CN110624593A - A kind of preparation method of VN@Co electrocatalyst - Google Patents
A kind of preparation method of VN@Co electrocatalyst Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 27
- 238000000227 grinding Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052573 porcelain Inorganic materials 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 23
- 239000011261 inert gas Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000153 supplemental effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 Transition metal nitrides Chemical class 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
本发明提供一种VN@Co电催化剂的制备方法，其制备方法的步骤包括：1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠按质量组份配比得到原料；2)将上述原料研磨后置于管式气氛炉中；3)在惰性气氛下加热管式气氛炉并保温；4)将反应后的产物再研磨，得到VN@Co电催化剂。本发明工艺简单，所得VN@Co电催化活性优异，电解时额外消耗的能量少、使用寿命长、电催化活性高。The invention provides a preparation method of a VN@Co electrocatalyst. The steps of the preparation method include: 1) obtaining raw materials by proportioning urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite by mass components; 2) ) grinding the above-mentioned raw materials and placing them in a tubular atmosphere furnace; 3) heating the tubular atmosphere furnace under an inert atmosphere and keeping the temperature; 4) regrinding the reacted product to obtain a VN@Co electrocatalyst. The process of the invention is simple, the obtained VN@Co has excellent electrocatalytic activity, less additional energy consumption during electrolysis, long service life and high electrocatalytic activity.
Description
技术领域technical field
本发明涉及电催化电解水，具体涉及一种VN@Co电催化剂的制备方法。The invention relates to electrocatalytic electrolysis of water, in particular to a preparation method of a VN@Co electrocatalyst.
背景技术Background technique
化石燃料被广泛用于生活中，但是化石燃料由于缺乏可持续性，且对环境造成了严重的影响，已经引起了能源专家和环保主义者的广泛质疑。而氢气，作为新一代的可持续清洁能源，可维持环境的清洁性，具有潜在的可再生能力，高能量密度，被认为是几乎完美的能源和能量载体。尽管氢能是最具吸引力和环境友好的能源，但是制备氢气的技术却并不成熟，目前用于生产氢气的工艺和材料成为探索的重点。由于生产成本问题，超过96％的氢能来自化石燃料，但是，使用化石燃料生产氢气违背了使用清洁能源生产氢气的主旨。为了降低氢能生产成本，我们需要进行更多相关研究工作来开发新材料，新技术。Fossil fuels are widely used in life, but their lack of sustainability and serious environmental impact have caused widespread skepticism from energy experts and environmentalists. And hydrogen, as a new generation of sustainable clean energy, can maintain the cleanness of the environment, has potential renewable ability, high energy density, and is considered as an almost perfect energy and energy carrier. Although hydrogen energy is the most attractive and environmentally friendly energy source, the technology for preparing hydrogen is not mature, and the current processes and materials for hydrogen production have become the focus of exploration. Over 96% of hydrogen energy comes from fossil fuels due to production costs, however, using fossil fuels to produce hydrogen defeats the purpose of using clean energy to produce hydrogen. In order to reduce the cost of hydrogen energy production, we need to carry out more related research work to develop new materials and new technologies.
过渡金属氮化物(TMNs)具有类Pt特性，高导电性，电化学稳定性以及电化学操作条件下的耐腐蚀性。氮化钒(VN)作为过渡金属氮化物(TMNs)的一种，不仅具有过渡金属氮化物(TMNs)的共性，并且有良好的导电性，在电化学领域受到了研究者的关注，氮化钒还可作为超级电器正极材料，电池材料，以及用于氧还原反应。由于氮化钒在合成过程中容易发生自发的团聚，会降低电化学比表面积和催化效果，且现有技术中合成的氮化钒结晶性较差，活性位点较少，氮化钒的整体催化活性并不高，现有技术制备氮化钒的工艺也较复杂，不适宜进行大规模化工业生产。Transition metal nitrides (TMNs) exhibit Pt-like properties, high electrical conductivity, electrochemical stability, and corrosion resistance under electrochemical operating conditions. As a kind of transition metal nitrides (TMNs), vanadium nitride (VN) not only has the commonality of transition metal nitrides (TMNs), but also has good electrical conductivity, which has attracted the attention of researchers in the field of electrochemistry. Vanadium can also be used as a cathode material for superelectric appliances, a battery material, and for oxygen reduction reactions. Since vanadium nitride is prone to spontaneous agglomeration during the synthesis process, the electrochemical specific surface area and catalytic effect will be reduced, and the vanadium nitride synthesized in the prior art has poor crystallinity and fewer active sites, and the overall vanadium nitride has poorer crystallinity and fewer active sites. The catalytic activity is not high, and the process for preparing vanadium nitride in the prior art is also complicated, which is not suitable for large-scale industrial production.
