CN113005477B - Phosphorus-sulfur co-doped graphene loaded Mo2Preparation method of C composite material - Google Patents
Phosphorus-sulfur co-doped graphene loaded Mo2Preparation method of C composite material Download PDFInfo
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- CN113005477B CN113005477B CN202110213147.9A CN202110213147A CN113005477B CN 113005477 B CN113005477 B CN 113005477B CN 202110213147 A CN202110213147 A CN 202110213147A CN 113005477 B CN113005477 B CN 113005477B
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Abstract
The invention discloses phosphorus and sulfur co-doped graphene loaded Mo2The preparation method of the material C comprises the following steps: firstly, dispersing graphene oxide in deionized water, adding phosphoric acid, performing ultrasonic treatment until the solution is uniformly mixed, then performing freeze drying, and calcining in a nitrogen environment to obtain phosphorus-doped graphene; then ultrasonically dispersing the phosphorus-doped graphene in deionized water, adding sulfuric acid, ultrasonically freeze-drying, calcining to obtain phosphorus-sulfur co-doped graphene, reacting the phosphorus-sulfur co-doped graphene with ammonium molybdate tetrahydrate, and calcining in a hydrogen atmosphere to obtain the phosphorus-sulfur co-doped graphene loaded Mo2And C, material. The material prepared by the method can be used for electrocatalytic nitrogen reduction, has excellent catalytic performance and has better market prospect.
Description
Technical Field
The invention relates to the field of nano-catalysts, in particular to phosphorus and sulfur co-doped graphene loaded Mo2C, a preparation method of the composite material.
Background
Ammonia (NH)3) As an important chemical substance in the industrial production in the world, the chemical substance is widely applied to the production of pharmacy, synthetic fiber, fertilizer and energy conversion process. However, currently, industrial ammonia production is primarily conducted by the conventional Haber-Bosch process to produce nitrogen (N)2) Reduction to NH3. The reaction process needs to be carried out with pure H2A large amount of fossil energy is consumed for the reactants and the process is carried out in a high-temperature and high-pressure environment. Therefore, it is an urgent task to find a cleaner and more efficient method for producing ammonia to replace the conventional Haber-Bosch process.
The electrocatalytic nitrogen reduction can synthesize ammonia at normal temperature and normal pressure, and the reactant is H2O and N2And is very easy to obtain, so that the method becomes a research hotspot at present. Breaking N is required for electrochemical synthesis of ammonia2The molecular N [ identical to ] N, however, the extremely stable N [ identical to ] N seriously hinders the nitrogen reduction process, so that the catalyst becomes the core of the whole electrocatalytic nitrogen reduction process, and a high-activity and high-selectivity active catalyst is searched for NH3Production of (b) is still highly desirable.
Graphene as an sp2Hybridization is only a substance m with a carbon atom layer of a two-dimensional honeycomb structure, and the substance m is widely applied to an electrocatalyst due to high electron mobility, ultra-large specific surface area and good electrical conductivity, but pure graphene often cannot show good performance in electrochemical reaction, and hetero atoms are doped in the graphene, so that the original structure of the pure graphene can be changed, and in addition, the doping of the hetero atoms can also improve the defect degree of the graphene, so that the impurity degree of the graphene can be improved, and the material m is enabled to be widely applied to the electrocatalystThe self pore diameter and pore volume of the graphene are increased, catalytic active sites are increased, and the electrochemical performance and stability of the material are improved.
Disclosure of Invention
The invention aims to provide phosphorus and sulfur co-doped graphene loaded Mo2In order to solve the technical problems, the preparation method of the C composite material adopts the following technical scheme:
(1) adding graphene oxide into deionized water, performing ultrasonic dispersion for 1h, adding phosphoric acid, performing ultrasonic treatment for 8h until the mixture is uniformly mixed, pouring the mixed sample into a watch glass, drying the watch glass in a drying oven, and then transferring the watch glass into a muffle furnace for calcination reaction;
(2) adding the product obtained in the step (1) into deionized water, performing ultrasonic dispersion for 1h, adding sulfuric acid, performing ultrasonic treatment for 2h until the mixture is uniformly mixed, performing freeze drying, and then performing a calcination reaction to obtain a phosphorus-sulfur co-doped graphene material;
(3) adding the product obtained in the step (2) into deionized water, performing ultrasonic treatment to completely disperse the product, adding ammonium molybdate tetrahydrate into the deionized water, stirring to completely dissolve the ammonium molybdate, dropwise adding the ammonium molybdate solution into the phosphorus and sulfur co-doped graphene solution, stirring for 10-12H, washing the product with deionized water and ethanol, performing vacuum drying, putting the product into a tube furnace, introducing half H, and drying2Discharging the gas inside the tube furnace, then at H2Calcining under atmosphere to obtain phosphorus-sulfur co-doped graphene loaded Mo2And C, a composite material.
