CN110368970B - Preparation method of activated carbon loaded tungsten carbide nano composite powder used as electrocatalyst - Google Patents
Preparation method of activated carbon loaded tungsten carbide nano composite powder used as electrocatalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000011858 nanopowder Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229920000404 heteropolyacid polymer Polymers 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B01J35/33—
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Abstract
The invention discloses a preparation method of activated carbon loaded tungsten carbide nano composite powder used as an electrocatalyst, which comprises the steps of firstly synthesizing activated carbon loaded purple tungsten precursor powder by adopting a liquid phase method, and then carbonizing the precursor in a mixed atmosphere of methane and hydrogen to obtain the activated carbon loaded tungsten carbide nano composite powder. The nano composite powder has high loading efficiency and large loading capacity, realizes the uniform distribution of tungsten carbide in the active carbon pore canal, and can inhibit the growth of tungsten carbide crystal grains; the porous structure of the active carbon improves the specific surface area, the transmission capability and the stability of the composite powder, and the nano composite powder has higher catalytic performance of Oxygen Reduction Reaction (ORR) and long-term stability.
Description
Technical Field
The invention belongs to the field of nano composite materials, and particularly relates to a preparation method of activated carbon loaded tungsten carbide nano composite powder used as an electrocatalyst.
Background
Since the discovery of the catalytic activity of platinum-like tungsten carbide in the fifties of the last century, tungsten carbide has become a key point of academic research as a potential substitute for noble metal catalysts. However, in view of the current research results, the catalytic activity of tungsten carbide is still far from the same as that of noble metals such as platinum. One of the main factors restricting the catalytic activity of tungsten carbide is that the specific surface area of tungsten carbide is very small and agglomeration is very easy to occur in the preparation process. Some researchers have attempted to improve the catalytic activity of tungsten carbide by using tungsten carbide as a carrier, which is loaded with a small amount of noble metal on the surface thereof. Based on the theory of matrix-catalytic material, another part of researchers propose that a material with high surface area is used as a matrix, and tungsten carbide is loaded on the matrix to form a composite material.
The activated carbon has rich pore structure, larger surface area and good chemical inertness and conductivity, if the activated carbon is used as a carrier, the catalytic activity and stability of the composite material can be improved, and the electrocatalytic activity of WC/C p-nitrophenol is reported in documents to be superior to that of tungsten carbide and activated carbon. Therefore, the development of a novel activated carbon-supported tungsten carbide nano powder used as an electrocatalyst has important practical value.
In recent years, researchers at home and abroad carry out a great deal of research on the preparation of the activated carbon loaded tungsten carbide nano powder and obtain a plurality of results. For example:
ma Chun et al (journal of chemical industry, 2010,61(05):1313-1318.) put activated carbon treated with nitric acid and ammonium metatungstate solution with a certain mass fraction into a tubular furnace filled with methane and hydrogen after ultrasonic dispersion, impregnation and vacuum drying, raise the temperature to 800 ℃, and preserve heat for 8 hours to obtain WC/C nano powder. The method is simple and feasible, but has long production time, and the obtained product has a small amount of W besides WC2C, purity is insufficient.
Chinese patent CN 105562119 a discloses a method for preparing graphene oxide supported molybdenum carbide or tungsten carbide catalyst. The method adopts heteropoly acid containing molybdenum or tungsten, a polymer conductor and graphene as raw materials, and synthesizes the heteropoly acid-polymer conductor/reduced graphene oxide composite material by a one-pot method. And then carrying out heat treatment on the obtained composite material at 700 ℃ in a nitrogen atmosphere for 2-5 hours, cooling, and carrying out acid washing to obtain the reduced graphene loaded tungsten carbide or molybdenum carbide electrocatalyst. The graphene oxide loaded tungsten carbide prepared by the method has good catalytic performance, but the preparation time is long and the cost is high.
In conclusion, a simple, efficient and low-cost preparation process of the activated carbon-loaded tungsten carbide nano composite powder is in urgent need of development.