因此，如何设计出制备工艺简单、具有良好催化活性的氮化钒基材料是当前待解决的问题。Therefore, how to design a vanadium nitride-based material with a simple preparation process and good catalytic activity is a problem to be solved at present.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种工艺简单、电催化活性优异的VN@Co电催化剂的制备方法。The purpose of the present invention is to provide a preparation method of VN@Co electrocatalyst with simple process and excellent electrocatalytic activity.
本发明的目的通过一下技术方案来实现：The purpose of the present invention is achieved through the following technical solutions:
步骤一：按CH4N2O：NH4VO3：CoCl2*6H2O：NaH2PO2＝(8～10)：(1～3)：(1～3)：(6～8)质量比取尿素、偏钒酸铵、六水合氯化钴、次磷酸钠；Step 1: Press CH 4 N 2 O: NH 4 VO 3 : CoCl 2 *6H 2 O: NaH 2 PO 2 =(8~10):(1~3):(1~3):(6~8) Take urea, ammonium metavanadate, cobalt chloride hexahydrate, sodium hypophosphite by mass ratio;
步骤二：将尿素、偏钒酸铵、六水合氯化钴混合后研磨，将研磨后的混合物过60目筛后装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，并在管式气氛炉两端各加炉塞；Step 2: Mix and grind urea, ammonium metavanadate, and cobalt chloride hexahydrate, pass the ground mixture through a 60-mesh sieve and put it into a small porcelain boat, place the small porcelain boat at one end of the large porcelain boat, and place the In step 1, the proportioned sodium hypophosphite is added to the other end of the large porcelain boat, the large porcelain boat is placed in the tubular atmosphere furnace, and furnace plugs are added at both ends of the tubular atmosphere furnace;
步骤三：向管式气氛炉中通入惰性气体，排出管式气氛炉内空气，控制管式气氛炉内气压为-1～0MPa，将管式气氛炉从室温以5～10℃/min的加热速率加热至700～800℃后保温；Step 3: Pour inert gas into the tubular atmosphere furnace, discharge the air in the tubular atmosphere furnace, control the air pressure in the tubular atmosphere furnace to be -1～0MPa, and set the tubular atmosphere furnace from room temperature to 5～10℃/min. The heating rate is heated to 700 ~ 800 ℃ and then kept warm;
步骤四：待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，得到VN@Co电催化剂。Step 4: After the tubular atmosphere furnace is cooled to room temperature, the sample in the small porcelain boat is ground to obtain the VN@Co electrocatalyst.
所述步骤二的研磨时间为20～30min。The grinding time of the second step is 20-30 min.
所述步骤二中将放次磷酸钠的管式气氛炉一端与进气口相连。In the second step, one end of the tubular atmosphere furnace where the sodium hypophosphite is placed is connected to the air inlet.
述步骤三向管式气氛炉内通入惰性气体进行3次抽气补气。In the above-mentioned step 3, the inert gas is introduced into the tubular atmosphere furnace for 3 times of gas extraction.
所述步骤三中保温的时间为120～180min。In the said step 3, the time of heat preservation is 120～180min.
所述步骤四中研磨的时间为20～30min。The grinding time in the step 4 is 20～30min.
本发明相比于现有技术具有以下有益效果：本发明将原料混合后研磨，于惰性气氛中在分散剂的作用下加热保温，再研磨即可得到VN@Co电催化剂，工艺简单，不涉及复杂的转变及苛刻的反应条件；次磷酸钠作为分散剂，在固相反应过程中，热解产生的磷化氢气体将样品分散的更加均匀，磷化氢气体不与原料反应，制备的VN@Co纳米材料化学组成均一，纯度较高；本发明制备所得的VN@CO过电势小，寿命长、塔菲尔斜率小，因此其在电催化电解水中电解时额外消耗的能量少、使用寿命长、电催化活性高。Compared with the prior art, the present invention has the following beneficial effects: in the present invention, the raw materials are mixed and then ground, heated and kept warm under the action of a dispersant in an inert atmosphere, and the VN@Co electrocatalyst can be obtained by grinding again. The process is simple and does not involve Complex transformation and harsh reaction conditions; sodium hypophosphite is used as a dispersant. During the solid-phase reaction, the phosphine gas generated by pyrolysis disperses the sample more uniformly, and the phosphine gas does not react with the raw materials. The prepared VN @Co nanomaterials have uniform chemical composition and high purity; the VN@CO prepared by the present invention has small overpotential, long life and small Tafel slope, so it consumes less energy during electrolysis in electrocatalytic water electrolysis and has a long service life. long and high electrocatalytic activity.
进一步的，通入惰性气体前补气抽气，保证空气完全被排出，有利于保证反应的进行和反应物的高纯度。Further, the air is supplemented and exhausted before the inert gas is introduced to ensure that the air is completely discharged, which is beneficial to ensure the progress of the reaction and the high purity of the reactants.
附图说明Description of drawings
图1是实施例6所制备的VN@Co电催化剂的XRD图谱；Fig. 1 is the XRD pattern of the prepared VN@Co electrocatalyst of embodiment 6;
图2是实施例6所制备的VN@Co电催化剂的SEM图；Fig. 2 is the SEM image of the VN@Co electrocatalyst prepared in Example 6;
图3是实施例6所制备的VN@Co电催化剂的产氢性能图。3 is a graph showing the hydrogen production performance of the VN@Co electrocatalyst prepared in Example 6.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步详细的描述：Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in further detail:
实施例1：Example 1:
1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠原料按照如下质量组分配比进行配料：CH4N2O:NH4VO3:CoCl2*6H2O:NaH2PO2＝8：1：1：6；1) The raw materials of urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite are proportioned according to the following mass components: CH 4 N 2 O:NH 4 VO 3 :CoCl 2 *6H 2 O:NaH 2 PO 2 = 8:1:1:6;
2)将步骤一配比后的尿素、偏钒酸铵、六水合氯化钴混合后研磨，研磨时间为20min，研磨后再将混合物过60目筛，筛除较大粒径的混合物，将研磨后的混合物装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，将放次磷酸钠的管式气氛炉一端与进气口相连，并在管式气氛炉两端各加两个炉塞；2) grinding after mixing the urea, ammonium metavanadate, cobalt chloride hexahydrate after the proportioning of step 1, the grinding time is 20min, after grinding, the mixture is crossed with a 60 mesh sieve, and the mixture of larger particle size is screened out, and the The ground mixture is put into a small porcelain boat, the small porcelain boat is placed at one end of the large porcelain boat, the sodium hypophosphite proportioned in step 1 is added to the other end of the large porcelain boat, and the large porcelain boat is placed in a tubular atmosphere In the furnace, one end of the tubular atmosphere furnace containing sodium hypophosphite is connected to the air inlet, and two furnace plugs are added at both ends of the tubular atmosphere furnace;
3)向管式气氛炉中通入惰性气体进行3次补气抽气，以此将管式气氛炉内的空气排出，再通入惰性气体使管式气氛炉内为惰性气氛环境，控制管式气氛炉内气压为-1～0MPa，以5℃/min的升温速率将管式气氛炉从室温加热至700℃后保温180min；3) Pour inert gas into the tubular atmosphere furnace for 3 times of supplemental gas extraction, so as to discharge the air in the tubular atmosphere furnace, and then introduce inert gas to make the tubular atmosphere furnace an inert atmosphere environment, and control the tube atmosphere. The air pressure in the type atmosphere furnace is -1～0MPa, and the tube type atmosphere furnace is heated from room temperature to 700℃ at a heating rate of 5℃/min and then kept for 180min;
4)待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，研磨时间为20min，得到VN@Co电催化剂。4) After the tubular atmosphere furnace was cooled to room temperature, the sample in the small porcelain boat was ground for 20 min to obtain a VN@Co electrocatalyst.