Preferably, in the step (1), the mass-to-volume ratio of the graphene oxide to the phosphoric acid is 1 mg: (1-2) μ l.
Preferably, in the step (1), the calcination temperature is 700-.
Preferably, in the step (2), the mass-to-volume ratio of the graphene oxide to the sulfuric acid is 1 mg: (1-2) μ l.
Preferably, in the step (2), the calcination temperature is 800-.
Preferably, in the step (3), the mass ratio of ammonium molybdate tetrahydrate to graphene oxide is (2-4): 1.
preferably, in the step (3), the calcination temperature is 800-.
Compared with the prior art, the invention has the following beneficial effects:
(1) the process is very simple, and the obtained phosphorus and sulfur co-doped graphene loaded Mo2The material C has good electrocatalytic performance, and the graphene oxide material has good conductivity and specific surface area, can provide a large number of catalytic active sites, and is widely used for electrocatalytic materials. P, S, the original structure of pure graphene can be changed, and in addition, the defect degree of graphene can be improved by doping the heteroatom, so that the pore diameter and pore volume of graphene are increased, and catalytic active sites are increased, thereby effectively increasing the specific surface area of graphene and further improving the catalytic activity and stability of the catalyst. Phosphorus and sulfur co-doped graphene loaded Mo prepared by the invention2The material C has low cost, simple processing method and good electrocatalytic nitrogen reduction performance.
(2) The invention has the advantages of simple raw materials, easy acquisition, low cost and environmental protection.
Drawings
FIG. 1 shows that phosphorus and sulfur co-doped graphene loaded Mo prepared by the method of example 12A Transmission Electron Microscope (TEM) image of the C composite;
FIG. 2 shows that the phosphorus and sulfur co-doped graphene loaded Mo prepared by the method of example 12C, an electrocatalytic nitrogen reduction performance graph of the composite material;
FIG. 3 shows that the phosphorus and sulfur co-doped graphene loaded Mo prepared by the method of example 12And C, a cycle stability performance graph of the composite material.
Detailed description of the preferred embodiments
Example 1:
phosphorus-sulfur co-doped graphene loaded Mo2The preparation method of the composite material comprises the following steps:
(1) adding 100mg of graphene oxide into 150ml of deionized water, performing ultrasonic dispersion for 1h, adding 150 mu l of phosphoric acid, performing ultrasonic treatment for 8h until the mixture is uniformly mixed, pouring the mixed sample into a watch glass, drying the mixed sample at 85 ℃ for 12h, transferring the dried sample into a muffle furnace, heating the mixed sample to 800 ℃ at the speed of 5 ℃/min, and calcining the mixed sample for 3 h;
(2) adding the product obtained in the step (1) into 200ml of deionized water, performing ultrasonic dispersion for 1h, adding 150 mu l of sulfuric acid, performing ultrasonic treatment for 2h until the mixture is uniformly mixed, performing freeze drying, heating to 1000 ℃ at the speed of 5 ℃/min, and calcining for 2h to obtain the phosphorus-sulfur co-doped graphene loaded Mo2And C, material.
(3) Adding the product obtained in the step (2) into deionized water, performing ultrasonic treatment for 45min, adding 300mg of ammonium molybdate tetrahydrate into 20ml of deionized water, stirring to completely dissolve the ammonium molybdate, dropwise adding the ammonium molybdate solution into the phosphorus and sulfur co-doped graphene solution, stirring for 11H, washing the product with deionized water and ethanol, performing vacuum drying, putting the product into a tubular furnace, and introducing H for half an hour2Discharging the gas inside the tube furnace, then at H2Calcining for 3h at 850 ℃ in the atmosphere to obtain phosphorus-sulfur co-doped graphene loaded Mo2And C, a composite material.
