CN108796553A - A kind of tetragonal phase CoSe and preparation method for catalytic hydrogen evolution - Google Patents
A kind of tetragonal phase CoSe and preparation method for catalytic hydrogen evolution Download PDFInfo
- Publication number
- CN108796553A CN108796553A CN201810715957.2A CN201810715957A CN108796553A CN 108796553 A CN108796553 A CN 108796553A CN 201810715957 A CN201810715957 A CN 201810715957A CN 108796553 A CN108796553 A CN 108796553A
- Authority
- CN
- China
- Prior art keywords
- powder
- cose
- tetragonal
- purity
- crucible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 43
- 239000010453 quartz Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000002542 deteriorative effect Effects 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002447 crystallographic data Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical class [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开一种用于催化析氢反应的四方相CoSe电催化剂的制备方法，包括以下步骤：材料的准备；制备KCo2Se2原材料；制备饱和LiOH溶液；制备四方相CoSe。本发明还公开一种四方相CoSe电催化剂，其采用如上所述的方法制备而成，应用于催化析氢领域。
The invention discloses a preparation method of tetragonal phase CoSe electrocatalyst for catalyzing hydrogen evolution reaction, comprising the following steps: preparation of materials; preparation of KCo 2 Se 2 raw material; preparation of saturated LiOH solution; preparation of tetragonal phase CoSe. The invention also discloses a tetragonal phase CoSe electrocatalyst, which is prepared by the above-mentioned method and applied to the field of catalytic hydrogen evolution.
Description
技术领域technical field
本发明涉及电催化材料应用领域，具体涉及一种用于催化析氢的四方相CoSe及制备方法。The invention relates to the application field of electrocatalytic materials, in particular to a tetragonal phase CoSe for catalyzing hydrogen evolution and a preparation method thereof.
技术背景technical background
随着能源资源的短缺，以及环境污染问题的日趋严重，可持续清洁能源的研究吸引了广泛关注。在清洁能源中，氢气因燃烧产物是水、储能密度高、地球氢元素含量丰富而成为理想的能源材料。电催化析氢反应，即通过电催化分解水获得氢气，被认为是有效获得氢气的方法。在电催化析氢反应当中，电催化剂起到决定性作用，设计和寻找具有低成本、高效率的电催化剂，是将氢能推向实际应用的重中之重。贵金属大多是良好的催化材料。目前，铂是在酸性环境中催化析氢活性最高的催化剂，但由于昂贵的价格和铂元素的稀缺性，铂材料的应用受到很大的限制。除贵金属之外，过渡金属硫化物、硒化物等地球上富集的元素或化合物同样得到了广泛的研究。With the shortage of energy resources and the increasingly serious problem of environmental pollution, the research on sustainable clean energy has attracted widespread attention. In clean energy, hydrogen has become an ideal energy material because the product of combustion is water, its energy storage density is high, and the earth is rich in hydrogen. The electrocatalytic hydrogen evolution reaction, that is, the electrocatalytic splitting of water to obtain hydrogen, has been considered as an efficient way to obtain hydrogen. In the electrocatalytic hydrogen evolution reaction, electrocatalysts play a decisive role. Designing and finding low-cost, high-efficiency electrocatalysts is the top priority for promoting hydrogen energy to practical applications. Most noble metals are good catalytic materials. At present, platinum is the catalyst with the highest activity in catalyzing hydrogen evolution in acidic environment, but due to the high price and the scarcity of platinum, the application of platinum materials is greatly limited. In addition to noble metals, earth-abundant elements or compounds such as transition metal sulfides and selenides have also been extensively studied.
六方相钴硫化合物具有差的电催化性能，严重地制约了钴硫化合物在电催化领域的应用。Hexagonal cobalt-sulfur compounds have poor electrocatalytic performance, which seriously restricts the application of cobalt-sulfur compounds in the field of electrocatalysis.
