CN117568843A - Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof - Google Patents
Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
本发明公开了一种富含硒缺陷的二硒化锡纳米片电催化剂的制备方法:将二氧化硒和金属锡盐溶解后加入水合肼溶液,搅拌混合,经过水热反应得到富含硒缺陷的二硒化锡纳米片电催化剂。本发明还公开了上述制备方法得到的富含硒缺陷的二硒化锡纳米片电催化剂及其作为工作电极在甲酸电合成中的应用。本发明提供的催化剂分别在碱性、中性和酸性电解质中实现HCOOH电合成的高选择性,对应的pH条件下HCOOH偏电流密度达到工业级水平,充分展现出其在全pH范围内优异的HCOOH电合成性能。
The invention discloses a method for preparing a tin selenide nanosheet electrocatalyst rich in selenium defects: dissolving selenium dioxide and metal tin salt, adding hydrazine hydrate solution, stirring and mixing, and obtaining selenium-rich defects through hydrothermal reaction. tin diselenide nanosheet electrocatalyst. The invention also discloses the selenium-deficient tin diselenide nanosheet electrocatalyst obtained by the above preparation method and its application as a working electrode in the electrosynthesis of formic acid. The catalyst provided by the invention achieves high selectivity for HCOOH electrosynthesis in alkaline, neutral and acidic electrolytes respectively. Under corresponding pH conditions, the HCOOH bias current density reaches the industrial level, fully demonstrating its excellent performance in the entire pH range. HCOOH electrosynthetic properties.
Description
技术领域Technical field
本发明涉及电催化剂技术领域,具体涉及一种富含硒缺陷的二硒化锡纳米片电催化剂及其制备方法和应用。The invention relates to the technical field of electrocatalysts, and in particular to a tin diselenide nanosheet electrocatalyst rich in selenium defects and its preparation method and application.
背景技术Background technique
利用可再生能源将二氧化碳(CO2)电还原为高附加值的含碳化学品(如一氧化碳、甲酸和甲烷),在各种还原产物中,甲酸(HCOOH)被认为是最具有技术经济性的产物之一,在实际应用中得到了广泛的应用。迄今为止,已经报道了几种主要的p区金属主族催化剂,包括Sn、In和Bi等,以及一系列相应的金属氧化物(如氧化锡和氧化铟)通过电还原CO2合成HCOOH。其中,由于金属锡基材料成本低,对电合成HCOOH过程中的*OOCH中间体的吸附能适中,因此被广泛应用于电还原CO2合成HCOOH。然而,目前报道的金属锡基催化剂在实现高选择性工业级电流密度下(>200mA cm-2)HCOOH电合成的方面仍面临着重大挑战。Renewable energy is used to electrically reduce carbon dioxide (CO 2 ) into high value-added carbon-containing chemicals (such as carbon monoxide, formic acid, and methane). Among various reduction products, formic acid (HCOOH) is considered to be the most technically and economically efficient. One of the products has been widely used in practical applications. To date, several major p-block metal main group catalysts, including Sn, In, and Bi, etc., as well as a series of corresponding metal oxides (such as tin oxide and indium oxide) have been reported for the synthesis of HCOOH via electroreduction of CO2 . Among them, metal tin-based materials are widely used in the electroreduction of CO2 to synthesize HCOOH due to their low cost and moderate adsorption energy for the * OOCH intermediate in the electrosynthesis of HCOOH. However, currently reported metallic tin-based catalysts still face significant challenges in achieving the electrosynthesis of HCOOH at highly selective industrial-grade current densities (>200 mA cm -2 ).
