CN111841575A - Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof - Google Patents
Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 25
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 64
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- 229920001021 polysulfide Polymers 0.000 claims abstract description 24
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a surface sulfur modified porous copper-based composite catalyst and a preparation method and application thereof, wherein the surface sulfur modified porous copper-based composite catalyst is prepared by mixing polysulfide solution and porous copper powder for reaction; the sulfur is adsorbed on the surface of the porous copper, and the molar ratio of S to Cu is 3: 100. the invention controls the sulfuration degree of the porous copper by polysulfide solution, sulfur is adsorbed on the surface of the porous copper to modify the porous copper, and sulfur atoms on the surface can not only enhance N by adjusting electronic properties2Adsorption, and can directly participate in the catalytic process by accepting and contributing H atoms, thereby remarkably improving the catalytic performance of the catalyst. The composite catalyst has simple preparation process, high activity and stable property, and can be reused for many times when being used for synthesizing ammonia by photocatalysis.
Description
Technical Field
The invention belongs to the technical field of photocatalytic synthesis of ammonia, and relates to a surface sulfur-modified porous copper-based composite catalyst, a preparation method thereof and application thereof in photocatalytic synthesis of ammonia.
Background
Ammonia (NH)3) Is an important chemical substance, and the annual ammonia production in the world Over 1.5 million tons, promoting population growth and development of modern society. Industrial production of ammonia N is produced by the Haber-Bosch process2And H2Conversion to NH at elevated temperature and pressure3The process consumes a large amount of energy and discharges millions of tons of CO2And the pollution to the earth environment is serious when the carbon dioxide enters the atmosphere. Thus N2Conversion to NH under mild conditions3Has attracted great attention because of its ability to meet current energy and environmental demands. Photocatalytic N, similar to biological nitrogenase under mild conditions2Reduction to NH3Is a cleaner, more sustainable NH3Production provides an alternative carbon-free strategy. N is a radical of2The molecular bond length is 107.8pm, the nonpolar nitrogen triple bond (N.ident.N) energy is 945KJ/mol, so N is2The molecule has extremely high stability, and its activation is considered to be N2Bottleneck in the reduction process, therefore, a new one capable of effectively activating N is developed2Molecular methods are of great interest. Through various efforts, N is proved from both theoretical and experimental aspects2The conversion of electrons to the anti-bonding orbitals during molecular activation is a critical step. This process can be achieved by photocatalysis, in which thermal electrons participate in the catalytic reaction. Albeit at N 2Some progress has been made in the activation and transformation of molecules, but there is still a strong need for new effective activated N2Molecular strategies.
In recent years, the Localized Surface Plasmon Resonance (LSPR) effect can provide sufficient photogenerated electrons to promote N2Has received a great deal of attention as a result of activation. Localized Surface Plasmon Resonance (LSPR) is a resonance photon-induced collective oscillation of valence electrons. When light is incident on the surface of the metal nano particle, if the frequency of the incident photon is consistent with the natural frequency of the surface electron, the photon can be captured by the electron which is vibrated collectively, and the free electron on the surface of the metal nano particle is coupled with the captured photoelectron to form a special electromagnetic mode, so that the local resonance phenomenon of the free electron is generated. The localized surface plasmon resonance effect is characterized by an increase in the optical extinction coefficient at the resonance frequency and an increase in the electric field at the surface of the nanoparticle. Optical eraserThe enhancement of the optical coefficient is manifested as localized surface plasmon resonance peaks in the diffuse reflectance ultraviolet-visible absorption spectrum. Research has shown that localized surface plasmon resonance effects of plasmonic metal particles (Ag, Au and Cu) can be used to induce a direct photochemical reaction.
Porous metal is a novel engineering material with dual attributes of both function and structure. The light functional material not only has good metal characteristics such as conductivity and excellent ductility, but also has the characteristics of high stability, low volume density, large specific surface area and the like, and can provide a large number of active sites for reaction when being used in photocatalysis. Therefore, a catalyst of porous copper base having plasmon resonance effect was developed in N2Has good prospect in the field of optical fixation.
