CN111841575B - 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
- Publication number
- CN111841575B CN111841575B CN202010656528.XA CN202010656528A CN111841575B CN 111841575 B CN111841575 B CN 111841575B CN 202010656528 A CN202010656528 A CN 202010656528A CN 111841575 B CN111841575 B CN 111841575B
- Authority
- CN
- China
- Prior art keywords
- porous copper
- sulfur
- composite catalyst
- based composite
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010949 copper Substances 0.000 title claims abstract description 137
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 22
- 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 72
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- 229920001021 polysulfide Polymers 0.000 claims abstract description 23
- 239000005077 polysulfide Substances 0.000 claims abstract description 23
- 150000008117 polysulfides Polymers 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 108010020943 Nitrogenase Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 properties 2 Adsorption, 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 may be reused in photocatalytic synthesis of ammonia.
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, the annual ammonia yield of the whole world exceeds 1.5 hundred million tons, and the population growth and the development of the modern society are promoted. Industrial production of ammonia N is produced by the Haber-Bosch process 2 And H 2 At high temperature and high pressureConversion to NH 3 The process consumes a large amount of energy and discharges millions of tons of CO 2 And the pollution to the earth environment is serious. Thus N 2 Conversion to NH under mild conditions 3 Has attracted great attention because of its ability to meet current energy and environmental demands. Photocatalytic N similar to biological nitrogenase under mild conditions 2 Reduction to NH 3 Is a cleaner, more sustainable NH 3 Production provides an alternative carbon-free strategy. N is a radical of hydrogen 2 The molecular bond length is 107.8pm, the nonpolar nitrogen triple bond (N.ident.N) energy is 945KJ/mol, so N is 2 The molecule has extremely high stability, and its activation is considered to be N 2 Bottleneck in the reduction process, therefore, a new one capable of effectively activating N is developed 2 Molecular methods are of great importance. Through various efforts, N is proved from both theoretical and experimental aspects 2 The 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 2 Some progress has been made in the activation and transformation of molecules, but there is still a strong need for new effective activated N 2 Molecular strategies.
In recent years, the Localized Surface Plasmon Resonance (LSPR) effect can provide sufficient photogenerated electrons to promote N 2 Has 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. The enhancement of the optical extinction coefficient appears as a localized surface plasmon resonance peak in the diffuse reflectance ultraviolet-visible absorption spectrum. Relevant research has proved that plasma metal can be usedThe localized surface plasmon resonance effect of the particles (Ag, au and Cu) causes 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 porous copper-based catalyst having plasmon resonance effect was developed in N 2 Has 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 thereof 2 Adsorption, 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 7mL/g.
Preferably, the polysulfide solution is prepared by the following steps:
(1) Na with the concentration of 50mmol/L is prepared first 2 S solution, then 11.7mLNa is taken 2 Mixing 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 Cu 40 Zn 60 Powder as raw material, etching Cu completely by acid 40 Zn 60 Zn 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% -Cu 2 S/Cu and 20% -Cu 2 The 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) 2 S/Cu and 20% -Cu 2 S/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% -Cu 2 S/Cu and 20% -Cu 2 In S/Cu, cu is obviously formed 2 And (4) S nanocrystals.
Table 1 fitting parameters for the EXAFS Cu K-edge for different samples.
Wherein, the first and the second end of the pipe are connected with each other, a n: a coordination number; b r: bond length; c σ 2 : debye-waller factor; d ΔE 0 : correcting the internal potential; r factor: goodness of fit; s 0 2 Set 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 properties 2 Adsorption, 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 N 2 The 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 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 properties 2 Adsorption, 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 has high activity and stable 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 invention 2 S/Cu and 20% -Cu in comparative example 5 2 X-ray diffraction pattern of S/Cu.
As shown in FIG. 2, as the degree of sulfidation increased, 7% -Cu 2 Weak appearance in S/CuCu of (2) 2 S characteristic peak of 20% -Cu 2 More 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, 3% -S/Cu and porous copper show an absorption peak at a wavelength of about 540nm 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 invention 2 S/Cu and 20% -Cu in comparative example 5 2 N of S/Cu 2 -temperature programmed desorption profile.