目前,HCOOH电合成大多在碱性或中性电解质中进行,因此不可避免地形成碳酸盐副产物,导致CO2利用效率降低。采用酸性电解液是解决这些问题的有效方法之一。然而,由于电还原CO2过程中竞争性的析氢副反应和不可避免的质子浓度变化,在酸性电解质中实现持续有效的CO2转化仍然面临着巨大挑战。因此,在工业应用中,开发在全pH范围内工作良好的理想催化剂是非常必要的。如公开号为CN115584522A的中国专利文献公开了一种三维多孔电极制备方法及其酸性电催化CO2还原制备甲酸的应用,将催化剂、聚合物、有机溶剂混合均匀配置复合浆料,用刮刀将糊状物均匀涂布在碳布上得到未成形胚体,最后经过干燥处理获得三维多孔电极,实现在pH小于3.77的酸性条件下电还原制备HCOOH。Currently, HCOOH electrosynthesis is mostly carried out in alkaline or neutral electrolytes, so carbonate by-products are inevitably formed, resulting in reduced CO utilization efficiency. Using acidic electrolyte is one of the effective ways to solve these problems. However, achieving sustained and efficient CO conversion in acidic electrolytes still faces huge challenges due to the competitive hydrogen evolution side reaction and inevitable proton concentration changes during the electroreduction of CO . Therefore, in industrial applications, it is very necessary to develop ideal catalysts that work well in the full pH range. For example, the Chinese patent document with publication number CN115584522A discloses a three-dimensional porous electrode preparation method and its application in acidic electrocatalytic CO 2 reduction to prepare formic acid. The catalyst, polymer, and organic solvent are mixed evenly to form a composite slurry, and the paste is spread with a scraper. The shape is uniformly coated on the carbon cloth to obtain an unshaped embryo body, and finally a three-dimensional porous electrode is obtained through drying, which enables the preparation of HCOOH by electroreduction under acidic conditions with a pH of less than 3.77.
由于质子形成和输运过程中的反应动力学缓慢,*OOCH中间体的生成通常是决定速率的反应步骤。因此,加速质子的生成和转移是提高*OOCH/HCOOH生成速率的有效方法。引入缺陷结构被认为是调控金属电子和表面结构最直接有效的方法之一,近年来得到了广泛的研究。如公开号CN116103680A的中国专利文献公开了一种富含氧空位的碳酸氧铋电催化剂及其制备方法,将铋盐溶解于乙二醇和水溶液中,加入适量辅助导电盐后冷藏得到电解液,利用恒电流法在工作电极上电化学沉积得到富含氧空位的碳酸氧铋纳米片,氧空位的引入改善了碳酸氧铋的导电性,提升了碳酸氧铋的水裂解能力以及HCOOH合成的本征活性。Due to the slow reaction kinetics during proton formation and transport, the formation of the *OOCH intermediate is usually the rate-determining reaction step. Therefore, accelerating the generation and transfer of protons is an effective method to increase the generation rate of *OOCH/HCOOH. The introduction of defect structures is considered to be one of the most direct and effective methods to regulate metal electronics and surface structures, and has been extensively studied in recent years. For example, the Chinese patent document No. CN116103680A discloses a bismuth oxycarbonate electrocatalyst rich in oxygen vacancies and its preparation method. The bismuth salt is dissolved in ethylene glycol and an aqueous solution, an appropriate amount of auxiliary conductive salt is added and then refrigerated to obtain an electrolyte. The galvanostatic method electrochemically deposits bismuth oxycarbonate nanosheets rich in oxygen vacancies on the working electrode. The introduction of oxygen vacancies improves the conductivity of bismuth oxycarbonate, enhances the water splitting ability of bismuth oxycarbonate and the intrinsic properties of HCOOH synthesis. active.
尽管对于不同电解液环境下电还原CO2合成HCOOH研究已经有了很大的进展,但是对于在全pH范围内实现工业级电流密度(>200mA cm-2)的HCOOH电合成仍然面临选择性低等问题。Although great progress has been made in the electroreduction of CO2 to synthesize HCOOH under different electrolyte environments, the electrosynthesis of HCOOH to achieve industrial-grade current density (>200mA cm -2 ) in the full pH range still faces low selectivity. And other issues.
发明内容Contents of the invention
本发明的目的在于提供一种富含硒缺陷的二硒化锡纳米片电催化剂的制备方法,制备得到的催化剂富含硒缺陷,展现了优异的HCOOH电合成的催化性能。The purpose of the present invention is to provide a method for preparing a tin diselenide nanosheet electrocatalyst rich in selenium defects. The prepared catalyst is rich in selenium defects and exhibits excellent catalytic performance for HCOOH electrosynthesis.