Disclosure of Invention
In order to solve the technical problem of low catalytic activity of the existing porous metal catalyst, the invention aims to provide a surface sulfur modified porous copper-based composite catalyst and a preparation method and application thereof2Adsorption, and can directly participate in the catalytic process by accepting and contributing H atoms, thereby remarkably improving the catalytic performance of the catalyst. The preparation process of the invention is simple, and when the catalyst is used for synthesizing ammonia by photocatalysis, the catalyst has high activity and stable property, and can be repeatedly used.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a surface sulfur modified porous copper-based composite catalyst is prepared by mixing polysulfide solution and porous copper powder for reaction; the sulfur is adsorbed on the surface of the porous copper, and the molar ratio of S to Cu is 3: 100.
the invention also provides a preparation method of the surface sulfur modified porous copper-based composite catalyst, and the composite catalyst is obtained by mixing and reacting polysulfide solution and porous copper powder.
Preferably, the concentration of sulfur in the polysulfide solution is 135.5mmol/L, and the liquid-solid ratio of the polysulfide solution to the porous copper is 7 mL/g.
Preferably, the polysulfide solution is prepared by the following steps:
(1) na with the concentration of 50mmol/L is prepared first2S solution, then 11.7mLNa is taken2Mixing the S solution with 32mg of sulfur powder to obtain a suspension;
(2) and (3) preserving the temperature of the suspension at 80 ℃ for 12h to obtain a polysulfide solution with the sulfur concentration of 135.5 mmol/L.
Preferably, the porous copper is Cu40Zn60Powder as raw material, etching Cu completely by acid40Zn60Zn in the powder.
The invention also provides application of the surface sulfur modified porous copper-based composite catalyst, which is used for synthesizing ammonia by photocatalysis.
According to the invention, the molar ratio of S to Cu is strictly controlled, the sulfurization degree of porous copper is controlled by polysulfide solution, and the polysulfide solution and porous copper powder are mixed and reacted to obtain the surface sulfur modified porous copper-based composite catalyst. As shown in table 1, fitting parameters for the EXAFS Cu K edge for different samples. Porous copper, 0.2-S/Cu, 1% -S/Cu, 3% -S/Cu, 7% -Cu2S/Cu and 20% -Cu2The Cu-Cu coordination numbers of S/Cu were 6.4, 5.7, 5.1, 4.7, 4.1, and 3.5, respectively. The inventors found that when the molar ratio of S to Cu is slightly small (0.2-S/Cu and 1% -S/Cu), no Cu-S coordination is observed in any of the prepared samples because of the extremely low degree of sulfidation; when the molar ratio of S to Cu is 3, Cu-S coordination occurs in the prepared sample, but the coordination number is only 0.2; and when the molar ratio of S to Cu is too large (7% -Cu)2S/Cu and 20% -Cu2S/Cu), the Cu-S coordination in the prepared sample is increased to 0.5 and 1.2, and the combination of XRD of different samples can show that S atoms in 0.2% -S/Cu, 1% -S/Cu and 3% -S/Cu mainly modify the Cu surface, and S atoms in 7% -Cu2S/Cu and 20% -Cu2In S/Cu, Cu is obviously formed2And (4) S nanocrystals.
Table 1 fitting parameters for the EXAFS Cu K-edge for different samples.
Wherein the content of the first and second substances,an: a coordination number; bR: bond length;cσ2: debye-walller factor;dΔE0: correcting the internal potential; r factor: goodness of fit; s0 2Set to 0.829.
In the composite catalyst, sulfur is adsorbed on the surface of porous copper to modify the porous copper, and S atoms on the surface can enhance N by adjusting electronic properties2Adsorption, but also direct participation in the catalytic process by accepting and donating H atoms. When the composite catalyst forms S-H bond under the condition of illumination and water existence, the interaction of hydrogen bond significantly enhances N2The adsorption and activation of the molecules further remarkably improve the catalytic performance of the catalyst.
