CN111298813B - Method for electrocatalytic nitrogen reduction catalyst - Google Patents
Method for electrocatalytic nitrogen reduction catalyst Download PDFInfo
- Publication number
- CN111298813B CN111298813B CN202010142542.8A CN202010142542A CN111298813B CN 111298813 B CN111298813 B CN 111298813B CN 202010142542 A CN202010142542 A CN 202010142542A CN 111298813 B CN111298813 B CN 111298813B
- Authority
- CN
- China
- Prior art keywords
- telluride
- nitrogen reduction
- stirring
- nitrogen
- reaction kettle
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 66
- 230000009467 reduction Effects 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 52
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910004613 CdTe Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000001308 synthesis method Methods 0.000 claims abstract description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- BFPJYWDBBLZXOM-UHFFFAOYSA-L potassium tellurite Chemical compound [K+].[K+].[O-][Te]([O-])=O BFPJYWDBBLZXOM-UHFFFAOYSA-L 0.000 claims abstract description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims abstract description 4
- 229960002167 sodium tartrate Drugs 0.000 claims abstract description 4
- 239000001433 sodium tartrate Substances 0.000 claims abstract description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002073 nanorod Substances 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000003860 storage Methods 0.000 abstract description 8
- 239000013256 coordination polymer Substances 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 230000002860 competitive effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- PCKPVGOLPKLUHR-UHFFFAOYSA-N indoxyl Chemical group C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 238000012546 transfer Methods 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- B01J35/23—
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
Abstract
The invention belongs to the technical field of electrocatalysis ammonia production, and discloses a method for electrocatalysis nitrogen reduction catalyst, wherein a telluride has hydrogen storage capacity and is introduced into electrocatalysis nitrogen reduction for the first time, wherein elements with good adsorption effect on nitrogen are selected, and high ammonia production is realized at 0V by virtue of hydrogen storage property of the telluride; the telluride includes: sb 2 Te 3 、Bi 3 Te 4 CoTe and CdTe 2 (ii) a With Sb 2 Te 3 For example, sb 2 Te 3 The synthesis method comprises the following steps: sbCl 3 Dissolving in water, sequentially adding 25mg of sodium tartrate, 25mL of ammonia water, 22mg of potassium tellurite and 10mL of hydrazine, stirring for 5min, and then putting into a reaction kettle to react for 5h at 180 ℃. The invention compares Sb 2 Te 3 ，Bi 3 Te 4 CoTe, the nitrogen reduction property of CdTe, has found great promise in the nitrogen reduction of telluride at low voltages.
Description
Technical Field
The invention belongs to the technical field of electro-catalysis ammonia production, and particularly relates to a method for electro-catalysis nitrogen reduction catalyst.
Background
Synthetic ammonia has been one of the most important industrial processes, and the product ammonia is not only an industrial product with wide application but also an ideal clean energy carrier. The traditional synthesis method adopts a Haber-Bosch method to promote high-purity hydrogen and nitrogen to react to generate ammonia gas through extreme harsh conditions such as high temperature and high pressure. The process has high energy consumption and discharges a large amount of greenhouse gases. Is not beneficial to the strategy of green sustainable development.
Therefore, it is particularly important to develop green sustainable alternatives. The current methods for producing ammonia include photocatalytic nitrogen reduction, electrocatalytic nitrogen reduction and azotase catalysis. Among these methods, electrocatalytic nitrogen reduction can realize high-efficiency, low-energy-consumption and zero-emission ammonia synthesis under mild conditions, and has attracted much attention in recent years.
Various electrocatalysts are currently designed, such as alloys (PdCu, angel. Chem. Int.ed.,2019doi 2 ，Adv.Energy Mater.2019，9，1803935，Fe 3 S 4 Chem, commun, 2018, 54, 13010-13013), oxide (CeO) 2 ，Chem.Commun.2019，55，2952-2955，BiVO 4 Small Methods 2018,3, 1800333), phosphide (CoP, small Methods 2018,2, 1800204), nitride (W 2 N 3 ，Adv.Mater.2019，31，1902709，Mo 2 N, ACS Energy Lett.2019,4, 1053-1054), monatomic catalyst (Fe) SA -N-C, nat. Commun.2019, 10, 341), and the like. However, the catalytic effect is mainly concentrated at high voltages, resulting in severe electrical energy losses. Therefore, how to solve the problem of high potential, achieving high ammonia yield at low potential is a great challenge of electrochemical nitrogen reduction.
The reason that high ammonia yield under low voltage is difficult to realize in nitrogen reduction is mainly reflected in that the mass transfer process is severely limited by low nitrogen solubility, the selectivity and activity are very low under low potential due to strong hydrogen evolution competitive reaction, and the energy barrier to be overcome by nitrogen hydrogenation reduction in nitrogen reduction is high and the speed is low. Therefore, it is important to design and develop a new catalyst to promote nitrogen adsorption, inhibit competitive reaction, reduce hydrogenation energy barrier and realize high ammonia yield at low voltage.
Telluride nanomaterials play an important role in inorganic functional materials and devices that are being developed vigorously. The materials have good optical, electrical and catalytic properties, and can be widely applied to the important research and production fields. However, as a catalyst with great application prospect, the contribution of nitrogen reduction to ammonia production is not researched yet.
In summary, the problems of the prior art are as follows:
(1) In the prior art, most catalysts have difficulty achieving high ammonia production at lower voltages.
(2) At present, some catalysts can produce ammonia under low voltage, but all are precious metals, so that the catalysts are expensive and have little reserve, and the catalysts have certain limitation in industrial production.
(3) Telluride nanomaterials play an important role in inorganic functional materials and devices that are being developed vigorously. The materials have good optical, electrical and catalytic properties, and can be widely applied to the important research and production fields. However, as a catalyst with great application prospect, the contribution of nitrogen reduction to ammonia production is not researched yet.
The difficulty of solving the technical problems is as follows:
(1) The Haber-Bosch process uses extreme harsh conditions such as high temperature and high pressure to promote the reaction of high purity hydrogen and nitrogen to produce ammonia. The process has high energy consumption and discharges a large amount of greenhouse gases. Is not beneficial to the strategy of green sustainable development. Therefore, it is very important to find a green, safe and efficient method to replace the traditional Haber-Bosch method.
(2) Because the solubility of nitrogen is low, the strong hydrogen evolution competition reaction and the energy barrier to be overcome by the nitrogen hydrogenation reduction in the nitrogen reduction are high, and the speed is low, the catalytic effect of the existing catalyst is mainly concentrated under high voltage, so that the design of the catalyst for increasing nitrogen adsorption, inhibiting hydrogen evolution, accelerating reduction and realizing high ammonia yield under low voltage is very important.
(3) Among a plurality of catalysts, a non-noble metal catalyst is designed to realize high ammonia yield under low voltage so as to solve the problems of low noble metal storage, high price and the like.
(4) Among a plurality of catalysts, the telluride nano material has better properties of optics, electrics, catalysis and the like, and can be widely applied to the important research and production fields. However, as a catalyst with great application prospect, the contribution of nitrogen reduction to ammonia production is not researched yet.
The significance of solving the technical problems is as follows:
(1) The electrocatalysis nitrogen reduction at normal temperature used in the invention is green, efficient and environment-friendly, and can better meet the policy of green environmental protection, energy conservation and emission reduction proposed by the state.
(2) The invention can realize high ammonia yield under low voltage, can effectively reduce the electric energy consumption, and realizes large ammonia yield by using less electric energy.
(3) Compared with a noble metal catalyst, the non-noble metal catalyst used in the invention has the advantages of low price, rich reserves and great advantages in industrial production.
(4) The telluride researched by the invention has high ammonia yield under 0V, opens the application of the telluride in nitrogen reduction ammonia production, and simultaneously provides a new idea for the design of other electrocatalytic nitrogen reduction catalysts.
Disclosure of Invention
Aiming at the problems in the prior art, the invention selects elements (Co, bi, cd and Sb) with strong adsorption on nitrogen, and introduces the telluride into electro-catalytic nitrogen reduction by virtue of the hydrogen storage property of the telluride. A novel non-noble metal electrocatalytic nitrogen reduction catalyst is provided. The catalyst can realize higher ammonia yield at 0V.
The present invention is achieved by a method of electrocatalytic nitrogen reduction catalyst, comprising: wherein the telluride is introduced into the electrocatalytic nitrogen reduction. The elements (Co, bi, cd and Sb) with good adsorption on nitrogen are selected, and the telluride has the hydrogen storage property of 0V, so that high ammonia yield is realized.
Further, the telluride includes: sb 2 Te 3 、Bi 3 Te 4 、CoTe 2 And CdTe.
Further, sb 2 Te 3 The synthesis method comprises the following steps: with 4mg of SbCl 3 Dissolving in 7.5mL of water, sequentially adding 25mg of sodium tartrate, 25mL of ammonia water, 22mg of potassium tellurite and 10mL of hydrazine, stirring for 5min, and then putting into a reaction kettle to react for 5h at 180 ℃.
Further, sb 2 Te 3 Is a hexagonal nano-sheet.
Further, bi 3 Te 4 The synthesis method comprises the following steps: 0.243g Bi (NO) 3 ) 3 ·5H 2 Dissolving O in 25mL of deionized water; after stirring for one hour, 0.126g K was added 2 TeO 3 Then stirring for 10 minutes; then 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol were added; and (3) placing the obtained uniformly dispersed suspension into a reaction kettle, maintaining the temperature of the reaction kettle at 200 ℃ for 24 hours, taking out the suspension, centrifuging the suspension, washing the suspension with water and ethanol, and drying the suspension in vacuum.
Further, bi 3 Te 4 Is a nano needle.