Example 2:
phosphorus-sulfur co-doped graphene loaded Mo2The preparation method of the composite material comprises the following steps:
(1) adding 100mg of graphene oxide into 150ml of deionized water, performing ultrasonic dispersion for 1h, adding 100 mu l of phosphoric acid, performing ultrasonic treatment for 8h until the mixture is uniformly mixed, pouring the mixed sample into a watch glass, drying the mixed sample at 85 ℃ for 12h, transferring the dried sample into a muffle furnace, heating the mixed sample to 700 ℃ at the speed of 2 ℃/min, and calcining the mixed sample for 2 h;
(2) adding the product obtained in the step (1) into 200ml of deionized water, performing ultrasonic dispersion for 1h, adding 100 mu l of sulfuric acid, performing ultrasonic treatment for 2h until the mixture is uniformly mixed, performing freeze drying, heating to 800 ℃ at the speed of 2 ℃/min, and calcining for 1h to obtain the phosphorus-sulfur co-doped graphene loaded Mo2And C, material.
(3) Adding the product obtained in the step (2) into deionized water, performing ultrasonic treatment for 30min, adding 200mg of ammonium molybdate tetrahydrate into 20ml of deionized water, stirring to completely dissolve the ammonium molybdate, dropwise adding the ammonium molybdate solution into the phosphorus and sulfur co-doped graphene solution, stirring for 10h, washing the product with deionized water and ethanol, performing vacuum drying, putting the product into a tubular furnace, introducing the product into the tubular furnace, and performing ultrasonic treatment for 30minHalf hour H2Discharging the gas inside the tube furnace, then at H2Calcining for 4 hours at 800 ℃ in the atmosphere to obtain phosphorus and sulfur co-doped graphene loaded Mo2And C, a composite material.
Example 3:
phosphorus and sulfur co-doped graphene loaded Mo2The preparation method of the composite material comprises the following steps:
(1) adding 100mg of graphene oxide into 150ml of deionized water, performing ultrasonic dispersion for 1h, adding 150 mu l of phosphoric acid, performing ultrasonic treatment for 8h until the mixture is uniformly mixed, pouring the mixed sample into a watch glass, drying the mixed sample at 85 ℃ for 12h, transferring the dried sample into a muffle furnace, heating the mixed sample to 900 ℃ at the speed of 8 ℃/min, and calcining the mixed sample for 4 h;
(2) and (2) adding the product obtained in the step (1) into 200ml of deionized water, performing ultrasonic dispersion for 1h, adding 150 mu l of sulfuric acid, performing ultrasonic treatment for 2h until the mixture is uniformly mixed, performing freeze drying, heating to 1200 ℃ at the speed of 8 ℃/min, and calcining for 3h to obtain the phosphorus-sulfur co-doped graphene loaded Mo2C material.
(3) Adding the product obtained in the step (2) into deionized water, performing ultrasonic treatment for 60min, adding 400mg of ammonium molybdate tetrahydrate into 20ml of deionized water, stirring to completely dissolve the ammonium molybdate, dropwise adding the ammonium molybdate solution into the phosphorus and sulfur co-doped graphene solution, stirring for 12H, washing the product with deionized water and ethanol, performing vacuum drying, putting the product into a tubular furnace, and introducing H for half an hour2Discharging the gas inside the tube furnace, then at H2Calcining for 2h at 900 ℃ in the atmosphere to obtain phosphorus-sulfur co-doped graphene loaded Mo2And C, a composite material.
Example 4:
phosphorus-sulfur co-doped graphene loaded Mo2The preparation method of the composite material comprises the following steps:
(1) adding 100mg of graphene oxide into 150ml of deionized water, performing ultrasonic dispersion for 1h, adding 200 mu l of phosphoric acid, performing ultrasonic treatment for 8h until the mixture is uniformly mixed, pouring the mixed sample into a watch glass, drying the mixed sample at 85 ℃ for 12h, transferring the dried sample into a muffle furnace, heating the mixed sample to 800 ℃ at the speed of 2 ℃/min, and calcining the dried sample for 3h to obtain a product a;
(2) adding the product a into 200ml of deionized water, and ultrasonically dispersingAdding 200 mul of sulfuric acid into the mixture for 1h, carrying out ultrasonic treatment for 2h until the mixture is uniformly mixed, carrying out freeze drying, then heating the mixture to 1200 ℃ at the speed of 2 ℃/min, and calcining the mixture for 2h to obtain the phosphorus and sulfur co-doped graphene loaded Mo2And C, material.