The invention has the advantages that:
(1) the invention can obtain the surface sulfur modified porous copper-based composite catalyst by strictly controlling the molar ratio of S to Cu and controlling the vulcanization degree of the porous copper by polysulfide solution, and the preparation method is simple and convenient and has good repeatability.
(2) In the composite catalyst, sulfur is adsorbed on the surface of porous copper to modify the porous copper, and S atoms on the surface can not only enhance N by adjusting electronic properties2Adsorption, and can directly participate in the catalytic process by accepting and contributing H atoms, thereby remarkably improving the catalytic performance of the catalyst.
(3) When the 3% -S/Cu composite catalyst is used for photocatalytic synthesis of ammonia, the catalyst is high in activity and stable in property and can be repeatedly used.
Drawings
FIG. 1 is an SEM surface topography of 3% -S/Cu in example 1 of the present invention.
As shown in FIG. 1, the 3% -S/Cu composite catalyst has a porous structure with an average pore diameter of about 0.7 μm.
FIG. 2 shows 3% -S/Cu in example 1, porous copper powder in comparative example 1, 0.2% -S/Cu in comparative example 2, 1% -S/Cu in comparative example 3, and 7% -Cu in comparative example 4 according to the present invention2S/Cu and 20% -Cu in comparative example 52S/CX-ray diffraction pattern of u.
As shown in FIG. 2, as the degree of sulfidation increased, 7% -Cu2Weak Cu in S/Cu2S characteristic peak of 20% -Cu2More pronounced in S/Cu.
FIG. 3 is a diffuse reflectance ultraviolet-visible (UV-Vis) spectrum of 3% -S/Cu in inventive example 2 and the porous copper powder in comparative example 1.
As shown in FIG. 3, an absorption peak occurs at a wavelength of about 540nm in 3% -S/Cu and porous copper, corresponding to a plasmon resonance effect of a Cu skeleton, and the absorption peak of 3% -S/Cu extends to a near infrared region, showing enhanced light trapping ability.
FIG. 4 shows 3% -S/Cu in example 1, porous copper powder in comparative example 1, 0.2% -S/Cu in comparative example 2, 1% -S/Cu in comparative example 3, and 7% -Cu in comparative example 4 according to the present invention2S/Cu and 20% -Cu in comparative example 52N of S/Cu2-temperature programmed desorption profile.
As shown in FIG. 4, the peak at 200-500 ℃ belongs to the pair N2Chemical adsorption of 3% -S/Cu to N2Shows the strongest chemisorption peak to N2The adsorption capacity of (1). In contrast 0.2% -S/Cu, 1% -S/Cu, 7% -Cu2S/Cu、20％-Cu2S/Cu to N2The chemisorption peak of (a) is weaker, while porous copper has no significant chemisorption peak.
FIG. 5 is a graph of the cycling stability of 3% -S/Cu in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
Preparation of polysulfide aqueous solution:
(1) na with the concentration of 50mmol/L is prepared first2S solution, 11.7mL of the solution and 32mg of sulfur powder are added into a 20mL glass bottle;
(2) and (3) placing the obtained suspension in an oven at 80 ℃ for 12h, wherein the color of the solution is changed into bright yellow, and the polysulfide aqueous solution with the sulfur concentration of 135.5mmol/L is obtained.
Preparing porous copper:
(1) a0.5 mol/L sulfuric acid solution was prepared, 200mL of the solution was put into a 500mL beaker, and 5.0g of Cu was added thereto while stirring 40Zn60Stirring the powder at room temperature for 2 hours;
(2) washing the obtained product with deionized water until the supernatant is neutral, centrifuging at 5000rpm for 10min to collect solid, and vacuum drying at 60 deg.C for 1h to obtain porous copper powder.
Example 1
Preparation of 3% -S/Cu catalyst:
(1) 0.7mL of prepared polysulfide solution and 100mg of porous copper powder are mixed in 20mL of aqueous solution and stirred for 1h at room temperature;
(2) washing the obtained product with deionized water for 3 times, centrifuging at the rotating speed of 5000rpm for 10min, collecting solid, and vacuum drying at 60 ℃ for 1h to obtain the product, wherein the product is marked as 3% -S/Cu.
Photocatalytic synthesis of ammonia:
(1) adding 10mg of 3% -S/Cu catalyst and 20mL of deionized water into a 100-mL photoreactor;
(2) blowing nitrogen gas into the suspension at a flow rate of about 30mL min < -1 > for 30min at room temperature, and then vigorously stirring the suspension while irradiating with a light source;
(3) the yield of synthetic ammonia was measured after the reaction, and the ammonia yields under different light sources are shown in table 2:
TABLE 23% -Ammonia yields of S/Cu catalysts under different light sources
The recycling experiment:
(1) centrifuging the suspension after the 3% -S/Cu catalyst photocatalytic reaction at the rotating speed of 8000rpm for 10min, carrying out ammonia detection on the obtained supernatant, washing the filtered precipitate with deionized water for several times, and using the washed precipitate as a catalyst for the next photocatalytic synthesis ammonia experiment;
(2) Adding the washed 3% -S/Cu catalyst into 20mL of deionized water, and reacting at room temperature for about 30mL min-1Nitrogen was bubbled through the suspension at a rate of 30 min. Then the light intensity is 250mW cm-2The lower side of the xenon lamp is irradiated and stirred for 30 min;
(3) the experimental steps are repeated for 10 times in a circulating experiment, and the result is shown in fig. 4, after 10 times of circulating reaction, 95% of the original reaction activity is retained, and the excellent catalytic stability of 3% -S/Cu is shown.
Comparative example 1
Directly adopting unvulcanized porous copper powder to carry out photocatalytic synthesis of ammonia:
(1) adding 10mg of porous copper powder and 20mL of deionized water into a 100-mL photoreactor;
(2) blowing nitrogen gas into the suspension at a flow rate of about 30mL min < -1 > for 30min at room temperature, and then vigorously stirring the suspension while irradiating with a light source;
(3) the yield of synthetic ammonia was determined after the reaction and the ammonia yields under different light sources are shown in table 3:
TABLE 3 Ammonia yield of porous copper catalysts under different light sources
Comparative example 2
Preparation of 0.2% -S/Cu catalyst:
(1) 0.047mL of prepared polysulfide solution and 100mg of porous copper powder are mixed in 20mL of aqueous solution and stirred for 1h at room temperature;
(2) washing the obtained product with deionized water for 3 times, centrifuging at 5000rpm for 10min, collecting solid, and vacuum drying at 60 deg.C for 1h to obtain the final product with concentration of 0.2% -S/Cu.
Photocatalytic synthesis of ammonia:
(1) adding 10mg of 0.2% -S/Cu catalyst and 20mL of deionized water into a 100-mL photoreactor;
(2) blowing nitrogen gas into the suspension at a flow rate of about 30mL min < -1 > for 30min at room temperature, and then vigorously stirring the suspension while irradiating with a light source;
(3) the yield of synthetic ammonia was determined after the reaction and the ammonia yields under different light sources are shown in table 4:
TABLE 40.2% -Ammonia yields of S/Cu catalysts under different light sources
Comparative example 3
Preparation of 1% -S/Cu catalyst:
(1) 0.23mL of prepared polysulfide solution and 100mg of porous copper powder are mixed in 20mL of aqueous solution and stirred for 1h at room temperature;
(2) washing the obtained product with deionized water for 3 times, centrifuging at the rotating speed of 5000rpm for 10min, collecting solid, and vacuum drying at 60 ℃ for 1h to obtain the product with the concentration of 1% -S/Cu.
