CN114011413A - Method for preparing ferrum-cobalt bimetallic single-atom anchoring nitrogen-doped graphene cocatalyst and application thereof - Google Patents
Method for preparing ferrum-cobalt bimetallic single-atom anchoring nitrogen-doped graphene cocatalyst and application thereof Download PDFInfo
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- 229920000877 Melamine resin Polymers 0.000 description 2
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A method for preparing an iron-cobalt bimetallic single-atom anchoring aza-graphene cocatalyst and application thereof. Adding graphene oxide into deionized water, uniformly mixing by ultrasonic waves, adding a mixed solution of a cobalt chloride aqueous solution and a ferric chloride aqueous solution, and uniformly dispersing in the mixed solution by ultrasonic waves to obtain a solution A; after the solution A is put into liquid nitrogen for quick freezing, after the freeze drying treatment is finished, calcining at high temperature in the atmosphere of argon and ammonia gas to obtain the nitrogen-doped graphene anchored by the iron-cobalt bimetallic single atom and used as a cocatalyst; adding the load material into an absolute ethyl alcohol solution, performing ultrasonic dispersion, compounding with aza-graphene anchored by a ferrous-cobalt bimetallic monoatomic atom, mechanically stirring at room temperature, centrifuging, cleaning, drying in vacuum, grinding, and performing annealing treatment to obtain the composite photocatalytic material. The iron-cobalt bimetallic single atom is uniformly anchored on the surface of the nitrogen-doped graphene, and the nitrogen-doped graphene is well combined with different mesoporous semiconductor materials, so that the nitrogen-doped graphene has excellent photocatalytic hydrogen production performance.
Description
Technical Field
The invention belongs to the technical field of energy and material preparation, and particularly relates to a method for preparing an iron-cobalt bimetallic single-atom anchoring aza-graphene cocatalyst and application thereof.
Background
Since the 21 st century, countries in the world are constantly accelerating their development steps, and the great energy consumption and severe environmental pollution seriously affect the sustainable development of human beings, so that the development of efficient, green and sustainable new energy is particularly necessary. Solar energy is abundant and widely distributed, and is considered as an ideal renewable energy source. The photocatalytic technology is a green technology which is efficient and safe and has a wide application prospect for converting solar energy into chemical energy, however, the existing photocatalyst has the defects of low solar energy utilization rate, high photoproduction electron-hole recombination rate, high cost and the like, so that the wide application of the photocatalytic technology is limited. Therefore, the development of a photocatalyst which has high efficiency, low cost and easy synthesis has wide prospect.
Graphite phase carbon nitride (g-C)3N4) As a typical polymer semiconductor, the C, N atom in its structure is sp2The hybridization forms a highly delocalized pi conjugated system, and the semiconductor has proper forbidden band width and band edge position of a semiconductor, photogenerated holes of the semiconductor can oxidize water to generate oxygen, and photogenerated electrons have strong reducing capability. Therefore, theoretically g-C3N4Can be used as a photocatalytic material with visible light response. At present, g-C3N4Have been used for photocatalytic water decomposition, photocatalytic degradation, and photocatalytic reduction of dioxidesCarbon, etc. But g-C3N4Still has a series of problems of low solar energy utilization rate, high photon-generated carrier recombination rate, small specific surface area and the like, and the g-C is seriously hindered by the problems3N4Large-scale application in the field of photocatalysis. In view of the above problems, scientists at home and abroad have developed a series of researches to improve g-C3N4Photocatalytic activity of (1). For example, researchers have started from optimizing the preparation method by regulating g-C3N4The specific surface area, the energy band structure and the like of the polymer improve the g-C3N4The photocatalytic performance of (a). The mesoporous g-C with larger specific surface area can be synthesized by using a hard template method3N4(mpg-C3N4) The larger specific surface area can promote the mass transfer and diffusion process on the surface of the catalyst, improve the light absorption performance of the catalyst and be more beneficial to the loading of a cocatalyst, thereby improving the mpg-C3N4The photocatalytic performance of (a).
