CN113862717B - Rose-type catalyst VS 2 @Bi 2 O 3 Preparation method of/CC and application thereof in nitrogen reduction - Google Patents
Rose-type catalyst VS 2 @Bi 2 O 3 Preparation method of/CC and application thereof in nitrogen reduction Download PDFInfo
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Abstract
Nitrogen is the most abundant gas in the atmosphere. The nitrogen-containing compound is widely applied to the fields of agriculture, medicine, chemical industry and the like, and the demand is high. Ammonia gas is a basic gas that plays an essential role in the synthesis of such compounds. Therefore, nitrogen synthesis ammonia is a major concern in the development of the world today. At present, the industrially synthesized ammonia mainly uses a habeboshi method, but the reaction conditions are harsh, the environment is polluted, and the environment is not in line with the current green sustainable development concept. Because heavy metal catalysts are expensive, catalysts for the production of non-noble metals are used for the electrocatalytic decomposition of N 2 The research on the realization of ammonia production by nitrogen reduction by saturated electrolyte is paid attention to, and the research has been the biggest heat in the energy field in recent years. The invention provides a method for hydrothermally synthesizing rose-shaped VS on carbon cloth 2 Electrodepositing Bi by an electrodeposition method 2 O 3 Is prepared through the steps of preparing and applying the electrocatalytic nitrogen reduction.
Description
Technical Field
The invention relates to the field of preparation and application of non-noble metal nano materials, in particular to a hydrothermal method-based preparation method of VS 2 Electrodepositing Bi on its surface after/CC 2 O 3 Is used in the field of electrocatalytic nitrogen reduction.
Background
Ammonia has gained widespread attention as an important chemical raw material for producing pesticides, explosives, dyes, fertilizers. And is a highly efficient energy carrier. With the continuous improvement of productivity level, the energy problem is also restricting the development of human society. Nitrogen, the most abundant gas in the atmosphere, is difficult to use due to its chemical inertness. Currently, the Haber-Bosch process is used industrially as a main means for producing ammonia. The habeboshi process synthesizes ammonia with nitrogen and hydrogen under the action of high temperature and high pressure iron-based catalyst. However, the Haber-Bosch process for producing ammonia has the disadvantages of high energy consumption, huge scale, severe reaction conditions and large amount of carbon dioxide greenhouse gases produced annually. Scientific researchers are constantly researching artificial nitrogen fixation, such as biological nitrogen fixation, photocatalytic nitrogen fixation, electrocatalytic nitrogen fixation and the like. The ability to fix reduction of nitrogen to ammonia under mild conditions is the focus of research today.
The preparation of ammonia by electrocatalytic reduction of nitrogen is remarkable in a plurality of ammonia preparation methods due to the advantages of mild reaction conditions (normal temperature and normal pressure), safe and easily controlled reaction and the like. But it also faces a great challenge-high efficiency catalysts. It is therefore imperative to explore the synthesis of suitable electrocatalysts to increase the rate and yield of electrocatalytic ammonia production. Since noble metal catalysts are expensive and unfavorable for mass use, researchers have begun to explore transition metal catalysts. A large number of documents report that transition metals are hopeful to become ideal catalysts for preparing ammonia by electrocatalytic nitrogen reduction due to the advantages of abundant content, low cost, no toxicity, easy control and the like. However, in the process of electrocatalytic nitrogen reduction to synthesize ammonia, competitive Hydrogen Evolution Reaction (HER) is extremely easy to occur, and nitrogen reduction is inhibited, so that reduction of competition of low hydrogen evolution reaction by various regulation means becomes an important link of electrocatalytic nitrogen reduction research. The bimetallic compound can effectively improve the property of electrocatalytic nitrogen reduction and effectively reduce the competition reaction interference due to the property difference and the combined action between two metals.
Nanomaterial imparts many novel properties to the material due to its unique size, and exhibits excellent activity for application in the field of electrocatalysis. Application of transition metal compounds in electrocatalytic nitrogen reduction has been describedCertain breakthrough is achieved, and the high activity of electrocatalytic nitrogen reduction is considered, so that the nitrogen reduction catalytic activity of the material can be greatly improved after Bi atoms are introduced. A great deal of literature describes that deposition onto the surface of catalytic materials by electrodeposition greatly increases the activity of the catalyst. In view of this, the present invention provides a method for synthesizing VS on carbon cloth by hydrothermal method 2 Post electrodeposition deposition of Bi 2 O 3 Is a high efficiency electrocatalytic nitrogen reduction catalyst.
