CN116726949A - Cd (cadmium sulfide) 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis - Google Patents
Cd (cadmium sulfide) 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 55
- 238000002474 experimental method Methods 0.000 title claims abstract description 22
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 6
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004201 L-cysteine Substances 0.000 claims description 5
- 235000013878 L-cysteine Nutrition 0.000 claims description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 30
- 239000011941 photocatalyst Substances 0.000 abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 6
- 241000282414 Homo sapiens Species 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 10
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- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
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- 230000029553 photosynthesis Effects 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000194101 Ginkgo biloba Species 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
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- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/28—Methods of preparing ammonium salts in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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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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- Analytical Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Cd 0.5 Zn 0.5 S and its experimental method for fixing nitrogen under photocatalysis, under the irradiation of visible light, the photo-generated electrons are excited to the conduction band, the vacancies are left in the valence band, and then the photo-generated electrons and the vacancies migrate to the surface of the catalyst and participate in the oxidation-reduction reaction. The invention provides hydrogen protons for reaction and reduces nitrogen to ammonia, and relates to the technical field of chemical catalysts. The Cd is 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis, and when the synthesis temperature is 200 ℃, the sample at other temperature is compared with the sample at other temperature, the photocatalyst Cd 0.5 Zn 0.5 S is at g =2.003, so that Cd is used in the reaction system for fixing nitrogen by photocatalysis 0.5 Zn 0.5 S is used as a catalyst, methanol is used as a proton source, nitrogen in the atmosphere can be effectively reduced to ammonia which is effective for human beings, and the methanol not only is used as the proton source, but also can react with photo-generated holes, so that the reaction can be more effectively operated.
Description
Technical Field
The invention relates to the technical field of chemical catalysts, in particular to a Cd 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis.
Background
We have entered the era of renewable and pollution-free energy development, and attention of researchers around the world has been paid to the increasing demand of human beings for fossil fuels, the limited energy, and the consequent problems of rapid emission of carbon dioxide and environmental degradation. Among the sustainable energy sources, inexhaustible clean solar energy is very promising. In the last few decades, photocatalytic technology has been applied to the decomposition of water, the reduction of carbon dioxide and N 2 Is fixed by the fixing device. Ammonia is known to be the primary element of biological circulation, and air contains about 78% N 2 . Ammonia is a precursor of most nitrogen-containing compounds, and N can be released into the atmosphere by nitrogen-fixing natural microorganisms 2 Reduction to NH 3 The huge demands of the chemical fertilizer industry at present can hardly be met. Ammonia is an essential chemical molecule for the earth's energy environment and biological processes, and also provides a basis for fertilizers and proteins required to sustain plant life. The conversion of nitrogen into ammonia in nature is green at room temperature and atmospheric pressure and can be maintainedAnd continuous natural photosynthesis.
N 2 And NH 3 Is thermodynamically feasible: n (N) 2 (g)+3H 2 (g)＝2NH 3 (g) Δh (298K) =92.2 kJ/mol. The great development of nitrogen reduction catalysis (NRR) is a continuing scientific challenge, requiring activation and cleavage of very strong nitrogen-nitrogen triple bonds (940.95 KJ/mol). To our knowledge the industrially used Haber-Bosch process requires the presence of an iron catalyst. Although it can be achieved, it needs to be done under huge energy and extreme conditions. The mild reaction conditions required for photocatalytic nitrogen fixation are a very attractive method, but their efficiency is far less than that of industrialization. The results of the study in 1977, 7, schrauzer and Guth show that semiconductor TiO 2 Photocatalysts exhibit nitrogen reduction catalytic activity under water and nitrogen, and photocatalytic nitrogen reduction has therefore attracted considerable attention, and many researchers are now trying to optimize the efficiency of photocatalytic nitrogen fixation. And many experimental and theoretical studies have shown that N 2 Dissociation is a rate limiting step. The defects on the surface of the sample can greatly enhance the activity of photocatalytic nitrogen fixation, effectively promote the adsorption of inert single molecules under mild conditions, promote the separation of excited electrons and holes, and reduce the band gap of the photocatalyst and the energy requirement of excitons.