In addition to optimizing g-C3N4The preparation method can improve g-C3N4In addition to the photocatalytic activity of (a), metal promoter particles are loaded to g-C3N4The surface of the semiconductor substrate is beneficial to the transmission of photo-generated electrons on a semiconductor interface, so that the photocatalytic performance of the semiconductor substrate is effectively improved. Currently, the most effective co-catalyst is platinum group metal, however, the platinum group metal is scarce in nature and its high cost limits the industrial application of platinum group metal. Therefore, the development of a non-noble metal cocatalyst with abundant reserves, high efficiency and stability has wide prospect. Recently, iron (Fe) and cobalt (Co) have entered the field of view as abundant non-noble metal promoters. In recent years, nitrogen-doped carbon materials have been developed rapidly, and in these nitrogen-doped carbon materials, various N functional groups, such as pyridine N, pyrrole N, graphite N, and quaternary ammonium N, provide abundant coordination sites for binding metal atoms, and at the same time, can effectively prevent aggregation of metals, thereby improving the photocatalytic performance of the materials. Therefore, the design and preparation of the mesoporous graphite phase carbon nitride nanomaterial taking the iron-cobalt bimetallic single-atom anchored aza-graphene as the cocatalyst has important significance in the field of photocatalytic hydrogen production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing an iron-cobalt bimetallic single-atom anchoring aza-graphene cocatalyst and application thereof.
A method for preparing an iron-cobalt bimetallic single-atom anchored nitrogen-doped graphene cocatalyst comprises the following steps:
and 4, adding the load material into an absolute ethyl alcohol solution by adopting an immersion method, performing ultrasonic dispersion, compounding with the aza-graphene anchored by the Fe-Co bimetal monoatomic atom, mechanically stirring for 6-8 h at room temperature, centrifuging, cleaning, performing vacuum drying for 6-8 h at 60 ℃, grinding and annealing a dried product, and thus obtaining the composite photocatalytic material.
The improvement is that the using amount of the graphene oxide is 100 mg, the concentrations of the iron chloride aqueous solution and the cobalt chloride aqueous solution are both 3mg/mL, the sum of the using amounts of the two is 1 mL, and the volume ratio is 1: 4-4:1.
The improvement is that in the step 3, the calcination temperature is 700-.
The improvement is that in the step 4, the load material is any one of mesoporous carbon nitride, mesoporous carbon, mesoporous titanium dioxide, mesoporous alumina, mesoporous silica, mesoporous tin dioxide or mesoporous metal organic framework.
As a changeFurther, in step 4, mpg-C3N4The dosage of the FeCo-NG is 100-300 mg, and the dosage of the FeCo-NG is 1-15 mg.
The improvement is that in the step 4, the stirring time at room temperature is 6-8 h, the vacuum drying time is 6-8 h, the calcining temperature is 300-400 ℃, and the argon flow is 160-200 mL/min.
The obtained mesoporous graphite phase carbon nitride nano material with the iron-cobalt bimetallic single-atom anchored aza-graphene as the cocatalyst is applied to photocatalytic hydrogen production.
Has the advantages that:
compared with the prior art, the invention provides a method for preparing an iron-cobalt bimetallic single-atom anchoring aza-graphene cocatalyst and application thereof. Compared with a common single-metal atom cocatalyst, the bimetallic single-atom anchoring nitrogen-doped graphene cocatalyst prepared by the method disclosed by the invention has excellent photocatalytic activity. This is because there is a synergistic effect between different metal atoms, and the charge transfer between atoms can effectively regulate the electronic structure, thereby leading to rapid photoproduction electron-hole separation and migration efficiency. Meanwhile, the invention researches the influence of different metal atom ratios on the activity and regulates and controls the catalytic activity from the atom level.
In addition, the preparation method is simple and convenient, the cost is low, and the obtained material can be used for photocatalytic water decomposition and has excellent photocatalytic hydrogen production performance.
Drawings
FIG. 1 is a TEM image of a mesoporous graphite phase carbon nitride nanomaterial with Fe-Co bimetallic single-atom anchored aza-graphene as a promoter prepared by the present invention;
FIG. 2 is a diagram showing the photocatalytic hydrogen production activity of a mesoporous graphite-phase carbon nitride nanomaterial with Fe-Co bimetallic single-atom anchored aza-graphene as a promoter.