发明内容Contents of the invention
本发明的目的在于针对六方相CoSe具有差的电催化析氢性能，提出一种用于催化析氢反应的四方相CoSe电催化剂，具有好的电催化析氢性能。The purpose of the present invention is to propose a tetragonal CoSe electrocatalyst for catalyzing the hydrogen evolution reaction, which has good electrocatalytic hydrogen evolution performance, in view of the poor electrocatalytic hydrogen evolution performance of the hexagonal phase CoSe.
本发明的实现包括以下步骤。The implementation of the present invention includes the following steps.
① 材料的准备：采用纯度为99.8%的块状K，在氩气保护氛围中，用剪刀去除表面氧化层；纯度为99.9%的Co粉；纯度为99.999%的Se粉；纯度为98%的LiOH颗粒。① Preparation of materials: use block K with a purity of 99.8%, remove the surface oxide layer with scissors in an argon protective atmosphere; Co powder with a purity of 99.9%; Se powder with a purity of 99.999%; Se powder with a purity of 98% LiOH particles.
② 制备KCo2Se2原材料：首先按配比K：Co：Se = 1：2：2称量原料，将Co粉和Se粉混合并研磨。将Co粉和Se粉的混合物倒入模具中，然后用压片机进行压制成片（压力达到8MPa），保压10分钟后释放压力。将压好的片状混合物敲成大小均等的两块放入坩埚中。将称量好的K块剪成几小块后，一并放进坩埚中，在坩埚的顶部盖上坩埚盖。将坩埚放入石英管内，在石英管内充入0.2 个大气压的高纯氩气后，密封石英管。将密封好的石英管4小时升温到1000 ℃，在1000 ℃温度下反应4小时后，在水中淬火进行快速冷却。将所得到的KCo2Se2原材料研磨成粉末。② Preparation of KCo 2 Se 2 raw materials: First, weigh the raw materials according to the ratio K: Co: Se = 1: 2: 2, mix and grind Co powder and Se powder. Pour the mixture of Co powder and Se powder into the mold, and then press it into tablets with a tablet machine (the pressure reaches 8MPa), and release the pressure after holding the pressure for 10 minutes. Knock the pressed flake mixture into two pieces of equal size and put them in a crucible. Cut the weighed K block into several small pieces, put them into the crucible together, and put the crucible lid on the top of the crucible. Put the crucible into the quartz tube, fill the quartz tube with 0.2 atmospheric pressure of high-purity argon, and then seal the quartz tube. Heat the sealed quartz tube to 1000 °C for 4 hours, react at 1000 °C for 4 hours, and then quench it in water for rapid cooling. The obtained KCo 2 Se 2 raw material was ground into powder.
③ 制备饱和LiOH溶液：纯度为98%的LiOH颗粒配置成饱和的LiOH溶液。③ Preparation of saturated LiOH solution: LiOH particles with a purity of 98% are prepared into a saturated LiOH solution.
④ 制备四方相粉末倒入装有饱和LiOH溶液的玻璃瓶内，盖上瓶盖。该过程需要在手套箱中进行，防止KCo2Se2变质。将玻璃瓶静置2天后，将所得到的样品离心清洗三遍，获得四方相CoSe样品。④ Prepare the tetragonal phase powder and pour it into a glass bottle filled with saturated LiOH solution, and cover the bottle cap. This process needs to be carried out in a glove box to prevent KCo2Se2 from deteriorating . After the glass bottle was left to stand for 2 days, the obtained sample was centrifuged and washed three times to obtain a tetragonal CoSe sample.