实施例2：Example 2:
1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠原料按照如下质量组分配比进行配料：CH4N2O:NH4VO3:CoCl2*6H2O:NaH2PO2＝9：2：2：7；1) The raw materials of urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite are proportioned according to the following mass components: CH 4 N 2 O:NH 4 VO 3 :CoCl 2 *6H 2 O:NaH 2 PO 2 = 9:2:2:7;
2)将步骤一配比后的尿素、偏钒酸铵、六水合氯化钴混合后研磨，研磨时间为25min，研磨后再将混合物过60目筛，筛除较大粒径的混合物，将研磨后的混合物装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，将放次磷酸钠的管式气氛炉一端与进气口相连，并在管式气氛炉两端各加两个炉塞；2) grinding after mixing the urea, ammonium metavanadate, cobalt chloride hexahydrate after the proportioning of step 1, the grinding time is 25min, after grinding, the mixture is crossed with a 60 mesh sieve, and the mixture of larger particle size is sieved out, and the The ground mixture is put into a small porcelain boat, the small porcelain boat is placed at one end of the large porcelain boat, the sodium hypophosphite proportioned in step 1 is added to the other end of the large porcelain boat, and the large porcelain boat is placed in a tubular atmosphere In the furnace, one end of the tubular atmosphere furnace containing sodium hypophosphite is connected to the air inlet, and two furnace plugs are added at both ends of the tubular atmosphere furnace;
3)向管式气氛炉中通入惰性气体进行3次补气抽气，以此将管式气氛炉内的空气排出，再通入惰性气体使管式气氛炉内为惰性气氛环境，控制管式气氛炉内气压为-1～0MPa，以8℃/min的升温速率将管式气氛炉从室温加热至750℃后保温150min；3) Pour inert gas into the tubular atmosphere furnace for 3 times of supplemental gas extraction, so as to discharge the air in the tubular atmosphere furnace, and then introduce inert gas to make the tubular atmosphere furnace an inert atmosphere environment, and control the tube atmosphere. The air pressure in the type atmosphere furnace is -1～0MPa, and the tube type atmosphere furnace is heated from room temperature to 750℃ at a heating rate of 8℃/min and then kept for 150min;
4)待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，研磨时间为28min，得到VN@Co电催化剂。4) After the tubular atmosphere furnace was cooled to room temperature, the sample in the small porcelain boat was ground for 28 min to obtain a VN@Co electrocatalyst.
实施例3：Example 3:
1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠原料按照如下质量组分配比进行配料：CH4N2O:NH4VO3:CoCl2*6H2O:NaH2PO2＝10：3：3：8；1) The raw materials of urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite are proportioned according to the following mass components: CH 4 N 2 O:NH 4 VO 3 :CoCl 2 *6H 2 O:NaH 2 PO 2 = 10:3:3:8;
2)将步骤一配比后的尿素、偏钒酸铵、六水合氯化钴混合后研磨，研磨时间为28min，研磨后再将混合物过60目筛，筛除较大粒径的混合物，将研磨后的混合物装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，将放次磷酸钠的管式气氛炉一端与进气口相连，并在管式气氛炉两端各加两个炉塞；2) the urea, ammonium metavanadate, cobalt chloride hexahydrate after the proportioning of step 1 are mixed and ground, and the grinding time is 28min. After grinding, the mixture is crossed with a 60 mesh sieve, and the mixture of larger particle size is screened out. The ground mixture is put into a small porcelain boat, the small porcelain boat is placed at one end of the large porcelain boat, the sodium hypophosphite proportioned in step 1 is added to the other end of the large porcelain boat, and the large porcelain boat is placed in a tubular atmosphere In the furnace, one end of the tubular atmosphere furnace containing sodium hypophosphite is connected to the air inlet, and two furnace plugs are added at both ends of the tubular atmosphere furnace;
3)向管式气氛炉中通入惰性气体进行3次补气抽气，以此将管式气氛炉内的空气排出，再通入惰性气体使管式气氛炉内为惰性气氛环境，控制管式气氛炉内气压为-1～0MPa，以6℃/min的升温速率将管式气氛炉从室温加热至700℃后保温160min；3) Pour inert gas into the tubular atmosphere furnace for 3 times of supplemental gas extraction, so as to discharge the air in the tubular atmosphere furnace, and then introduce inert gas to make the tubular atmosphere furnace an inert atmosphere environment, and control the tube atmosphere. The air pressure in the type atmosphere furnace is -1 ~ 0MPa, and the tube atmosphere furnace is heated from room temperature to 700℃ at a heating rate of 6℃/min and then kept for 160min;
4)待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，研磨时间为25min，得到VN@Co电催化剂。4) After the tubular atmosphere furnace was cooled to room temperature, the sample in the small porcelain boat was ground for 25 min to obtain a VN@Co electrocatalyst.