Disclosure of Invention
The invention aims to provide a preparation method of activated carbon loaded tungsten carbide nano composite powder used as an electrocatalyst, and aims to obtain the activated carbon loaded tungsten carbide nano composite powder with large specific surface area and good catalytic performance by a simple and efficient method.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention discloses a preparation method of activated carbon loaded tungsten carbide nano composite powder used as an electrocatalyst, which is characterized by comprising the following steps:
(1) ball-milling and screening the activated carbon, and then putting the activated carbon in nitric acid for activation to obtain activated carbon;
(2) ammonium metatungstate (NH)4)6H2W12O40Ammonium nitrate NH4NO3Adding the ethylenediamine tetraacetic acid, the auxiliary agent and the activated carbon into deionized water, and magnetically stirring uniformly at normal temperature to obtain a mixed solution;
(3) placing the mixed solution in a muffle furnace, heating to 200 ℃, and heating at constant temperature for 2-4 h to obtain an activated carbon-loaded purple tungsten precursor;
(4) and putting the precursor into a tubular furnace, and carbonizing the precursor in the mixed atmosphere of methane and hydrogen to obtain the activated carbon loaded tungsten carbide nano composite powder serving as the electrocatalyst.
Further, in the step (1), the screening is performed by using a screen of 200-400 meshes.
Further, in the step (1), the activation is to place the screened activated carbon in nitric acid with the concentration of 0.5-1.5 mol/L, keep the temperature and activate for 2-6 h under the condition of oil bath at the temperature of 75-95 ℃, filter after cooling, wash to be neutral, and dry to obtain the activated carbon.
Further, in the step (2), the adjuvant is at least one of glycine, citric acid, urea and thiourea.
Further, in the step (2), the mass ratio of ammonium metatungstate to activated carbon is 1-20: 1, the molar ratio of ammonium nitrate to ammonium metatungstate is 12-36: 1, the molar ratio of ethylenediaminetetraacetic acid to ammonium metatungstate is 0.5-1: 1, and the molar ratio of adjuvant to ammonium metatungstate is 5-15: 1.
Further, in the step (2), the stirring time is 6-16 h.
Further, in the step (4), the carbonization temperature is 700-1000 ℃, the carbonization time is 2-4 h, and the gas flow is 50-200 mL/min.
Further, the volume ratio of methane to hydrogen in the mixed atmosphere in the step (4) is 20%: 80 percent.
Compared with the prior art, the invention has the beneficial effects that:
1. the method takes the tungstate and the activated carbon as raw materials, and has the characteristics of short flow and low cost.
2. The invention adopts an impregnation method and a solution combustion synthesis method to prepare the precursor powder of the activated carbon-loaded purple tungsten, and has high loading efficiency and large loading capacity.
3. The active carbon is added in the preparation process of the precursor, and the porous structure of the active carbon is beneficial to the entering of reaction solution, so that the reaction is fully carried out in the pore canal, the growth of the purple tungsten is limited, and the growth of tungsten carbide grains is limited in the carbonization process.
4. According to the invention, the activated carbon is adopted to load the tungsten carbide, so that the tungsten carbide is uniformly dispersed on the activated carbon carrier, the activated carbon has a high specific surface area, and forms a synergistic effect with the tungsten carbide, the electronic conduction capability of the composite powder is improved, the transmission and migration of reactants and intermediate products are facilitated, and the stability of the tungsten carbide powder is improved. The prepared activated carbon loaded tungsten carbide composite powder has good conductivity, catalytic activity and long-term stability.
Drawings
FIG. 1 is a scanning electron micrograph of the precursor powder obtained in example 1;
FIG. 2 is a scanning electron micrograph of the activated carbon-supported tungsten carbide nanocomposite powder obtained in example 1;
fig. 3 is a TEM spectrum of the activated carbon-supported tungsten carbide nanocomposite powder obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Ball milling the active carbon, and sieving with a 200-mesh sieve; and (3) placing the screened active carbon into nitric acid with the concentration of 1mol/L, preserving heat and activating for 4 hours under the condition of an oil bath at 85 ℃, cooling, filtering, washing to be neutral, and drying for 5 hours at 120 ℃ to obtain the activated active carbon.
(2) Weighing ammonium metatungstate ((NH) according to a reaction stoichiometric ratio4)6H2W12O40)0.01mol, activated active carbon 12g and ammonium Nitrate (NH)4NO3)0.24mol, 0.0072mol of ethylenediamine tetraacetic acid and 0.072mol of glycine; dissolving the raw material powder in 50mL of deionized water, and magnetically stirring for 8 hours at normal temperature to obtain a mixed solution;
(3) heating the mixed solution in a muffle furnace at the constant temperature of 200 ℃ for 3h to obtain porous nano needle-shaped active carbon-loaded purple tungsten precursor powder;
(4) and putting the precursor powder into a tubular furnace, and carbonizing at 850 ℃ for 4h under the mixed atmosphere of methane and hydrogen (the flow of the gas is 150mL/min) to obtain the activated carbon loaded tungsten carbide nano composite powder serving as the electrocatalyst.