为实现上述目的,本发明采用的技术方案是:In order to achieve the above objects, the technical solution adopted by the present invention is:
一种富含硒缺陷的二硒化锡纳米片电催化剂的制备方法,所述制备方法包括以下步骤:将二氧化硒和金属锡盐溶解后加入水合肼溶液,搅拌混合,经过水热反应得到富含硒缺陷的二硒化锡纳米片电催化剂。A method for preparing a selenium-deficient tin diselenide nanosheet electrocatalyst. The preparation method includes the following steps: dissolving selenium dioxide and metal tin salt, adding hydrazine hydrate solution, stirring and mixing, and obtaining through hydrothermal reaction Selenium-rich tin diselenide nanosheet electrocatalysts.
本发明提供的富含硒缺陷的二硒化锡纳米片电催化剂的制备原理为:二氧化硒和金属锡盐均匀分散的混合溶液中加入还原试剂水合肼,强还原性的水合肼分子将溶液中的Sn2+和Se4+还原成原子,具有高反应活性的Sn原子和Se原子结合形成二硒化锡分子,同时伴随硒缺陷的形成。其中,硒缺陷的引入使得更多的电子从Se位点转移到Sn位点,有效加速水分子的解离,提高了质子转移速率,进而加速CO2在锡活性位点的高效转化。The preparation principle of the selenium-deficient tin diselenide nanosheet electrocatalyst provided by the invention is: adding the reducing reagent hydrazine hydrate to a uniformly dispersed mixed solution of selenium dioxide and metal tin salts, and the strongly reducing hydrazine hydrate molecules convert the solution into Sn 2+ and Se 4+ are reduced to atoms, and the highly reactive Sn atoms and Se atoms combine to form tin diselenide molecules, accompanied by the formation of selenium defects. Among them, the introduction of selenium defects causes more electrons to be transferred from Se sites to Sn sites, effectively accelerating the dissociation of water molecules, increasing the proton transfer rate, and thereby accelerating the efficient conversion of CO 2 at the tin active site.
所述金属锡盐为可溶性盐,优选地,所述金属锡盐为二水合氯化亚锡。The metal tin salt is a soluble salt. Preferably, the metal tin salt is stannous chloride dihydrate.
所述二氧化硒和金属锡盐的摩尔比为1.5~2.5:1。本发明通过改变二氧化硒的用量,制备出不同纯度的富含硒缺陷的二硒化锡纳米片。当二氧化硒的摩尔浓度过低时,得到的二硒化锡的纯度就会有所降低,会有杂相锡的存在,对于电还原CO2合成HCOOH性能没有明显的提高;当二氧化硒的摩尔浓度过高时,会出现硒杂相,使得HCOOH电合成的性能明显降低。The molar ratio of selenium dioxide and metal tin salt is 1.5-2.5:1. The present invention prepares tin diselenide nanosheets rich in selenium defects of different purity by changing the dosage of selenium dioxide. When the molar concentration of selenium dioxide is too low, the purity of the obtained tin diselenide will be reduced, and there will be the presence of heterogeneous tin. The performance of the electroreduction of CO 2 to synthesize HCOOH will not be significantly improved; when selenium dioxide When the molar concentration is too high, selenium impurity phases will appear, significantly reducing the performance of HCOOH electrosynthesis.
进一步的,将二氧化硒和金属锡盐溶解于水中,得到的混合溶液中,二氧化硒的质量浓度为7.4~22.2g L-1,锡盐的质量浓度为15.0g L-1。优选地,二氧化硒的质量浓度为14.8g L-1。Further, selenium dioxide and metal tin salt are dissolved in water. In the obtained mixed solution, the mass concentration of selenium dioxide is 7.4-22.2g L -1 and the mass concentration of tin salt is 15.0g L -1 . Preferably, the mass concentration of selenium dioxide is 14.8g L -1 .
其中,二氧化硒和金属锡盐溶解于一定量的水溶液,反应温度为室温,搅拌时间为10~20min。优选地,所述搅拌时间为20min。Among them, selenium dioxide and metal tin salt are dissolved in a certain amount of aqueous solution, the reaction temperature is room temperature, and the stirring time is 10 to 20 minutes. Preferably, the stirring time is 20 minutes.
进一步的,加入水合肼后的混合溶液中,水合肼的质量浓度为54.8g L-1。Further, in the mixed solution after adding hydrazine hydrate, the mass concentration of hydrazine hydrate was 54.8g L -1 .