(3) Adding the product obtained in the step (2) into deionized water, performing ultrasonic treatment for 45min, adding 300mg of ammonium molybdate tetrahydrate into 20ml of deionized water, stirring to completely dissolve the ammonium molybdate, dropwise adding the ammonium molybdate solution into the phosphorus and sulfur co-doped graphene solution, stirring for 11H, washing the product with deionized water and ethanol, performing vacuum drying, putting the product into a tubular furnace, and introducing H for half an hour2Discharging the gas inside the tube furnace, then at H2Calcining for 3 hours at 900 ℃ in the atmosphere to obtain phosphorus and sulfur co-doped graphene loaded Mo2And C, a composite material.
And (3) performance testing:
the nitrogen reduction test was performed in a typical H-cell, with two cells separated by a perfluorosulfonic acid 211 membrane, and all electrochemical tests were performed at ambient temperature and pressure. The two cells were separated and all electrochemical tests were performed at ambient temperature and pressure. The perfluorosulfonic acid 211 membrane was first pretreated prior to testing. Firstly, treating a perfluorosulfonic acid 211 membrane in boiling distilled water for 1 h; secondly, putting the mixture into a hydrogen peroxide aqueous solution with the volume fraction of 5 percent for treatment for 1h at the temperature of 80 ℃; third, the film was placed in 0.5M H2SO4Treating in the solution at 80 deg.C for 3 h; and fourthly, soaking the treated membrane in distilled water for 6 hours. The electrochemical experiment was carried out on an electrochemical workstation of model CHI 660E, which employs a three-electrode system, and the phosphorus and sulfur co-doped graphene prepared in examples 1 to 4 supports Mo2The glassy carbon electrode modified by the C catalyst is used as a working electrode, the graphite electrode is used as a counter electrode, and the Ag/AgCl electrode is used as a reference electrode. Nitrogen reduction was tested at 0.1M Na saturated with nitrogen2SO4Potentiostatic tests were carried out in solution.
Product NH3The concentration of (b) was determined by indophenol blue spectrophotometry. 2ml of HCl electrolyte is taken in a 10ml centrifuge tube in a cathode electrolytic cell, and then 2ml of salicylic acid and lemon with the mixed mass fraction of 5 percent are addedSodium hydroxide solution of sodium, and finally 1ml of 0.05M sodium hypochlorite solution and 0.2ml of 1% sodium nitrosoferricyanide solution by mass are added. Placing the mixture for 2 hours in a dark room and then carrying out ultraviolet test to obtain a product NH3The concentration of (c).
Faraday Efficiency (FE) of nitrogen reduction reaction defined as synthesis of NH3The amount of charge required is divided by the charge passing through the electrodes during electrolysis.
The Faraday efficiency calculation formula is as follows:
rate of ammonia production (v)NH3) The calculation formula is as follows:
wherein F is the Faraday constant of 96485C/mol, [ NH ]3]For measuring the resulting NH3Concentration, V is the collected NH3Na of (2)2SO4Volume of electrolyte, total amount of charge passed through the electrodes during electrolysis of Q, t is reduction time, mcat.Is the catalyst mass. The invention collects NH3Na of (2)2SO4The electrolyte volumes V were 40ml each, the reduction times were 2 hours each, and the composite materials prepared in examples 1 to 4 were used as electrocatalysts, and the masses were 10mg each.
FIG. 1 shows that phosphorus and sulfur co-doped graphene loaded Mo prepared by the method of embodiment 1 of the invention2The transmission electron microscope picture of the C material shows that the graphene oxide is in a nano-sheet shape, and a large number of particles are loaded in the graphene oxide, which proves that Mo2Successful loading of the C particles.
FIG. 2 shows phosphorus and sulfur co-doped graphene loaded Mo prepared by the method of embodiment 1 of the invention2Electrocatalytic nitrogen reduction performance diagram of material C. In the embodiment 1 of the invention, NH in the electrolyte is added after the test is carried out for 2h at-0.5V3The concentration was 2.63. mu.g/ml, and the charge amount Q was 2.88C, as can be seen from FIG. 2, under neutral conditions,phosphorus and sulfur co-doped graphene loaded Mo prepared in example 12When the material C is used as an electro-catalyst for the electrochemical synthesis of ammonia, the maximum ammonia yield and the Faraday efficiency are obtained when the voltage is-0.5V, and the maximum ammonia yield is 14.6 mu g h-1mg-1cat, maximum faraday efficiency 6.2%.
FIG. 3 shows that phosphorus and sulfur co-doped graphene loaded Mo prepared by the method of embodiment 1 of the invention2The cyclic stability performance diagram of the material C can be seen from fig. 3 that the ammonia yield and the Faraday efficiency of the sample are not obviously reduced after 5 times of continuous tests under-0.5V voltage, which indicates that the phosphorus and sulfur co-doped graphene prepared by the method in example 1 of the present invention supports Mo2The C material has good stability.
Phosphorus and sulfur co-doped graphene loaded Mo prepared in embodiments 2-4 of the invention2The maximum Faraday efficiency and ammonia yield of the C composite material are both obtained when the Faraday efficiency and the ammonia yield are-0.5V, and the performance of the electrochemical synthesis of ammonia under-0.5V is shown in Table 1.
Table 1: electrochemical ammonia Synthesis Performance of the composite materials prepared in examples 1-4 of the present invention
From Table 1, it can be seen that the phosphorus and sulfur co-doped graphene prepared in examples 2 to 4 supports Mo2The electrochemical ammonia synthesis performance of the C composite material is similar to that of the C composite material in example 1, and the difference between the ammonia yield and the Faraday efficiency at-0.5V is not large from that of the C composite material in example 1, so that the C composite material is proved to have good electrocatalytic nitrogen reduction performance.
Claims (5)
1. Phosphorus-sulfur co-doped graphene loaded Mo2The preparation method of the C composite material is characterized in that the phosphorus and sulfur co-doped graphene loaded Mo2The material C is prepared by the following steps:
(1) adding graphene oxide into deionized water, performing ultrasonic dispersion for 1h, adding phosphoric acid, performing ultrasonic treatment for 8h until the mixture is uniformly mixed, pouring the mixed sample into a watch glass, drying the watch glass in a drying oven, and then transferring the watch glass into a muffle furnace for calcination reaction;
(2) adding the product obtained in the step (1) into deionized water, performing ultrasonic dispersion for 1h, adding sulfuric acid, performing ultrasonic treatment for 2h until the mixture is uniformly mixed, performing freeze drying, and then performing a calcination reaction to obtain a phosphorus-sulfur co-doped graphene material;
(3) adding the product obtained in the step (2) into deionized water, performing ultrasonic treatment to completely disperse the product, adding ammonium molybdate tetrahydrate into the deionized water, stirring to completely dissolve the ammonium molybdate, dropwise adding the ammonium molybdate solution into the phosphorus and sulfur co-doped graphene solution, stirring for 10-12H, washing the product with deionized water and ethanol, performing vacuum drying, putting the product into a tube furnace, introducing H, and performing ultrasonic treatment2Discharging the gas inside the tube furnace, then at H2Calcining under atmosphere to obtain phosphorus-sulfur co-doped graphene loaded Mo2C, a composite material;
wherein, in the step (1), the calcining temperature is 700-; in the step (2), the calcination temperature is 800-; in the step (3), the calcination temperature is 800-900 ℃, and the calcination time is 2-4 h.
2. The phosphorus-sulfur co-doped graphene loaded Mo of claim 12The preparation method of the C composite material is characterized in that in the step (1), the mass-to-volume ratio of the graphene oxide to the phosphoric acid is 1 mg: and (1-2) mu L.
3. The phosphorus-sulfur co-doped graphene loaded Mo of claim 22The preparation method of the C composite material is characterized in that in the step (2), the mass-to-volume ratio of the graphene oxide to the sulfuric acid is 1 mg: and (1-2) mu L.
4. The phosphorus-sulfur co-doped graphene loaded Mo of claim 12The preparation method of the C composite material is characterized in that in the step (3), the mass ratio of ammonium molybdate tetrahydrate to graphene oxide is (2-4): 1.
5. a process as claimed in any one of claims 1 to 4The phosphorus and sulfur co-doped graphene loaded Mo2The preparation method of the C composite material is characterized in that the phosphorus and sulfur co-doped graphene loaded Mo2The material C is applied to electrochemical synthesis of ammonia.
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| Can graphene with intrinsic defects electrocatalyze N2 to NH3 reduction;Fei Wang;《Diamond & Related Materials》;20200817;全文 * |
| Single Faceted Two-Dimensional Mo2C Electrocatalyst for Highly;Kun Ba;《ACS Catal.》;20200618;全文 * |
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