The characterization shows that the particle size of the tungsten carbide in the activated carbon loaded tungsten carbide nano composite powder obtained in the embodiment is 20-100 nm and is 0.1 mol.L-1The initial potential of oxygen reduction in the potassium hydroxide solution is 970mV, and the catalyst has better catalytic performance.
Example 2
(1) Ball milling the active carbon, and sieving with a 250-mesh sieve; and (3) placing the screened activated carbon in nitric acid with the concentration of 1mol/L, preserving heat and activating for 4 hours under the condition of an oil bath at 85 ℃, cooling, filtering, washing to be neutral, and drying for 5 hours at 120 ℃ to obtain the activated carbon.
(2) Weighing ammonium metatungstate ((NH) according to a reaction stoichiometric ratio4)6H2W12O40)0.01mol, activated active carbon 4g and ammonium Nitrate (NH)4NO3)0.24mol, 0.0072mol of ethylenediamine tetraacetic acid and 0.072mol of glycine; dissolving the raw material powder in 50mL of deionized water, and magnetically stirring for 8 hours at normal temperature to obtain a mixed solution;
(3) heating the mixed solution in a muffle furnace at the constant temperature of 200 ℃ for 3h to obtain porous nano needle-shaped active carbon-loaded purple tungsten precursor powder;
(4) and putting the precursor powder into a tubular furnace, and carbonizing at 800 ℃ for 4h under the mixed atmosphere of methane and hydrogen (the flow of the gas is 150mL/min) to obtain the activated carbon-supported tungsten carbide nano composite powder serving as the electrocatalyst.
The characterization shows that the particle size of the tungsten carbide in the activated carbon loaded tungsten carbide nano composite powder obtained in the embodiment is 35-90 nm. At 0.1 mol. L-1The initial potential of oxygen reduction in the potassium hydroxide solution is 1.10V, and the catalyst has better catalytic performance.
Example 3
(1) Ball milling the active carbon, and sieving with a 400-mesh sieve; and (3) placing the screened activated carbon in nitric acid with the concentration of 1mol/L, preserving heat and activating for 4 hours under the condition of an oil bath at 85 ℃, cooling, filtering, washing to be neutral, and drying for 5 hours at 120 ℃ to obtain the activated carbon.
(2) Weighing ammonium metatungstate ((NH) according to a reaction stoichiometric ratio4)6H2W12O40)0.01mol, activated active carbon 3g and ammonium Nitrate (NH)4NO3)0.24mol, 0.0072mol of ethylenediamine tetraacetic acid and 0.1mol of citric acid; dissolving the raw material powder in 50mL of deionized water, and magnetically stirring for 8 hours at normal temperature to obtain a mixed solution;
(3) heating the mixed solution in a muffle furnace at the constant temperature of 200 ℃ for 3h to obtain porous nano needle-shaped active carbon-loaded purple tungsten precursor powder;
(4) and (3) putting the precursor powder into a tube furnace, and carbonizing at 800 ℃ for 3h under the mixed atmosphere of methane and hydrogen (the flow of the gas is 150mL/min) to obtain the activated carbon supported tungsten carbide nano composite powder used as the electrocatalyst.
The characterization shows that the particle size of the tungsten carbide in the activated carbon-supported tungsten carbide nano composite powder obtained in the embodiment is 40-90 nm, the initial oxygen reduction potential in a 0.1 mol.L < -1 > potassium hydroxide solution is 950mV, and the activated carbon-supported tungsten carbide nano composite powder has better catalytic performance.
Example 4
(1) Ball milling the active carbon, and sieving with a 400-mesh sieve; and (3) placing the screened activated carbon in nitric acid with the concentration of 1mol/L, preserving heat and activating for 4 hours under the condition of an oil bath at 85 ℃, cooling, filtering, washing to be neutral, and drying for 5 hours at 120 ℃ to obtain the activated carbon.
(2) Weighing ammonium metatungstate ((NH) according to a reaction stoichiometric ratio4)6H2W12O40)0.01mol, activated active carbon 0.6g, ammonium Nitrate (NH)4NO3)0.24mol, 0.0072mol of ethylenediamine tetraacetic acid and 0.05mol of thiourea; dissolving the raw material powder in 50mL of deionized water, and magnetically stirring for 8 hours at normal temperature to obtain a mixed solution;
(3) heating the mixed solution in a muffle furnace at the constant temperature of 200 ℃ for 3h to obtain porous nano needle-shaped active carbon-loaded purple tungsten precursor powder;
(4) and putting the precursor powder into a tubular furnace, and carbonizing at 850 ℃ for 2h under the mixed atmosphere of methane and hydrogen (the flow of the gas is 150mL/min) to obtain the activated carbon loaded tungsten carbide nano composite powder serving as the electrocatalyst.
The characterization shows that the particle size of the tungsten carbide in the activated carbon loaded tungsten carbide nano powder obtained in the embodiment is 20-60 nm and is 0.1 mol.L-1The initial potential of oxygen reduction in the potassium hydroxide solution is 1.05V, and the catalyst has better catalytic performance.
Example 5
(1) Ball-milling active carbon, and sieving with 200 mesh sieve; and (3) placing the screened activated carbon in nitric acid with the concentration of 1mol/L, preserving heat and activating for 4 hours under the condition of an oil bath at 85 ℃, cooling, filtering, washing to be neutral, and drying for 5 hours at 120 ℃ to obtain the activated carbon.
(2) Weighing ammonium metatungstate ((NH) according to a reaction stoichiometric ratio4)6H2W12O40)0.01mol, activated active carbon 2.5g, ammonium Nitrate (NH)4NO3)0.24mol, 0.0072mol of ethylenediamine tetraacetic acid and 0.072mol of urea; dissolving the raw material powder in 50mL of deionized water, and magnetically stirring for 8 hours at normal temperature to obtain a mixed solution;
(3) heating the mixed solution in a muffle furnace at the constant temperature of 200 ℃ for 3h to obtain porous nano needle-shaped active carbon-loaded purple tungsten precursor powder;
(4) and putting the precursor powder into a tubular furnace, and carbonizing at 900 ℃ for 2h under the mixed atmosphere of methane and hydrogen (the flow of the gas is 150mL/min) to obtain the activated carbon-supported tungsten carbide nano composite powder serving as the electrocatalyst.
The characterization shows that the particle size of the tungsten carbide in the activated carbon loaded tungsten carbide nano powder obtained in the embodiment is 15-50 nm and is 0.1 mol.L-1The initial potential of oxygen reduction in the potassium hydroxide solution is 943mV, and the catalyst has better catalytic performance.
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 preparation method of activated carbon loaded tungsten carbide nano composite powder used as an electrocatalyst is characterized by comprising the following steps:
(1) ball-milling and screening activated carbon, then placing the activated carbon in nitric acid with the concentration of 0.5-1.5 mol/L, preserving heat and activating for 2-6 hours under the condition of an oil bath at the temperature of 75-95 ℃, cooling, filtering, washing to be neutral, and drying to obtain activated carbon;
(2) ammonium metatungstate (NH)4)6H2W12O40Ammonium nitrate NH4NO3Adding the ethylenediamine tetraacetic acid, the auxiliary agent and the activated carbon into deionized water, and magnetically stirring uniformly at normal temperature to obtain a mixed solution;
(3) placing the mixed solution in a muffle furnace, gradually heating to 200 ℃ and heating at constant temperature for 2-4 h to obtain an activated carbon-loaded purple tungsten precursor;
(4) putting the precursor into a tube furnace, and carbonizing the precursor in a mixed atmosphere of methane and hydrogen to obtain the activated carbon loaded tungsten carbide nano composite powder used as the electrocatalyst, wherein: the carbonization temperature is 700-1000 ℃, the carbonization time is 2-4 h, and the gas flow is 50-200 mL/min; the volume ratio of methane to hydrogen in the mixed atmosphere is 20%: 80 percent.
2. The method of claim 1, wherein: in the step (1), the screening is performed by using a screen of 200-400 meshes.
3. The method of claim 1, wherein: in the step (2), the auxiliary agent is at least one of glycine, citric acid, urea and thiourea.
4. The method of claim 1, wherein: in the step (2), the mass ratio of ammonium metatungstate to active carbon is 1-20: 1, the molar ratio of ammonium nitrate to ammonium metatungstate is 12-36: 1, the molar ratio of ethylenediaminetetraacetic acid to ammonium metatungstate is 0.5-1: 1, and the molar ratio of adjuvant to ammonium metatungstate is 5-15: 1.
5. The method of claim 1, wherein: in the step (2), the stirring time is 6-16 h.
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