其中,所述二氧化硒和金属锡盐溶解的混合溶液加入水合肼溶液后,反应温度为常温,搅拌时间为3~8min。搅拌时间过长会影响二硒化锡的形貌不够均匀,以及硒缺陷的形成,从而影响电催化剂性能。优选地,搅拌时间为3min。Wherein, after the mixed solution of selenium dioxide and metal tin salt is added to the hydrazine hydrate solution, the reaction temperature is normal temperature, and the stirring time is 3 to 8 minutes. Excessive stirring time will affect the uneven morphology of tin diselenide and the formation of selenium defects, thereby affecting the performance of the electrocatalyst. Preferably, the stirring time is 3 minutes.
所述水热反应温度为160~200℃。通过改变水热反应温度,制备出不同含量的硒缺陷的二硒化锡纳米片。当水热反应温度过低时,不易形成富含硒缺陷的二硒化锡纳米片;当水热反应温度过高时,二硒化锡的纳米片容易在高温时发生晶相转变,从而使得电还原CO2制备HCOOH性能降低。The hydrothermal reaction temperature is 160-200°C. By changing the hydrothermal reaction temperature, tin diselenide nanosheets with different contents of selenium defects were prepared. When the hydrothermal reaction temperature is too low, it is difficult to form tin diselenide nanosheets rich in selenium defects; when the hydrothermal reaction temperature is too high, the tin diselenide nanosheets are prone to crystal phase transformation at high temperatures, resulting in The performance of electroreduction of CO2 to prepare HCOOH is reduced.
优选地,所述二氧化硒和金属锡盐的摩尔比为1.5~2:1,所述水热反应温度为180~200℃。通过限定上述摩尔比和反应温度,制备得到的二硒化锡纳米片中硒缺陷的纯度以及含量更利于提高电还原CO2制备HCOOH的选择性。Preferably, the molar ratio of selenium dioxide and metal tin salt is 1.5-2:1, and the hydrothermal reaction temperature is 180-200°C. By limiting the above molar ratio and reaction temperature, the purity and content of selenium defects in the prepared tin diselenide nanosheets are more conducive to improving the selectivity of electroreduction of CO 2 to prepare HCOOH.
本发明还提供了一种根据上述制备方法得到的富含硒缺陷的二硒化锡纳米片电催化剂。The invention also provides a selenium-deficient tin diselenide nanosheet electrocatalyst obtained according to the above preparation method.
所述催化剂中丰富的硒缺陷存在二硒化锡纳米片中,所述二硒化锡纳米片电催化剂中硒与锡的原子比1.8~2.0:1。Abundant selenium defects in the catalyst exist in tin diselenide nanosheets, and the atomic ratio of selenium to tin in the tin diselenide nanosheet electrocatalyst is 1.8 to 2.0:1.
本发明还提供了一种上述富含硒缺陷的二硒化锡纳米片电催化剂作为工作电极在甲酸电合成中的应用。The present invention also provides an application of the above-mentioned tin diselenide nanosheet electrocatalyst rich in selenium defects as a working electrode in the electrosynthesis of formic acid.
进一步的,所述富含硒缺陷的二硒化锡纳米片电催化剂作为工作电极在全pH范围内工业级电流密度下的甲酸电合成中的应用。Further, the selenium-deficient tin diselenide nanosheet electrocatalyst is used as a working electrode in the electrosynthesis of formic acid at industrial-grade current density in the full pH range.
本发明提供的富含硒缺陷的二硒化锡纳米片电催化剂在工业电流密度下(>200mAcm-2)实现高选择性的性能。其中,在碱性、中性和酸性电解质中的最高HCOOH的选择性分别为94.1%、81.7%和78.1%,HCOOH的偏电流密度峰值分别为800、568和495mA cm-2,其电催化性能远胜于商业的二硒化锡催化剂。The selenium-deficient tin diselenide nanosheet electrocatalyst provided by the present invention achieves high selectivity performance under industrial current density (>200mAcm -2 ). Among them, the highest selectivities of HCOOH in alkaline, neutral and acidic electrolytes are 94.1%, 81.7% and 78.1% respectively. The peak bias current density of HCOOH is 800, 568 and 495mA cm -2 respectively. Its electrocatalytic performance Far better than commercial tin diselenide catalysts.