实施例4：Example 4:
1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠原料按照如下质量组分配比进行配料：CH4N2O:NH4VO3:CoCl2*6H2O:NaH2PO2＝8：2：1：7；1) The raw materials of urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite are proportioned according to the following mass components: CH 4 N 2 O:NH 4 VO 3 :CoCl 2 *6H 2 O:NaH 2 PO 2 = 8:2:1:7;
2)将步骤一配比后的尿素、偏钒酸铵、六水合氯化钴混合后研磨，研磨时间为23min，研磨后再将混合物过60目筛，筛除较大粒径的混合物，将研磨后的混合物装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，将放次磷酸钠的管式气氛炉一端与进气口相连，并在管式气氛炉两端各加两个炉塞；2) the urea, ammonium metavanadate, cobalt chloride hexahydrate after the proportioning of step 1 are mixed and ground, and the grinding time is 23min. After grinding, the mixture is crossed with a 60-mesh sieve, and the mixture of larger particle size is sieved out. The ground mixture is put into a small porcelain boat, the small porcelain boat is placed at one end of the large porcelain boat, the sodium hypophosphite proportioned in step 1 is added to the other end of the large porcelain boat, and the large porcelain boat is placed in a tubular atmosphere In the furnace, one end of the tubular atmosphere furnace containing sodium hypophosphite is connected to the air inlet, and two furnace plugs are added at both ends of the tubular atmosphere furnace;
3)向管式气氛炉中通入惰性气体进行3次补气抽气，以此将管式气氛炉内的空气排出，再通入惰性气体使管式气氛炉内为惰性气氛环境，控制管式气氛炉内气压为-1～0MPa，以10℃/min的升温速率将管式气氛炉从室温加热至800℃后保温120min；3) Pour inert gas into the tubular atmosphere furnace for 3 times of supplemental gas extraction, so as to discharge the air in the tubular atmosphere furnace, and then introduce inert gas to make the tubular atmosphere furnace an inert atmosphere environment, and control the tube atmosphere. The air pressure in the type atmosphere furnace is -1～0MPa, and the tube type atmosphere furnace is heated from room temperature to 800℃ at a heating rate of 10℃/min, and then kept for 120min;
4)待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，研磨时间为23min，得到VN@Co电催化剂。4) After the tubular atmosphere furnace was cooled to room temperature, the samples in the small porcelain boat were ground for 23 min to obtain a VN@Co electrocatalyst.
实施例5：Example 5:
1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠原料按照如下质量组分配比进行配料：CH4N2O:NH4VO3:CoCl2*6H2O:NaH2PO2＝9：1：2：8；1) The raw materials of urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite are proportioned according to the following mass components: CH 4 N 2 O:NH 4 VO 3 :CoCl 2 *6H 2 O:NaH 2 PO 2 = 9:1:2:8;
2)将步骤一配比后的尿素、偏钒酸铵、六水合氯化钴混合后研磨，研磨时间为30min，研磨后再将混合物过60目筛，筛除较大粒径的混合物，将研磨后的混合物装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，将放次磷酸钠的管式气氛炉一端与进气口相连，并在管式气氛炉两端各加两个炉塞；2) the urea, ammonium metavanadate, cobalt chloride hexahydrate after the proportioning of step 1 are mixed and ground, and the grinding time is 30min. After grinding, the mixture is crossed with a 60 mesh sieve, and the mixture of larger particle size is screened out, and the The ground mixture is put into a small porcelain boat, the small porcelain boat is placed at one end of the large porcelain boat, the sodium hypophosphite proportioned in step 1 is added to the other end of the large porcelain boat, and the large porcelain boat is placed in a tubular atmosphere In the furnace, one end of the tubular atmosphere furnace containing sodium hypophosphite is connected to the air inlet, and two furnace plugs are added at both ends of the tubular atmosphere furnace;
3)向管式气氛炉中通入惰性气体进行3次补气抽气，以此将管式气氛炉内的空气排出，再通入惰性气体使管式气氛炉内为惰性气氛环境，控制管式气氛炉内气压为-1～0MPa，以9℃/min的升温速率将管式气氛炉从室温加热至780℃后保温130min；3) Pour inert gas into the tubular atmosphere furnace for 3 times of supplemental gas extraction, so as to discharge the air in the tubular atmosphere furnace, and then introduce inert gas to make the tubular atmosphere furnace an inert atmosphere environment, and control the tube atmosphere. The air pressure in the type atmosphere furnace is -1～0MPa, and the tube type atmosphere furnace is heated from room temperature to 780℃ at a heating rate of 9℃/min and then kept for 130min;
4)待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，研磨时间为30min，得到VN@Co电催化剂。4) After the tubular atmosphere furnace was cooled to room temperature, the sample in the small porcelain boat was ground for 30 min to obtain a VN@Co electrocatalyst.
实施例6：Example 6:
1)将尿素、偏钒酸铵、六水合氯化钴、次磷酸钠原料按照如下质量组分配比进行配料：CH4N2O:NH4VO3:CoCl2*6H2O:NaH2PO2＝10：3：3：8；1) The raw materials of urea, ammonium metavanadate, cobalt chloride hexahydrate and sodium hypophosphite are proportioned according to the following mass components: CH 4 N 2 O:NH 4 VO 3 :CoCl 2 *6H 2 O:NaH 2 PO 2 = 10:3:3:8;
2)将步骤一配比后的尿素、偏钒酸铵、六水合氯化钴混合后研磨，研磨时间为30min，研磨后再将混合物过60目筛，筛除较大粒径的混合物，将研磨后的混合物装入一个小瓷舟中，将小瓷舟置于大瓷舟一端，将步骤一配比后的次磷酸钠加至大瓷舟另一端，将大瓷舟置于管式气氛炉中，将放次磷酸钠的管式气氛炉一端与进气口相连，并在管式气氛炉两端各加两个炉塞；2) the urea, ammonium metavanadate, cobalt chloride hexahydrate after the proportioning of step 1 are mixed and ground, and the grinding time is 30min. After grinding, the mixture is crossed with a 60 mesh sieve, and the mixture of larger particle size is screened out, and the The ground mixture is put into a small porcelain boat, the small porcelain boat is placed at one end of the large porcelain boat, the sodium hypophosphite proportioned in step 1 is added to the other end of the large porcelain boat, and the large porcelain boat is placed in a tubular atmosphere In the furnace, one end of the tubular atmosphere furnace containing sodium hypophosphite is connected to the air inlet, and two furnace plugs are added at both ends of the tubular atmosphere furnace;
3)向管式气氛炉中通入惰性气体进行3次补气抽气，以此将管式气氛炉内的空气排出，再通入惰性气体使管式气氛炉内为惰性气氛环境，控制管式气氛炉内气压为-1～0MPa，以10℃/min的升温速率将管式气氛炉从室温加热至800℃后保温180min；3) Pour inert gas into the tubular atmosphere furnace for 3 times of supplemental gas extraction, so as to discharge the air in the tubular atmosphere furnace, and then introduce inert gas to make the tubular atmosphere furnace an inert atmosphere environment, and control the tube atmosphere. The air pressure in the type atmosphere furnace is -1～0MPa, and the tube type atmosphere furnace is heated from room temperature to 800℃ at a heating rate of 10℃/min and then kept for 180min;
4)待管式气氛炉冷却至室温后，将小瓷舟中的样品进行研磨，研磨时间为30min，得到VN@Co电催化剂。4) After the tubular atmosphere furnace was cooled to room temperature, the sample in the small porcelain boat was ground for 30 min to obtain a VN@Co electrocatalyst.
图1是实施例6所制备的VN@Co电催化剂的XRD图谱，从图中可以看出样品VN和Co的衍射峰与标准卡片匹配较好，且强度高，说明该实施例得到的VN@Co结晶性很好。Fig. 1 is the XRD pattern of the VN@Co electrocatalyst prepared in Example 6. It can be seen from the figure that the diffraction peaks of the samples VN and Co are well matched with the standard card, and the intensity is high, indicating that the VN@Co obtained in this example Co crystallinity is very good.
图2是实施例6所制备的VN@Co电催化剂的SEM图，从图中可以看出样品形貌为均匀细小的纳米颗粒，存在疏松的孔隙，分散较好，暴露了较多的活性位点。Figure 2 is the SEM image of the VN@Co electrocatalyst prepared in Example 6. It can be seen from the figure that the morphology of the sample is uniform and fine nanoparticles, there are loose pores, the dispersion is good, and more active sites are exposed. point.
图3是实施例6所制备的VN@Co电催化剂的产氢性能图，表示在碱性测试条件下，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为160mV，说明制备的纳米VN@Co具有优异的催化活性。Figure 3 is a graph showing the hydrogen production performance of the VN@Co electrocatalyst prepared in Example 6, indicating that under the alkaline test conditions, when the current density is 10mA/cm2 and the scan rate is 3mV/s, the overpotential of the sample is 160mV , indicating that the prepared nano-VN@Co has excellent catalytic activity.
本发明中的次磷酸钠作为分散剂，在固相反应过程中，热解产生的磷化氢气体将样品分散的更加均匀。The sodium hypophosphite in the present invention is used as a dispersant, and in the solid-phase reaction process, the phosphine gas generated by pyrolysis disperses the sample more uniformly.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135553A (en) * | 2021-04-22 | 2021-07-20 | 陕西科技大学 | Tungsten nitride coated vanadium nitride powder and preparation method and application thereof |
| CN116651484A (en) * | 2023-05-17 | 2023-08-29 | 上海大学 | A kind of cobalt-based vanadium nitride ammonia synthesis catalyst and its preparation method and application |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347342A (en) * | 1999-04-15 | 2002-05-01 | 纳幕尔杜邦公司 | Vanadium phosphorus oxide catalyst with thermally conductive carrier |
| EP1487575A2 (en) * | 2002-03-15 | 2004-12-22 | Basf Aktiengesellschaft | Method for the production of a catalyst containing vanadium, phosphorus, and oxygen |
| CN101798072A (en) * | 2010-04-23 | 2010-08-11 | 中南大学 | Method for preparing ultra-fine aluminum nitride powder |
| CN102500412A (en) * | 2011-10-26 | 2012-06-20 | 天津科技大学 | Method for preparing duplex metal phosphide by based mechanical mixture based on hypophosphite and metal salt |
| CN106268905A (en) * | 2016-08-11 | 2017-01-04 | 广西南宁胜祺安科技开发有限公司 | A kind of novel high-activity bismuth vanadate photocatalyst |
| CN107252700A (en) * | 2017-06-26 | 2017-10-17 | 中国石油大学(华东) | A kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method |
| CN107381515A (en) * | 2017-08-08 | 2017-11-24 | 陕西科技大学 | A kind of preparation method and product of vanadium nitride elctro-catalyst |
| CN107999114A (en) * | 2017-12-19 | 2018-05-08 | 成都玖奇新材料科技有限公司 | Electrochemical reduction nitrogen ammonia non-precious metal catalyst |
| CN108380229A (en) * | 2018-04-25 | 2018-08-10 | 华中农业大学 | A kind of preparation method and products thereof of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent |
| EP3379626A1 (en) * | 2016-02-02 | 2018-09-26 | LG Chem, Ltd. | Carrier-nanoparticle composite, catalyst containing same, and method for producing same |
| CN108579788A (en) * | 2018-04-29 | 2018-09-28 | 浙江工业大学 | A kind of compound cobalt vanadium nitride nanowires elctro-catalyst and its preparation method and application |
| CN109731604A (en) * | 2019-01-31 | 2019-05-10 | 陕西科技大学 | A kind of preparation method of cobalt-doped porous vanadium nitride nanosheet bifunctional electrocatalyst |
| WO2019151714A1 (en) * | 2018-02-05 | 2019-08-08 | 엘지전자 주식회사 | Electrode and electrochemical cell comprising electrode |
| CN110127655A (en) * | 2019-05-31 | 2019-08-16 | 江苏大学 | Method for preparing biomass carbon-supported cobalt phosphide electrode material by one-step calcination |
| CN110252373A (en) * | 2019-06-14 | 2019-09-20 | 湖北中和普汇环保股份有限公司 | A kind of magnetism Co-V/C3N3The preparation method and application of complex carrier particle |
-
2019
- 2019-09-30 CN CN201910942522.6A patent/CN110624593A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347342A (en) * | 1999-04-15 | 2002-05-01 | 纳幕尔杜邦公司 | Vanadium phosphorus oxide catalyst with thermally conductive carrier |
| EP1487575A2 (en) * | 2002-03-15 | 2004-12-22 | Basf Aktiengesellschaft | Method for the production of a catalyst containing vanadium, phosphorus, and oxygen |
| CN101798072A (en) * | 2010-04-23 | 2010-08-11 | 中南大学 | Method for preparing ultra-fine aluminum nitride powder |
| CN102500412A (en) * | 2011-10-26 | 2012-06-20 | 天津科技大学 | Method for preparing duplex metal phosphide by based mechanical mixture based on hypophosphite and metal salt |
| EP3379626A1 (en) * | 2016-02-02 | 2018-09-26 | LG Chem, Ltd. | Carrier-nanoparticle composite, catalyst containing same, and method for producing same |
| CN106268905A (en) * | 2016-08-11 | 2017-01-04 | 广西南宁胜祺安科技开发有限公司 | A kind of novel high-activity bismuth vanadate photocatalyst |
| CN107252700A (en) * | 2017-06-26 | 2017-10-17 | 中国石油大学(华东) | A kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method |
| CN107381515A (en) * | 2017-08-08 | 2017-11-24 | 陕西科技大学 | A kind of preparation method and product of vanadium nitride elctro-catalyst |
| CN107999114A (en) * | 2017-12-19 | 2018-05-08 | 成都玖奇新材料科技有限公司 | Electrochemical reduction nitrogen ammonia non-precious metal catalyst |
| WO2019151714A1 (en) * | 2018-02-05 | 2019-08-08 | 엘지전자 주식회사 | Electrode and electrochemical cell comprising electrode |
| CN108380229A (en) * | 2018-04-25 | 2018-08-10 | 华中农业大学 | A kind of preparation method and products thereof of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent |
| CN108579788A (en) * | 2018-04-29 | 2018-09-28 | 浙江工业大学 | A kind of compound cobalt vanadium nitride nanowires elctro-catalyst and its preparation method and application |
| CN109731604A (en) * | 2019-01-31 | 2019-05-10 | 陕西科技大学 | A kind of preparation method of cobalt-doped porous vanadium nitride nanosheet bifunctional electrocatalyst |
| CN110127655A (en) * | 2019-05-31 | 2019-08-16 | 江苏大学 | Method for preparing biomass carbon-supported cobalt phosphide electrode material by one-step calcination |
| CN110252373A (en) * | 2019-06-14 | 2019-09-20 | 湖北中和普汇环保股份有限公司 | A kind of magnetism Co-V/C3N3The preparation method and application of complex carrier particle |
Non-Patent Citations (1)
| Title |
|---|
| YANG, H ET AL.: ""Efficient hydrogen and oxygen evolution electrocatalysis by cobalt and phosphorus dual-doped vanadium nitride nanowires"", 《MATERIALS TODAY CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135553A (en) * | 2021-04-22 | 2021-07-20 | 陕西科技大学 | Tungsten nitride coated vanadium nitride powder and preparation method and application thereof |
| CN116651484A (en) * | 2023-05-17 | 2023-08-29 | 上海大学 | A kind of cobalt-based vanadium nitride ammonia synthesis catalyst and its preparation method and application |
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