Detailed Description
Example 1
and 3, putting the sample into an ammonia gas and argon gas atmosphere to calcine for 1h at the temperature of 750 ℃, wherein the flow rate of the argon gas is 170 mL/min, the flow rate of the ammonia gas is 70 mL/min, the heating rate is 12 ℃/min, and the ferrum-cobalt bimetallic monoatomic anchored aza graphene is obtained and recorded as Fe0.2Co0.8-NG for standby;
Example 2
and 3, putting the sample into an ammonia gas and argon gas atmosphere to calcine for 1h at the temperature of 750 ℃, wherein the flow rate of the argon gas is 170 mL/min, the flow rate of the ammonia gas is 70 mL/min, the heating rate is 12 ℃/min, and the ferrum-cobalt bimetallic monoatomic anchored aza graphene is obtained and recorded as Fe0.5Co0.5-NG for standby;
Example 3
and 3, putting the sample into an ammonia gas and argon gas atmosphere to calcine for 1h at the temperature of 750 ℃, wherein the flow rate of the argon gas is 170 mL/min, the flow rate of the ammonia gas is 70 mL/min, the heating rate is 12 ℃/min, and the ferrum-cobalt bimetallic monoatomic anchored aza graphene is obtained and recorded as Fe0.8Co0.2-NG for standby;
Comparative example 1
Weighing 100 mg of graphene oxide, adding 50 mL of deionized water, uniformly mixing by ultrasonic, then dropwise adding 1 mL and 3mg/mL of iron chloride aqueous solution, uniformly dispersing in the mixed solution by ultrasonic, quickly freezing the mixed solution by liquid nitrogen, carrying out freeze drying treatment for 48 h, then putting a sample into an ammonia gas and argon gas atmosphere to calcine for 1h at 700 ℃, wherein the flow of argon gas is 160 mL/min, the flow of ammonia gas is 60 mL/min, and the heating rate during calcination is 11 ℃/min, so that the iron metal monoatomic anchored aza-graphene is obtained, and is recorded as Fe-NG for later use.
Weighing 10 mg of Fe-NG, adding into 60 mL of absolute ethyl alcohol, carrying out ultrasonic homogenization, and then adding 200 mg of mpg-C3N4Ultrasonically homogenizing, mechanically stirring at room temperature for 8 h, centrifuging, cleaning, vacuum drying at 60 deg.C for 8 h, grinding the dried product, and annealing at 350 deg.C to obtain 5 wt% Fe-NG/mpg-C3N4。
Comparative example 2
Weighing 100 mg of graphene oxide, adding the graphene oxide into 50 mL of deionized water, uniformly mixing by ultrasonic, dropwise adding 1 mL of 3mg/mL of cobalt chloride aqueous solution, uniformly dispersing in the mixed solution by ultrasonic, quickly freezing the mixed solution by liquid nitrogen, carrying out freeze drying treatment for 48 hours, putting a sample into an ammonia gas and argon gas atmosphere, calcining for 1 hour at 750 ℃, wherein the argon gas flow is 170 mL/min, the ammonia gas flow is 70 mL/min, and the heating rate is 12 ℃/min, so that cobalt metal monoatomic anchored aza-graphene is obtained, and is recorded as Co-NG for later use.
Weighing 5mg of Co-NG, adding into 30mL of absolute ethyl alcohol, carrying out ultrasonic homogenization, and adding 100 mg of mpg-C3N4Ultrasonically homogenizing, mechanically stirring at room temperature for 7 h, centrifuging, cleaning, vacuum drying at 60 deg.C for 7 h, grinding the dried product, and annealing at 300 deg.C. Finally obtaining 5 wt% Co-NG/mpg-C3N4。
Comparative example 3
Weighing 3 g of melamine, putting the melamine on a nickel screen, heating to 550 ℃ at the heating rate of 2.1 ℃/min, and calcining for 4 h to obtain mpg-C3N4As a blank comparison.
Topography characterization
To study FeCo-NG/mpg-C3N4The morphology structure of the composite material is analyzed by a transmission electron microscope, the result is shown in figure 1 (a), and it can be seen from the figure that the mpg-C prepared by the preparation method of the invention3N4Exhibits an ultra-thin porous structure; FIG. 1 (b) is a TEM image of FeCo-NG, and it can be seen from the image that the prepared FeCo-NG also exhibits an ultra-thin structure, and the surface thereof does not detect the presence of FeCo atoms in the low-magnification TEM image due to the small size and high dispersion of FeCo bimetallic atoms.
Performance testing
Photocatalytic activity measurement method: experiments were performed using an on-line system (Labsolalar-6A, PerfectLight, Beijing) to photocatalytic water splitting to generate hydrogen. First, 50mg of the composite photocatalyst was put into a 300mL quartz glass reactor, 100 mL of an aqueous solution containing 10 mL of Triethanolamine (TEOA) was measured in a graduated cylinder, poured into the reactor and ultrasonically dispersed for 5 min to complete photocatalyst dispersion. In the hydrogen production reaction, a 300W Xenon lamp (PLS-SXE 300 (BF) Perfect Light, Beijing) is used as a Light source, and a cooling circulating water system is controlled within 10 ℃ so as to avoid overhigh temperature for a long time and ensure stable reaction. Every 1 hour, hydrogen production was measured by an on-line gas chromatograph (GC D7900P).