Disclosure of Invention
One of the objects of the present invention is a VS 2 @Bi 2 O 3 Novel preparation method of CC nanosheets.
The second purpose of the invention is to apply the synthesized nano-sheet array catalyst to an electrocatalytic nitrogen reduction system.
The technical scheme of the invention is as follows:
1. nanosheet catalyst VS 2 @Bi 2 O 3 The preparation of/CC is to prepare 0-5 g sodium orthovanadate Na 3 VO 4 And 0 to 10 g thioacetamide CH 3 CSNH 2 Adding into 40mL water, stirring thoroughly, and adding carbon cloth; transferring the solution and the carbon cloth into a polytetrafluoroethylene lining reaction kettle, reacting at 120-200 ℃ for 10-30 h, cooling to room temperature after the reaction is finished, washing the obtained product for 3-5 times to obtain the vanadium disulfide nanosheets VS grown on the carbon cloth 2 Dissolving 0-5-g bismuth chloride in 20-40 mL of ethylene glycol to obtain electroplating solution, and electrodepositing bismuth oxide Bi by using a chronopotentiometric method 2 O 3 Obtaining a nano flower-shaped vanadium disulfide hybridized bismuth oxide nano sheet array VS composed of nano sheets 2 @Bi 2 O 3 and/CC, exposing the catalytically active sites, facilitating the subsequent electrocatalytic process,
2.VS 2 @Bi 2 O 3 the performance of the CC nano-sheet, the ammonia yield of the electrocatalytic nitrogen reduction reaction reaches 24.3X10 -10 mol s -1 cm -2 The Faraday efficiency is as high as 11.5%, and the ammonia yield and Faraday efficiency are more excellent.
Description of the preferred embodiments
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, which are provided to further illustrate the features and advantages of the invention, and not to limit the claims of the invention.
Example 1
The first step: a laboratory 50-mL high-temperature hydrothermal reaction kettle is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene lining. 40mL deionized water is added into a 50mL polytetrafluoroethylene liner, sodium orthovanadate (0.1839 g,1 mmol) and thioacetamide (0.1503 g,2 mmol) are added and stirred for 60min to form a clear and transparent solution, and then a piece of carbon cloth with the thickness of 2 multiplied by 4cm is added. After sealing the hydrothermal autoclave, it was placed in an oven at 180 ℃ for heat preservation 24 h. Naturally cooling, washing with deionized water and absolute ethanol, and vacuum drying to obtain VS 2 CC precursor.
And a second step of: 0.3000. 0.3000 g anhydrous bismuth chloride is weighed into a 100mL beaker, 25mL deionized water is weighed into the beaker, and 20mL of the mixture is added into an electrolytic cell after the mixture is fully stirred for 60 min. Taking 1X 1cm VS 2 a/CC precursor, clamping the precursor by a platinum electrode clamp as a working electrode, a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, setting constant current to 0.001A by adopting a chronopotentiometry, washing with deionized water and absolute ethyl alcohol for several times after scanning time is 300 s, and drying to obtain nano sheet-shaped VS 2 @Bi 2 O 3 /CC。
And a third step of: at VS 2 @Bi 2 O 3 and/CC is a working electrode, and the sample is activated by performing cyclic voltammetry in a three-electrode system. The cyclic voltammetry test voltage interval is-1.0-0V, the highest potential is 0V, the lowest potential is-1.0V, the starting potential is-1.0V, and the ending potential is 0V. The scanning rate was 0.05V/s. The sampling interval was 0.001 and V, the rest time was 2 and s, and the number of scan segments was 500.
Fourth step: after cyclic voltammetry testing, with VS 2 @Bi 2 O 3 And (2) CC is a working electrode, and linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is-1.0-0V. Initial potential of-1.0V, endThe potential was 0V. The scanning rate was 5 mV/s. The sampling interval is 0.001 and V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30min, and a first linear voltage scanning test is performed after the argon is saturated. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
Fifth step: at VS 2 @Bi 2 O 3 and/CC is a working electrode, and the catalyst is subjected to a long-time nitrogen reduction test, wherein the potentials are respectively set to 0.00V, -0.10V, -0.20V, -0.30V, -0.40V and the running time is 7200 s.
