CN110743551B - Ammonia porous copper-iron bimetallic catalyst synthesized by photocatalysis and application thereof - Google Patents
Ammonia porous copper-iron bimetallic catalyst synthesized by photocatalysis and application thereof Download PDFInfo
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- CN110743551B CN110743551B CN201910938293.0A CN201910938293A CN110743551B CN 110743551 B CN110743551 B CN 110743551B CN 201910938293 A CN201910938293 A CN 201910938293A CN 110743551 B CN110743551 B CN 110743551B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000717 retained effect Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 10
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108010038629 Molybdoferredoxin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001297 nitrogen containing inorganic group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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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
- 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
-
- 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
- B01J23/745—Iron
-
- 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
- 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
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Abstract
The invention discloses a photocatalytic synthesis ammonia porous copper-iron bimetallic catalyst and application thereof, wherein the molecular formula is CuxFeyWherein x is 80-99, y is 1-20, and the porous copper-iron bimetallic catalyst is used for etching Cu by a sulfuric acid solution21Fe79And (5) obtaining the alloy powder. The invention selectively etches away the raw material Cu by using a sulfuric acid solution21Fe79Fe in the alloy powder, thereby preparing the nano porous copper-iron bimetallic catalyst for synthesizing ammonia by photocatalysis. By controlling the amount of the sulfuric acid, the porous nano copper-iron bimetallic catalyst with different Cu and Fe molar ratios can be obtained. The preparation method is simple and efficient, the components are easy to control, particularly when the molar ratio of Cu to Fe is 96:4, high ammonia yield is obtained, the catalyst can be recycled, 100% of original reaction activity is almost retained after 10 times of cyclic reaction, and the reaction stability is extremely high.
Description
Technical Field
The invention belongs to the technical field of ammonia photocatalytic synthesis, and relates to a porous copper-iron bimetallic catalyst for ammonia photocatalytic synthesis and application thereof.
Background
Ammonia is an extremely important chemical product, and concerns agriculture, energy and the environment. Global annual NH3The yield can reach more than one hundred million tons, and most of the yield is used for fertilizer production to promote agricultural development; besides, ammonia is also used as a raw material for producing other chemical products, such as synthetic fibers, nitric acid, nitrogen-containing inorganic salts, and the like, in the aspects of organic chemistry and inorganic chemistry. At the same time, NH3Has obvious energy carrier property due to the characteristics of high hydrogen content, large energy density, easy liquefaction and the likeCan be used as a potential good energy storage material. Industrially, mainly using H2N fixation by Haber-Bosch procedure2To synthesize ammonia. The process is based on iron-based catalysts, which require high temperatures>673K) High pressure (>20atm) and has extremely high energy consumption, and the energy consumed by the industrial synthesis of ammonia per year accounts for about 1.4 percent of the total energy supplied globally every year according to statistics. While H required for the process2Mainly comes from the reforming of coal or natural gas and is easy to generate a large amount of CO2It has extremely bad influence on the ecological environment.
The nitrogen-fixing enzyme is a substance capable of dissolving N at room temperature2Conversion to NH3The biological enzyme of (1). In the process of biological nitrogen fixation, MoFe protein in nitrogen fixation enzyme can effectively adsorb N2And activating N by accepting electrons transferred from Fe protein2. Therefore, the reasonable design of the photocatalyst structure can realize the ammonia synthesis process at room temperature, which is inspired by azotase. N is a radical of2The nitrogen-nitrogen triple bond (N.ident.N) with extremely high stability in the nitrogen-nitrogen triple bond severely limits N2Efficiency of light fixation. Theoretically, the N ≡ N bond can be weakened, its bond length increased and its bond energy decreased by either donating electrons from the bonding orbital or accepting electrons to the anti-bonding orbital to be N ≡ N bond2Provides a kinetic pathway that can be accomplished. Thus, in general, two separate units are present together in the photocatalyst, i.e. for the adsorption of N2Active site and thermionic electron donor.
The metal with plasmon resonance effect is an ideal donor of thermal electrons, and can be used for N2The field of optical fixation. 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. At the resonant frequency, the enhanced photo-species interaction results in an increase in the electric field at the metal surface, promoting a greater number of energetic charge carriers (electron-hole pairs). Metals having a plasmon resonance effect in the visible light region are mainly Au, Ag, Cu, and the like. Wherein the Cu nanocrystal isThe susceptibility to corrosion and oxidation in water and even in air severely limits the use of Cu nanocrystals in plasma catalysis.
Nanoporous metals are a class of functional materials with interconnected three-dimensional porous network structures. The nano porous metal has wider application in the field of catalysis due to larger specific surface area, rich high-index crystal faces and high-density atomic steps and kinks. More importantly, nanoporous metals exhibit higher stability during catalysis than nanoparticles. Based on the size dependence of the thermodynamic equilibrium of metals, the increased stability of nanoporous metals may be due to their surface energy and low tension. Therefore, the nano-porous copper-based catalyst with the plasmon resonance effect is developed and applied to N2Light fixation is of great significance.
Disclosure of Invention
In order to solve the technical problem of designing the nano-porous copper-based catalyst in the prior art, the invention aims to provide the photo-catalytic synthesis ammonia porous copper-iron bimetallic catalyst prepared by using the etching method, the copper-iron ratio in the nano-porous copper-iron bimetallic catalyst is controlled by controlling the amount of sulfuric acid, the preparation method is simple and efficient, and the obtained catalyst has high activity and stable property and can be repeatedly used.
In order to realize the technical purpose, the invention provides a photocatalytic synthesis ammonia porous copper-iron bimetallic catalyst with a molecular formula of CuxFeyWherein x is 80-99, y is 1-20, and the porous copper-iron bimetallic catalyst is used for etching Cu by a sulfuric acid solution21Fe79And (5) obtaining the alloy powder.
Cu in the present invention21Fe79The alloy powder can be prepared by a conventional gas atomization method or directly purchased, and is not mechanical mixed powder of copper powder and iron powder.
Preferably, in the formula, x is 96 and y is 4.
Preferably, the sulfuric acid etching process specifically comprises: with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 1.0-1.5: 1 two by twoMixing, heating to 80 ℃ for reaction for 30min, and carrying out solid-liquid separation, washing and drying to obtain the porous copper-iron bimetallic catalyst.
Preferably, the sulfuric acid solution and Cu21Fe79The liquid-solid ratio of the alloy powder is 15-25 mL/g.
The invention also provides the application of the photocatalytic synthesis ammonia porous copper-iron bimetallic catalyst, and the application of the photocatalytic synthesis ammonia porous copper-iron bimetallic catalyst in the photocatalytic synthesis of ammonia comprises the following specific processes: in the photocatalytic synthesis of ammonia, a porous copper-iron bimetallic catalyst is added into deionized water to obtain a suspension, nitrogen is blown into the suspension, and the ammonia synthesis reaction is carried out under the irradiation of a xenon lamp light source.
In the present invention, Cu as a raw material is selectively etched away by using sulfuric acid21Fe79Fe in the alloy powder, thereby preparing the nano porous copper-iron bimetallic catalyst for synthesizing ammonia by photocatalysis. By controlling the amount of the sulfuric acid, the porous nano copper-iron bimetallic catalyst with different Cu and Fe molar ratios can be obtained. The preparation method is simple and efficient, the components are easy to control, particularly when the molar ratio of Cu to Fe is 96:4, high ammonia yield is obtained, the catalyst can be recycled, 100% of original reaction activity is almost retained after 10 times of cyclic reaction, and the reaction stability is extremely high.
Drawings
FIG. 1 shows Cu obtained in example 2 of the present invention96Fe4Sample and unetched Cu21Fe79SEM image of alloy powder, wherein a is Cu96Fe4Sample, b is Cu21Fe79And (3) alloying powder.
FIG. 2 shows Cu obtained in example 1 of the present invention80Fe20Cu obtained in example 296Fe4Cu obtained in example 399Fe1Comparative example 2 Cu57Fe43And Cu obtained in comparative example 399.9Fe0.1Graph comparing yield at full spectrum and visible range.
FIG. 3 shows Cu obtained in example 1 of the present invention80Fe20Cu obtained in example 296Fe4Cu obtained in example 399Fe1Comparative example 2 Cu57Fe43And Cu obtained in comparative example 399.9Fe0.1N of (A)2-temperature programmed desorption profile.
FIG. 4 shows Cu obtained in example 2 of the present invention96Fe4The stability chart of recycling (1).
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. Modifications and adaptations of the present invention may occur to those skilled in the art and are intended to be within the scope of the present invention.
Example 1
A method for preparing a nano porous copper-iron bimetallic catalyst by using an etching method comprises the following steps:
Cu80Fe20preparing a nano porous copper-iron bimetallic catalyst:
(1) with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 1.136: 1 mixing the two: firstly, 19.32mL of sulfuric acid with the concentration of 0.6mol/L is prepared and added into a 100mL vacuum thick-wall pressure-resistant bottle, and then 1g of Cu is added21Fe79Adding the bimetal powder while stirring;
(2) placing the vacuum thick-wall pressure-resistant bottle into an oil bath pan, stirring and heating the system at 80 ℃ for 30 min;
(3) after cooling to room temperature, the obtained product was washed several times with water until the pH of the supernatant was about 7, and then centrifuged at 3500rpm for 10min to collect the powder;
(4) vacuum drying the collected powder at 60 ℃ for 1h to obtain the porous copper-iron bimetallic catalyst Cu80Fe20。
Photocatalytic synthesis of ammonia:
(1) taking 10mg of prepared Cu80Fe20Adding the nano porous copper-iron bimetallic catalyst into 20mL of deionized water;
(2) at room temperature at about 30mL min-1Blowing nitrogen gas into the suspension at a speed of 30min, and then irradiating at an intensity of 250mW cm-2The lower side of the xenon lamp is irradiated and stirred for 30 min;
(3) the yield of synthetic ammonia after the reaction was found to be 109. mu. mol. gcat. –1·h–1。
Example 2
Cu96Fe4Preparing a nano porous copper-iron bimetallic catalyst:
(1) with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 1.205: 1 mixing the two: firstly, 20.5mL of sulfuric acid with the concentration of 0.6mol/L is prepared and added into a 100mL vacuum thick-wall pressure-resistant bottle, and then 1g of Cu is added21Fe79Adding the bimetal powder while stirring;
(2) placing the vacuum thick-wall pressure-resistant bottle into an oil bath pan, stirring and heating the system at 80 ℃ for 30 min;
(3) after cooling to room temperature, the obtained product was washed several times with water until the pH of the supernatant was about 7, and then centrifuged at 3500rpm for 10min to collect the powder;
(4) vacuum drying the collected powder at 60 ℃ for 1h to obtain the porous copper-iron bimetallic catalyst Cu96Fe4。
As shown in FIG. 1, Cu21Fe79The surface of the alloy powder is of a compact structure; after etching with a sulfuric acid solution, Cu was observed96Fe4The pore size of the obvious nano-porous structure is about 50nm-200 nm.
Photocatalytic synthesis of ammonia:
(1) taking 10mg of prepared Cu96Fe4Adding the nano porous copper-iron bimetallic catalyst into 20mL of deionized water;
(2) at room temperature at 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 yield of synthetic ammonia after the reaction was determined to be 342. mu. mol. gcat. –1·h–1。
As shown in FIG. 3, the peak at about 80 ℃ is vs. N2The peak at 150-500 ℃ belongs to the pair N2Chemisorption of (1), wherein Cu96Fe4The maximum area of the chemisorption peak of (A) indicates the maximum value for N2The most strongly chemisorbed.
The recycling experiment:
(1) centrifuging the reacted suspension at 8000rpm for 10min, taking the supernatant for synthetic ammonia detection, washing the precipitate with deionized water and washing again, and then taking the precipitate as a catalyst for next cycle of photocatalytic synthetic ammonia experiment;
(2) taking Cu after each circulation experiment washing96Fe4Adding the nano-porous copper-iron bimetallic 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 mixture was vigorously stirred for 30min while being irradiated under a xenon lamp.
(3) The above operation was repeated for a total of 10 cycles.
As shown in FIG. 4, after 10 cycles of reaction, Cu was present96Fe4Almost 100% of the original reactivity was retained, indicating that Cu96Fe4The nano porous copper-iron bimetallic catalyst has extremely high reaction stability.
Example 3
Cu99Fe1Preparing a nano porous copper-iron bimetallic catalyst:
(1) with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 1.264: 1 mixing the two solutions, preparing 21.5mL of sulfuric acid with the concentration of 0.6mol/L, adding the sulfuric acid into a 100mL vacuum thick-wall pressure-resistant bottle, and then adding 1g of Cu21Fe79Adding the bimetal powder while stirring;
(2) placing the vacuum thick-wall pressure-resistant bottle into an oil bath pan, stirring and heating the system at 80 ℃ for 30 min;
(3) after cooling to room temperature, the obtained product was washed several times with water until the pH of the supernatant was about 7, and then centrifuged at 3500rpm for 10min to collect the powder;
(4) vacuum drying the collected powder at 60 ℃ for 1h to obtain the porous copper-iron bimetallic catalyst Cu99Fe1。
Photocatalytic synthesis of ammonia:
(1) taking 10mg of prepared Cu99Fe1Adding the nano porous copper-iron bimetallic catalyst into 20mL of deionized water;
(2) at room temperature at 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 yield of synthetic ammonia after the reaction was found to be 146. mu. mol. gcat. –1·h–1。
Comparative example 1
Direct use of unetched Cu21Fe79Photocatalytic synthesis of ammonia from bimetallic powder:
(1) 10mg of unetched Cu were taken21Fe79Adding the bimetal powder into 20mL of deionized water;
(2) at room temperature at about 30mL min-1Blowing nitrogen gas into the suspension at a speed of 30min, and then irradiating at an intensity of 250mW cm-2The lower side of the xenon lamp is irradiated and stirred for 30 min;
(3) the yield of synthetic ammonia after the reaction was found to be 8.32. mu. mol. gcat. –1·h–1。
Comparative example 2
Cu57Fe43Preparing a nano porous copper-iron bimetallic catalyst:
(1) with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 0.883: 1 mixing the two. Firstly preparing 15mL of 0.6mol/L sulfuric acid, adding the sulfuric acid into a 100mL vacuum thick-wall pressure-resistant bottle, and then adding 1g of Cu21Fe79Adding the bimetal powder while stirring;
(2) placing the vacuum thick-wall pressure-resistant bottle into an oil bath pan, stirring and heating the system at 80 ℃ for 30 min;
(3) after cooling to room temperature, the obtained product was washed several times with water until the pH of the supernatant was about 7, and then centrifuged at 3500rpm for 10min to collect the powder;
(4) vacuum drying the collected powder at 60 ℃ for 1h to obtain the porous copper-iron bimetallic catalyst Cu57Fe43。
Photocatalytic synthesis of ammonia:
(1) taking 10mg of prepared Cu57Fe43Adding the nano porous copper-iron bimetallic catalyst into 20mL of deionized water;
(2) at room temperature at 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 yield of synthetic ammonia after the reaction was found to be 52. mu. mol. gcat. –1·h–1。
Comparative example 3
Cu99.9Fe0.1Preparing a nano porous copper-iron bimetallic catalyst:
(1) with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 1.89: 1 mixing the two: preparing 32.2mL of sulfuric acid with the concentration of 0.6mol/L, adding the sulfuric acid into a 100mL vacuum thick-wall pressure-resistant bottle, and then adding 1g of Cu21Fe79Adding the bimetal powder while stirring;
(2) placing the vacuum thick-wall pressure-resistant bottle into an oil bath pan, stirring and heating the system at 80 ℃ for 30 min;
(3) after cooling to room temperature, the obtained product was washed several times with water until the pH of the supernatant was about 7, and then centrifuged at 3500rpm for 10min to collect the powder;
(4) vacuum drying the collected powder at 60 ℃ for 1h to obtain the porous copper-iron bimetallic catalyst Cu99.9Fe0.1。
Photocatalytic synthesis of ammonia:
(1) taking 10mg of prepared Cu99.9Fe0.1Adding the nano porous copper-iron bimetallic catalyst into 20mL of deionized water;
(2) at room temperature at about 30mL min-1Nitrogen was bubbled through the suspension at a rate of 30 min. Then at the intensity of illuminationIs 250mW cm-2The lower side of the xenon lamp is irradiated and stirred for 30 min;
(3) the yield of synthetic ammonia after the reaction was found to be 5. mu. mol. gcat. –1·h–1。
Claims (5)
1. A photocatalytic synthesis ammonia porous copper-iron bimetallic catalyst is characterized in that: molecular formula is CuxFeyWherein x is 80-99, y is 1-20, and the porous copper-iron bimetallic catalyst is used for etching Cu by a sulfuric acid solution21Fe79And (5) obtaining the alloy powder.
2. The photocatalytic synthesis ammonia porous copper iron bimetallic catalyst of claim 1, characterized by: in the formula, x is 96, and y is 4.
3. The photocatalytic synthesis ammonia porous copper-iron bimetallic catalyst according to claim 1 or 2, characterized in that: the specific process of the sulfuric acid etching is as follows: with H in sulfuric acid solution2SO4And Cu21Fe79The mass ratio of the alloy powder is 1.0-1.5: 1 mixing the two, heating to 80 ℃ for reaction for 30min, and carrying out solid-liquid separation, washing and drying to obtain the porous copper-iron bimetallic catalyst.
4. The photocatalytic synthesis ammonia porous copper iron bimetallic catalyst of claim 3, characterized by: the sulfuric acid solution and Cu21Fe79The liquid-solid ratio of the alloy powder is 15-25 mL/g.
5. Use of the photocatalytically synthesized ammonia porous copper-iron bimetallic catalyst of any one of claims 1 to 4, characterized in that: the method is used for synthesizing ammonia by photocatalysis, and comprises the following specific processes: in the photocatalytic synthesis of ammonia, a porous copper-iron bimetallic catalyst is added into deionized water to obtain a suspension, nitrogen is blown into the suspension, and the ammonia synthesis reaction is carried out under the irradiation of a xenon lamp light source.
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