The photocatalytic hydrogen production test was performed using examples 1 to 3 and comparative examples 1 to 3, and the results are shown in fig. 2.
As can be seen from FIG. 2, the original mpg-C prepared in comparison with comparative example 13N4In contrast, Fe-NG or Co-NG as promoters with mpg-C3N4After the composition, the photocatalytic hydrogen production performance can be effectively improved. Meanwhile, when Fe-Co metal coexists, compared with a single-metal compound, the introduction of the bimetal can effectively improve the photocatalytic hydrogen production performance of the composite material due to the synergistic effect. In addition, the materials of comparative example 1, example 2 and example 3 were prepared according to the procedure of photocatalytic hydrogen production described above, and the results were: 5 wt% Fe0.2Co0.8-NG/mpg-C3N4(volume ratio of cobalt chloride aqueous solution to ferric chloride aqueous solution is 4: 1) the highest hydrogen production in 4 hours reaches 1957.8 mu mol/g, 5 wt% Fe0.5Co0.5-NG/mpg-C3N4(volume ratio of cobalt chloride aqueous solution to ferric chloride aqueous solution is 1: 1) hydrogen production in 4 hours, secondly, 1400.4. mu. mol/g, 5 wt% Fe0.8Co0.2-NG/mpg-C3N4(the volume ratio of the aqueous solution of cobalt chloride to the aqueous solution of iron chloride was 1: 4) the worst hydrogen production in 4 hours, 568.9. mu. mol/g,
the above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (7)
1. A method for preparing an iron-cobalt bimetallic single-atom anchored nitrogen-doped graphene cocatalyst is characterized by comprising the following steps:
step 1, adding graphene oxide into deionized water, uniformly mixing by ultrasonic waves, adding a mixed solution of a cobalt chloride aqueous solution and a ferric chloride aqueous solution, and uniformly dispersing in the mixed solution by ultrasonic waves to obtain a solution A;
step 2, putting the solution A into liquid nitrogen for quick freezing, and then carrying out freeze drying treatment for 48 hours;
step 3, after the freeze drying is finished, calcining the mixture at high temperature for 1h in the atmosphere of argon and ammonia gas to obtain the nitrogen-doped graphene anchored by the Fe-Co bimetallic monoatomic group, which is marked as FeCo-NG and is used as a cocatalyst;
and 4, adding the load material into an absolute ethyl alcohol solution by adopting an immersion method, performing ultrasonic dispersion, compounding with the aza-graphene anchored by the Fe-Co bimetal monoatomic atom, mechanically stirring for 6-8 h at room temperature, centrifuging, cleaning, performing vacuum drying for 6-8 h at 60 ℃, grinding and annealing a dried product, and thus obtaining the composite photocatalytic material.
2. The method for preparing the Fe-Co bimetallic monoatomic anchoring aza-graphene promoter as claimed in claim 1, wherein: in the step 1, the usage amount of the graphene oxide is 100 mg, the concentrations of the iron chloride aqueous solution and the cobalt chloride aqueous solution are both 3mg/mL, the sum of the usage amounts of the two is 1 mL, and the volume ratio is 1: 4-4:1.
3. The method for preparing the Fe-Co bimetallic monoatomic anchoring aza-graphene promoter as claimed in claim 1, wherein: in the step 3, the calcination temperature is 700-.
4. The preparation method of the promoter for the Fe-Co bimetallic monoatomic anchored aza-graphene according to claim 1, wherein the promoter comprises: in the step 4, the load material is any one of mesoporous carbon nitride, mesoporous carbon, mesoporous titanium dioxide, mesoporous alumina, mesoporous silica, mesoporous tin dioxide or mesoporous metal organic framework.
5. The preparation method of the promoter for the Fe-Co bimetallic monoatomic anchored aza-graphene according to claim 4, wherein the promoter comprises the following steps: when the load material is mpg-C in the step 43N4At first, mpg-C3N4The dosage of the FeCo-NG is 100-300 mg, and the dosage of the FeCo-NG is 1-15 mg.
6. The method for preparing the Fe-Co bimetallic monoatomic anchoring aza-graphene promoter as claimed in claim 1, wherein: in the step 4, the stirring time at room temperature is 6-8 h, the vacuum drying time is 6-8 h, the calcining temperature is 300-.
7. The application of the mesoporous graphite phase carbon nitride nano material taking the iron-cobalt bimetallic single-atom anchored aza-graphene prepared according to the claims 1-6 as a cocatalyst in photocatalytic hydrogen production.
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