As shown in FIG. 4, the peak at 200-500 ℃ belongs to the Pair N 2 Chemical adsorption of 3% -S/Cu to N 2 Shows the strongest chemisorption peak to N 2 The adsorption capacity of (1). In contrast 0.2% -S/Cu, 1% -S/Cu, 7% -Cu 2 S/Cu、20％-Cu 2 S/Cu to N 2 The 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 first 2 S 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 heat preservation 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 40 Zn 60 Stirring the powder at room temperature for 2 hours;
(2) And washing the obtained product with deionized water until the supernatant is neutral, centrifuging at the rotating speed of 5000rpm for 10min, collecting the solid, and performing vacuum drying at 60 ℃ for 1h to obtain the 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 2% ammonia yield 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 washed 3% -S/Cu catalyst into 20mL deionized waterAgent, about 30 mL/min at room temperature -1 Nitrogen was bubbled through the suspension at the rate of 30min. Then the illumination intensity is 250mW cm -2 The lower side of the xenon lamp is irradiated and stirred for 30min violently;
(3) The experimental steps are repeated for 10 times in a circulating experiment, the result is shown in figure 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
0.2% -S/Cu catalyst preparation:
(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 4 ammonia yields of 0.2% -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) And washing the obtained product with deionized water for 3 times, centrifuging at the rotating speed of 5000rpm for 10min, collecting solids, and carrying out vacuum drying at the temperature of 60 ℃ for 1h to obtain the product, wherein the product is marked as 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 5% Ammonia yield of S/Cu catalysts under different light sources
Comparative example 4
7％-Cu 2 Preparation 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 1h;
(2) Washing the obtained product with deionized water for 3 times, centrifuging at 5000rpm for 10min to collect solid, and vacuum drying at 60 deg.C for 1h to obtain 7% -Cu powder 2 S/Cu。
Photocatalytic synthesis of ammonia:
(1) Adding 10mg of 7% -Cu into a 100-mL photoreactor 2 S/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 stirring the suspension vigorously 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 6% Cu 2 Ammonia yield of S/Cu catalyst under different light sources
Comparative example 5
20％-Cu 2 Preparation 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, and vacuum drying at 60 deg.C for 1 hr to obtain 20% -Cu powder 2 S/Cu。
Photocatalytic synthesis of ammonia:
(1) 10mg of 20% -Cu was added to a 100-mL photoreactor 2 S/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 measured after the reaction, and the yields of ammonia under different light sources are shown in Table 7:
TABLE 7 20% -Cu 2 Ammonia yield of S/Cu catalyst under different light sources
Claims (4)
1. The application of the porous copper-based composite catalyst with the surface modified by sulfur is characterized in that: the composite catalyst is prepared by mixing and reacting polysulfide solution and porous copper powder; the sulfur is adsorbed on the surface of the porous copper, and the molar ratio of S to Cu is 3:100, respectively; used for photocatalytic synthesis of ammonia.
2. The use of the surface sulfur-modified porous copper-based composite catalyst according to claim 1, 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 7mL/g.
3. The use of the surface sulfur-modified porous copper-based composite catalyst according to claim 1 or 2, wherein the polysulfide solution is formulated by:
(1) Na with the concentration of 50mmol/L is prepared first 2 S solution, then 11.7mLNa is taken 2 Mixing 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.
4. The use of the surface sulfur-modified porous copper-based composite catalyst according to claim 1, characterized in that: the porous copper is Cu 40 Zn 60 Powder as raw material, etching Cu completely by acid 40 Zn 60 Zn in the powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010656528.XA CN111841575B (en) | 2020-07-09 | 2020-07-09 | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010656528.XA CN111841575B (en) | 2020-07-09 | 2020-07-09 | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111841575A CN111841575A (en) | 2020-10-30 |
| CN111841575B true CN111841575B (en) | 2022-11-22 |
Family
ID=73153561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010656528.XA Active CN111841575B (en) | 2020-07-09 | 2020-07-09 | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111841575B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499788A (en) * | 2021-07-16 | 2021-10-15 | 中南大学 | Diatomite-surface cobalt-doped nano pyrite composite material and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB574641A (en) * | 1940-08-23 | 1946-01-15 | Du Pont | Improvements in and relating to catalysts |
| FR1272087A (en) * | 1960-08-08 | 1961-09-22 | Aquitaine Petrole | Process for preparing mercaptans |
| CN105655131A (en) * | 2016-01-08 | 2016-06-08 | 吉林大学 | Solar cell Cu2S/FTO counter electrode and electrochemical deposition preparation method thereof |
| CN107497455A (en) * | 2017-09-28 | 2017-12-22 | 福州大学 | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification |
| CN107768629A (en) * | 2017-09-30 | 2018-03-06 | 哈尔滨工业大学 | A kind of preparation method and applications of sea urchin shape cupric oxide, carbon and sulphur composite |
| CN110743551A (en) * | 2019-09-30 | 2020-02-04 | 中南大学 | Ammonia porous copper-iron bimetallic catalyst synthesized by photocatalysis and application thereof |
-
2020
- 2020-07-09 CN CN202010656528.XA patent/CN111841575B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB574641A (en) * | 1940-08-23 | 1946-01-15 | Du Pont | Improvements in and relating to catalysts |
| FR1272087A (en) * | 1960-08-08 | 1961-09-22 | Aquitaine Petrole | Process for preparing mercaptans |
| CN105655131A (en) * | 2016-01-08 | 2016-06-08 | 吉林大学 | Solar cell Cu2S/FTO counter electrode and electrochemical deposition preparation method thereof |
| CN107497455A (en) * | 2017-09-28 | 2017-12-22 | 福州大学 | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification |
| CN107768629A (en) * | 2017-09-30 | 2018-03-06 | 哈尔滨工业大学 | A kind of preparation method and applications of sea urchin shape cupric oxide, carbon and sulphur composite |
| CN110743551A (en) * | 2019-09-30 | 2020-02-04 | 中南大学 | Ammonia porous copper-iron bimetallic catalyst synthesized by photocatalysis and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Chemical Immobilization and Conversion of Active Polysulfides Directly by Copper Current Collector: A New Approach to Enabling Stable Room-Temperature Li-S and Na-S Batteries;Li, PR et.al;《ADVANCED ENERGY MATERIALS》;20180516;第8卷(第22期);第2页左栏第2-4段，图2 * |
| Li, PR et.al.Chemical Immobilization and Conversion of Active Polysulfides Directly by Copper Current Collector: A New Approach to Enabling Stable Room-Temperature Li-S and Na-S Batteries.《ADVANCED ENERGY MATERIALS》.2018,第8卷(第22期), * |
| 多硫化钠法表征纯铜带表面清洁度;彭展南等;《中南大学学报(自然科学版)》;20170730;第48卷(第7期);第1720页1.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111841575A (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Iqbal et al. | Shape and phase-controlled synthesis of specially designed 2D morphologies of l-cysteine surface capped covellite (CuS) and chalcocite (Cu2S) with excellent photocatalytic properties in the visible spectrum | |
| Patnaik et al. | An overview of the structural, textural and morphological modulations of gC 3 N 4 towards photocatalytic hydrogen production | |
| Diarmand-Khalilabad et al. | g-C3N4 nanosheets decorated with carbon dots and CdS nanoparticles: novel nanocomposites with excellent nitrogen photofixation ability under simulated solar irradiation | |
| Tahir et al. | Au-NPs embedded Z–scheme WO3/TiO2 nanocomposite for plasmon-assisted photocatalytic glycerol-water reforming towards enhanced H2 evolution | |
| Liu et al. | Microwave-assisted one-pot synthesis of Ag decorated flower-like ZnO composites photocatalysts for dye degradation and NO removal | |
| Chen et al. | The effect of the Cu+/Cu2+ ratio on the redox reactions by nanoflower CuNiOS catalysts | |
| Cai et al. | Enhanced visible light photocatalytic performance of g-C3N4/CuS pn heterojunctions for degradation of organic dyes | |
| Zhang et al. | Heterojunction nanoarchitectonics of WOx/Au-g-C3N4 with efficient photogenerated carrier separation and transfer toward improved NO and benzene conversion | |
| Wang et al. | Optimized design of BiVO4/NH2-MIL-53 (Fe) heterostructure for enhanced photocatalytic degradation of methylene blue and ciprofloxacin under visible light | |
| Rodríguez et al. | CO2 photocatalytic reduction with CNT/TiO2 based nanocomposites prepared by high-pressure technology | |
| CN108855131B (en) | Preparation and application of silver-nickel bimetal doped titanium dioxide nano composite material | |
| CN105233850A (en) | Magnetic nanometer composite photocatalysis material, and preparation method thereof | |
| CN104941662A (en) | Preparation method of Ag/BFeO3 compound photocatalyst | |
| Azam et al. | In-situ synthesis of TiO2/La2O2CO3/rGO composite under acidic/basic treatment with La3+/Ti3+ as mediators for boosting photocatalytic H2 evolution | |
| Upadhyay et al. | Photoactive CdO: TiO2 nanocomposites for dyes degradation under visible light | |
| CN111359652A (en) | Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof | |
| Gu et al. | Construction of dual Z-scheme UNiMOF/BiVO4/S-C3N4 photocatalyst for visible-light photocatalytic tetracycline degradation and Cr (VI) reduction | |
| CN111841575B (en) | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof | |
| Liu et al. | Photocatalytic activity study of ZnO modified with nitrogen–sulfur co-doped carbon quantum dots under visible light | |
| She et al. | Photocatalytic activation of saturated C–H bond over the CdS mixed-phase under visible light irradiation | |
| CN112973744B (en) | Photoelectric catalyst and preparation method thereof | |
| Chen et al. | In situ growing Cu2 (OH) 2CO3 on oxidized carbon nitride with enhanced photocatalytic hydrogen evolution and pollutant degradation | |
| Wang et al. | Fabrication of g-C3N4 nanosheets anchored with controllable CdS nanoparticles for enhanced visible-light photocatalytic performance | |
| Yuan et al. | Synthesis of N-TiO2@ NH2-MIL-88 (Fe) core-shell structure for efficient Fenton effect assisted methylene blue degradation under visible light | |
| Wang et al. | A novel route to synthesize tantalum nitride nanoparticles for organic dye removal under visible-light irradiation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |