CN111298813A - Method for electrocatalytic nitrogen reduction catalyst - Google Patents

Method for electrocatalytic nitrogen reduction catalyst Download PDF

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CN111298813A
CN111298813A CN202010142542.8A CN202010142542A CN111298813A CN 111298813 A CN111298813 A CN 111298813A CN 202010142542 A CN202010142542 A CN 202010142542A CN 111298813 A CN111298813 A CN 111298813A
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nitrogen reduction
suspension
reduction catalyst
telluride
reaction kettle
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CN111298813B (en
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王磊
韩艺
赖建平
李彬
宗玲博
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Qingdao University of Science and Technology
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    • 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
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    • 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: sb2Te3、Bi3Te4CoTe and CdTe2(ii) a With Sb2Te3For example, Sb2Te3The synthesis method comprises the following steps: SbCl3Dissolving 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 DEG C. The invention compares Sb2Te3，Bi3Te4CoTe, the nitrogen reduction property of CdTe, has found great promise in the nitrogen reduction of telluride at low voltages.

Description

Method for electrocatalytic nitrogen reduction catalyst
Technical Field
The invention belongs to the technical field of electrocatalysis ammonia production, and particularly relates to a method for electrocatalysis nitrogen reduction catalyst.
Background
Synthetic ammonia has historically been one of the most important industrial processes, and the product ammonia is both a widely used industrial product and 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, developing a green sustainable alternative is of particular importance. 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, angelw. chem. int.ed., 2019DOI:10.1002/anie.201913122), sulphides (MoS)2，Adv.Energy Mater.2019，9，1803935，Fe3S4chem.Commun.2018, 54, 13010-2，Chem.Commun.2019，55，2952-2955，BiVO4 Small Methods 2018, 3, 1800333), phosphide (CoP, Small Methods 2018, 2, 1800204), nitride (W)2N3，Adv.Mater.2019，31，1902709，Mo2N, ACS Energy Lett.2019, 4, 1053-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 electrocatalytic 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 noble metal catalysts, the non-noble metal catalyst used in the invention has the advantages of low price, abundant 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: sb2Te3、Bi3Te4、CoTe2And CdTe.
Further, Sb2Te3The synthesis method comprises the following steps: with 4mg of SbCl3Dissolving 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, Sb2Te3Is a hexagonal nano-sheet.
Further, Bi3Te4The synthesis method comprises the following steps: 0.243g Bi (NO)3)3·5H2Dissolving O in 25mL of deionized water; after stirring for one hour, 0.126g K was added2TeO3Then 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, Bi3Te4Is a nano needle.
Further, CoTe2The synthesis method comprises the following steps: 0.15g Co (NO)3)2·6H2Dissolving O in 15mL of deionized water; after stirring for one hour, 0.126g K was added2TeO3Then 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, CoTe2Is a spindle-shaped nano rod.
Further, the CdTe synthesis method comprises the following steps: 0.159g Cd (NO)3)3·5H2O after stirring for one hour, 0.126gK was added2TeO3Then 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, and using water and ethanolWashing and vacuum drying.
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, put 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: telluride (Sb)2Te3、Bi3Te4、CoTe2And CdTe) can achieve better ammonia yield at low voltage, wherein Sb is used2Te3Ammonia 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 Sb2Te3The 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 performing theoretical simulation studies on the catalytic process (fig. 24-29), it is concluded that a synergistic diatomic site exists. With Sb2Te3For example, Sb sites adsorb nitrogen, and 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 Sb2Te3For 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 examples of the present invention2Te3Synthetic 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 invention3Te4Synthetic flow diagram.
FIG. 4 shows an embodiment of the present inventionCoTe provided by the examples2Synthetic flow diagram.
FIG. 5 is a CdTe synthesis flow diagram provided by an embodiment of the invention.
FIG. 6 is Sb2Te3XRD patterns of the Compounds
FIG. 7 is Sb2Te3Scanning electron micrographs (a) and transmission electron micrographs (b) of the compounds.
FIG. 8 shows Bi3Te4XRD 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 CoTe2XRD 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 hours4 +UV-Vis absorption spectrum of concentration (a). And associated calculated NH4 +Calibration curve of concentration (b).
FIG. 13 shows Sb provided in the embodiment of the present invention2Te3Electrocatalytic 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, Sb2Te3And ammonia production of CP compared to (d).
FIG. 14 is a series of NH4 +Ion chromatogram of ion concentration (a) and method for calculating NH4Calibration curve (b) for Cl concentration.
FIG. 15 shows NH in electrolyte4 +Ion chromatogram of ions (a) and detection of Sb at 0V (relative to RHE) by indophenol blue method and ion chromatography2Te3NH of/CP3Yield chart (b).
FIG. 16 is a series of N after standing at room temperature for 2 hours2H4UV-Vis absorption spectrum of concentration (a). And the associated calculation N2H4Calibration 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 N2And in Ar atmosphere, Sb2Te3NH of/CP at 0V (vs RHE) potential3The yield chart.
FIG. 20 is at-0.2V (vs. RHE)14N2Of electrolytes which electrolyze under saturated conditions1H-NMR spectrum (a) and at-0.2V (vs RHE)15N2Of electrolytes electrolysed under saturated conditions1H-NMR spectrum (b).
FIG. 21 shows Sb provided in the examples of the present invention2Te3And 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), Sb2Te3Ammonia production profile (e), Sb, cycling at 0V (vs RHE)2Te3Time 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 invention2Temperature programmed desorption measurement chart. Obtained Sb2Te3And N of Sb2Temperature programmed desorption measurement chart.
FIG. 23 is CoTe provided in the embodiments of the present invention2，Bi3Te4Ultraviolet-visible absorption spectrum (a) of CdTe at 0V (vs RHE) and CoTe2，Bi3Te4Graph (b) for ammonia production of CdTe at 0V (vs. RHE).
FIG. 24 is N adsorbed on catalyst2Charge difference map of (a): sb (a) and Sb2Te3(b)。
FIG. 25 is a DOS plot of a catalyst: sb2Te3General diagrams (a) and Sb2Te3And (b) splitting the graph.
FIG. 26 shows Sb hydrogenated on the surface2Te3N of proceeding2Adsorption (a) and nnh (b) figures.
FIG. 27 shows Sb provided in the examples of the present invention2Te3And (4) calculating adsorbed hydrogen.
FIG. 28 shows Sb provided in the embodiments of the present invention2Te3Calculated plot of nitrogen reduction hydrogenation free energy of-H and Sb.
FIG. 29 shows Sb provided in the example of the present invention2Te3Diatomic site assisted electrocatalysis of NH3The 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 cannot be taken advantage of, 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 electrocatalysis of the nitrogen reduction 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 Sb2Te3The synthesis step is a flow chart, and specifically 4mg of SbCl is adopted3Dissolving 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 Bi3Te4Scheme of synthetic procedure, specifically 0.243g Bi (NO)3)3·5H2O was dissolved in 25mL of deionized water. After stirring for one hour, 0.126g K was added2TeO3And stirring was continued for another 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.
FIG. 4 is CoTe2Scheme of synthetic procedure, specifically 0.15g Co (NO)3)2·6H2O was dissolved in 15mL of deionized water. After stirring for one hour, 0.126g K was added2TeO3And 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)3·5H2O after stirring for one hour, 0.126g K was added2TeO3And 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 at 200 ℃ for 24 hours, taking out the solution, centrifuging, washing with water and ethanol, and drying in vacuum.
FIG. 6 is Sb2Te3XRD patterns of the Compounds
FIG. 7 is Sb2Te3Scanning electron micrographs (a) and transmission electron micrographs (b) of the compounds. Sb obtained as shown in the figure2Te3Is a hexagonal nanosheet.
FIG. 8 shows Bi3Te4XRD pattern (a) and transmission electron micrograph (b) of the compound. Bi as shown in the figure3Te4The 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 CoTe2XRD patterns (a) and (b) of the compoundsTransmission electron micrograph (b). CoTe as shown2The 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 of catalyst, 0.9mL of ethanol and 0.1mL of 5 wt% Nafion was sonicated for more than 30 minutes to form a uniform ink. Then at a catalyst loading of 0.2mg cm-2In the case of (1 cm), 40. mu.L of the prepared ink was dropped onto carbon paper2) 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, 40sccm) 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 hours4 +UV-Vis absorption spectrum of concentration (a). And associated calculated NH4 +Calibration graph (b) of concentration. From this map, the ammonia production amount can be calculated.
FIG. 13 is Sb2Te3Electrocatalytic 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, Sb2Te3And ammonia production of CP compared to (d). As can be seen, plot a shows the i-t curves with different potentials. After electrolysis, NH3The corresponding ultraviolet-visible absorption spectrum (U-vis) of (A) is shown in FIG. b. Discovery of Sb2Te3Exhibits excellent NRR performance at low overpotential, N2Reducing power started at 0.1V (vs. RHE), but NH3The yield is low. And NH3The yield and FE of (1) respectively reach 34.6 mu g h at 0V-1mg-1And 27.7% (v)Rhe) (figure c), superior to many NRR electrocatalysts (table 1). And reaches a maximum at-0.2V. However, as the applied potential increases, FE and NH3The yield of (2) is decreased. FE and NH3This decrease in yield can be attributed to the reacted HER, resulting in lower FE and lower rates for N2Reduction to NH3. As can be seen from FIG. d, Sb2Te3NH of/CP3The yield was greater than CP, indicating NH detected3Derived from Sb2Te3The excellent performance of (2).
FIG. 14 is a series of NH4 +Ion chromatogram (a) of ions and method for calculating NH4Calibration curve (b) for Cl concentration. The ammonia produced can be further accurately detected and calculated.
FIG. 15 shows NH in electrolyte4 +Ion chromatogram of ion (a) and detection of Sb at 0V (vs. RHE) by indophenol blue method and ion chromatography2Te3NH of/CP3Yield chart (b). As can be seen from the figure, NH was detected by ion chromatography at 0V (vs. RHE)3The 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 hours2H4UV-Vis absorption spectrum of concentration (a). And the associated calculation N2H4Calibration graph (b) of concentration. For calculating by-product N2H4Presence 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 produced2H4Generation, identification of Sb2Te3Has 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 detected3The yield is completely from Sb2Te3By catalysis of
FIG. 19 at N2And in Ar atmosphere, Sb2Te3/CPNH at 0V (vs RHE) potential3The yield chart. As is clear from the figure, it was found that no ammonia was produced in the Ar atmosphere, the influence of other contamination sources was removed, and it was confirmed that ammonia produced in the solution originated from nitrogen gas, and further, NH was confirmed3The yield is completely from Sb2Te3Catalytic nitrogen reduction of
FIG. 20 is at-0.2V (vs. RHE)14N2Of electrolytes which electrolyze under saturated conditions1H-NMR spectrum (a) and at-0.2V (vs RHE)15N2Of electrolytes electrolysed under saturated conditions1H-NMR spectrum (b). As can be seen from the figures, the figure,15N2of electrolytes electrolysed under saturated conditions1H-NMR spectrum having two peaks, different from14N2Of electrolytes which electrolyze under saturated conditions1H-NMR spectrum, which proves that the ammonia generated in the solution is derived from nitrogen, further removes other influences, and proves that NH3The yield is completely from Sb2Te3Catalytic nitrogen reduction of
FIG. 21 shows Sb2Te3And 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), Sb2Te3Cyclic ammonia production profile at 0V (vs RHE) (e), Sb2Te350 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 potential2Te3The current density of/CP is higher (FIG. a), indicating that Sb2Te3More 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, NH3The yields and FE are shown in FIGS. b-d, respectively. Sb at 0V (vs RHE) and-0.2V (vs RHE)2Te3NH of/CP3The yield is higher than that of Sb/CP, which means that Sb2Te3Higher NH can be obtained at low overpotential3The yield is higher than that of Sb. As seen in FIG. e, the ammonia yield remained essentially unchanged for 6 cycles, demonstrating that Sb2Te3Has better stabilityAnd (5) performing qualitative determination. In fig. f, it was found that the current density remained substantially unchanged after 50 hours, further demonstrating its higher stability.
FIG. 22 is N2Temperature programmed desorption measurement chart. As shown in the figure, Sb2Te3Has stronger N2Chemical adsorption proves that Te element in telluride can promote N of Sb2And (4) adsorbing.
FIG. 23 is CoTe provided in the embodiments of the present invention2，Bi3Te4RHE ultraviolet and visible absorption spectrum (a) of CdTe at 0V vs. RHE and CoTe2，Bi3Te4Graph (b) for ammonia production of CdTe at 0V vs. RHE. As shown, CoTe, Bi3Te4，CdTe2All have better NH at 0V (relative to RHE)3Indicating that the telluride has catalytic N at low voltage2The potential for development of (1).