Until now, the greatest difficulty in how to fix nitrogen in the atmosphere has been known in how to activate the nitrogen-nitrogen triple bond. Therefore, strategies to decompose water into hydrogen and reduce nitrogen to ammonia are at the front of chemical research. Inspired by these natural photosynthesis. The first step of these two synthesis processes is a photoexcitation process in which holes are formed in the valence band and electrons are excited to the conduction band. Next, the photogenerated electron-hole pairs are transferred to the surface of the catalyst, the electrons are separated from the hole traps, and the photocatalyst diffuses from the surface to the reaction site. Finally, N adsorbed at these sites 2 Is catalyzed into NH by residual electrons 3 . Finding out an efficient photocatalyst is a key for realizing solar nitrogen fixation. The vacancies can accommodate the poly-electronic Lewis bases and unsaturation sites for catalytic reactions, thereby introducing chemical reactions requiring high thermodynamic activation energies through other pathwaysLeading to the desired energy barrier on the crystal surface. It is reported that defect engineering of photocatalysts can improve carrier separation efficiency, in which defects can be received as trapping centers and electrons are photoexcited, thereby preventing them from recombining with photo-generated holes. It is worth noting that these conflicting effects of defects are due to the complex structure of conventionally prepared photocatalysts and the lack of direct defect surface technology.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a Cd 0.5 Zn 0.5 The preparation method of S and the experimental method of nitrogen fixation under photocatalysis solve the problems of complex structure and lack of direct defect surface technology of the existing prepared photocatalyst.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: cd (cadmium sulfide) 0.5 Zn 0.5 The preparation method of S specifically comprises the following steps:
t1, 1mmol of [ Cd (NO 3 ) 2 ·4H 2 O]1mmol of [ Zn (NO) 3 ) 2 ·6H 2 O]And 4mmol of L-cysteine are dissolved in deionized water, and the mixed solution is obtained after stirring for half an hour;
t2, transferring the mixed solution obtained in the step T1 into a polytetrafluoroethylene lining, after sealing, placing the reaction kettle in an oven, setting the temperature to be 180-220 ℃ for reaction for 18 hours, and naturally cooling the system to room temperature to obtain a yellow-green suspension;
t3, washing with deionized water and ethanol for 2-4 times, and drying in a vacuum oven to obtain yellow-green Cd 0.5 Zn 0.5 S, collecting powder for later use.
Preferably, the deionized water in the step T1 has a volume of 60ml.
Preferably, the polytetrafluoroethylene lining in the step T2 has a volume of 100ml.
Preferably, the step T3 is placed in a vacuum oven to dry at 60 ℃ for 12 hours.
The invention also provides a Cd 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, specifically comprising the following steps:
e1, centrifuging 5ml of reaction solution to obtain supernatant, placing the supernatant into a 10ml test tube, and adding 100 mu L of potassium sodium tartrate solution into a sample tube;
e2, after uniformly mixing, adding 150 mu L of Nessler reagent into the same test tube, then placing the solution for 10 minutes, and finally placing the solution into an ultraviolet spectrophotometer to detect absorbance at lambda=420 nm;
and E3, evaluating an experimental result.
Preferably, the Nessler reagent in the step E2 is Nahner reagent, which is a reagent for measuring ammonia nitrogen content in air and water by utilizing the principle of ultraviolet-visible spectrophotometry.
Preferably, in step E3, for evaluating CH 3 OH availability in improving photocatalytic efficiency, photocatalytic ammonia decomposition of the prepared sample, CH under 300W xenon lamp of 420nm cut-off filter 3 OH served as a photo-catalytic sacrificial electron donor, and it can be seen that the sample Cd was synthesized when the temperature of hydrothermal synthesis was 200 ℃ 0.5 Zn 0.5 S shows better activity, the nitrogen yield reaches 2.93mmol/L after 2 hours of irradiation of visible light, and Cd at 180 DEG C 0.5 Zn 0.5 S sample and Cd at 220 DEG C 0.5 Zn 0.5 The photocatalytic yields of the S samples were 0.1217 and 0.1175mmol/L, respectively, and it was found that the sample catalyst could convert N when the temperature of the hydrothermal synthesis was 200deg.C 2 Reduction to NH 4 + 。
Preferably, the ultraviolet spectrophotometer in the step E2 is of a model number of shimadzu UV-2550.
(III) beneficial effects
The invention provides a Cd 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis. Compared with the prior art, the method has the following beneficial effects: the Cd is 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis by lightThe electrons are excited to the conduction band, leaving vacancies in the valence band after which some electrons and holes recombine with each other, while other electrons and holes migrate to the catalyst surface and participate in the redox reaction. Methanol provides hydrogen protons for the reaction, nitrogen is reduced to ammonia, a series of catalysts are prepared by a hydrothermal synthesis method, then the catalysts are added into a photocatalytic nitrogen fixation reaction system, wherein methanol provides protons for the reaction system, and a series of researches show that the nitrogen can be reduced to NH only when the temperature of the hydrothermal synthesis is 200 DEG C 4 + The photocatalyst nitrogen fixation is active, when the catalyst is put into a system and irradiated under visible light for 2 hours, the ammonia generated in a reaction container is 2.93mmol/L, then a series of characterization is carried out on the synthesized catalyst, and in the detection of electron paramagnetic spectrum (EPR) on the catalyst, we find that when the synthesis temperature is 200 ℃, the photocatalyst Cd is compared with samples at other temperatures 0.5 Zn 0.5 S has a strong signal at g=2.003, so Cd is used in the reaction system for photocatalytic nitrogen fixation 0.5 Zn 0.5 S is used as a catalyst, methanol is used as a proton source, nitrogen in the atmosphere can be effectively reduced to ammonia which is effective for human beings, and the methanol not only is used as the proton source, but also can react with holes generated by light excitation, so that the reaction can be more effectively operated.
Drawings
FIG. 1 shows a photocatalyst Cd synthesized at different temperatures according to the invention 0.5 Zn 0.5 Schematic of ammonia production for S;
FIG. 2 shows the different temperature syntheses of Cd of the invention 0.5 Zn 0.5 XRD pattern of S catalyst;
FIG. 3 is a schematic diagram of a Cd of the invention 0.5 Zn 0.5 S sample XPS spectrogram;
FIG. 4 is a schematic diagram of a Cd of the invention 0.5 Zn 0.5 S, a nitrogen adsorption-desorption isotherm and a corresponding pore size distribution curve graph of the sample;
FIG. 5 shows a photocatalyst Cd synthesized at 200℃in the hydrothermal synthesis according to the invention 0.5 Zn 0.5 S, scanning electron microscope images;
FIG. 6 is a schematic diagram of a Cd of the invention 0.5 Zn 0.5 TEM, HR-TEM and EDS diagram of the S catalyst;
FIG. 7 shows the different temperature syntheses of Cd of the invention 0.5 Zn 0.5 A UV-Vis diffuse reflectance spectrum (a) of S and a corresponding band gap energy schematic;
FIG. 8 shows a photocatalyst Cd synthesized at different temperatures according to the present invention 0.5 Zn 0.5 An EPR spectrum of S;
FIG. 9 shows a catalyst Cd before and after irradiation with visible light according to the invention 0.5 Zn 0.5 EPR profile of S.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-9, the embodiments of the present invention provide three technical solutions: cd (cadmium sulfide) 0.5 Zn 0.5 The preparation method of S and the experimental method of nitrogen fixation under photocatalysis concretely comprise the following examples:
example 1
Cd (cadmium sulfide) 0.5 Zn 0.5 The preparation method of S specifically comprises the following steps:
t1, 1mmol of [ Cd (NO 3 ) 2 ·4H 2 O]1mmol of [ Zn (NO) 3 ) 2 ·6H 2 O]And 4mmol of L-cysteine are dissolved in deionized water, and the solution is stirred for half an hour to obtain a mixed solution, wherein the volume of the deionized water is 60ml;
t2, transferring the mixed solution obtained in the step T1 into a polytetrafluoroethylene lining, sealing, placing the reaction kettle in an oven, reacting for 18 hours at the set temperature of 200 ℃, and naturally cooling the system to room temperature to obtain a yellow-green suspension, wherein the volume of the polytetrafluoroethylene lining is 100ml;
t3, washing with deionized water and ethanol for 3 times, and standing in true conditionDrying in an empty oven to obtain yellow-green Cd 0.5 Zn 0.5 S powder is collected for standby, and is placed in a vacuum oven to be dried for 12 hours at 60 ℃.
The embodiment of the invention also provides a Cd 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, specifically comprising the following steps:
e1, centrifuging 5ml of reaction solution to obtain supernatant, placing the supernatant into a 10ml test tube, and adding 100 mu L of potassium sodium tartrate solution into a sample tube;
e2, after uniformly mixing, adding 150 mu L of Nessler reagent into the same test tube, then placing the solution for 10 minutes, and finally placing the solution into an ultraviolet spectrophotometer to detect absorbance at lambda=420 nm, wherein the Nessler reagent is Nashi reagent, which is a reagent for measuring ammonia nitrogen content in air and water by utilizing the principle of ultraviolet-visible spectrophotometry, and the model adopted by the ultraviolet spectrophotometer is shimadzu UV-2550;
e3, evaluating the experimental results to evaluate CH 3 OH is effective in improving photocatalytic efficiency, and prepared samples are subjected to photocatalytic ammonia decomposition, and catalyst samples Cd with different hydrothermal synthesis temperatures are prepared 0.5 Zn 0.5 The photocatalytic nitrogen fixation activity of S is shown in FIG. 1. CH under 300W xenon lamp of 420nm cut-off filter 3 OH served as a photo-catalytic sacrificial electron donor, and it can be seen that the sample Cd was synthesized when the temperature of hydrothermal synthesis was 200 ℃ 0.5 Zn 0.5 S shows better activity, the nitrogen yield reaches 2.93mmol/L after 2 hours of irradiation of visible light, and Cd at 180 DEG C 0.5 Zn 0.5 S sample and Cd at 220 DEG C 0.5 Zn 0.5 The photocatalytic yields of the S samples were 0.1217 and 0.1175mmol/L, respectively, and it was found that the sample catalyst could convert N when the temperature of the hydrothermal synthesis was 200deg.C 2 Reduction to NH 4 + 。
Example 2
Cd (cadmium sulfide) 0.5 Zn 0.5 The preparation method of S specifically comprises the following steps:
t1, 1mmol of [ Cd (NO 3 ) 2 ·4H 2 O]1mmol of [ Z ]n(NO 3 ) 2 ·6H 2 O]And 4mmol of L-cysteine are dissolved in deionized water, and the solution is stirred for half an hour to obtain a mixed solution, wherein the volume of the deionized water is 60ml;
t2, transferring the mixed solution obtained in the step T1 into a polytetrafluoroethylene lining, sealing, placing the reaction kettle in an oven, setting the temperature to be 180 ℃ for reaction for 18 hours, and naturally cooling the system to room temperature to obtain a yellow-green suspension, wherein the volume of the polytetrafluoroethylene lining is 100ml;
t3, washing with deionized water and ethanol for 2 times, and then drying in a vacuum oven to obtain yellowish green Cd 0.5 Zn 0.5 S powder is collected for standby, and is placed in a vacuum oven to be dried for 12 hours at 60 ℃.
The embodiment of the invention also provides a Cd 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, specifically comprising the following steps:
e1, centrifuging 5ml of reaction solution to obtain supernatant, placing the supernatant into a 10ml test tube, and adding 100 mu L of potassium sodium tartrate solution into a sample tube;
e2, after uniformly mixing, adding 150 mu L of Nessler reagent into the same test tube, then placing the solution for 10 minutes, and finally placing the solution into an ultraviolet spectrophotometer to detect absorbance at lambda=420 nm, wherein the Nessler reagent is Nashi reagent, which is a reagent for measuring ammonia nitrogen content in air and water by utilizing the principle of ultraviolet-visible spectrophotometry, and the model adopted by the ultraviolet spectrophotometer is shimadzu UV-2550;
e3, evaluating the experimental results to evaluate CH 3 OH is effective in improving photocatalytic efficiency, and prepared samples are subjected to photocatalytic ammonia decomposition, and catalyst samples Cd with different hydrothermal synthesis temperatures are prepared 0.5 Zn 0.5 The photocatalytic nitrogen fixation activity of S is shown in FIG. 1. CH under 300W xenon lamp of 420nm cut-off filter 3 OH served as a photo-catalytic sacrificial electron donor, and it can be seen that the sample Cd was synthesized when the temperature of hydrothermal synthesis was 200 ℃ 0.5 Zn 0.5 S shows better activity, the nitrogen yield reaches 2.93mmol/L after 2 hours of irradiation of visible light, and the temperature is 180 DEG CCd at DEG C 0.5 Zn 0.5 S sample and Cd at 220 DEG C 0.5 Zn 0.5 The photocatalytic yields of the S samples were 0.1217 and 0.1175mmol/L, respectively, and it was found that the sample catalyst could convert N when the temperature of the hydrothermal synthesis was 200deg.C 2 Reduction to NH 4 + 。
Example 3
Cd (cadmium sulfide) 0.5 Zn 0.5 The preparation method of S specifically comprises the following steps:
t1, 1mmol of [ Cd (NO 3 ) 2 ·4H 2 O]1mmol of [ Zn (NO) 3 ) 2 ·6H 2 O]And 4mmol of L-cysteine are dissolved in deionized water, and the solution is stirred for half an hour to obtain a mixed solution, wherein the volume of the deionized water is 60ml;
t2, transferring the mixed solution obtained in the step T1 into a polytetrafluoroethylene lining, sealing, placing the reaction kettle in an oven, setting the temperature to 220 ℃ for reaction for 18 hours, and naturally cooling the system to room temperature to obtain a yellow-green suspension, wherein the volume of the polytetrafluoroethylene lining is 100ml;
t3, washing with deionized water and ethanol for 4 times, and then drying in a vacuum oven to obtain yellowish green Cd 0.5 Zn 0.5 S powder is collected for standby, and is placed in a vacuum oven to be dried for 12 hours at 60 ℃.
The embodiment of the invention also provides a Cd 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, specifically comprising the following steps:
e1, centrifuging 5ml of reaction solution to obtain supernatant, placing the supernatant into a 10ml test tube, and adding 100 mu L of potassium sodium tartrate solution into a sample tube;
e2, after uniformly mixing, adding 150 mu L of Nessler reagent into the same test tube, then placing the solution for 10 minutes, and finally placing the solution into an ultraviolet spectrophotometer to detect absorbance at lambda=420 nm, wherein the Nessler reagent is Nashi reagent, which is a reagent for measuring ammonia nitrogen content in air and water by utilizing the principle of ultraviolet-visible spectrophotometry, and the model adopted by the ultraviolet spectrophotometer is shimadzu UV-2550;
e3, evaluating the experimental results to evaluate CH 3 OH is effective in improving photocatalytic efficiency, and prepared samples are subjected to photocatalytic ammonia decomposition, and catalyst samples Cd with different hydrothermal synthesis temperatures are prepared 0.5 Zn 0.5 The photocatalytic nitrogen fixation activity of S is shown in FIG. 1. CH under 300W xenon lamp of 420nm cut-off filter 3 OH served as a photo-catalytic sacrificial electron donor, and it can be seen that the sample Cd was synthesized when the temperature of hydrothermal synthesis was 200 ℃ 0.5 Zn 0.5 S shows better activity, the nitrogen yield reaches 2.93mmol/L after 2 hours of irradiation of visible light, and Cd at 180 DEG C 0.5 Zn 0.5 S sample and Cd at 220 DEG C 0.5 Zn 0.5 The photocatalytic yields of the S samples were 0.1217 and 0.1175mmol/L, respectively, and it was found that the sample catalyst could convert N when the temperature of the hydrothermal synthesis was 200deg.C 2 Reduction to NH 4 + 。
Catalytic Activity test experiments
Photocatalytic N 2 Fixing experiment: in a 100ml reaction tank with circulating water, a photocatalysis nitrogen fixation experiment is carried out at normal temperature and normal pressure. In a typical experiment, a 300W xenon lamp (Ginko Ind. Chemie Co., ltd. In Beijing) with a 420nm cutoff filter was used as the light source. 30mg of the photocatalyst powder and 50ml of methanol (a photogenerated hole scavenger) solution were placed in a 100ml polytetrafluoroethylene reaction vessel, and N was bubbled in the dark for 30 minutes 2 (99.999%) to establish adsorption. Then, the nitrogen pressure was kept at 0.2Mpa, and the apparatus was magnetically stirred in the dark for 30 minutes to reach adsorption/desorption equilibrium. During the light irradiation, 5ml of the suspension was removed from the reaction solution at intervals, the solution was centrifuged at 10000r/min to remove the catalyst, and the supernatant was taken for the subsequent NH 4 + Concentration analysis. NH (NH) 3 /NH 4 + Concentration analysis: detection of NH in a reactant with Navier's reagent 4 + Concentration generally, 5ml of the centrifuged supernatant is first placed in a 10ml tube, then 100. Mu.l of potassium sodium tartrate solution is added to the sample tube, and after mixing well, 150. Mu.l of Nahner reagent is added. After the mixed solution was left for 10 minutes, it was separated by ultravioletThe reaction solution was tested for absorbance at 420nm using a spectrophotometer (shimadzu UV-2550).
Characterization of the catalyst
1. Analysis of XRD: the crystalline phase structure and particle size of the catalyst were detected by X-ray diffraction (XRD), which is a powder X-ray diffraction analysis of the synthesized samples using a Bruker D8 advanced X-ray diffractometer (XRD) with Cu ka radiation (k= 0.154056 nm) to determine the phase structure and crystallite size of the photocatalyst. As can be seen from fig. 2, all samples exhibited similar XRD patterns. The XRD sample peaks can be clearly seen at (100), (002), (101), (102), (110), (103) and (112), respectively. The peak positions were approximately 26.11 °,27.76 °,29.62 °,38.49 °,46.02 °,50.25 °, and 54.58 °. Therefore, through the information, we can know that the crystal face measured by XRD corresponds to the crystal face of sphalerite, which shows that all synthesized photocatalytic materials Cd with different temperatures 0.5 Zn 0.5 Cd having S in hexagonal crystal phase 0.5 Zn 0.5 S (JCPDS number 89-2943). The diffraction peaks in the XRD pattern are most evident from Cd formed at a synthesis temperature of 200deg.C 0.5 Zn 0.5 S, S. Furthermore, we are in all semiconductor materials Cd 0.5 Zn 0.5 No impurity peak was detected on the S samples, indicating higher purity of the synthesized product. More specifically, catalyst Cd with defects 0.5 Zn 0.5 The XRD diffraction peak of S is stronger than that of other samples without defects.
2. XPS detection analysis: the synthesized sample Cd is subjected to X-ray electron spectroscopy (XPS) 0.5 Zn 0.5 S has been studied intensively in terms of its surface chemical composition and element valence, FIG. 3 is a catalyst Cd 0.5 Zn 0.5 XPS test spectra and elements of S and high resolution spectra of Cd 3d, zn 2p and S2 p. The peaks of Cd, zn, S, C and O elements can be seen from the figure. This occurs because of the graphite conductive paste and absorbed gas molecules. From FIG. 3, it can be observed that Cd 3d is divided into two peaks of Cd 3d5/2 and Cd 3d3/2 at 405.35eV and 412.15eV, which indicates that it belongs to Cd 2 + . It is further known from the figure that the Zn 2p peak is at both 1022.21eV (Zn 2p 3/2) and 1045.2eV (Zn 2p 1/2), becauseThis is known as element Zn 2 + . The semiconductor material Cd is seen in the figure 0.5 Zn 0.5 The two peaks S2 p peaks of the S sample at 161.3eV and 162.5eV are S 2 - This is due to the coordination of S with Zn and Cd in the sample (fig. 3). It is finally clear that this test result is consistent with the sample we synthesized. This conclusion was also confirmed in many previous reported studies. From this, it can be concluded that the synthesized material Cd 0.5 Zn 0.5 S is a high-efficiency pollution-free catalyst prepared under a simple condition.
3. BET detection analysis: the specific surface area and pore size distribution of the synthesized samples were measured using a physical chemisorber (BET). The adsorption-desorption isotherm curves of the prepared samples are shown in fig. 4. From IUPAC classification it can be found that all samples belong to the type IV adsorption isotherm. It can thus be determined that the sample has a mesoporous structure. We have studied more deeply from the scanning electron microscope image and found that the catalyst Cd 0.5 Zn 0.5 The morphology of S is a mesoporous structure. The pores detected from the specific surface area are thus formed by the accumulation of the photocatalyst particles. It can be seen from the scanning electron microscope image that this is a gap generated by the accumulation of catalyst particles, and is consistent with the specific surface area and pore size distribution of the detection result. The larger the specific surface area, the better the activity of the catalyst, while the smaller the particle size, the larger the specific surface area, cd 0.5 Zn 0.5 S has a specific surface area of 23.51m 2 /g and 29.09m 2 And/g. The pore volumes of the samples were 0.059cm, respectively 3 Per g and 0.066cm 3 And/g. In addition to Cd 0.5 Zn 0.5 The average pore diameters of S were 10.041nm and 9.064nm. To compare the sample Cd 0.5 Zn 0.5 Nitrogen adsorption capacity of S, nitrogen adsorption experiments were performed at normal temperature. As can be seen from the results, the photocatalyst Cd with a synthesis temperature of 200℃was used 0.5 Zn 0.5 S has relatively good nitrogen adsorption capacity, so that the introduction of defects is beneficial to photocatalytic nitrogen fixation, and the occurrence of the defects improves the efficiency of photocatalytic nitrogen fixation.
4. SEM and TEM analysis detection: analysis of microstructure and Table of photocatalyst Using SEM and TEMSurface morphology. As shown in FIG. 5, it can be seen that Cd 0.5 Zn 0.5 S is composed of a few small irregular nanoparticles. Overlapping black in transmission electron microscopy is caused by the aggregation of certain particles. Cd (cadmium sulfide) 0.5 Zn 0.5 High resolution map HRTEM for S samples is shown in fig. 6. These nanoparticles have lattice fringes of different directions, indicating that they have polycrystalline characteristics and are randomly oriented. The results show that sample [110]The interplanar spacing of the planes of (2) is 0.22nm, which is consistent with the previously reported interplanar spacing, and the elemental map image shows the same profile as that shown in the rectangular region.
5. UV-Vis analysis detection: the absorbance of the semiconductor catalyst material was measured using ultraviolet visible Diffuse Reflectance Spectroscopy (DRS). Synthesized Cd 0.5 Zn 0.5 The UV-Vis absorption spectrum of the S sample is shown in FIG. 7. From the figure, cd can be seen 0.5 Zn 0.5 S sample absorption is in the visible range and drops sharply at 500nm, indicating that visible light absorption is caused by band gap transitions, the graph showing the photocatalyst Cd with a synthesis temperature of 200deg.C 0.5 Zn 0.5 S absorption edge vs. sample Cd with synthesis temperature at 180 DEG C 0.5 Zn 0.5 S red shifted to 510nm, and in addition, the catalyst Cd synthesized with a single 180 DEG C 0.5 Zn 0.5 The S sample has stronger light absorption capacity in the visible light range of 450-750nm compared with the sample with the synthesis temperature of 200 ℃. It is well known that the bandgap energy of a semiconductor can be calculated by the following formula:
αhV＝A(hv-Eg) n/2 (1)
where α, h, t, eg and n correspond to constants, planck constants, optical frequencies, functional coefficients, band gap energies and absorption coefficients, where n is determined by the semiconductor type (direct transition n=1; indirect transition n=4). Semiconductor catalyst Cd 0.5 Zn 0.5 The band gap value of S is about 2.38eV, as determined by the Taucs plot shown in the figure, consistent with the values reported previously. As the synthesis temperature increases, the absorption intensity in the visible region increases significantly, which also coincides with the color of the sample. The VB and CB values of the photocatalyst samples can be calculated by formulas (2) and (3).
ECB＝X–0.5Eg–4.5 (2)
EVB＝X+0.5Eg–4.5 (3)
Wherein ECB, EVB, X and Eg are potential energy at the bottom of CB, potential energy at the top of VB, and Mulliken electronegativity and band gap energy of constituent atoms, respectively. According to the above calculation, sample Cd 0.5 Zn 0.5 CB and VB values for S are-0.24 and 1.96eV. The increase of the absorption of visible light and the increase of the forbidden bandwidth can improve the photocatalytic performance, but when the temperature is too high, the performance of the synthesized sample catalyst is destroyed. When the synthesis temperature is higher than 200 ℃, the sample catalyst is agglomerated, and defects in the catalyst are reduced, so that the photocatalytic nitrogen fixation capacity is greatly reduced. As shown in the figure, the DRS results further confirm that the synthesis temperature has a significant effect on the efficient use of visible light
6. EPR detection analysis: paramagnetic resonance spectroscopy is used to detect whether a sample contains defects. As shown in FIG. 8, the photo-catalyst Cd with different hydro-thermal synthesis temperatures 0.5 Zn 0.5 Paramagnetic resonance spectrum of S. From the figure we can clearly see that the EPR spectra of all samples show a clear signal at 348mT (g=2.003) whereas the hydrothermal synthesis temperature is 200 ℃ for sample Cd 0.5 Zn 0.5 The EPR spectrum signal peak of S is stronger, which proves that the surface of the sample catalyst has defects. It is known that the formation of defects in the sample results in vacancies in the s-bonds, which can accommodate electrons and increase the surface charge of the sample. According to previous reports, defects can delocalize electrons, thereby preventing the recombination of photogenerated electrons and holes, thus leading to an increase in photocatalytic activity in this system of photocatalytic nitrogen fixation. As shown in FIG. 9, we detected the photocatalyst Cd before and after the reaction 0.5 Zn 0.5 The EPR spectrum of S, from the signal of the EPR spectrum in FIG. 9, shows that there was no change both before and after irradiation with visible light, indicating that after irradiation with visible light for 4 hours, the semiconductor catalyst Cd 0.5 Zn 0.5 The defects of the S surface are not reduced or increased. This shows that the synthesized sample can be reused and has stable performance.
And all that is not described in detail in this specification is well known to those skilled in the art.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. Cd (cadmium sulfide) 0.5 Zn 0.5 The preparation method of S is characterized in that: the method specifically comprises the following steps:
t1, 1mmol of [ Cd (NO 3 ) 2 ·4H 2 O]1mmol of [ Zn (NO) 3 ) 2 ·6H 2 O]And 4mmol of L-cysteine are dissolved in deionized water, and the mixed solution is obtained after stirring for half an hour;
t2, transferring the mixed solution obtained in the step T1 into a polytetrafluoroethylene lining, after sealing, placing the reaction kettle in an oven, setting the temperature to be 180-220 ℃ for reaction for 18 hours, and naturally cooling the system to room temperature to obtain a yellow-green suspension;
t3, washing with deionized water and ethanol for 2-4 times, and drying in a vacuum oven to obtain yellow-green Cd 0.5 Zn 0.5 S, collecting powder for later use.
2. A Cd according to claim 1 0.5 Zn 0.5 The preparation method of S is characterized in that: the deionized water in the step T1 has a volume of 60ml.
3. A Cd according to claim 1 0.5 Zn 0.5 The preparation method of S is characterized in that: the volume of the polytetrafluoroethylene lining in the step T2 is 100ml.
4. A Cd according to claim 1 0.5 Zn 0.5 The preparation method of S is characterized in that: and in the step T3, a vacuum oven is arranged for drying at 60 ℃ for 12 hours.
5. A Cd as defined by any one of claims 1 to 4 0.5 Zn 0.5 Cd prepared by S preparation method 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, which is characterized in that: the method specifically comprises the following steps:
e1, centrifuging 5ml of reaction solution to obtain supernatant, placing the supernatant into a 10ml test tube, and adding 100 mu L of potassium sodium tartrate solution into a sample tube;
e2, after uniformly mixing, adding 150 mu L of Nessler reagent into the same test tube, then placing the solution for 10 minutes, and finally placing the solution into an ultraviolet spectrophotometer to detect absorbance at lambda=420 nm;
and E3, evaluating an experimental result.
6. A Cd according to claim 5 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, which is characterized in that: the Nessler reagent in the step E2 is Nahner reagent, which is a reagent for measuring the ammonia nitrogen content in air and water by utilizing the principle of ultraviolet-visible spectrophotometry.
7. A Cd according to claim 5 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, which is characterized in that: in step E3, for the purpose of evaluating CH 3 OH availability in improving photocatalytic efficiency, subjecting the prepared sample to photocatalytic ammoniaDecomposition under 300W xenon lamp of 420nm cut-off filter, CH 3 OH served as a photo-catalytic sacrificial electron donor, and it can be seen that the sample Cd was synthesized when the temperature of hydrothermal synthesis was 200 ℃ 0.5 Zn 0.5 S shows better activity, the nitrogen yield reaches 2.93mmol/L after 2 hours of irradiation of visible light, and Cd at 180 DEG C 0.5 Zn 0.5 S sample and Cd at 220 DEG C 0.5 Zn 0.5 The photocatalytic yields of the S samples were 0.1217 and 0.1175mmol/L, respectively, and it was found that the sample catalyst could convert N when the temperature of the hydrothermal synthesis was 200deg.C 2 Reduction to NH 4 + 。
8. A Cd according to claim 5 0.5 Zn 0.5 S is the experimental method of nitrogen fixation under photocatalysis, which is characterized in that: the model adopted by the ultraviolet spectrophotometer in the step E2 is shimadzu UV-2550.
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