⑤ 制备六方相CoSe：首先按配比Co：Se = 1：·1称量原料，将Co粉和Se粉混合并研磨均匀，用压片机进行压制成片（压力达到8 MPa），保压10分钟后释放压力。将压好的片状混合物放进坩埚中，密封在充有0.2 个大气压的高纯氩气的石英管内。将密封好的石英管10小时升温到850 ℃。在850 ℃反应48小时后，炉冷到室温，获得四方相CoSe样品。⑤ Preparation of hexagonal phase CoSe: First, weigh the raw materials according to the ratio of Co:Se = 1: 1, mix and grind the Co powder and Se powder evenly, and press them into tablets with a tablet machine (the pressure reaches 8 MPa), and hold the pressure for 10 Release the pressure after a few minutes. Put the pressed flake mixture into a crucible and seal it in a quartz tube filled with high-purity argon at 0.2 atmospheres. Heat the sealed quartz tube to 850 °C for 10 hours. After reacting at 850 °C for 48 hours, the furnace was cooled to room temperature to obtain tetragonal CoSe samples.
上述步骤中用到的研磨均采用研钵或球磨机等仪器，优选球磨机进行研磨。The grinding used in the above steps all adopts instruments such as a mortar or a ball mill, preferably a ball mill for grinding.
与现有技术相比，本发明所述的样品合成方法具有以下的优点：一、通过KCo2Se2原材料在饱和LiOH溶液的作用下，制备得到四方相的CoSe材料，具有好的电催化性能。二、在制备KCo2Se2原材料过程中，通过将石英管4小时升温到1000 ℃，在1000 ℃反应4小时后，在水中淬火进行快速冷却，能够实现快速制备KCo2Se2粉末，有助于四方相CoSe材料的实际生产应用。Compared with the prior art, the sample synthesis method of the present invention has the following advantages: 1. The CoSe material of tetragonal phase is prepared by KCo 2 Se 2 raw material under the action of saturated LiOH solution, which has good electrocatalytic performance . 2. In the process of preparing KCo 2 Se 2 raw materials, by heating the quartz tube to 1000 ° C for 4 hours, and reacting at 1000 ° C for 4 hours, quenching in water for rapid cooling can realize rapid preparation of KCo 2 Se 2 powder, which is helpful In the actual production and application of tetragonal CoSe materials.
附图说明Description of drawings
图1 四方相CoSe和六方相CoSe的X射线衍射图谱。Figure 1 X-ray diffraction patterns of tetragonal CoSe and hexagonal CoSe.
图2 四方相CoSe和六方相CoSe的线性扫描伏安曲线图。Fig. 2 Linear sweep voltammetry curves of tetragonal CoSe and hexagonal CoSe.
图3 四方相CoSe和六方相CoSe的Tafel斜率图。Fig. 3 Tafel slope plots of tetragonal CoSe and hexagonal CoSe.
具体实施方式Detailed ways
以下结合具体实施例对本发明的实现进行详细的描述。The implementation of the present invention will be described in detail below in conjunction with specific embodiments.
本实施例的具体步骤如下：The concrete steps of this embodiment are as follows:
① 材料的准备：采用纯度为99.8%的块状K，在氩气保护氛围中，用剪刀去除表面氧化层；纯度为99.9%的Co粉；纯度为99.999%的Se粉；纯度为98%的LiOH颗粒。① Preparation of materials: use block K with a purity of 99.8%, remove the surface oxide layer with scissors in an argon protective atmosphere; Co powder with a purity of 99.9%; Se powder with a purity of 99.999%; Se powder with a purity of 98% LiOH particles.