FIG. 24 is N adsorbed on catalyst2Charge difference map of (a): sb (a) and Sb2Te3(b) In that respect As can be seen from the figure, it was found that Sb was adsorbed2Te3N of (A) to2E of (A)adsAbout-0.032 eV, much lower than E for Sbads(-0.0084 eV). This is shown in Sb2Te3And N2Stronger covalent interaction is formed between the two, indicating that N is2In the telluride (Sb)2Te3) 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: sb2Te3General diagrams (a) and Sb2Te3And (b) splitting the graph. Comparison of Sb to Sb as shown by the figure2Te3Has a higher charge density at the Fermi level, favoring N2By reduction of
FIG. 26 shows Sb hydrogenated on the surface2Te3N of proceeding2Adsorption (a) and nnh (b) figures. As shown in the figure at Sb2Te3Has two sites on the surface, the site of Sb is used for N2Adsorption of Te atoms to provide H to reduce N2。
FIG. 27 is Sb2Te3And (4) calculating adsorbed hydrogen. Known from the figure，Sb2Te3H on-H desorbs free energy higher, which means Sb2Te3HER is very difficult to generate on-H, and the hydrogen evolution can be effectively inhibited, so that the selectivity is improved.
FIG. 28 is Sb2Te3Calculated plot of nitrogen reduction hydrogenation free energy of-H and Sb. As shown in the figure, Sb2Te3-N on H2Is hydrogenated faster than on Sb. Comparison of Sb2Te3Free energy of formation of upper NNH, H on Te can be easily transferred to N2On the contrary, N is greatly accelerated2In Sb2Te3Hydrogenation on-H and lowering the initiation potential of NRR, which explains NH3High yield and low overpotential.
FIG. 29 is Sb2Te3Diatomic site assisted electrocatalysis of NH3The 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 Sb2To accelerate N2Reducing to form NNH, and continuously hydrogenating to NH3And (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.
Figure BDA0002399575960000121
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 (10)

1. A method of electrocatalytic nitrogen reduction catalyst, comprising: elements Sb, Bi, Co and Cd which have good adsorption effect on nitrogen are selected, and by means of the characteristic that telluride adsorbs hydrogen, telluride is introduced into electro-catalytic nitrogen reduction for the first time, and ammonia is generated under a series of voltages.
2. The method of electrocatalytic nitrogen reduction catalyst as set forth in claim 1, wherein the telluride comprises: sb2Te3、Bi3Te4CoTe and CdTe2。
3. The method of electrocatalytic nitrogen reduction catalyst of claim 2, wherein Sb is2Te3The synthesis method comprises the following steps: with 4mg of SbCl3Dissolving 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 ℃.
4. The method of electrocatalytic nitrogen reduction catalyst of claim 3, wherein Sb is2Te3Is a hexagonal nano-sheet.
5. The method of electrocatalytic nitrogen reduction catalyst of claim 2, wherein Bi3Te4The synthesis method comprises the following steps: 0.243g Bi (NO)3)3·5H2Dissolving O in 25mL of deionized water; after stirring for one hour, 0.126g K was added2TeO3Then 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.
6. The method of electrocatalytic nitrogen reduction catalyst of claim 5, wherein Bi3Te4Is in the shape of nanometer needle.
7. The method of electrocatalytic nitrogen reduction catalyst of claim 2, wherein CoTe2The synthesis method comprises the following steps: 0.15g Co (NO)3)2·6H2Dissolving O in 15mL of deionized water; after stirring for one hour, 0.126g K was added2TeO3Then is continued againStirring 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.
8. The method of electrocatalytic nitrogen reduction catalyst of claim 7, wherein CoTe2Is a spindle-shaped nano rod.
9. The method of electrocatalytic nitrogen reduction catalyst as set forth in claim 2, wherein the CdTe synthesis process comprises: 0.159g Cd (NO)3)3·5H2O after stirring for one hour, 0.126g K was added2TeO3Then 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 vacuum drying;
CdTe is a nanorod.
10. The method of electrocatalytic nitrogen reduction catalyst of claim 1, wherein the Sb synthesis process comprises: placing 20mg of Sb into a mortar, grinding into powder, placing the powder into isopropanol, performing ultrasonic treatment for 8 hours in an argon atmosphere, centrifuging, washing with ethanol for three times, and drying at 60 ℃ overnight;
sb is a nano sheet.
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