CN110560050A - boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and preparation method thereof - Google Patents
boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and preparation method thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 54
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 71
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 34
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 28
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 28
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000005457 ice water Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KPSZQYZCNSCYGG-UHFFFAOYSA-N [B].[B] Chemical compound [B].[B] KPSZQYZCNSCYGG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
a boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia is prepared by the following steps: respectively preparing N, N-Dimethylformamide (DMF) solution and aqueous solution of silver nitrate and sodium borohydride with the concentration of 0.01-1.0M; taking 1.0mL of a DMF (dimethyl formamide) solution of silver nitrate and an aqueous solution of silver nitrate with the concentration of 0.01-1.0M, adding 5.0mL of DMF solution of sodium borohydride and an aqueous solution of sodium borohydride with the concentration of 0.01-1.0M, respectively stirring and reacting for 1.5-2.5 hours in an ice water bath at normal temperature, washing, centrifuging and drying to obtain the boron-doped silver nano sponge catalyst. And provides a preparation method of the boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia. The preparation method is simple in preparation process and short in reaction time, and the prepared material has excellent electrochemical nitrogen reduction performance at low temperature and normal pressure.
Description
Technical Field
The invention relates to a boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and a preparation method thereof, and the catalyst can be used for research on electro-catalytic nitrogen reduction reaction.
background
ammonia (NH)3) Is an important synthetic chemical substance and has wide application in the fields of chemical fertilizers, textiles, medicines and the like. And, NH3Is considered to be a promising carbon-free energy carrier, has high hydrogen content and is convenient to store and transport. At present, the conventional Haber-Bosch process is carried out in NH3In which N is a large proportion2And H2The reaction is carried out on an iron-based or ruthenium-based catalyst under the harsh reaction conditions of 400-600 ℃, 150-350atm and the like. Due to N2Is more than 1% of the annual global energy supply for the production of NH3. At the same time, H required for the reaction2mainly from fossil fuels, which results in large amounts of CO2And (5) discharging. In order to reduce energy consumption and greenhouse gas emissions, there is an urgent need to develop an environmentally friendly, sustainable method for ammonia production to meet the ever-increasing social needs. In recent years, electrocatalytic nitrogen reduction (NRR) has been considered as a desirable alternative to the synthesis of artificial ammonia, which can be driven at ambient temperature and pressure with renewable electrical power.
Currently, the key to NRR is the development of highly efficient electrocatalysts that can break strong N ≡ N triple bonds and suppress competitive Hydrogen Evolution Reactions (HER). Although a great deal of theoretical and experimental research has been conducted in developing noble metal-based NRR electrocatalysts, their low NH content3The yield and the faraday efficiency are far from being applied to the industrial field. Researches show that the catalytic performance of the noble metal-based electrocatalyst is closely related to the morphology and the composition of the noble metal-based electrocatalyst. Porous nanostructures with interconnected nanoscale frameworks and large spaces have attracted extensive research interest, which not only provide large specific surface areas and abundant active sites, promote the activity of the catalyst, but also prevent the aggregation of the catalyst. The addition of another element to the noble metal catalyst can change the activation energy of the intermediate by transfer of the d-band center or by electron strain effects. In recent years, boron doping in carbon materials can redistribute the electron density of boron and carbon due to their different electronegativities, the electron deficient boron site pair N2the binding ability of (c) is enhanced. Based on the idea, the development of a simple and efficient method for synthesizingBoron doped porous noble metal catalyst to enhance electrochemical NH3The production of (1).
Disclosure of Invention
The invention aims to provide a controllable preparation method of a boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and research on an electro-catalytic nitrogen reduction reaction.
The technical scheme adopted by the invention is as follows:
A boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia is prepared by the following steps:
(1) Respectively preparing N, N-dimethylformamide DMF solution and aqueous solution of silver nitrate and sodium borohydride with the concentration of 0.01-1.0M;
(2) taking 1.0mL of a DMF (dimethyl formamide) solution of silver nitrate and an aqueous solution of silver nitrate with the concentration of 0.01-1.0M, adding 5.0mL of DMF solution of sodium borohydride and an aqueous solution of sodium borohydride with the concentration of 0.01-1.0M, respectively stirring and reacting for 1.5-2.5 hours in an ice water bath at normal temperature, washing, centrifuging and drying to obtain the boron-doped silver nano spongy electrochemical synthesis ammonia catalyst.
In the invention, the selection of reaction conditions has important influence on the structure of the catalyst for preparing the boron-doped silver nano spongy electrochemical synthesis ammonia, and DMF is added in the reaction by utilizing the DMF to Na+Has stronger solvation effect, improves BH4-Stability in DMF solution, which facilitates tunable decomposition and deposition of B atoms on Ag surfaces. NaBH4Are reducing agents and dopants. In the preparation process, the morphology and the structure of Ag can be controlled by changing the adding proportion of the precursor.
A preparation method of a boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia comprises the following steps:
(1) Respectively preparing N, N-dimethylformamide DMF solution and aqueous solution of silver nitrate and sodium borohydride with the concentration of 0.01-1.0M;
(2) Taking 1.0mL of a DMF (dimethyl formamide) solution of silver nitrate and an aqueous solution of silver nitrate with the concentration of 0.01-1.0M, adding 5.0mL of DMF solution of sodium borohydride and an aqueous solution of sodium borohydride with the concentration of 0.01-1.0M, respectively stirring and reacting for 1.5-2.5 hours in an ice water bath at normal temperature, washing, centrifuging and drying to obtain the boron-doped silver nano spongy electrochemical synthesis ammonia catalyst.
Further, the concentration and volume of silver nitrate and sodium borohydride and the reaction temperature are controlled to control the morphology and structure of Ag.
Carrying out electrochemical catalytic nitrogen reduction reaction at normal temperature and normal pressure, wherein the specific performance test operation process is as follows:
(1) Weighing about 5mg of catalyst, dispersing the catalyst in ultrapure water, adding 100 mu L of Nafion solution (5 wt%), performing ultrasonic treatment for 30 minutes to obtain uniform dispersion liquid, and coating 10-50 mu L of the dispersion liquid on carbon paper (0.5 multiplied by 0.5 cm)2) Drying at 50 ℃;
(2) the experiment for preparing ammonia by nitrogen reduction was carried out using catalyst-loaded carbon paper as an electrode material. In an H-cell, carbon paper was used as the working electrode, and a saturated Ag/AgCl electrode and a carbon rod were used as the reference electrode and the counter electrode, respectively. Before testing, nitrogen gas is introduced for 30 minutes to saturate the solution with nitrogen gas, test programs of linear sweep cyclic voltammetry and chronoamperometry are selected, and the current condition of the working electrode under different potentials is monitored by a computer. And then testing the concentration of ammonia in the catalyzed electrolyte by an ultraviolet-visible spectrophotometer, and finally calculating the ammonia production rate and the Faraday efficiency of the catalyst.
The boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and the preparation method thereof provided by the invention have the main beneficial effects that:
(1) The preparation method is simple and mild, the product is directly obtained by a one-step method, and the yield of the boron-doped silver nano spongy product is high.
(2) the morphology and structure of silver can be controlled by changing the concentration and volume of the precursor, thus the performance in nitrogen reduction application is different.
(3) the synthesized boron-doped silver nano spongy electrocatalyst shows outstanding activity and stability in the nitrogen reduction reaction, and the Ag nano material has a very high application prospect as the electrocatalyst.
Drawings
fig. 1 is an SEM image of a boron-doped silver nanosponge-like electrochemical synthesis ammonia catalyst according to embodiment 1 of the present invention.
fig. 2 is TEM and HRTEM images of boron-doped silver nanosponges electrochemical synthesis ammonia catalyst according to embodiment 1 of the present invention.
fig. 3 is an XRD chart of the electrochemical synthesis ammonia catalyst in the form of boron-doped silver nanosponges according to embodiment 1 of the present invention.
Fig. 4 is an XPS chart of the electrochemical synthesis ammonia catalyst in the form of boron-doped silver nano sponge according to embodiment 1 of the present invention.
FIG. 5 is a linear cyclic voltammogram of the boron-doped silver nanosponges electrochemical ammonia synthesis catalyst in 0.1M HCl solution according to example 1 of the present invention.
fig. 6 is a diagram of the catalytic performance of the boron-boron doped silver nano sponge-like electrochemical ammonia synthesis catalyst according to embodiment 1 of the present invention.
Fig. 7 is an SEM image of the silver nanosponge-like electrochemical ammonia synthesis catalyst according to embodiment 2 of the present invention.
Fig. 8 is a diagram of the catalytic performance of the silver nanosponge-like electrochemical ammonia synthesis catalyst according to embodiment 2 of the present invention.
