example 5 were used 2 In situ IR measurements of C/N-CNT found in beta-Mo 2 On the surface of the C/N-CNT, at 1800-2100cm -1 No absorption peak of CO tensile vibration was detected between them, indicating Mo 2 The main reaction pathway of the C/N-CNT surface may not involve CO intermediates. At 1300-1600cm -1 Three obvious peaks are arranged among the three peaks and are positioned at 1653-1640cm -1 Is caused by bending vibration of interfacial water, 1377cm -1 And 1437cm -1 The peak at (A) is caused by C-H bending vibration and O-C-O asymmetric stretching of OCHO, indicating that beta-Mo 2 The main reaction pathway of the C/N-CNT surface involves oxygen bonding (— OCHO) intermediates. While on the surface of Mo/N-CNT, an absorption peak of CO stretching vibration and a peak caused by O-C-O asymmetric stretching of COOH can be clearly observed, indicating that the main reaction pathway of the surface of Mo/N-CNT involves carbon bonds and (— CO) intermediates. The above results confirm that beta-Mo 2 C promotes the formation and adsorption of oxygen-bonded intermediates, thereby avoiding the loss of oxygen atoms and improving the selectivity of oxygen-containing products. The selectivity of the methanol can reach 80.4 percent at most.
CO at 4MPa for 1mg of catalyst prepared in examples 1-3 2 Electrolyte solution pH 5.4 under pressure, applied potential CH at-1.1V vs. SHE 3 The OH product selectivity is shown in table 4.
TABLE 4
Therefore, the beta-Mo with the grain diameter distribution of 3-10nm provided by the invention 2 C/N-CNT all having good electrocatalyst CO 2 The performance of methanol preparation by reduction.
In summary, the present invention provides a method for regulating and controlling CO by metal-carbon hybridization 2 Strategies for reducing the adsorption energy of intermediates promote the formation and conversion of oxygen-binding intermediates by increasing the adsorption energy of oxygen atoms. According to DFT calculation, hybridization between d state and carbon s state of Mo obtains the generated Mo 2 The sp state of C splits as shown in FIG. 10. This hybridization allows the sp and d states to work together in controlling the adsorption energy of the intermediate, as shown in FIG. 11, in contrast to Mo, β -Mo 2 The oxygen bond strength of the C surface is obviously improved. In situ ATR-SEIRAS confirmation, CH 3 The OH formation pathway changes from the "CO pathway" (determined by carbon-bound intermediates) to the thermodynamically preferred "formate pathway" (determined by oxygen-bound intermediates). Effectively avoids the reduction of selectivity of oxygen-containing products caused by the attack of protons on oxygen atoms. Promote CH 3 High selectivity of OH formation.
Although the preferred embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are only illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the scope of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The nitrogen-doped carbon nanotube-loaded molybdenum carbide catalyst is characterized by comprising nitrogen-doped carbon nanotubes, wherein beta-Mo is uniformly loaded on the surfaces of the nitrogen-doped carbon nanotubes 2 C particles of said beta-Mo 2 The particle size of the C particles is 3-10nm.
2. The preparation method of the nitrogen-doped carbon nanotube supported molybdenum carbide catalyst according to claim 1, comprising the following steps:
(1) Adding CNT to excess concentrated HNO 3 In the solution, performing ultrasonic dispersion to obtain a suspension; will be suspended in waterThe liquid is refluxed in an oil bath for 6 to 9 hours at the temperature of between 100 and 120 ℃; after the sample is cooled to room temperature, separating the solid sample to obtain CNT with defects on the surface;
(2) Uniformly mixing the CNT obtained in the step (1) with an excessive nitrogen source; roasting for 1-2 hours at the temperature of 700-800 ℃ under the protection of inert atmosphere to obtain N-CNT;
(3) Dispersing the N-CNT obtained in the step (2) into deionized water to obtain an N-CNT suspension; under the condition of violent stirring, dropwise adding an ammonium molybdate aqueous solution with the mass percent of ammonium molybdate accounting for 25-50% of the N-CNT; after the dropwise addition is finished, continuously stirring the mixture fully at room temperature, and then collecting a solid sample;
(4) Under the protection of inert atmosphere, roasting the solid sample for 1-2 hours at the temperature of 600-700 ℃; after the sample is cooled to the room temperature, the inert atmosphere is switched to oxygen-nitrogen mixed gas containing trace oxygen, and the sample is kept for 0.5 to 2 hours at the room temperature; to obtain beta-Mo 2 C/N-CNT and storing in inert atmosphere.
3. The method for preparing the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst according to claim 2, wherein in the step (1), the carbon nanotubes and the concentrated HNO are 3 The mass ratio of the solution is not more than 1.
4. The method for preparing nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst according to claim 2, wherein in the step (1), the concentrated HNO is 3 The mass fraction of the solution is 60-65%.
5. The method for preparing the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst according to claim 2, wherein in the step (2), the nitrogen source is 2-methylimidazole or urea.
6. The method for preparing the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst according to claim 2, wherein in the step (2), the mass ratio of the carbon nanotubes to the nitrogen source is not more than 1:10.
7. the method of claim 2, wherein in the step (4), the oxygen gas accounts for no more than 1% of the oxygen-nitrogen gas mixture.
8. Use of the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst of claim 1 in the electrocatalytic reduction of carbon dioxide to methanol.
9. The use of the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst of claim 8 in the electrocatalytic carbon dioxide reduction to methanol, wherein the β -Mo is added 2 C/N-CNT is dripped on a glassy carbon electrode to be used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt sheet is used as a counter electrode, and the assembly is carried out in an electrochemical cell; continuously introducing CO into the electrochemical cell 2 And electrifying to perform the electrocatalytic reaction until the gas pressure in the electrochemical cell reaches 2-4 MPa.
10. The use of the nitrogen-doped carbon nanotube-supported molybdenum carbide catalyst in the electrocatalytic carbon dioxide reduction for methanol production according to claim 9, wherein 0.1-1mg β -Mo per square centimeter of the glassy carbon electrode is dripped 2 C/N-CNT。
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Non-Patent Citations (1)
| Title |
|---|
| YUE-JUN SONG ET AL: ""Facile synthesis of Mo2C nanoparticles on N-doped carbon nanotubes with enhanced electrocatalytic activity for hydrogen evolution and oxygen reduction reactions", JOURNAL OF ENERGY CHEMISTRY, vol. 38, 9 January 2019 (2019-01-09), pages 68 - 77, XP085728785, DOI: 10.1016/j.jechem.2019.01.002 * |
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