② 制备KCo2Se2原材料：首先按配比K：Co：Se = 1：2：2称量原料，将Co粉和Se粉混合并研磨。将Co粉和Se粉的混合物倒入模具中，然后用压片机进行压制成片（压力达到8MPa），保压10分钟后释放压力。将压好的片状混合物敲成大小均等的两块放入坩埚中。将称量好的K块剪成几小块后，一并放进坩埚中，在坩埚的顶部盖上坩埚盖。将坩埚放入石英管内，在石英管内充入0.2 个大气压的高纯氩气后，密封石英管。将密封好的石英管4小时升温到1000 ℃，在1000 ℃温度下反应4小时后，在水中淬火进行快速冷却。将所得到的KCo2Se2原材料研磨成粉末。② Preparation of KCo 2 Se 2 raw materials: First, weigh the raw materials according to the ratio K: Co: Se = 1: 2: 2, mix and grind Co powder and Se powder. Pour the mixture of Co powder and Se powder into the mold, and then press it into tablets with a tablet machine (the pressure reaches 8MPa), and release the pressure after holding the pressure for 10 minutes. Knock the pressed flake mixture into two pieces of equal size and put them in a crucible. Cut the weighed K block into several small pieces, put them into the crucible together, and put the crucible lid on the top of the crucible. Put the crucible into the quartz tube, fill the quartz tube with 0.2 atmospheric pressure of high-purity argon, and then seal the quartz tube. Heat the sealed quartz tube to 1000 °C for 4 hours, react at 1000 °C for 4 hours, and then quench it in water for rapid cooling. The obtained KCo 2 Se 2 raw material was ground into powder.
③ 制备饱和LiOH溶液：纯度为98%的LiOH颗粒配置成饱和的LiOH溶液。③ Preparation of saturated LiOH solution: LiOH particles with a purity of 98% are prepared into a saturated LiOH solution.
④ 制备四方相CoSe：将研磨好的KCo2Se2粉末倒入装有饱和LiOH溶液的玻璃瓶内，盖上瓶盖。该过程需要在手套箱中进行，防止KCo2Se2变质。将玻璃瓶静置2天后，将所得到的样品离心清洗三遍，获得四方相CoSe样品。④ Preparation of tetragonal CoSe: Pour the ground KCo 2 Se 2 powder into a glass bottle filled with saturated LiOH solution, and cover the bottle. This process needs to be carried out in a glove box to prevent KCo2Se2 from deteriorating . After the glass bottle was left to stand for 2 days, the obtained sample was centrifuged and washed three times to obtain a tetragonal CoSe sample.
⑤ 制备六方相CoSe：首先按配比Co：Se = 1：·1称量原料，将Co粉和Se粉混合并研磨均匀，用压片机进行压制成片（压力达到8 MPa），保压10分钟后释放压力。将压好的片状混合物放进坩埚中，密封在充有0.2 个大气压的高纯氩气的石英管内。将密封好的石英管10小时升温到850 ℃。在850 ℃反应48小时后，炉冷到室温，获得四方相CoSe样品。⑤ Preparation of hexagonal phase CoSe: First, weigh the raw materials according to the ratio of Co:Se = 1: 1, mix and grind the Co powder and Se powder evenly, and press them into tablets with a tablet machine (the pressure reaches 8 MPa), and hold the pressure for 10 Release the pressure after a few minutes. Put the pressed flake mixture into a crucible and seal it in a quartz tube filled with high-purity argon at 0.2 atmospheres. Heat the sealed quartz tube to 850 °C for 10 hours. After reacting at 850 °C for 48 hours, the furnace was cooled to room temperature to obtain tetragonal CoSe samples.
上述步骤中用到的研磨均采用研钵或球磨机等仪器，优选球磨机进行研磨。The grinding used in the above steps all adopts instruments such as a mortar or a ball mill, preferably a ball mill for grinding.
为了说明本实施例的技术效果，按照以下步骤制备样品作为本实施例的对比例：In order to illustrate the technical effect of the present embodiment, prepare the sample according to the following steps as the comparative example of the present embodiment:
① 材料的准备：采用纯度为99.8%的块状K，在氩气保护氛围中，用剪刀去除表面氧化层；纯度为99.9%的Co粉；纯度为99.999%的Se粉；纯度为98%的LiOH颗粒。① Preparation of materials: use block K with a purity of 99.8%, remove the surface oxide layer with scissors in an argon protective atmosphere; Co powder with a purity of 99.9%; Se powder with a purity of 99.999%; Se powder with a purity of 98% LiOH particles.