Fig. 9 is an SEM image of boron-doped silver nanoparticles according to embodiment 3 of the present invention.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
referring to fig. 1 to 9, in this embodiment, the catalytic performance test of the silver nano sponge-like electrochemical synthesis ammonia catalyst and the boron-doped silver nano sponge-like electrochemical synthesis ammonia catalyst is performed on a CHI 660E electrochemical workstation, and the operation process is as follows:
First, about 5mg of the catalyst was weighed and dispersed in 0.9mL of ultrapure water, then 100. mu.L of Nafion solution (5 wt%) was added, and ultrasonic treatment was performed for 30 minutes to obtain a uniform dispersion, and then 50. mu.L of the dispersion was coated on carbon paper (0.5X 0.5 cm)2) Drying at 50 ℃;
And secondly, taking the carbon paper loaded with the catalyst as an electrode material, and carrying out an experiment for preparing ammonia by nitrogen reduction. Before testing, nitrogen gas is introduced for 30 minutes to saturate the solution with nitrogen gas, test programs of linear sweep cyclic voltammetry and chronoamperometry are selected, and the current condition of the working electrode under different potentials is monitored by a computer. And then testing the concentration of ammonia in the catalyzed electrolyte by an ultraviolet-visible spectrophotometer, and finally calculating the ammonia production rate and the Faraday efficiency of the catalyst.
Example 1
A preparation method of a boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia comprises the following steps:
(1) Preparing DMF solutions of silver nitrate and sodium borohydride with the concentration of 0.1M respectively;
(2) And taking 1.0mL of a 0.1M silver nitrate DMF solution, adding 5.0mL of a 0.1M sodium borohydride DMF solution, stirring and reacting for 1.5 hours under the condition of ice-water bath, washing, centrifuging and drying to obtain the boron-doped silver nano sponge catalyst.
the SEM image of the obtained boron-doped silver nanosponge-like electrochemical synthesis ammonia catalyst is shown in fig. 1. The TEM image of the obtained boron doped silver nanosponge-like electrochemical synthesis ammonia catalyst is seen in fig. 2. The XRD pattern of the obtained boron-doped silver nano sponge-shaped electrochemical synthesis ammonia catalyst is shown in figure 3. The XPS diagram of the obtained boron-doped silver nanosponge-like electrochemical ammonia synthesis catalyst is shown in fig. 4. The linear cyclic voltammogram of the obtained boron-doped silver nano sponge-shaped electrochemical synthesis ammonia catalyst in 0.1M HCl solution is shown in figure 5. The catalytic performance diagram of the obtained boron-doped silver nano sponge-shaped electrochemical synthesis ammonia catalyst is shown in figure 6.
as seen from the SEM image, the yield of the boron-doped silver nano sponge-shaped electrochemical synthesis ammonia catalyst is close to 100%, and the catalyst has a nano-scale framework and a porous nano structure with larger space which are connected with each other. The material successfully incorporated a large number of B atoms by HRTEM, XRD and XPS analysis. According to the performance graph of the boron-doped silver nano spongy electro-chemical synthesis ammonia catalyst for the catalytic nitrogen reduction reaction measured in 0.1M HCl, the boron-doped silver nano spongy electro-catalyst with high nitrogen content and high nitrogen content can be calculatedThe original activity and the ammonia production rate are 26.48 mu g h-1mg-1 cat.The Faraday efficiency was 8.86%.
Example 2
A preparation method of a silver nano sponge-shaped catalyst for electrochemical synthesis of ammonia comprises the following steps:
(1) Preparing aqueous solutions of silver nitrate and sodium borohydride with the concentration of 0.1M respectively;
(2) And taking 1.0mL of 0.1M silver nitrate aqueous solution, adding 5.0mL of 0.1M sodium borohydride aqueous solution, stirring and reacting for 2 hours under the condition of ice-water bath, washing, centrifuging and drying to obtain the silver nano sponge catalyst.
SEM images of the silver nanosponge-like catalyst obtained are shown in fig. 7; the performance diagram of the silver nanosponge catalyst in catalyzing the reduction of nitrogen to produce ammonia is shown in fig. 8.
From the SEM images, silver nanosponges like electrochemical ammonia synthesis catalysts have been formed. The performance chart of preparing ammonia by nitrogen reduction shows that the ammonia production rate of the silver nano sponge-shaped electrochemical synthesis ammonia catalyst is 16.89 mu g h-1mg-1 cat.the Faraday efficiency was 6.31%.
Example 3:
A method for preparing boron-doped silver nanoparticles, the method comprising the steps of:
(1) Preparing DMF solutions of silver nitrate and sodium borohydride with the concentration of 0.5M respectively;
(2) And taking 1.0mL of a 0.5M silver nitrate DMF solution, adding 5.0mL of a 0.5M sodium borohydride DMF solution, stirring and reacting for 2.5 hours under the condition of ice-water bath, washing, centrifuging and drying to obtain the boron-doped silver nanoparticle catalyst.
An SEM image of the boron doped silver nanoparticles obtained is shown in fig. 9.
From the SEM images, it can be seen that boron-doped silver nanoparticles have been formed. This is mainly due to the change in the concentration of the precursor resulting in a change in the morphology of the boron doped silver.
Example 4
a preparation method of a boron-doped silver bulk nanoparticle catalyst for electrochemical synthesis of ammonia comprises the following steps:
(1) Preparing DMF solutions of silver nitrate and sodium borohydride with the concentration of 0.01M respectively;
(2) And taking 1.0mL of a 0.01M silver nitrate DMF solution, adding 5.0mL of a 0.01M sodium borohydride DMF solution, stirring and reacting for 1.5 hours under the condition of ice-water bath, washing, centrifuging and drying to obtain the boron-doped silver nano sponge catalyst.
The obtained boron-doped silver bulk nanoparticle catalyst has lower precursor concentration and short reaction time, slows down the reduction rate, obtains larger bulk nanoparticles, and has lower electrocatalytic nitrogen reduction activity and Faraday efficiency
example 5
a preparation method of a random boron-doped silver nanoparticle catalyst for electrochemically synthesizing ammonia comprises the following steps:
(1) Preparing DMF solutions of silver nitrate and sodium borohydride with the concentration of 1.0M respectively;
(2) And taking 1.0mL of 1.0M silver nitrate DMF solution, then adding 5.0mL of 1.0M sodium borohydride DMF solution, stirring and reacting for 1.5 hours under the condition of ice-water bath, washing, centrifuging and drying to obtain the boron-doped silver nano sponge catalyst.
The irregular boron-doped silver nanoparticle catalyst is obtained, and because the concentration of the precursor is too high and the reaction speed is too high, the irregular nanoparticles with smaller particle size are obtained, and the performance of electrochemically synthesizing ammonia is poorer.
Claims (3)
1. The electrochemical synthesis ammonia catalyst is characterized by being prepared by the following steps:
(1) Respectively preparing N, N-dimethylformamide DMF solution and aqueous solution of silver nitrate and sodium borohydride with the concentration of 0.01-1.0M;
(2) Taking 1.0mL of a DMF (dimethyl formamide) solution of silver nitrate and an aqueous solution of silver nitrate with the concentration of 0.01-1.0M, adding 5.0mL of DMF solution of sodium borohydride and an aqueous solution of sodium borohydride with the concentration of 0.01-1.0M, respectively stirring and reacting for 1.5-2.5 hours in an ice water bath at normal temperature, washing, centrifuging and drying to obtain the boron-doped silver nano spongy electrochemical synthesis ammonia catalyst.
2. The method for preparing the boron-doped silver nanosponge-like electrochemical synthesis ammonia catalyst according to claim 1, characterized in that the method comprises the following steps:
(1) respectively preparing N, N-dimethylformamide DMF solution and aqueous solution of silver nitrate and sodium borohydride with the concentration of 0.01-1.0M;
(2) taking 1.0mL of a DMF (dimethyl formamide) solution of silver nitrate and an aqueous solution of silver nitrate with the concentration of 0.01-1.0M, adding 5.0mL of DMF solution of sodium borohydride and an aqueous solution of sodium borohydride with the concentration of 0.01-1.0M, respectively stirring and reacting for 1.5-2.5 hours in an ice water bath at normal temperature, washing, centrifuging and drying to obtain the boron-doped silver nano spongy electrochemical synthesis ammonia catalyst.
3. the method of claim 2, wherein the reaction temperature, the concentration and volume of sodium borohydride and silver nitrate are controlled to control the morphology and structure of Ag and boron doped Ag.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957323A (en) * | 2020-08-21 | 2020-11-20 | 中国地质大学（武汉） | Boron-doped core-shell structure catalyst and preparation method and application thereof |
| CN112981451A (en) * | 2021-02-07 | 2021-06-18 | 安徽农业大学 | Preparation method of catalytic electrode for preparing ammonia by electrochemical reduction of nitrate or nitrite |
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