Further, coTe 2 The synthesis method comprises the following steps: 0.15g Co (NO) 3 ) 2 ·6H 2 Dissolving O in 15mL of deionized water; after stirring for one hour, 0.126g K was added 2 TeO 3 Then stirring for 10 minutes; 1g ascorbic acid, and 15mL ethylene glycol were added. And (3) placing the obtained uniformly dispersed suspension into a reaction kettle, maintaining the temperature of the reaction kettle at 200 ℃ for 12 hours, taking out the suspension, centrifuging the suspension, washing the suspension with water and ethanol, and drying the suspension in vacuum.
Further, coTe 2 Is a spindle-shaped nano rod.
Further, the CdTe synthesis method comprises the following steps: 0.159g Cd (NO) 3 ) 3 ·5H 2 O was stirred for one hour, 0.126g K was added 2 TeO 3 Then stirring for 10 minutes; then 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol were added; putting the obtained uniformly dispersed solution into a reaction kettle, and maintaining the temperature of the reaction kettle at 200 ℃ for 24 hours; taking out and centrifuging, washing with water and ethanol, and drying in vacuum.
Further, cdTe is a nanorod.
Further, the Sb synthesis method comprises the following steps: 20mg of Sb was put into a mortar and ground into powder, the powder was placed into isopropanol, subjected to ultrasonic treatment for 8 hours in an argon atmosphere, centrifuged, washed three times with ethanol, and dried overnight at 60 ℃.
In summary, the advantages and positive effects of the invention are as follows: telluride (Sb) 2 Te 3 、Bi 3 Te 4 、CoTe 2 And CdTe) can achieve better ammonia yield at low voltage, wherein Sb is used 2 Te 3 Ammonia production was best at 0V (vs RHE) (FIG. 23). And as the voltage continued to increase, the ammonia production reached a maximum at-0.2V (relative to RHE) (figure 13). Comparison of Sb shows that telluride has better catalytic effect in nitrogen reduction (fig. 21). In order to eliminate the influence of other pollution sources, some isotope experiments and comparison experiments also prove that Sb 2 Te 3 The effect of high ammonia yield. Compared with the currently reported catalyst, the catalyst has great advantages in ammonia production (Table 1), and opens the application of telluride in ammonia production by nitrogen reduction. By theoretical simulation studies on its catalytic process (fig. 24-29), it was concluded that there is a synergistic diatomic site. With Sb 2 Te 3 For example, sb sites adsorb nitrogen, te sites adsorb H. A synergistic effect exists between the Sb and the Te, so that the adsorption of Sb to nitrogen can be promoted, and H adsorbed on Te can inhibit a competitive reaction in the reduction process and can be quickly transferred to N to realize reduction. This provides a new idea for the design of other electrocatalytic nitrogen reduction catalysts. The invention uses Sb 2 Te 3 For example, comparing the pure ammonia-generating capacity of Sb, it is found that telluride has great prospect in nitrogen reduction at low voltage.
Drawings
FIG. 1 shows Sb provided in the embodiments of the present invention 2 Te 3 Synthetic flow diagram.
FIG. 2 is a flow chart of Sb synthesis provided in the examples of the present invention.
FIG. 3 shows Bi provided in an embodiment of the present invention 3 Te 4 Synthetic flow diagram.
FIG. 4 shows CoTe provided in the embodiment of the present invention 2 Synthetic flow diagram.
FIG. 5 is a CdTe synthesis flow diagram provided by an embodiment of the invention.
FIG. 6 is Sb 2 Te 3 XRD patterns of the Compounds
FIG. 7 is Sb 2 Te 3 Scanning electron micrographs (a) and transmission electron micrographs (b) of the compounds.
FIG. 8 shows Bi 3 Te 4 XRD pattern (a) and transmission electron micrograph (b) of the compound.
FIG. 9 is XRD pattern (a) and transmission electron micrograph (b) of CdTe compound.
FIG. 10 shows CoTe 2 XRD pattern (a) and transmission electron micrograph (b) of the compound.
Fig. 11 shows XRD pattern (a) and transmission electron micrograph (b) of Sb.
FIG. 12 is a series of NH after standing at room temperature for 2 hours 4 + UV-Vis absorption spectrum of concentration (a). And associated calculated NH 4 + Calibration curve of concentration (b).
FIG. 13 shows Sb provided in the embodiment of the present invention 2 Te 3 Electrocatalytic nitrogen reduction property test chart of (1): time-current curve (a) at different voltages, UV-visible absorption spectrum (b) at different voltages, ammonia production (c) at different voltages, sb 2 Te 3 And the ammonia production of CP as compared with (d).
FIG. 14 is a series of NH 4 + Ion chromatogram of ion concentration (a) and method for calculating NH 4 Calibration curve (b) for Cl concentration.
FIG. 15 shows NH in electrolyte 4 + Ion chromatogram of ions (a) and detection of Sb at 0V (vs RHE) by indophenol blue method and ion chromatography 2 Te 3 NH of/CP 3 Yield graph (b).
FIG. 16 is a series of N after standing at room temperature for 2 hours 2 H 4 UV-Vis absorption spectrum of concentration (a). And the associated calculation N 2 H 4 Calibration graph (b) of concentration.
FIG. 17 is a graph of the UV-Vis spectra of the electrolyte before and after electrolysis at 0V (vs RHE).
FIG. 18 is a graph of the UV-Vis spectra of the electrolyte after electrolysis at open circuit potential and before electrolysis.
FIG. 19 at N 2 And in Ar atmosphere, sb 2 Te 3 NH of/CP at 0V (vs RHE) potential 3 The yield chart.
FIG. 20 is at-0.2V (vs. RHE) 14 N 2 Of electrolytes which electrolyze under saturated conditions 1 H-NMR spectrum (a) and at-0.2V (vs RHE) 15 N 2 Of electrolytes electrolysed under saturated conditions 1 H-NMR spectrum (b).
FIG. 21 shows Sb provided in the embodiments of the present invention 2 Te 3 And electrocatalytic nitrogen reduction property test pattern of Sb: polarization curve (a), UV-vis absorption spectrum (b), ammonia yield at-0.2V (vs RHE) (c), ammonia yield at 0V (vs RHE) (d), sb 2 Te 3 Ammonia production profile (e), sb, cycling at 0V (vs RHE) 2 Te 3 Time current plot (f) at 0V (vs RHE) for 50 hours.
FIG. 22 shows a schematic representation of N in accordance with an embodiment of the present invention 2 Temperature programmed desorption measurement chart. Obtained Sb 2 Te 3 And N of Sb 2 Temperature programmed desorption measurement chart.
FIG. 23 is CoTe provided in the embodiments of the present invention 2 ，Bi 3 Te 4 Ultraviolet and visible absorption spectra (a) of CdTe at 0V (vs RHE) and CoTe 2 ，Bi 3 Te 4 Graph (b) for ammonia production of CdTe at 0V (vs. RHE).
FIG. 24 is N adsorbed on catalyst 2 Charge difference map of (a): sb (a) and Sb 2 Te 3 (b)。
FIG. 25 is a DOS plot of a catalyst: sb 2 Te 3 General diagrams (a) and Sb 2 Te 3 And (c) splitting the graph (b).
FIG. 26 shows Sb hydrogenated on the surface 2 Te 3 N of proceeding 2 Adsorption (a) and NNH (b) figures.
FIG. 27 shows Sb provided in the examples of the present invention 2 Te 3 And (4) calculating adsorbed hydrogen.
FIG. 28 shows Sb provided in the embodiments of the present invention 2 Te 3 of-H and SbFree energy calculation chart for nitrogen reduction and hydrogenation.
FIG. 29 shows Sb provided in the example of the present invention 2 Te 3 Diatomic site assisted electrocatalysis of NH 3 The mechanism of the reduction method is shown schematically.
Table 1 reports the catalytic performance of the catalyst at low voltage at the present stage. As shown in the table, the telluride has better prospect in catalyzing nitrogen reduction at low voltage.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the prior art, no telluride tool is used for introducing electrocatalytic nitrogen reduction, so that nitrogen cannot be well adsorbed, and the property of hydrogen storage of the telluride cannot be used, so that high ammonia yield cannot be realized at 0V.
In view of the problems of the prior art, the present invention provides a method for electrocatalytic nitrogen reduction catalyst, and the present invention is described in detail below with reference to the accompanying drawings.
The method for electrocatalytic nitrogen reduction of the catalyst provided by the embodiment of the invention comprises the following steps: the method utilizes the hydrogen storage capacity of the telluride to introduce the telluride into electro-catalytic nitrogen reduction, wherein elements with good adsorption on nitrogen are selected, and the high ammonia production is realized at 0V by virtue of the hydrogen storage property of the telluride. Tellurides have found great promise in nitrogen reduction.
As shown in FIG. 1 as Sb 2 Te 3 The synthesis step is a flow chart, and specifically 4mg of SbCl is adopted 3 Dissolving in 7.5mL of water, sequentially adding 25mg of sodium tartrate, 25mL of ammonia water, 22mg of potassium tellurite and 10mL of hydrazine, stirring for 5min, and then putting into a reaction kettle to react for 5h at 180 ℃.
FIG. 2 is a flow chart of Sb synthesis steps, specifically, 20mg of Sb is put into a mortar and ground into powder, then the powder is put into isopropanol and subjected to ultrasonic treatment for 8 hours in an argon atmosphere, then the powder is centrifuged, washed with ethanol for three times, and dried at 60 ℃ overnight.
FIG. 3 is Bi 3 Te 4 Scheme of synthetic procedure, specifically 0.243g Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 25mL of deionized water. After stirring for one hour, 0.126g K was added 2 TeO 3 And stirring was continued for another 10 minutes. Then 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol were added. And (3) putting the obtained uniformly dispersed suspension into a reaction kettle, maintaining the temperature at 200 ℃ for 24 hours, taking out, centrifuging, washing with water and ethanol, and drying in vacuum.
FIG. 4 is CoTe 2 Scheme of synthetic procedure, specifically 0.15g Co (NO) 3 ) 2 ·6H 2 O was dissolved in 15mL of deionized water. After stirring for one hour, 0.126g K was added 2 TeO 3 And stirring was continued for another 10 minutes. Then 1g ascorbic acid, and 15mL ethylene glycol were added. And (3) placing the obtained uniformly dispersed suspension into a reaction kettle, maintaining the temperature of the reaction kettle at 200 ℃ for 12 hours, taking out the suspension, centrifuging the suspension, washing the suspension with water and ethanol, and drying the suspension in vacuum.
FIG. 5 is a flow chart of the CdTe synthesis step, specifically 0.159g Cd (NO) 3 ) 3 ·5H 2 O after stirring for one hour, 0.126g K was added 2 TeO 3 And stirring was continued for another 10 minutes. Then 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol were added. And (3) putting the obtained uniformly dispersed solution into a reaction kettle, maintaining the temperature of the reaction kettle at 200 ℃ for 24 hours, taking out the solution, centrifuging the solution, washing the solution with water and ethanol, and drying the solution in vacuum.
FIG. 6 is Sb 2 Te 3 XRD patterns of the Compounds
FIG. 7 is Sb 2 Te 3 Scanning electron micrographs (a) and transmission electron micrographs (b) of the compounds. Sb obtained as shown in the figure 2 Te 3 Is a hexagonal nanosheet.
FIG. 8 shows Bi 3 Te 4 XRD pattern (a) and transmission electron micrograph (b) of the compound. Bi as shown in the figure 3 Te 4 The preparation is successful.
FIG. 9 is XRD pattern (a) and transmission electron micrograph (b) of CdTe compound. As shown in the figure, cdTe is successfully prepared.
FIG. 10 shows CoTe 2 XRD pattern (a) and transmission electron micrograph (b) of the compound. CoTe as shown 2 The preparation is successful.
Fig. 11 shows XRD pattern (a) and transmission electron micrograph (b) of Sb. Sb nanoplates were obtained as shown.
Electrochemical measurements were performed on a CHI760 workstation (chenhua instruments ltd, shanghai, china). A three-electrode system was used, using two electrolytic cells connected by a salt bridge. To prepare the working electrode, a solution containing 5mg catalyst, 0.9mL ethanol and 0.1mL 5wt% Nafion was sonicated for 30 minutes or more to form a uniform ink. Then at a catalyst loading of 0.2mg cm -2 In the case of (1 cm), 40. Mu.L of the prepared ink was dropped onto carbon paper 2 ) The above. Before the electrochemical tests were carried out, the cells used, the electrodes, were rinsed thoroughly 3 more times with deionized water and the gas (99.999% pure, 40 sccm) was bubbled into 0.1M KOH for more than 30 minutes. Electrochemical tests were carried out after the CV curve had stabilized, on the polarization curve (scan rate 5mV s) -1 ) iR correction was performed and chronoamperometric testing was performed under agitation (450 rpm).
The technical effects of the present invention will be described in detail below with reference to the accompanying drawings.
FIG. 12 is a series of NH after standing at room temperature for 2 hours 4 + UV-Vis absorption spectrum of concentration (a). And related calculation of NH 4 + Calibration graph (b) of concentration. From this map, the ammonia production amount can be calculated.
FIG. 13 shows Sb 2 Te 3 Electrocatalytic nitrogen reduction property test chart of (1): time-current curve (a) at different voltages, UV-visible absorption spectrum (b) at different voltages, ammonia production (c) at different voltages, sb 2 Te 3 And ammonia production of CP compared to (d). As can be seen, plot a shows the i-t curves with different potentials. After electrolysis, NH 3 The corresponding ultraviolet-visible absorption spectrum (U-vis) of (A) is shown in FIG. b. Discovery of Sb 2 Te 3 Exhibits excellent NRR performance at low overpotentials, N 2 Reducing power started at 0.1V (vs. RHE), but NH 3 The yield is low. And NH 3 The yield and FE of (1) respectively reach 34.6 mu g h at 0V -1 mg -1 And 27.7% (vs. rhe) (figure c), superior to many NRR electrocatalysts (table 1). And can reach the maximum at-0.2V. However, as the applied potential increases, FE and NH 3 The yield of (2) is decreased. FE and NH 3 This decrease in yield can be attributed to the reacted HER, resulting in lower FE and lower rates for N 2 Reduction to NH 3 . As can be seen from FIG. d, sb 2 Te 3 NH of/CP 3 The yield was greater than CP, indicating NH detected 3 Derived from Sb 2 Te 3 The excellent performance of (2).
FIG. 14 is a series of NH 4 + Ion chromatogram (a) of ions and method for calculating NH 4 Calibration curve (b) for Cl concentration. The ammonia produced can be further accurately detected and calculated.
FIG. 15 shows NH in electrolyte 4 + Ion chromatogram of ion (a) and detection of Sb at 0V (vs. RHE) by indophenol blue method and ion chromatography 2 Te 3 NH of/CP 3 Yield chart (b). As can be seen from the figure, NH was detected by ion chromatography at 0V (vs. RHE) 3 The yield is similar to the result of indoxyl blue method determination, and the accuracy of experimental determination is further proved.