本发明提供的富含硒缺陷的二硒化锡纳米片电催化剂能够有效提高其对水分子的吸附与解离能力,加速质子转移和中间体的形成速率,从而进一步提升其电催化活性,对实现工业条件下制备HCOOH是极具意义的。The selenium-deficient tin diselenide nanosheet electrocatalyst provided by the present invention can effectively improve its adsorption and dissociation ability of water molecules, accelerate proton transfer and the formation rate of intermediates, thereby further improving its electrocatalytic activity, and It is of great significance to prepare HCOOH under industrial conditions.
与现有技术相比,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明提供的富含硒缺陷的二硒化锡纳米片电催化剂实现了高选择性CO2催化转化为HCOOH,且具有较宽的可操作pH窗口(2.0~14.0)。实现了在不同pH环境下的工业级电流密度的HCOOH电合成,为进一步工业大规模应用提供了可能性。(1) The selenium-deficient tin diselenide nanosheet electrocatalyst provided by the present invention achieves highly selective catalytic conversion of CO 2 into HCOOH and has a wide operable pH window (2.0-14.0). The electrosynthesis of HCOOH at industrial-grade current densities under different pH environments was achieved, providing the possibility for further industrial large-scale applications.
(2)本发明提供的富含硒缺陷的二硒化锡纳米片电催化剂,通过引入硒缺陷,有效调节了二硒化锡的电子结构,使得锡位点周围的电子密度更加丰富,有效加速水分子解离出更多质子,进而加速中间体*COOH形成,最终加速HCOOH合成过程。(2) The tin diselenide nanosheet electrocatalyst rich in selenium defects provided by the present invention effectively adjusts the electronic structure of tin diselenide by introducing selenium defects, making the electron density around the tin site richer and effectively accelerating Water molecules dissociate more protons, thereby accelerating the formation of the intermediate *COOH, and ultimately accelerating the HCOOH synthesis process.
附图说明Description of the drawings
图1为实施例1制备的催化剂的扫描电镜SEM图;Figure 1 is a scanning electron microscope SEM image of the catalyst prepared in Example 1;
图2为实施例1制备的催化剂的X射线衍射XRD图;Figure 2 is an X-ray diffraction XRD pattern of the catalyst prepared in Example 1;
图3为实施例1和实施例2~3制备的催化剂的电子顺磁共振EPR图;Figure 3 is an electron paramagnetic resonance EPR pattern of the catalyst prepared in Example 1 and Examples 2-3;
图4为实施例1制备的催化剂在应用例中电还原CO2制备HCOOH的法拉第效率。Figure 4 shows the Faradaic efficiency of the catalyst prepared in Example 1 for the electroreduction of CO 2 to prepare HCOOH in application examples.
图5为实施例1和实施例2~3制备的催化剂在应用例中电还原CO2制备HCOOH的法拉第效率。Figure 5 shows the Faradaic efficiency of the catalysts prepared in Example 1 and Examples 2-3 in the electroreduction of CO 2 to prepare HCOOH in application examples.
图6为实施例1和实施例4~5制备的催化剂在应用例中pH=14.0环境下电还原CO2制备HCOOH的法拉第效率。Figure 6 shows the Faradaic efficiency of the catalyst prepared in Example 1 and Examples 4-5 in the application example of electroreduction of CO 2 to prepare HCOOH in an environment of pH = 14.0.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。本领域技术人员在理解本发明的技术方案基础上进行修改或等同替换,而未脱离本发明技术方案的精神和范围,均应涵盖在本发明的保护范围内。以下具体实施方式中所使用的原料均购于市场。In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with examples. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention. Modifications or equivalent substitutions made by those skilled in the art on the basis of understanding the technical solutions of the present invention, without departing from the spirit and scope of the technical solutions of the present invention, shall be covered by the protection scope of the present invention. The raw materials used in the following specific embodiments were all purchased from the market.