② 制备KCo2Se2原材料：首先按配比K：Co：Se = 1：2：2称量原料，将Co粉和Se粉混合并研磨。将Co粉和Se粉的混合物倒入模具中，然后用压片机进行压制成片（压力达到8MPa），保压10分钟后释放压力。将压好的片状混合物敲成大小均等的两块放入坩埚中。将称量好的K块剪成几小块后，一并放进坩埚中，在坩埚的顶部盖上坩埚盖。将坩埚放入石英管内，在石英管内充入0.2 个大气压的高纯氩气后，密封石英管。将密封好的石英管4小时升温到1000 ℃，在1000 ℃温度下反应4小时后，在水中淬火进行快速冷却。将所得到的KCo2Se2原材料研磨成粉末。② Preparation of KCo 2 Se 2 raw materials: First, weigh the raw materials according to the ratio K: Co: Se = 1: 2: 2, mix and grind Co powder and Se powder. Pour the mixture of Co powder and Se powder into the mold, and then press it into tablets with a tablet machine (the pressure reaches 8MPa), and release the pressure after holding the pressure for 10 minutes. Knock the pressed flake mixture into two pieces of equal size and put them in a crucible. Cut the weighed K block into several small pieces, put them into the crucible together, and put the crucible lid on the top of the crucible. Put the crucible into the quartz tube, fill the quartz tube with 0.2 atmospheric pressure of high-purity argon, and then seal the quartz tube. Heat the sealed quartz tube to 1000 °C for 4 hours, react at 1000 °C for 4 hours, and then quench it in water for rapid cooling. The obtained KCo 2 Se 2 raw material was ground into powder.
③ 制备饱和LiOH溶液：纯度为98%的LiOH颗粒配置成饱和的LiOH溶液。③ Preparation of saturated LiOH solution: LiOH particles with a purity of 98% are prepared into a saturated LiOH solution.
④制备四方相CoSe：将研磨好的KCo2Se2粉末倒入装有饱和LiOH溶液的玻璃瓶内，盖上瓶盖。该过程需要在手套箱中进行，防止KCo2Se2变质。将玻璃瓶静置2天后，将所得到的样品离心清洗三遍，获得四方相CoSe样品。④Preparation of tetragonal CoSe: Pour the ground KCo 2 Se 2 powder into a glass bottle filled with saturated LiOH solution, and cover the bottle. This process needs to be carried out in a glove box to prevent KCo2Se2 from deteriorating . After the glass bottle was left to stand for 2 days, the obtained sample was centrifuged and washed three times to obtain a tetragonal CoSe sample.
⑤ 制备六方相CoSe：首先按配比Co：Se = 1：·1称量原料，将Co粉和Se粉混合并研磨均匀，用压片机进行压制成片（压力达到8 MPa），保压10分钟后释放压力。将压好的片状混合物放进坩埚中，密封在充有0.2 个大气压的高纯氩气的石英管内。将密封好的石英管10小时升温到850 ℃。在850 ℃反应48小时后，炉冷到室温，获得四方相CoSe样品。⑤ Preparation of hexagonal phase CoSe: First, weigh the raw materials according to the ratio of Co:Se = 1: 1, mix and grind the Co powder and Se powder evenly, and press them into tablets with a tablet machine (the pressure reaches 8 MPa), and hold the pressure for 10 Release the pressure after a few minutes. Put the pressed flake mixture into a crucible and seal it in a quartz tube filled with high-purity argon at 0.2 atmospheres. Heat the sealed quartz tube to 850 °C for 10 hours. After reacting at 850 °C for 48 hours, the furnace was cooled to room temperature to obtain tetragonal CoSe samples.
上述步骤中用到的研磨均采用研钵或球磨机等仪器，优选球磨机进行研磨。The grinding used in the above steps all adopts instruments such as a mortar or a ball mill, preferably a ball mill for grinding.