FIG. 16 is a series of N after standing at room temperature for 2 hours 2 H 4 UV-Vis absorption spectrum of concentration (a). And the associated calculation N 2 H 4 Calibration graph (b) of concentration. For calculating by-product N 2 H 4 Presence of (2)
FIG. 17 is a UV-Vis spectrum (relative to RHE) of the electrolyte before and after electrolysis at 0V. As seen from the figure, it was found that by-product N was not produced 2 H 4 Generation, identification of Sb 2 Te 3 Has better selectivity
FIG. 18 is a graph of the UV-Vis spectra of the electrolyte after electrolysis at open circuit potential and before electrolysis. As can be seen from the figure, the absence of ammonia, the elimination of the effect of the contamination source present in the electrolyte itself, confirms the NH detected 3 The yield is completely from Sb 2 Te 3 By catalysis of
FIG. 19 at N 2 And in Ar atmosphere, sb 2 Te 3 NH of/CP at 0V (vs RHE) potential 3 The yield chart. As can be seen from the figure, it was found thatUnder the atmosphere, no ammonia is generated, the influence of other pollution sources is removed, the ammonia generated in the solution is proved to be derived from nitrogen, and further NH is proved 3 The yield is completely from Sb 2 Te 3 Catalytic nitrogen reduction of
FIG. 20 is at-0.2V (vs RHE) 14 N 2 Of electrolytes which electrolyze under saturated conditions 1 H-NMR spectrum (a) and at-0.2V (vs RHE) 15 N 2 Of electrolytes electrolysed under saturated conditions 1 H-NMR spectrum (b). As can be seen from the figures, the figure, 15 N 2 of electrolytes electrolysed under saturated conditions 1 H-NMR spectrum having two peaks, different from 14 N 2 Of electrolytes which electrolyze under saturated conditions 1 H-NMR spectrum, which proves that the ammonia generated in the solution is derived from nitrogen, further removes other influences, and proves that NH 3 The yield is completely from Sb 2 Te 3 Catalytic nitrogen reduction of
FIG. 21 shows Sb 2 Te 3 And Sb electrocatalytic nitrogen reduction property test chart: polarization curve (a), UV-vis absorption spectrum (b), -ammonia yield at 0.2V (vs RHE) (c), ammonia yield at 0V (vs RHE) (d), sb 2 Te 3 Cyclic ammonia production profile at 0V (vs RHE) (e), sb 2 Te 3 50 hour time-current plot (f) at 0V (vs RHE). As can be seen, sb is shown in the Linear Sweep Voltammetry (LSV) graph at the same potential 2 Te 3 The current density of/CP is higher (FIG. a), indicating that Sb is 2 Te 3 More active sites are present per CP. It is more active than Sb/CP in 0.1M KOH. While the U-vis absorption spectrum of NRR of Sb/CP, NH 3 The yields and FE are shown in FIGS. b-d, respectively. Sb at 0V (vs RHE) and-0.2V (vs RHE) 2 Te 3 NH of/CP 3 The yield is higher than that of Sb/CP, which means that Sb 2 Te 3 Higher NH can be obtained at low overpotential 3 The yield is higher than that of Sb. As seen in FIG. e, the ammonia yield remained essentially unchanged for 6 cycles, demonstrating that Sb 2 Te 3 Has better stability. Graph f, which shows that after 50 hours, the current density remains substantially unchanged, further proving thatIt has high stability.
FIG. 22 is N 2 Temperature programmed desorption measurement chart. As shown in the figure, sb 2 Te 3 Has stronger N 2 Chemical adsorption proves that Te element in telluride can promote N of Sb 2 And (4) adsorbing.
FIG. 23 is CoTe provided in the embodiments of the present invention 2 ，Bi 3 Te 4 RHE ultraviolet-visible absorption spectrum (a) at 0V vs. Te and CoTe 2 ，Bi 3 Te 4 FIG. 0V vs. RHE for ammonia production of CdTe (b). As shown in the figure, coTe, bi 3 Te 4 ，CdTe 2 All have better NH at 0V (relative to RHE) 3 Indicating that the telluride has catalytic N at low voltage 2 The potential for development of (1).
FIG. 24 is N adsorbed on catalyst 2 Charge difference map of (a): sb (a) and Sb 2 Te 3 (b) In that respect As can be seen from the figure, it was found that Sb was adsorbed 2 Te 3 N of (A) to 2 E of (A) ads About-0.032 eV, much lower than E for Sb ads (-0.0084 eV). This is shown in Sb 2 Te 3 And N 2 Stronger covalent interaction is formed between the two, indicating that N is 2 In the telluride (Sb) 2 Te 3 ) Is more efficiently adsorbed and activated on the surface than on Sb. This is consistent with the TPD results.
FIG. 25 is a DOS plot of a catalyst: sb 2 Te 3 General diagrams (a) and Sb 2 Te 3 And (b) splitting the graph. Comparison of Sb to Sb as shown by the figure 2 Te 3 Has a higher charge density at the Fermi level, favoring N 2 By reduction of
FIG. 26 shows Sb hydrogenated on the surface 2 Te 3 N of proceeding 2 Adsorption (a) and NNH (b) figures. As shown in the figure at Sb 2 Te 3 Has two sites on the surface, the site of Sb is used for N 2 Adsorption of Te atoms to provide H to reduce N 2 。
FIG. 27 is Sb 2 Te 3 And (4) calculating adsorbed hydrogen. As shown in the figure, sb 2 Te 3 H on-H desorbs with higher free energy, which means Sb 2 Te 3 HER is very difficult to generate on-H, and the hydrogen evolution can be effectively inhibited, so that the selectivity is improved.
FIG. 28 is Sb 2 Te 3 Calculated plot of nitrogen reduction hydrogenation free energy of-H and Sb. As shown in the figure, sb 2 Te 3 -N on H 2 Is hydrogenated faster than on Sb. Comparison of Sb 2 Te 3 Free energy of formation of upper NNH, H on Te can be easily transferred to N 2 Above, greatly accelerate N 2 In Sb 2 Te 3 Hydrogenation on-H and lowering the initiation potential of NRR, which explains NH 3 High yield and low overpotential.
FIG. 29 is Sb 2 Te 3 Diatomic site assisted electrocatalysis of NH 3 The mechanism of the reduction method is shown schematically. From the figure, it can be seen that: the nitrogen is adsorbed on Sb atoms, H is adsorbed on Te atoms, and the H atoms on Te-H are rapidly transferred to the N of Sb 2 To accelerate N 2 Reducing to form NNH, and continuously hydrogenating to NH 3 And (4) desorbing.
Table 1 reports the catalytic performance of the catalyst at low voltage at the present stage. As shown in the table, the telluride has better prospect in catalyzing nitrogen reduction at low voltage.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A method of electrocatalytic nitrogen reduction catalyst for electrocatalytic nitrogen reduction, the method for electrocatalytic nitrogen reduction comprising: selecting Sb, bi and Cd which have good adsorption effect on nitrogen, introducing telluride into electro-catalytic nitrogen reduction by virtue of the characteristic that the telluride adsorbs hydrogen, and producing ammonia under a series of voltages;
the telluride includes: sb 2 Te 3 、Bi 3 Te 4 And CdTe;
Sb 2 Te 3 the synthesis method comprises the following steps: with 4mgSbCl 3 Dissolving in 7.5mL of water, sequentially adding 25mg of sodium tartrate, 25mL of ammonia water, 22mg of potassium tellurite and 10mL of hydrazine, stirring for 5min, and then putting into a reaction kettle to react for 5h at 180 ℃.
2. The method of claim 1, wherein Sb 2 Te 3 Is a hexagonal nano-sheet.
3. The method of claim 1, wherein Bi is 3 Te 4 The synthesis method comprises the following steps:
0.243gBi(NO 3 ) 3 ·5H 2 dissolving O in 25mL of deionized water; after stirring for one hour, 0.126gK was added 2 TeO 3 Then stirring for 10 minutes; then 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol were added; and (3) placing the obtained uniformly dispersed suspension into a reaction kettle, maintaining the temperature of the reaction kettle at 200 ℃ for 24 hours, taking out the suspension for centrifugation, washing the suspension with water and ethanol, and drying the suspension in vacuum.
4. The method of claim 3, wherein Bi 3 Te 4 Is in the shape of nanometer needle.
5. The process according to claim 1, characterized in that the CdTe synthesis process comprises:
0.159gCd(NO 3 ) 3 ·5H 2 o after stirring for one hour, 0.126gK was added 2 TeO 3 Then stirring for 10 minutes; then 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol were added; putting the obtained uniformly dispersed solution into a reaction kettle, and maintaining the temperature of the reaction kettle at 200 ℃ for 24 hours; taking out, centrifuging, washing with water and ethanol, and vacuum drying;
CdTe is a nanorod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010142542.8A CN111298813B (en) | 2020-03-04 | 2020-03-04 | Method for electrocatalytic nitrogen reduction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010142542.8A CN111298813B (en) | 2020-03-04 | 2020-03-04 | Method for electrocatalytic nitrogen reduction catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111298813A CN111298813A (en) | 2020-06-19 |
| CN111298813B true CN111298813B (en) | 2023-01-10 |
Family
ID=71155083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010142542.8A Active CN111298813B (en) | 2020-03-04 | 2020-03-04 | Method for electrocatalytic nitrogen reduction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111298813B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113252838B (en) * | 2021-05-12 | 2023-03-24 | 北京化工大学 | In-situ differential ammonia measurement characterization test method for electrocatalysis nitrogen fixation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4240882A (en) * | 1979-11-08 | 1980-12-23 | Institute Of Gas Technology | Gas fixation solar cell using gas diffusion semiconductor electrode |
| CN106661740A (en) * | 2014-06-13 | 2017-05-10 | 冰岛大学 | Electrolytic production of ammonia |
| CN108636428A (en) * | 2018-03-13 | 2018-10-12 | 北京化工大学 | A kind of preparation method of metal telluride as two-functional electrolytic catalyst |
| CN109659540A (en) * | 2018-12-21 | 2019-04-19 | 合肥工业大学 | A kind of preparation method of porous carbon coating antimony telluride nanometer sheet and its application as metal ion cell negative electrode material |
| CN110676064A (en) * | 2019-09-12 | 2020-01-10 | 天津大学 | Preparation method of CoTe nanowire for supercapacitor electrode |
-
2020
- 2020-03-04 CN CN202010142542.8A patent/CN111298813B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4240882A (en) * | 1979-11-08 | 1980-12-23 | Institute Of Gas Technology | Gas fixation solar cell using gas diffusion semiconductor electrode |
| CN106661740A (en) * | 2014-06-13 | 2017-05-10 | 冰岛大学 | Electrolytic production of ammonia |
| CN108636428A (en) * | 2018-03-13 | 2018-10-12 | 北京化工大学 | A kind of preparation method of metal telluride as two-functional electrolytic catalyst |
| CN109659540A (en) * | 2018-12-21 | 2019-04-19 | 合肥工业大学 | A kind of preparation method of porous carbon coating antimony telluride nanometer sheet and its application as metal ion cell negative electrode material |
| CN110676064A (en) * | 2019-09-12 | 2020-01-10 | 天津大学 | Preparation method of CoTe nanowire for supercapacitor electrode |
Non-Patent Citations (3)
| Title |
|---|
| Doping single transition metal atom into PtTe sheet for catalyzing nitrogen reduction and hydrogen evolution reactions;Ye Yang et al.;《J. Chem. Phys.》;20191014;第151卷;摘要、第2页左栏第3段和第6页右栏第2段 * |
| Nanostructures of Metal Tellurides (PbTe, CdTe, CoTe2, Bi2Te3, and Cu7Te4) with Various Morphologies: A General Solvothermal Synthesis and Optical Properties;Ling Jiang et al.;《Eur. J. Inorg. Chem.》;20100519;摘要、第3006页左栏最后1段和图2、第3007页左栏最后1段至第3008页左栏第1段、图5、第3010页实验部分 * |
| Ye Yang et al..Doping single transition metal atom into PtTe sheet for catalyzing nitrogen reduction and hydrogen evolution reactions.《J. Chem. Phys.》.2019,第151卷摘要、第2页左栏第3段和第6页右栏第2段. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111298813A (en) | 2020-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111841600B (en) | Platinum-based catalyst and preparation method and application thereof | |
| CN107267124B (en) | MOFs (metal-organic frameworks) nitrogen-containing graphitized carbon material containing Ni/Fe bimetal | |
| CN109518216B (en) | Cobalt phosphide nano-framework and preparation and application thereof | |
| CN108543530B (en) | Zinc oxide nanosheet with oxygen-enriched vacancy as well as preparation method and application thereof | |
| CN106732649A (en) | A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst | |
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| KR101340009B1 (en) | Method for the synthesis of carbon materials using carbon dioxide | |
| CN111663152B (en) | Preparation method and application of foam nickel-loaded amorphous phosphorus-doped nickel molybdate bifunctional electrocatalytic electrode | |
| CN111659443A (en) | Monoatomic iron-sulfur-nitrogen co-doped carbon aerogel electrocatalyst, preparation method and application | |
| Zhang et al. | Enhancing electrochemical nitrogen reduction with Ru nanowires via the atomic decoration of Pt | |
| Li et al. | MoP-NC nanosphere supported Pt nanoparticles for efficient methanol electrolysis | |
| CN111298813B (en) | Method for electrocatalytic nitrogen reduction catalyst | |
| Liu et al. | Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction | |
| CN112023922B (en) | Pt-MnO2Material, preparation method and application thereof | |
| CN109317205B (en) | Nickel-iron-based metal organic framework material rich in cyano-vacancy, preparation method and application thereof | |
| Wang et al. | High Faraday efficiency of Cu 1 Co 1–BCN based on a dodecahydro-closo-dodecaborate hybrid for electrocatalytic reduction of nitrate to ammonia | |
| LU501314B1 (en) | Method for electrocatalytic nitrogen reduction catalyst | |
| CN113322476B (en) | Preparation method and application of silver-doped copper nanosheet catalyst | |
| CN113684499A (en) | Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency | |
| CN111697241A (en) | Nickel selenide composite material loaded with nickel iron tannate and preparation method and application thereof | |
| CN115058725B (en) | Preparation method of three-dimensional graphitized carbon material containing metal and application of three-dimensional graphitized carbon material containing metal in nitrate electrocatalytic reduction synthesis of ammonia | |
| CN115650317B (en) | Amorphous polymetallic boride catalysts and their use | |
| CN114957698B (en) | Preparation method and application of three-dimensional metal coordination polymer | |
| CN114045514B (en) | Preparation method of V@CoxP catalyst | |
| CN115094466B (en) | Hollow carbon dodecahedron packaging WC, W 2 C or diphase WC/W 2 Preparation method of C nanoparticle electrocatalyst |
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 |