实施例1Example 1
(1)称取443.8mg二氧化硒固体颗粒和451.3mg二水合氯化亚锡固体颗粒,溶解于30mL去离子水溶液中,常温搅拌20min,备用;(1) Weigh 443.8 mg selenium dioxide solid particles and 451.3 mg stannous chloride dihydrate solid particles, dissolve them in 30 mL deionized water solution, stir at room temperature for 20 minutes, and set aside;
(2)将步骤(1)已经配置好的溶液加入2mL的85wt.%水合肼溶液,搅拌5min;将得到的混合溶液转移到50mL的水热釜中,在180℃下水热反应24h;(2) Add 2 mL of 85wt.% hydrazine hydrate solution to the solution prepared in step (1), and stir for 5 minutes; transfer the obtained mixed solution to a 50 mL hydrothermal kettle, and conduct a hydrothermal reaction at 180°C for 24 hours;
(3)将步骤(2)得到的初产物离心分离,用水和乙醇分别洗涤3次以上,最后在真空烘箱内60℃干燥12h,得到富含硒缺陷的二硒化锡纳米片催化剂。(3) Centrifuge the primary product obtained in step (2), wash it more than three times with water and ethanol, and finally dry it in a vacuum oven at 60°C for 12 hours to obtain a tin diselenide nanosheet catalyst rich in selenium defects.
将制备的催化剂通过扫描电镜SEM观察其微观形貌,SEM结果如图1所示,可以看到富含硒缺陷的二硒化锡催化剂的形态结构为六边形片状结构,片层厚度约为50nm。本实施例制备的富含硒缺陷的二硒化锡的X射线衍射XRD图如图2所示,可以看到二硒化锡的晶相特征峰,电子顺磁共振EPR图如图3所示,可以明显看出硒缺陷的存在,说明富含硒缺陷的二硒化锡纳米片电催化剂的成功制备。The microscopic morphology of the prepared catalyst was observed through scanning electron microscopy (SEM). The SEM results are shown in Figure 1. It can be seen that the morphological structure of the tin diselenide catalyst rich in selenium defects is a hexagonal lamellar structure, and the lamellar thickness is about is 50nm. The X-ray diffraction XRD pattern of the selenium-deficient tin diselenide prepared in this embodiment is shown in Figure 2. The characteristic peaks of the crystal phase of tin diselenide can be seen, and the electron paramagnetic resonance EPR pattern is shown in Figure 3. , the existence of selenium defects can be clearly seen, indicating the successful preparation of tin diselenide nanosheet electrocatalysts rich in selenium defects.
实施例2Example 2
按照实施例1的制备工艺,将步骤(2)中的水热反应温度更改为160℃得到实施例2催化剂。According to the preparation process of Example 1, the hydrothermal reaction temperature in step (2) was changed to 160°C to obtain the catalyst of Example 2.
实施例3Example 3
按照实施例1的制备工艺,将步骤(2)中的水热反应温度更改为200℃得到实施例3催化剂。According to the preparation process of Example 1, the hydrothermal reaction temperature in step (2) was changed to 200°C to obtain the catalyst of Example 3.
实施例4Example 4
按照实施例1的制备工艺,将步骤(1)中的二氧化硒固体颗粒质量更改为332.8mg得到实施例4催化剂。According to the preparation process of Example 1, the mass of the selenium dioxide solid particles in step (1) was changed to 332.8 mg to obtain the catalyst of Example 4.
实施例5Example 5
按照实施例1的制备工艺,将步骤(1)中的二氧化硒固体颗粒质量更改为554.7mg得到实施例5催化剂。According to the preparation process of Example 1, the mass of the selenium dioxide solid particles in step (1) was changed to 554.7 mg to obtain the catalyst of Example 5.
应用例 全pH范围内工业级电流密度下的HCOOH电合成Application Example HCOOH electrosynthesis at industrial-grade current density in the full pH range
首先将上述制备的10mg催化剂分散于1000μL的乙醇/Nafion体积比为9:1的分散液中,随后将100μL的分散液喷涂至0.5*0.5cm2的气体扩散电极上,待自然干燥后,将其作为工作电极放置于三电极流动池测量装置中,该装置由两个隔间组成,由阴离子交换膜隔开。其中,采用1.0M KOH溶液作为碱性电解质,1.0M KHCO3溶液作为中性电解质,0.5M K2SO4和H2SO4混合溶液作为酸性电解质。碱性和中性电解液的对电极为泡沫镍,酸性电解液的对电极铂片,参比电极为银/氯化银电极。First, 10 mg of the catalyst prepared above was dispersed in 1000 μL of ethanol/Nafion dispersion with a volume ratio of 9:1, and then 100 μL of the dispersion was sprayed onto a 0.5* 0.5cm2 gas diffusion electrode. After natural drying, It is placed as a working electrode in a three-electrode flow cell measurement device, which consists of two compartments separated by an anion exchange membrane. Among them, 1.0M KOH solution is used as the alkaline electrolyte, 1.0M KHCO3 solution is used as the neutral electrolyte, and 0.5MK2SO4 and H2SO4 mixed solution is used as the acidic electrolyte. The counter electrode for alkaline and neutral electrolytes is nickel foam, the counter electrode for acidic electrolyte is platinum sheet, and the reference electrode is silver/silver chloride electrode.