Photocatalytic synthesis of ammonia:
(1) adding 10mg of 1% -S/Cu catalyst and 20mL of deionized water into a 100-mL photoreactor;
(2) blowing nitrogen gas into the suspension at a flow rate of about 30mL min < -1 > for 30min at room temperature, and then vigorously stirring the suspension while irradiating with a light source;
(3) the yield of synthetic ammonia was determined after the reaction and the ammonia yields under different light sources are shown in table 5:
TABLE 51% -Ammonia yields of S/Cu catalysts under different light sources
Comparative example 4
7％-Cu2Preparation of S/Cu catalyst:
(1) mixing 1.63mL of prepared polysulfide solution and 100mg of porous copper powder in 20mL of aqueous solution, and stirring at room temperature for 1 h;
(2) washing the obtained product with deionized water for 3 times, centrifuging at 5000rpm for 10min to collect solid, vacuum drying at 60 deg.C for 1h to obtain7％-Cu2S/Cu。
Photocatalytic synthesis of ammonia:
(1) 10mg of 7% -Cu was added to a 100-mL photoreactor2S/Cu catalyst and 20mL deionized water;
(2) blowing nitrogen gas into the suspension at a flow rate of about 30mL min < -1 > for 30min at room temperature, and then vigorously stirring the suspension while irradiating with a light source;
(3) the yield of synthetic ammonia was determined after the reaction and the ammonia yields under different light sources are shown in table 6:
TABLE 67% -Cu2Ammonia yield of S/Cu catalyst under different light sources
Comparative example 5
20％-Cu2Preparation of S/Cu catalyst:
(1) 4.67mL of the prepared polysulfide solution and 100mg of porous copper powder are mixed in 20mL of aqueous solution and stirred for 1h at room temperature;
(2) washing the obtained product with deionized water for 3 times, centrifuging at 5000rpm for 10min to collect solid, vacuum drying at 60 deg.C for 1h to obtain 20% -Cu powder2S/Cu。
Photocatalytic synthesis of ammonia:
(1) 10mg of 20% -Cu was added to a 100-mL photoreactor 2S/Cu catalyst and 20mL deionized water;
(2) blowing nitrogen gas into the suspension at a flow rate of about 30mL min < -1 > for 30min at room temperature, and then vigorously stirring the suspension while irradiating with a light source;
(3) the yield of synthetic ammonia was determined after the reaction and the ammonia yields under different light sources are shown in table 7:
TABLE 720% -Cu2Ammonia yield of S/Cu catalyst under different light sources
Claims (6)
1. A surface sulfur modified porous copper-based composite catalyst is characterized in that: prepared by mixing polysulfide solution and porous copper powder for reaction; the sulfur is adsorbed on the surface of the porous copper, and the molar ratio of S to Cu is 3: 100.
2. the method for preparing the surface sulfur-modified porous copper-based composite catalyst according to claim 1, characterized in that: and mixing the polysulfide solution and the porous copper powder for reaction to obtain the composite catalyst.
3. The method for preparing a surface sulfur-modified porous copper-based composite catalyst according to claim 2, characterized in that: the concentration of sulfur in the polysulfide solution is 135.5mmol/L, and the liquid-solid ratio of the polysulfide solution to the porous copper is 7 mL/g.
4. The method for preparing the surface sulfur-modified porous copper-based composite catalyst according to claim 2 or 3, wherein the polysulfide solution is prepared by the following steps:
(1) Na with the concentration of 50mmol/L is prepared first2S solution, then 11.7mLNa is taken2Mixing the S solution with 32mg of sulfur powder to obtain a suspension;
(2) and (3) preserving the temperature of the suspension at 80 ℃ for 12h to obtain a polysulfide solution with the sulfur concentration of 135.5 mmol/L.
5. The method for preparing a surface sulfur-modified porous copper-based composite catalyst according to claim 2, characterized in that: the porous copper is Cu40Zn60Powder as raw material, etching Cu completely by acid40Zn60Zn in the powder.
6. Use of the surface sulfur-modified porous copper-based composite catalyst according to claim 1 or the surface sulfur-modified porous copper-based composite catalyst produced by the production method according to any one of claims 2 to 5, characterized in that: it is used for the photocatalytic synthesis of ammonia.
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