Fourth step: ammonia production test
1. Drawing a working curve: with NH 4 Cl is a standard reagent, and standard solutions of 0.0, 0.1, 0.2, 0.3 and 0.4,0.5,0.6,0.7,0.8,0.9,1.0 mug/mL are respectively prepared in 0.1 mol/L sodium sulfate solution and subjected to chromogenic reaction to test absorbance. Standard solution 4 is taken and mL is added with 0.75 mol/L oxidant solution 50 multiplied by 10 -3 mL (containing 75 wt% NaOH and 75 wt% NaClO), followed by 0.05 mol/L colorant solution 0.5 mL (containing 40 wt% sodium salicylate and 32 wt% NaOH), and finally 5 wt% catalyst Na 2 [Fe(NO)(CN) 5 ] ·2H 2 O solution 50X 10 -3 And (3) mL. And standing at room temperature for developing 1 h, performing spectral scanning by using an ultraviolet-visible spectrophotometer within the wavelength range of 550 nm-800 nm, and recording the absorbance value at 655 nm and plotting the concentration to obtain a standard curve.
2. Ammonia production test: respectively taking electrolyte 4 mL after 2 h operation under each potential, adding 0.75 mol/L oxidant solution 50×10 -3 mL (containing 75 wt% NaOH and 75 wt% NaClO), followed by 0.05 mol/L colorant solution 0.5 mL (containing 40 wt% sodium salicylate and 32 wt% NaOH), and finally 5 wt% catalyst Na 2 [Fe(NO)(CN) 5 ] ·2H 2 O solution 50X 10 -3 And (3) mL. And standing at room temperature for developing 1 h, performing spectral scanning in 550 nm-800 nm by using ultraviolet spectrum, and recording absorbance values at 655 nm to finally obtain the concentration of ammonia. After data processing and calculation, VS 2 @Bi 2 O 3 Excellent effect of CC applied to NRR, -ammonia yield of 22.3X10 under 0.10V (relative to standard hydrogen electrode) -10 mol s -1 cm -2 . The faraday efficiency is as high as 11.0%.
Example 2
The first step: a 50mL high-temperature hydrothermal reaction kettle for a laboratory is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene liner. 40mL deionized water was added to a 50mL polytetrafluoroethylene liner, sodium vanadate (0.2065 g,1 mmol) was added to the liner, and the mixture was stirred for 60 minutes to form a clear and transparent solution, followed by a 2X 4cm piece of carbon cloth. After sealing the hydrothermal autoclave, it was placed in an oven at 180 ℃ for heat preservation 24 h. Naturally cooling, washing with deionized water and absolute ethanol, and vacuum drying to obtain VS 2 CC precursor.
And a second step of: weighing 0.3000 and g anhydrous bismuth chloride and a 100mL beaker, weighing 50mL of deionized water, adding the deionized water into the beaker, adding the magneton, fully stirring for 30min, and then weighing 20mL of the mixture into an electrolytic cell. Taking 1X 1cm VS 2 a/CC precursor, clamping the precursor by a platinum electrode clamp as a working electrode, a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, setting constant current to 0.001A by adopting a chronopotentiometry, washing with deionized water and absolute ethyl alcohol for several times after scanning time is 300 s, and drying to obtain nano sheet-shaped VS 2 @Bi 2 O 3 /CC。
And a third step of: at VS 2 @Bi 2 O 3 and/CC is a working electrode, and the sample is activated by performing cyclic voltammetry in a three-electrode system. The cyclic voltammetry test voltage interval is-1.0-0V, the highest potential is 0V, the lowest potential is-1.0V, the starting potential is-1.0V, and the ending potential is 0V. The scanning rate was 0.05V/s. The sampling interval was 0.001 and V, the rest time was 2 and s, and the number of scan segments was 500.
Fourth step: after cyclic voltammetry testing, with VS 2 @Bi 2 O 3 And (2) CC is a working electrode, and linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is 0 to-1.0V. The initial potential was-1.0V and the final potential was 0V. The scanning rate was 5 mV/s. Sampling interval is 0.001V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30min, and a first linear voltage scanning test is performed after the argon is saturated. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
Fifth step: at VS 2 @Bi 2 O 3 and/CC is a working electrode, and the catalyst is subjected to a long-time nitrogen reduction test, wherein the potentials are respectively set to 0.00V, -0.10V, -0.20V, -0.30V, -0.40V and the running time is 7200 s.
Fourth step: ammonia production test
1. Drawing a working curve: with NH 4 Cl is a standard reagent, and standard solutions of 0.0, 0.1, 0.2, 0.3 and 0.4,0.5,0.6,0.7,0.8,0.9,1.0 mug/mL are respectively prepared in 0.1 mol/L sodium sulfate solution and subjected to chromogenic reaction to test absorbance. Standard solution 4 is taken and mL is added with 0.75 mol/L oxidant solution 50 multiplied by 10 -3 mL (containing 75 wt% NaOH and 75 wt% NaClO), followed by 0.05 mol/L colorant solution 0.5 mL (containing 40 wt% sodium salicylate and 32 wt% NaOH), and finally 5 wt% catalyst Na 2 [Fe(NO)(CN) 5 ] ·2H 2 O solution 50X 10 -3 And (3) mL. And standing at room temperature for developing 1 h, performing spectral scanning by using an ultraviolet-visible spectrophotometer within the wavelength range of 550 nm-800 nm, and recording the absorbance value at 655 nm and plotting the concentration to obtain a standard curve.
2. Ammonia production test: respectively taking electrolyte 4 mL after 2 h operation under each potential, adding 0.75 mol/L oxidant solution 50×10 -3 mL (containing 75 wt% NaOH and 75 wt% NaClO), followed by 0.05 mol/L colorant solution 0.5 mL (containing 40 wt% sodium salicylate and 32 wt% NaOH), and finally 5 wt% catalyst Na 2 [Fe(NO)(CN) 5 ] ·2H 2 O solution 50X 10 -3 And (3) mL. And standing at room temperature for developing 1 h, performing spectral scanning in 550 nm-800 nm by using ultraviolet spectrum, and recording absorbance values at 655 nm to finally obtain the concentration of ammonia. After data processing and calculation, VS 2 @Bi 2 O 3 Excellent effect of CC applied to NRR, -0.10V (relative StandardHydrogen electrode) the ammonia yield reaches 24.3X10 -10 mol s -1 cm -2 The Faraday efficiency is as high as 11.5%.
Example 3
The first step: a 50mL high-temperature hydrothermal reaction kettle for a laboratory is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene liner. 40mL deionized water is added into a 50mL polytetrafluoroethylene liner, sodium molybdate (0.1760 g,1 mmol) thiourea (0.503 g,2 mmol) is added, and after stirring for 60min to form a clear and transparent solution, a piece of carbon cloth with the length of 2X 4cm is placed. After sealing the hydrothermal autoclave, it was placed in an oven at 180 ℃ for heat preservation 24 h. Naturally cooling, washing with deionized water and absolute ethanol, and vacuum drying to obtain VS 2 CC precursor.
And a second step of: weighing 0.3000 and g anhydrous bismuth chloride and a 100mL beaker, weighing 25mL of deionized water, adding the deionized water into the beaker, adding the magneton, fully stirring for 30min, and then weighing 20mL of the mixture into an electrolytic cell. Taking 1X 1cm VS 2 a/CC precursor, clamping the precursor by a platinum electrode clamp as a working electrode, a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, setting constant current to 0.001A by adopting a chronopotentiometry, washing with deionized water and absolute ethyl alcohol for several times after scanning time is 300 s, and drying to obtain nano sheet-shaped VS 2 @Bi 2 O 3 /CC。
And a third step of: at VS 2 @Bi 2 O 3 and/CC is a working electrode, and the sample is activated by performing cyclic voltammetry in a three-electrode system. The cyclic voltammetry test voltage interval is-1.0-0V, the highest potential is 0V, the lowest potential is-1.0V, the starting potential is-1.0V, and the ending potential is 0V. The scanning rate was 0.05V/s. The sampling interval was 0.001 and V, the rest time was 2 and s, and the number of scan segments was 500.
Fourth step: after cyclic voltammetry testing, with VS 2 @Bi 2 O 3 And (2) CC is a working electrode, and linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is 0 to-1.0V. The initial potential was-1.0V and the final potential was 0V. The scanning rate was 5 mV/s. The sampling interval is 0.001 and V. The standing time was 2 s. Firstly, introducing argon into the electrolyte for 30min until the electrolyte is saturated with the argonAnd then performing a first linear voltage sweep test. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
Fifth step: at VS 2 @Bi 2 O 3 and/CC is a working electrode, and the catalyst is subjected to a long-time nitrogen reduction test, wherein the potentials are respectively set to 0.00V, -0.10V, -0.20V, -0.30V, -0.40V and the running time is 7200 s.
Fourth step: ammonia production test
1. Drawing a working curve: with NH 4 Cl is a standard reagent, and standard solutions of 0.0, 0.1, 0.2, 0.3 and 0.4,0.5,0.6,0.7,0.8,0.9,1.0 mug/mL are respectively prepared in 0.1 mol/L sodium sulfate solution and subjected to chromogenic reaction to test absorbance. Standard solution 4 is taken and mL is added with 0.75 mol/L oxidant solution 50 multiplied by 10 -3 mL (containing 75 wt% NaOH and 75 wt% NaClO), followed by 0.05 mol/L colorant solution 0.5 mL (containing 40 wt% sodium salicylate and 32 wt% NaOH), and finally 5 wt% catalyst Na 2 [Fe(NO)(CN) 5 ] ·2H 2 O solution 50X 10 -3 And (3) mL. And standing at room temperature for developing 1 h, performing spectral scanning by using an ultraviolet-visible spectrophotometer within the wavelength range of 550 nm-800 nm, and recording the absorbance value at 655 nm and plotting the concentration to obtain a standard curve.
2. Ammonia production test: respectively taking electrolyte 4 mL after 2 h operation under each potential, adding 0.75 mol/L oxidant solution 50×10 -3 mL (containing 75 wt% NaOH and 75 wt% NaClO), followed by 0.05 mol/L colorant solution 0.5 mL (containing 40 wt% sodium salicylate and 32 wt% NaOH), and finally 5 wt% catalyst Na 2 [Fe(NO)(CN) 5 ] ·2H 2 O solution 50X 10 -3 And (3) mL. And standing at room temperature for developing 1 h, performing spectral scanning in 550 nm-800 nm by using ultraviolet spectrum, and recording absorbance values at 655 nm to finally obtain the concentration of ammonia. After data processing and calculation, VS 2 @Bi 2 O 3 Excellent effect of CC applied to NRR, -ammonia yield of 24.3X10 under 0.10V (relative to standard hydrogen electrode) -10 mol s -1 cm -2 . The Faraday efficiency is as high as 10.2%.
Claims (2)
1. Catalyst VS 2 @Bi 2 O 3 Use of/CC in electrocatalytic nitrogen reduction for ammonia synthesis, characterized in that said catalyst VS 2 @Bi 2 O 3 Preparation of/CC comprising the steps of:
(1) 0.1839 g to 5 g sodium orthovanadate Na 3 VO 4 And 0.1503 g to 10 g thioacetamide CH 3 CSNH 2 Adding into 40mL water, stirring thoroughly, and adding pretreated carbon cloth;
(2) Transferring the solution and the carbon cloth into a polytetrafluoroethylene lining reaction kettle, reacting at 120-200 ℃ for 10-30 h, cooling to room temperature after the reaction is finished, washing the obtained product for 3-5 times to obtain the vanadium disulfide nanosheets VS grown on the carbon cloth 2 /CC；
(3) The obtained VS 2 placing/CC in a plating tank, wherein the plating solution adopts anhydrous bismuth chloride solution, dissolving the anhydrous bismuth chloride in water to prepare 0.1-2.0 mol/L anhydrous bismuth chloride solution, and electrodepositing bismuth oxide Bi by adopting a chronopotentiometric method 2 O 3 Setting constant current to be 0.001-1.0A and scanning time to be 300 s to obtain a nano flower-shaped vanadium disulfide hybridized bismuth oxide nano sheet array VS consisting of nano sheets 2 @Bi 2 O 3 /CC。
2. Catalyst VS according to claim 1 2 @Bi 2 O 3 Use of/CC in electrocatalytic nitrogen reduction of ammonia synthesis, said electrocatalytic nitrogen reduction of ammonia synthesis comprising the steps of: the electrocatalytic nitrogen reduction process adopts a three-electrode system, and is tested by an electrochemical workstation, wherein the electrolytic tank used for the test is an H-type electrolytic tank, and VS is adopted 2 @Bi 2 O 3 and/CC is a working electrode, a carbon rod is a counter electrode, an Ag/AgCl electrode is a reference electrode, and 0.1-1.0 mol/L sodium sulfate solution is used as electrolyte.
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| A Flower-like Bismuth Oxide as an Efficient, Durable and Selective Electrocatalyst for Artificial N2 Fixation in Ambient Condition;Bing Chang 等;《CHEMCATCHEM》;第 11 卷;第1884-1888 页 * |
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