循环伏安(CV)活化:使用上海辰华CHI 760E电化学工作站,采用CV程序,测试区间在0~-1.4V vs.RHE,扫速为50mV s-1,循环扫描40圈后电极达到稳定状态。Cyclic voltammetry (CV) activation: Shanghai Chenhua CHI 760E electrochemical workstation is used, using the CV program, the test range is 0 ~ -1.4V vs. RHE, the scanning speed is 50mV s -1 , and the electrode reaches stability after 40 cycles of scanning. state.
线性扫描伏安法(LSV)测试:CV活化后,切换程序到LSV程序,测试区间为0~-1.4Vvs.RHE,扫速为5mV s-1。Linear sweep voltammetry (LSV) test: After CV activation, switch the program to the LSV program, the test range is 0~-1.4Vvs.RHE, and the sweep speed is 5mV s -1 .
法拉第效率(FE)测试:切换程序为恒电流电压-时间测试,在执行恒电流测试期间,使用气相色谱测定气相产物浓度,计算产物的FE。气相色谱(GC,Fuli 9790II)在线定量,用1H核磁共振仪分析液体产物的FE,采用内标法即以二甲基亚砜为标准进行测定。Faraday efficiency (FE) test: Switch the program to a galvanostatic voltage-time test. During the galvanostatic test, use gas chromatography to measure the gas phase product concentration and calculate the FE of the product. Gas chromatography (GC, Fuli 9790II) was used for online quantification, and a 1 H nuclear magnetic resonance instrument was used to analyze the FE of the liquid product, and the internal standard method was used, that is, dimethyl sulfoxide was used as the standard.
其结果如图4所示,实施例1所制备的富含硒缺陷的二硒化锡纳米片电催化剂展现了优异的全pH范围内的HCOOH电合成性能,在碱性、中性和酸性电解质中分别实现了HCOOH的94.1%、81.7%和78.1%的选择性,对应的HCOOH分电流密度800、568和495mA cm-2达到了工业级水平。The results are shown in Figure 4. The selenium-deficient tin diselenide nanosheet electrocatalyst prepared in Example 1 exhibits excellent HCOOH electrosynthesis performance in the entire pH range, in alkaline, neutral and acidic electrolytes. The selectivities of HCOOH were 94.1%, 81.7% and 78.1% respectively, and the corresponding HCOOH partial current densities of 800, 568 and 495mA cm -2 reached the industrial level.
将实施例1与实施例2~3所制备的电催化剂在电压-0.8V vs.RHE不同pH环境下的HCOOH法拉第效率进行对比,结果如图5所示,实施例1所制备的富含硒缺陷的二硒化锡纳米片电催化剂的全pH范围内HCOOH电合成性能远优于实施例2和实施例3。The HCOOH Faradaic efficiencies of the electrocatalysts prepared in Example 1 and Examples 2-3 were compared under different pH environments of voltage -0.8V vs. RHE. The results are shown in Figure 5. The selenium-rich electrocatalyst prepared in Example 1 The HCOOH electrosynthesis performance of the defective tin diselenide nanosheet electrocatalyst in the full pH range is far better than that of Example 2 and Example 3.
将实施例1与实施例4~5所制备的电催化剂在pH=14.0环境下对比HCOOH电合成性能,结果如图6所示,实施例1所制备的富含硒缺陷的二硒化锡纳米片电催化剂HCOOH电合成选择性远高于实施例4和实施例5。The HCOOH electrosynthesis performance of the electrocatalysts prepared in Example 1 and Examples 4-5 was compared in an environment of pH=14.0. The results are shown in Figure 6. The tin diselenide nanoparticles rich in selenium defects prepared in Example 1 The HCOOH electrosynthesis selectivity of the sheet electrocatalyst is much higher than that of Example 4 and Example 5.
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