对按照实施例和对比例获得的样品，分别用X射线衍射方法测得衍射数据（测试条件为：在室温下采用Cu靶作为辐射源；设置仪器电压为40 KV，电流为40 mA; 从10°测试到80°）。四方相CoSe的X射线衍射谱如图1所示，对衍射数据进行指标化，可以用空间群I4/mmm进行指标化，指标化的晶格常数为： a=3.708(1) Å，c=5.348(2) Å。六方相CoSe的X射线衍射谱如图1所示，对衍射数据进行指标化，可以用空间群P63 /mmc进行指标化，指标化的晶格常数为： a=3.620(1) Å，c=5.293(1) Å。该指标化结果进一步说明四方相和六方相CoSe被成功地制备出来。For the samples obtained according to the examples and comparative examples, the diffraction data were recorded by the X-ray diffraction method respectively (the test conditions were: at room temperature, a Cu target was used as the radiation source; the instrument voltage was set to 40 KV, and the current was 40 mA; from 10 ° tested to 80°). The X-ray diffraction spectrum of tetragonal CoSe is shown in Figure 1. The diffraction data can be indexed, and the space group I4/mmm can be used for indexing. The indexed lattice constant is: a =3.708(1) Å, c = 5.348(2) Å. The X-ray diffraction spectrum of hexagonal CoSe is shown in Figure 1. The diffraction data can be indexed, and the space group P 6 3 /mmc can be used for indexing. The indexed lattice constant is: a =3.620(1) Å, c = 5.293(1) Å. The indexed results further demonstrate that tetragonal and hexagonal CoSe were successfully prepared.
四方相和六方相CoSe的线性扫描伏安数据如图2所示，测试的扫描速度为5 mV/s。从图中可以看出，六方相CoSe在10 mA/cm2电流密度下相对于可逆氢电极的过电位是352mV; 四方相CoSe在10 mA/cm2电流密度下相对于可逆氢电极的过电位是175 mV，说明四方相CoSe具有比六方相CoSe更好的电催化能力。The linear sweep voltammetry data of tetragonal and hexagonal CoSe are shown in Fig. 2, and the scanning speed of the test is 5 mV/s. It can be seen from the figure that the overpotential of the hexagonal CoSe relative to the reversible hydrogen electrode at a current density of 10 mA/cm 2 is 352 mV; the overpotential of the tetragonal CoSe relative to the reversible hydrogen electrode at a current density of 10 mA/cm 2 is 175 mV, indicating that tetragonal CoSe has better electrocatalytic ability than hexagonal CoSe.
四方相和六方相CoSe的Tafel斜率数据如图3所示，六方相CoSe的Tafel斜率是105mV dec-1; 四方相CoSe的Tafel斜率是36mV dec-1; 进一步说明四方相CoSe具有比六方相CoSe更好的电催化能力。The Tafel slope data of tetragonal and hexagonal CoSe are shown in Figure 3. The Tafel slope of hexagonal CoSe is 105mV dec -1 ; the Tafel slope of tetragonal CoSe is 36mV dec -1 ; further illustrating that tetragonal CoSe has a higher Better electrocatalytic ability.
综上所述，通过如实施例所述的方法可以制备得到一种用于催化析氢反应的四方相CoSe电催化剂。In summary, a tetragonal CoSe electrocatalyst for catalyzing the hydrogen evolution reaction can be prepared by the method as described in the examples.
本发明还公开了一种用于催化析氢的四方相CoSe，其采用如实施例所述的方法制备而成。该化合物具有352 mV的过电位（在10 mA/cm2电流密度下），Tafel斜率是36mV dec-1。The invention also discloses a tetragonal phase CoSe for catalyzing hydrogen evolution, which is prepared by the method as described in the examples. This compound has an overpotential of 352 mV (at a current density of 10 mA/cm 2 ), and a Tafel slope of 36 mV dec -1 .
需要声明的是，以上所述的仅是本发明的优选实施方式，本发明不限于以上实施例。可以理解，本领域技术人员在不脱离本发明的基本构思的前提下直接导出或联想到的其他改进和变化，均应认为包含在本发明的保护范围之内。It should be noted that what is described above is only a preferred embodiment of the present invention, and the present invention is not limited to the above examples. It can be understood that other improvements and changes directly derived or conceived by those skilled in the art without departing from the basic idea of the present invention shall be considered to be included in the protection scope of the present invention.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810715957.2A CN108796553B (en) | 2018-06-29 | 2018-06-29 | Tetragonal phase CoSe for catalytic hydrogen evolution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810715957.2A CN108796553B (en) | 2018-06-29 | 2018-06-29 | Tetragonal phase CoSe for catalytic hydrogen evolution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108796553A true CN108796553A (en) | 2018-11-13 |
| CN108796553B CN108796553B (en) | 2020-05-22 |
Family
ID=64074203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810715957.2A Expired - Fee Related CN108796553B (en) | 2018-06-29 | 2018-06-29 | Tetragonal phase CoSe for catalytic hydrogen evolution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108796553B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923268A (en) * | 2015-06-08 | 2015-09-23 | 中国科学院长春应用化学研究所 | Self-support transition metal selenide catalyst as well as preparation method and application thereof |
-
2018
- 2018-06-29 CN CN201810715957.2A patent/CN108796553B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923268A (en) * | 2015-06-08 | 2015-09-23 | 中国科学院长春应用化学研究所 | Self-support transition metal selenide catalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIUQUAN ZHOU ET AL: ""Metastable Layered Cobalt Chalcogenides from Topochemical Deintercalation"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108796553B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6678405B2 (en) | Lithium solid electrolyte | |
| CN102931335B (en) | A kind of Graphene is combined thermoelectric material of cobalt stibide based skutterudite and preparation method thereof | |
| CN103979507A (en) | Method for preparing spherical aluminum nitride powder under assistance of high atmospheric pressure and fluoride additive | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| CN107176589B (en) | It is a kind of to prepare nanosizing Mg3Sb2The method of thermoelectric material | |
| CN103915627B (en) | Adopt high temperature insostatic pressing (HIP) method to prepare the method for ferrous silicate lithium anode material | |
| CN113526474A (en) | Lithium nitride particles, and method and apparatus for producing same | |
| JPWO2012161055A1 (en) | Manufacturing method of material used for at least one of energy device and power storage device | |
| CN105329901B (en) | It is a kind of that the method that zinc compound removes boron impurity in industrial silicon is added into calcium silicates | |
| CN102198933B (en) | A kind of preparation method of high-capacity composite hydrogen storage material calcium borohydride/monoammine lithium borohydride | |
| CN101956110A (en) | A method for preparing Mg2BIV-based thermoelectric materials by solid-state reaction at low temperature | |
| CN108063249B (en) | A kind of preparation method of high-purity copper nitride nanocrystals | |
| CN1876859A (en) | Process for preparing anti-perovskite type manganese-based nitride | |
| CN108796553A (en) | A kind of tetragonal phase CoSe and preparation method for catalytic hydrogen evolution | |
| JP5058880B2 (en) | Conductive ceramic materials | |
| CN1272460C (en) | RE-Mg-Ni series three-element or more system hydrogen-storage alloy and amorphous preparing method thereof | |
| CN103626495B (en) | Preparation method for CIGS target material through pressureless sintering | |
| CN106927815A (en) | Titanate solid electrolyte and preparation method thereof | |
| CN103253668A (en) | Low-temperature solid-phase synthesis method for titanium carbide ceramic powder | |
| CN109956742B (en) | A kind of method for preparing high-purity cerium aluminate by high temperature buried carbon method | |
| CN102324509A (en) | Preparation method of metastable phase LiC6 alloy | |
| CN117276642B (en) | Sodium ion sulfide electrolyte and preparation method and application thereof | |
| CN116178019A (en) | Method for preparing porous MAX phase ceramic material by pressureless wrapping calcination | |
| CN102731109A (en) | AlON material synthetic method | |
| JP2011195385A (en) | Lithium silicon nitride and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200522 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |