CN112899723B - Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof - Google Patents
Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof Download PDFInfo
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Abstract
金属有机框架衍生的铁镍金属硫化物催化剂及制备与应用，涉及可再生能源催化材料。通过简易的溶剂热硫化得到的铁镍金属硫化物催化剂，对于电催化析氧反应表现出较好的活性。制备方法包括如下步骤：取硫代乙酰胺溶于乙醇，然后加入MIL‑88，搅拌一定时间后，转移至反应釜中进行溶剂热反应；溶剂热处理后，依次经过冷却，洗涤，干燥即得到所述催化剂。其结构内部的硫化物种能够增强导电性，并且可以原位生成羟基氧化物种，暴露更多的活性位点，富含介孔的孔道结构有利于快速的电子传输以及水分子吸附和气体产物的释放，提升电催化活性。该电催化剂具有催化活性高、稳定性好，制备工艺简便的优点，具有较强的应用价值。
Metal-organic framework-derived iron-nickel metal sulfide catalyst, preparation and application, involving renewable energy catalytic materials. The iron-nickel metal sulfide catalyst obtained by simple solvothermal sulfidation showed good activity for electrocatalytic oxygen evolution reaction. The preparation method includes the following steps: dissolving thioacetamide in ethanol, then adding MIL-88, stirring for a certain period of time, and then transferring to a reaction kettle for solvothermal reaction; after solvothermal treatment, sequentially cooling, washing, and drying to obtain the obtained product. described catalyst. The sulfide species inside its structure can enhance electrical conductivity, and can generate oxyhydroxide species in situ, exposing more active sites, and the mesoporous-rich pore structure is conducive to fast electron transport as well as water molecule adsorption and gas product release. , to enhance the electrocatalytic activity. The electrocatalyst has the advantages of high catalytic activity, good stability and simple preparation process, and has strong application value.
Description
技术领域technical field
本发明涉及可再生能源催化材料，尤其是涉及一种金属有机框架衍生的铁镍金属硫化物催化剂及制备与应用。The invention relates to renewable energy catalytic materials, in particular to a metal-organic framework-derived iron-nickel metal sulfide catalyst and its preparation and application.
背景技术Background technique
氢能作为备受瞩目的二次能源，具有安全环保，高能清洁的特点，因此被广泛应用于发电、动力汽车、燃料电池等领域。我国在科技发展“十五”计划和2015年远景规划中将氢能技术列入能源领域中，这意味着氢能在能源发展战略中的重要地位。电解水制氢技术是一种高效制取高纯度氢能源的途径，其核心是阳极的析氧反应(OER)和阴极的析氢反应(HER)。其中，由于析氧反应是一个具有较高能垒的多步质子耦合电子转移的过程，所以限制全水分解反应的进行。目前商业用催化剂多是价格昂贵的贵金属催化剂，如IrO2和RuO2，为了降低催化剂的制备成本及提高催化活性，亟需研究一种高效廉价的电催化剂加速OER反应的进行。As a high-profile secondary energy, hydrogen energy has the characteristics of safety, environmental protection, high energy and cleanliness, so it is widely used in power generation, power vehicles, fuel cells and other fields. my country has included hydrogen energy technology in the energy field in the "Tenth Five-Year" plan for scientific and technological development and the 2015 long-term plan, which means that hydrogen energy plays an important role in the energy development strategy. Hydrogen production by electrolysis of water is an efficient way to produce high-purity hydrogen energy. Its core is the oxygen evolution reaction (OER) at the anode and the hydrogen evolution reaction (HER) at the cathode. Among them, since the oxygen evolution reaction is a multi-step proton-coupled electron transfer process with a high energy barrier, the progress of the total water splitting reaction is limited. At present, most of the commercial catalysts are expensive noble metal catalysts, such as IrO 2 and RuO 2 . In order to reduce the preparation cost of the catalyst and improve the catalytic activity, it is urgent to develop an efficient and cheap electrocatalyst to accelerate the OER reaction.
在众多非贵金属电催化剂中，金属有机框架催化剂以其较大的比表面积，高度分散的金属中心，多样化的有机配体引起研究人员的关注。例如，中国专利CN111921560A公开一种超薄金属有机框架(MOF)纳米片催化剂的制备方法和析氧性能的研究，该方法将二茂铁甲酸和对苯二甲酸溶解于N,N-二甲基甲酰胺、乙醇和水的混合溶液后，引入钴盐及缚酸剂后超声剥离，再通过离心洗涤得到纳米片催化剂。该金属有机框架纳米片由于晶格畸变以及较大的比表面积活性有所提升。Xie等人(M.Xie,Y.Ma,D.Lin,C.Xu,F.Xie,W.Zeng,Nanoscale2020,12,67-71)报道一种MIL-53(Co-Fe)催化剂应用于析氧反应的研究，该金属有机框架通过钴铁金属的协同作用以及片状形貌的特点提高电催化的活性。Li等人(F.-L.Li,Q.Shao,X.Huang,J.-P.Lang,Angew.Chem.Int.Ed.Engl.2018,57,1888-1892)报道一种超薄Ni-Fe-MOF纳米片材料应用与析氧反应的研究，该金属有机框架通过自下而上的湿化学合成方法得到高产率以及较好均一性的2D超薄纳米片，通过形貌工程提高反应的活性。但所述金属有机框架中有机配体的存在导致材料导电性能不佳，限制析氧反应的发生。Among many non-noble metal electrocatalysts, metal-organic framework catalysts have attracted the attention of researchers due to their large specific surface area, highly dispersed metal centers, and diverse organic ligands. For example, Chinese patent CN111921560A discloses a preparation method of ultra-thin metal-organic framework (MOF) nanosheet catalyst and research on oxygen evolution performance. The method dissolves ferrocene formic acid and terephthalic acid in N,N-dimethyl After the mixed solution of formamide, ethanol and water, cobalt salt and acid binding agent are introduced, ultrasonic peeling is performed, and the nanosheet catalyst is obtained by centrifugal washing. The metal-organic framework nanosheets have improved activity due to lattice distortion and larger specific surface area. Xie et al. (M.Xie, Y.Ma, D.Lin, C.Xu, F.Xie, W.Zeng, Nanoscale 2020, 12, 67-71) reported a MIL-53(Co-Fe) catalyst applied in For the study of oxygen evolution reaction, this metal-organic framework enhances the electrocatalytic activity through the synergistic effect of cobalt-iron metal and the characteristics of sheet-like morphology. Li et al. (F.-L. Li, Q. Shao, X. Huang, J.-P. Lang, Angew. Chem. Int. Ed. Engl. 2018, 57, 1888-1892) reported an ultrathin Ni -Research on the application of Fe-MOF nanosheet materials and oxygen evolution reaction, the metal-organic framework obtains 2D ultrathin nanosheets with high yield and better uniformity through bottom-up wet chemical synthesis method, and improves the reaction through morphology engineering activity. However, the presence of organic ligands in the metal-organic framework leads to poor electrical conductivity of the material, which limits the occurrence of oxygen evolution reaction.
过渡金属硫化物由于其具有高的导电性，在电催化领域被广泛研究。例如，中国专利CN111774071A公开一种三元金属硫化物纳米片材料的制备方法，通过将泡沫金属(Ni、Cu、Ti、Al、Co、Zn)，氯化铁及硫化钠加入水溶液中一锅水热得到三元金属硫化物纳米片。该材料的超薄形貌拥有较大比表面积，促进快速的传质和电子传输，杂原子掺杂降低活性中心电子云的密度，降低对中间体的吸附自由能，从而促进析氧反应的进行。中国专利CN112023946A公开一种通过水热法硫化合成的镍铁层状双氢氧化物硫化物催化剂。该催化剂利用硫的掺入使镍铁层状双氢氧化物的催化活性和导电性提高，有利于电子的转移。Transition metal sulfides have been widely studied in the field of electrocatalysis due to their high electrical conductivity. For example, Chinese patent CN111774071A discloses a preparation method of ternary metal sulfide nanosheet material, by adding foam metal (Ni, Cu, Ti, Al, Co, Zn), ferric chloride and sodium sulfide to a pot of water in an aqueous solution Heat to obtain ternary metal sulfide nanosheets. The ultra-thin morphology of the material has a large specific surface area, which promotes rapid mass transfer and electron transport, and heteroatom doping reduces the density of the electron cloud in the active center and reduces the adsorption free energy of intermediates, thereby promoting the oxygen evolution reaction. . Chinese patent CN112023946A discloses a nickel-iron layered double hydroxide sulfide catalyst synthesized by hydrothermal vulcanization. The catalyst utilizes the incorporation of sulfur to improve the catalytic activity and conductivity of the nickel-iron layered double hydroxide, which is beneficial to the transfer of electrons.
目前，对金属有机框架材料进行电子和结构协同调节得到衍生催化剂用于析氧反应的研究鲜有报道，Huang等人(Z.Q.Huang,B.Wang,D.S.Pan,L.L.Zhou,Z.H.Guo,J.L.Song,ChemSusChem 2020,13,2564-2570.)报道氮硫掺杂钴铁基MOF的析氧反应电催化剂。以杂原子掺杂修饰孔道结构促进质量和电荷的传输。中国专利CN109908963A通过将Ni-BDC硫化后得到Ni-BDC@NiS纳米阵列，复合高导电性的硫化物材料以及保留MOF的形态，提高OER的活性。但目前基于金属有机框架材料衍生催化剂的较差性能，较高成本，以及繁琐的制备过程等缺点，因此本发明探究金属有机框架衍生的铁镍金属硫化物催化剂的制备方法为得到低过电位，高稳定性以及廉价易制的析氧反应催化剂具有重大意义。At present, there are few reports on the synergistic adjustment of electron and structure of metal-organic framework materials to obtain derivative catalysts for oxygen evolution reaction. Huang et al. ChemSusChem 2020, 13, 2564-2570.) reported an electrocatalyst for oxygen evolution reaction of nitrogen-sulfur-doped cobalt-iron-based MOFs. Modification of the pore structure with heteroatom doping facilitates mass and charge transport. Chinese patent CN109908963A obtains Ni-BDC@NiS nanoarrays after vulcanization of Ni-BDC, composites highly conductive sulfide materials and retains the morphology of MOF to improve the activity of OER. However, at present, based on the disadvantages of metal-organic framework-derived catalysts, such as poor performance, high cost, and cumbersome preparation process, the present invention explores the preparation method of metal-organic framework-derived iron-nickel metal sulfide catalysts to obtain low overpotential, High stability and cheap and easy preparation of oxygen evolution reaction catalysts are of great significance.
发明内容SUMMARY OF THE INVENTION
本发明的第一目的在于克服现有技术存在的上述缺陷，提供一种有利于反应过程中水分子的吸附和氧气的析出，促进析氧反应，电化学性能优异，金属有机框架衍生的铁镍金属硫化物催化剂。The first object of the present invention is to overcome the above-mentioned defects in the prior art, and to provide a kind of iron-nickel derived from metal organic framework, which is beneficial to the adsorption of water molecules and the precipitation of oxygen in the reaction process, promotes the oxygen evolution reaction, and has excellent electrochemical performance. Metal sulfide catalysts.
本发明的第二目的在于提供成本低廉、原料丰富且制备过程简单的铁镍金属硫化物催化剂的制备方法。The second object of the present invention is to provide a preparation method of iron-nickel metal sulfide catalyst with low cost, abundant raw materials and simple preparation process.
本发明的第三目的在于提供所述铁镍金属硫化物催化剂在电解水的析氧反应中的应用。The third object of the present invention is to provide the application of the iron-nickel metal sulfide catalyst in the oxygen evolution reaction of electrolyzed water.
所述铁镍金属硫化物催化剂的主要组成为黄铁矿晶型的铁镍双金属硫化物，其中，催化剂中铁元素的质量含量为10％～30％，镍元素的质量含量为1％～10％，硫元素的质量含量约为5％～30％。The iron-nickel metal sulfide catalyst is mainly composed of iron-nickel bimetallic sulfide of pyrite crystal form, wherein the mass content of iron element in the catalyst is 10% to 30%, and the mass content of nickel element is 1% to 10%. %, the mass content of sulfur is about 5% to 30%.
所述铁镍金属硫化物催化剂的制备方法，包括如下步骤：The preparation method of the iron-nickel metal sulfide catalyst comprises the following steps:
1)称取铁盐、镍盐和对苯二甲酸溶于N,N-二甲基甲酰胺溶解后搅拌，形成均匀溶液；1) Weigh iron salt, nickel salt and terephthalic acid and dissolve in N,N-dimethylformamide and stir to form a homogeneous solution;
2)量取氢氧化钠溶液加入步骤1)所得溶液中搅拌均匀；2) measure the sodium hydroxide solution and add it to the solution obtained in step 1) and stir it evenly;
3)将步骤2)中的混合液转移至反应釜中进行一次溶剂热反应；3) the mixed solution in step 2) is transferred to the reactor to carry out a solvothermal reaction;
4)将步骤3)中的混合液进行离心洗涤，然后进行干燥；4) the mixed solution in step 3) is centrifuged and washed, and then dried;
5)将步骤4)所得固体进行研磨，得前驱体MIL-88；5) grinding the solid obtained in step 4) to obtain precursor MIL-88;
6)称取硫代乙酰胺加乙醇溶解形成均匀溶液后，硫代乙酰胺的浓度为1～15g/L，加入前驱体MIL-88，并充分搅拌，混合液搅拌时间为5～60min；6) After weighing the thioacetamide and dissolving it in ethanol to form a uniform solution, the concentration of the thioacetamide is 1～15g/L, the precursor MIL-88 is added, and the mixture is fully stirred, and the stirring time of the mixed solution is 5～60min;
7)将步骤6)中的混合液转移至反应釜中进行二次溶剂热反应；7) The mixed solution in step 6) is transferred to the reactor to carry out secondary solvothermal reaction;
8)将步骤7)中的混合液进行离心洗涤，然后进行干燥；8) The mixed solution in step 7) is centrifuged and washed, and then dried;
9)将步骤8)所得物料经过干燥、研磨后，即得所述金属有机框架衍生的铁镍金属硫化物催化剂；9) after drying and grinding the material obtained in step 8), the iron-nickel metal sulfide catalyst derived from the metal organic framework is obtained;
在步骤1)中，所述铁盐选自六水合氯化铁、硫酸铁、硝酸铁等中的至少一种，优选六水合三氯化铁，所述镍盐选自六水合硝酸镍、氯化镍和乙酰丙酮镍等中的至少一种，优选六水合硝酸镍；铁盐的质量浓度为1～50g/L，镍盐的质量浓度为1～50g/L，对苯二甲酸的质量浓度为1～50g/L；优选，所述对苯二甲酸的质量浓度为5～25g/L；所述搅拌的时间为5～60min，优选10～30min。In step 1), the iron salt is selected from at least one of ferric chloride hexahydrate, ferric sulfate, ferric nitrate, etc., preferably ferric chloride hexahydrate, and the nickel salt is selected from nickel nitrate hexahydrate, chlorine At least one of nickel oxide and nickel acetylacetonate etc., preferably nickel nitrate hexahydrate; the mass concentration of iron salt is 1～50g/L, the mass concentration of nickel salt is 1～50g/L, the mass concentration of terephthalic acid is 1-50 g/L; preferably, the mass concentration of the terephthalic acid is 5-25 g/L; the stirring time is 5-60 min, preferably 10-30 min.
在步骤2)中，所述氢氧化钠溶液的质量浓度为1～50g/L，优选5～25g/L；所述搅拌的时间为0.5～8h，搅拌时间为1～3h。In step 2), the mass concentration of the sodium hydroxide solution is 1-50 g/L, preferably 5-25 g/L; the stirring time is 0.5-8 h, and the stirring time is 1-3 h.
在步骤3)中，所述一次溶剂热反应的温度为60～150℃，反应的时间为1～24h；优选反应温度80～120℃，反应时间12～18h。In step 3), the temperature of the first solvothermal reaction is 60-150 °C, and the reaction time is 1-24 h; preferably, the reaction temperature is 80-120 °C, and the reaction time is 12-18 h.
在步骤4)中，所述干燥的温度为30～95℃，干燥的时间为0.5～1.5d；优选干燥的温度为50～70℃，干燥的时间为0.7～1.2d。In step 4), the drying temperature is 30-95°C, and the drying time is 0.5-1.5d; preferably, the drying temperature is 50-70°C, and the drying time is 0.7-1.2d.
在步骤6)中，所述硫代乙酰胺的质量浓度为1～15g/L，搅拌的时间为5～60min；优选所述硫代乙酰胺的质量浓度为5～10g/L，搅拌时间为10～30min。In step 6), the mass concentration of the thioacetamide is 1～15g/L, and the stirring time is 5～60min; preferably, the mass concentration of the thioacetamide is 5～10g/L, and the stirring time is 10 to 30 minutes.
在步骤7)中，所述反应的温度为60～180℃，反应的时间为1～48h；优选反应的温度为90～160℃，反应的时间为3～24h。In step 7), the reaction temperature is 60-180°C, and the reaction time is 1-48h; preferably, the reaction temperature is 90-160°C, and the reaction time is 3-24h.
在步骤8)中，所述干燥的温度为30～95℃，干燥的时间为0.5～1.5d；优选干燥的温度为50～70℃，干燥的时间为0.7～1.2d。In step 8), the drying temperature is 30-95°C, and the drying time is 0.5-1.5d; preferably, the drying temperature is 50-70°C, and the drying time is 0.7-1.2d.
所述铁镍金属硫化物催化剂孔道结构含有更多的介孔，有利于反应过程中水分子的吸附和氧气的析出，可在电解水的析氧反应中应用。The pore structure of the iron-nickel metal sulfide catalyst contains more mesopores, which is beneficial to the adsorption of water molecules and the precipitation of oxygen during the reaction process, and can be used in the oxygen evolution reaction of electrolyzed water.
所述应用的具体方法可为：将制成的铁镍金属硫化物催化剂用于电催化析氧反应中，在所制备的铁镍金属硫化物催化剂存在下，温度10～50℃，扫描速度为1～20mV/s，实现高活性和高稳定性。The specific method of the application can be as follows: using the prepared iron-nickel metal sulfide catalyst in the electrocatalytic oxygen evolution reaction, in the presence of the prepared iron-nickel metal sulfide catalyst, the temperature is 10-50 ° C, and the scanning speed is 1～20mV/s, to achieve high activity and high stability.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明制备的催化剂主要活性物质为铁镍金属硫化物，催化剂形貌为均匀的棒状结构。在反应条件下铁镍金属硫化物原位生成羟基氧化物种，促进活性物种的增加，且两种物种间发生协同作用，提升析氧反应活性。1. The main active material of the catalyst prepared by the present invention is iron-nickel metal sulfide, and the morphology of the catalyst is a uniform rod-like structure. Under the reaction conditions, iron-nickel metal sulfide generates oxyhydroxide species in situ, which promotes the increase of active species, and synergistic effect occurs between the two species to improve the activity of oxygen evolution reaction.
2、本发明制备的催化剂的孔道结构含有更多的介孔，有利于反应过程中水分子的吸附和氧气的析出，促进析氧反应的进行。2. The pore structure of the catalyst prepared by the present invention contains more mesopores, which is beneficial to the adsorption of water molecules and the precipitation of oxygen during the reaction process, and promotes the progress of the oxygen evolution reaction.
3、本发明制备的催化剂为非贵金属催化剂，成本低廉，原料丰富且制备过程简单，其电化学性能优于大部分已报道的析氧反应催化剂以及贵金属Ir基催化剂。3. The catalyst prepared by the present invention is a non-precious metal catalyst with low cost, abundant raw materials and simple preparation process, and its electrochemical performance is better than most of the reported oxygen evolution reaction catalysts and precious metal Ir-based catalysts.
附图说明Description of drawings
图1为实施例1中制备的铁镍金属硫化物催化剂的X射线衍射图(XRD)；Fig. 1 is the X-ray diffraction pattern (XRD) of the iron-nickel metal sulfide catalyst prepared in Example 1;
图2为实施例1中制备的铁镍金属硫化物催化剂(左图)和经过电化学活化的铁镍金属硫化物催化剂(右图)的透射电镜图(TEM)；Fig. 2 is the transmission electron microscope (TEM) of the iron-nickel metal sulfide catalyst prepared in Example 1 (left image) and the electrochemically activated iron-nickel metal sulfide catalyst (right image);
图3为实施例1中制备的铁镍金属硫化物催化剂和经过电化学活化的铁镍金属硫化物催化剂的X射线光电子能谱图(XPS)；3 is the X-ray photoelectron spectroscopy (XPS) of the iron-nickel metal sulfide catalyst prepared in Example 1 and the electrochemically activated iron-nickel metal sulfide catalyst;
图4为实施例2～4中制备的不同硫化温度下铁镍金属硫化物催化剂的线性伏安扫描曲线图；Fig. 4 is the linear voltammetry curve diagram of the iron-nickel metal sulfide catalyst prepared under different vulcanization temperatures prepared in Examples 2-4;
图5为实施例1、3、5～7中制备的不同硫化时长下铁镍金属硫化物催化剂的线性伏安扫描曲线图；Fig. 5 is the linear voltammetry curve diagram of the iron-nickel metal sulfide catalyst prepared in Examples 1, 3, 5-7 under different vulcanization time lengths;
图6为实施例1中制备的铁镍金属硫化物催化剂的计时电位图。FIG. 6 is a chronopotentiogram of the iron-nickel metal sulfide catalyst prepared in Example 1. FIG.
具体实施方式Detailed ways
以下实施例将结合附图对本发明的技术方案进一步的说明和描述。下面的实施例仅用作举例说明，本发明内容并不局限于此。The following embodiments will further illustrate and describe the technical solutions of the present invention in conjunction with the accompanying drawings. The following examples are only used for illustration, and the content of the present invention is not limited thereto.
在下列实施例中，析氧反应测试中的电压换算以及过电势由以下公式定义：In the following examples, the voltage scaling and overpotential in the oxygen evolution reaction test are defined by the following equations:
ERHE＝ESCE+0.244+0.059×pHE RHE = E SCE +0.244+0.059×pH
在每次测试前均采用循环伏安法在测试区间扫描10圈以活化催化剂，并以电流密度为10mA/cm2所对应的过电势作为评价析氧反应活性的标准Before each test, cyclic voltammetry was used to scan 10 times in the test interval to activate the catalyst, and the overpotential corresponding to the current density of 10 mA/cm 2 was used as the standard for evaluating the activity of oxygen evolution reaction.
分析催化剂电催化性能所用的仪器为CHI660E电化学工作站。The instrument used to analyze the electrocatalytic performance of the catalyst was CHI660E electrochemical workstation.
实施例1Example 1
(1)称取0.811g六水合氯化铁，0.872g六水合硝酸镍和0.997g对苯二甲酸溶于60mL的N,N-二甲基甲酰胺溶解后搅拌30min，形成均匀溶液；(1) take by weighing 0.811g of ferric chloride hexahydrate, 0.872g of nickel nitrate hexahydrate and 0.997g of terephthalic acid dissolved in 60mL of N,N-dimethylformamide dissolved and stirred for 30min to form a uniform solution;
(2)量取12mL氢氧化钠溶液加入步骤(1)所得溶液中搅拌3h至均匀，氢氧化钠溶液浓度为16g/L；(2) Measure 12mL of sodium hydroxide solution and add it to the solution obtained in step (1) and stir for 3h until uniform, and the concentration of sodium hydroxide solution is 16g/L;
(3)将步骤(2)中的混合液转移至反应釜中进行溶剂热，反应温度为100℃，反应时间为15h；(3) transfer the mixed solution in step (2) to the reaction kettle for solvothermal, the reaction temperature is 100°C, and the reaction time is 15h;
(4)将步骤(3)中的混合液离心洗涤(水洗，醇洗)，然后在70℃烘箱中进行彻夜干燥；(4) centrifugal washing (water washing, alcohol washing) of the mixed solution in step (3), and then drying overnight in an oven at 70°C;
(5)将步骤(4)所得固体进行研磨，得前驱体MIL-88；(5) grinding the solid obtained in step (4) to obtain precursor MIL-88;
(6)称取0.450g硫代乙酰胺加60mL乙醇溶解形成均匀溶液后，加入0.1g前驱体MIL-88并充分搅拌30min；(6) After weighing 0.450g of thioacetamide and dissolved in 60mL of ethanol to form a uniform solution, add 0.1g of precursor MIL-88 and fully stir for 30min;
(7)将步骤(6)中的混合液转移至反应釜中进行溶剂热，反应温度为120℃，反应时间为12h；(7) transfer the mixed solution in step (6) to the reaction kettle for solvothermal, the reaction temperature is 120°C, and the reaction time is 12h;
(8)将步骤(7)中的混合液进行离心洗涤(醇洗)，然后在70℃烘箱中进行彻夜干燥；(8) centrifugal washing (alcohol washing) of the mixed solution in step (7), and then drying overnight in an oven at 70°C;
(9)将步骤(8)所得物料经过干燥、研磨后，即得即得所述金属有机框架衍生的铁镍金属硫化物催化剂(9) after drying and grinding the material obtained in step (8), the iron-nickel metal sulfide catalyst derived from the metal organic framework can be obtained
(10)催化剂墨水的配置及工作电极的制备：将3mg催化剂和1mg商用炭黑加入990μL的乙醇水溶液中(乙醇︰水＝1︰1)，超声1h后加入10μL的5wt％Nafion溶液，再超声30min后得催化剂墨水；将10μL催化剂墨水均匀涂覆在抛光的玻碳电极表面(直径为5mm)，在室温下自然干燥，得工作电极；(10) Configuration of catalyst ink and preparation of working electrode: Add 3 mg of catalyst and 1 mg of commercial carbon black to 990 μL of ethanol aqueous solution (ethanol:water=1:1), add 10 μL of 5wt% Nafion solution after ultrasonication for 1 h, and then ultrasonicate again After 30 minutes, the catalyst ink was obtained; 10 μL of the catalyst ink was evenly coated on the surface of the polished glassy carbon electrode (5 mm in diameter), and it was naturally dried at room temperature to obtain the working electrode;
(11)采用三电极体系进行电催化反应，以涂覆有墨水的玻碳电极为工作电极，饱和甘汞电极为参比电极，碳棒为对电极；量取60mL氢氧化钾溶液(浓度为1.0M)作为电解液；(11) adopt the three-electrode system to carry out electrocatalytic reaction, take the glassy carbon electrode coated with ink as the working electrode, the saturated calomel electrode as the reference electrode, and the carbon rod as the counter electrode; measure 60 mL of potassium hydroxide solution (concentration is 1.0M) as electrolyte;
(12)以CHI 660E电化学工作站作为电源，活性评价采用线性扫描伏安法，取扫速为10mV/s；稳定性测试采用恒电流法，取催化剂性能为10mA/cm2时所对应的电势为电压条件。(12) Using CHI 660E electrochemical workstation as the power source, linear sweep voltammetry was used for activity evaluation, and the sweep rate was 10mV/s; stability test was galvanostatic method, and the potential corresponding to catalyst performance was 10mA/cm 2 is the voltage condition.
图1为实施例1中制备的铁镍金属硫化物催化剂的X射线衍射图(XRD)。从图1看出，催化剂在30.2°、32.8°、36.8°、48.0°、52.6°处有五个特征峰，分别对应于pyrite(Fe,Ni)S2相的(200)、(210)、(211)、(220)、(311)晶面(JCPDF#02-0850)，峰位置的偏移是由于前驱体MOF的主要金属元素是铁元素，催化剂中镍含量较少，金属有机框架衍生的硫化物能有效提高材料导电性能，提升析氧反应活性。1 is an X-ray diffraction pattern (XRD) of the iron-nickel metal sulfide catalyst prepared in Example 1. It can be seen from Figure 1 that the catalyst has five characteristic peaks at 30.2°, 32.8°, 36.8°, 48.0°, and 52.6°, corresponding to ( 200 ), (210), (211), (220), (311) crystal planes (JCPDF#02-0850), the shift of the peak position is due to the fact that the main metal element of the precursor MOF is iron, the content of nickel in the catalyst is less, and the metal organic framework is derived The sulfide can effectively improve the electrical conductivity of the material and enhance the oxygen evolution reaction activity.
图2为实施例1中制备的铁镍金属硫化物催化剂和经过电化学活化的铁镍金属硫化物催化剂的的透射电镜图(TEM)。从图2看出，催化剂具有均匀的棒状形貌，其尺寸长约为840nm，宽约为210nm，在经过循环伏安法扫描活化后，表面新生成无定性的结构，增加活性位点，促进析氧反应活性的提升。2 is a transmission electron microscope (TEM) image of the iron-nickel metal sulfide catalyst prepared in Example 1 and the electrochemically activated iron-nickel metal sulfide catalyst. It can be seen from Figure 2 that the catalyst has a uniform rod-like morphology with a length of about 840 nm and a width of about 210 nm. After activation by cyclic voltammetry scanning, an amorphous structure is newly formed on the surface, which increases the active site and promotes The oxygen evolution reaction activity was improved.
图3为实施例1中制备的铁镍金属硫化物催化剂和经过电化学活化的铁镍金属硫化物催化剂的X射线光电子能谱图(XPS)。从图3看出，经过循环伏安法扫描活化后，催化剂Ni 2p谱图中出现位于857.8eV，876.2eV的峰，分别对应于Ni3+的2p3/2轨道以及2p1/2轨道，表明羟基氧化镍物种的生成，原位生成的羟基氧化物种能促进催化剂对反应中间体的吸附和转化。3 is an X-ray photoelectron spectroscopy (XPS) diagram of the iron-nickel metal sulfide catalyst prepared in Example 1 and the electrochemically activated iron-nickel metal sulfide catalyst. It can be seen from Figure 3 that after activation by cyclic voltammetry scanning, peaks at 857.8 eV and 876.2 eV appear in the Ni 2p spectrum of the catalyst, corresponding to the 2p 3/2 orbital and 2p 1/2 orbital of Ni 3+ , respectively. It is indicated that the formation of nickel oxyhydroxide species, the in situ generated oxyhydroxide species can promote the adsorption and conversion of the reaction intermediates by the catalyst.
图6实施例1中制备的铁镍金属硫化物催化剂的计时电位图。从图6看出催化剂可以在10mA/cm2的条件下稳定反应40h，远大于贵金属催化剂Ir/C的12h，表明催化剂具有优异的稳定性。Figure 6 Chronopotentiometry of the iron-nickel metal sulfide catalyst prepared in Example 1. It can be seen from Figure 6 that the catalyst can react stably for 40 h under the condition of 10 mA/cm 2 , which is much greater than that of the noble metal catalyst Ir/C for 12 h, indicating that the catalyst has excellent stability.
实施例2Example 2
与实施例1类似，其区别在于第(7)步中的二次溶剂热反应温度为120℃改为100℃，反应时间改为6h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the secondary solvothermal reaction temperature in step (7) is changed from 120°C to 100°C, the reaction time is changed to 6h, and the other steps are carried out by the method of Example 1, to obtain the present invention. described catalyst.
实施例3Example 3
与实施例1类似，其区别在于第(7)步中的二次溶剂热反应时间改为6h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the secondary solvothermal reaction time in step (7) is changed to 6h, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例4Example 4
与实施例1类似，其区别在于第(7)步中的二次溶剂热反应温度为120℃改为150℃，反应时间改为6h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the secondary solvothermal reaction temperature in step (7) is changed from 120°C to 150°C, and the reaction time is changed to 6h. described catalyst.
图4为实施例2～4中制备的不同硫化温度下铁镍金属硫化物催化剂的线性伏安扫描曲线图。从图4看出，随着硫化温度的升高，催化剂的析氧反应性能先升高后降低，最佳的硫化温度为120℃。FIG. 4 is a linear voltammetric scan curve diagram of the iron-nickel metal sulfide catalysts prepared in Examples 2-4 at different sulfidation temperatures. It can be seen from Figure 4 that with the increase of sulfidation temperature, the oxygen evolution reaction performance of the catalyst first increased and then decreased, and the optimal sulfidation temperature was 120 °C.
实施例5Example 5
与实施例1类似，其区别在于第(7)步中的反应时间为12h改为3h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the reaction time in step (7) is changed from 12h to 3h, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例6Example 6
与实施例1类似，其区别在于第(7)步中的反应时间为12h改为18h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the reaction time in step (7) is changed from 12h to 18h, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例7Example 7
与实施例1类似，其区别在于第(7)步中的反应时间为12h改为24h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the reaction time in step (7) is changed from 12h to 24h, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
图5为实施例1、3、5～7中制备的不同硫化时长下铁镍金属硫化物催化剂的线性伏安扫描曲线图。从图5看出，随着硫化时间的延长，催化剂的析氧反应性能呈现先升高后降低的性能，最佳的硫化时间为12h，最优催化剂在10mA/cm2的电流密度下，过电位仅为247mV。FIG. 5 is a linear voltammetric scan curve diagram of the iron-nickel metal sulfide catalysts prepared in Examples 1, 3, 5-7 under different vulcanization time lengths. It can be seen from Figure 5 that the oxygen evolution reaction performance of the catalyst increases first and then decreases with the extension of the vulcanization time. The optimal vulcanization time is 12h. The potential is only 247mV.
实施例8Example 8
与实施例1类似，其区别在于第(1)步中铁盐选取为九水合硝酸铁，镍盐选取为六水合氯化镍，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to embodiment 1, its difference is that in the (1) step, iron salt is selected as ferric nitrate nonahydrate, nickel salt is selected as nickel chloride hexahydrate, and other steps are carried out by the method of embodiment 1 to obtain catalyst of the present invention.
实施例9Example 9
与实施例1类似，其区别在于第(1)步中称取铁盐的质量为1.081g，镍盐的质量为0.582g，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (1), the weight of iron salt is weighed to be 1.081g, and the quality of nickel salt is 0.582g, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例10Example 10
与实施例1类似，其区别在于第(1)步中称取铁盐的质量为0.541g，镍盐的质量为1.163g，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (1), the weight of iron salt was weighed to be 0.541 g, the quality of nickel salt to be 1.163 g, and the method of Example 1 was used for other steps to obtain the catalyst of the present invention.
实施例11Example 11
与实施例1类似，其区别在于第(1)步中称取对苯二甲酸的质量为1.496g，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (1), the mass of terephthalic acid is weighed to be 1.496 g, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例12Example 12
与实施例1类似，其区别在于第(2)步中氢氧化钠溶液浓度为24g/L，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the concentration of sodium hydroxide solution in step (2) is 24 g/L, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例13Example 13
与实施例1类似，其区别在于第(3)步中一次溶剂热反应温度为100℃改为80℃，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (3), the temperature of the first solvothermal reaction is changed from 100°C to 80°C, and the other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例14Example 14
与实施例1类似，其区别在于第(3)步中一次溶剂热反应温度为100℃改为120℃，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (3), the temperature of the first solvothermal reaction is changed from 100°C to 120°C, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例15Example 15
与实施例1类似，其区别在于第(3)步中的反应时间为15h改为12h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the reaction time in step (3) is changed from 15h to 12h, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例16Example 16
与实施例1类似，其区别在于第(3)步中的反应时间为15h改为18h，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the reaction time in step (3) is changed from 15h to 18h, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例17Example 17
与实施例1类似，其区别在于第(6)步中称取硫代乙酰胺的质量为0.3g，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (6), the weight of thioacetamide was weighed to be 0.3 g, and other steps were carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例18Example 18
与实施例1类似，其区别在于第(6)步中称取硫代乙酰胺的质量为0.6g，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that in step (6), the weight of thioacetamide is 0.6 g, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention.
实施例19Example 19
与实施例1类似，其区别在于第(4)步和第(9)步中干燥的温度为60℃，干燥的时长为1d，其它步骤采用实施例1的方法进行，得本发明所述催化剂。Similar to Example 1, the difference is that the drying temperature in steps (4) and (9) is 60°C, and the drying time is 1 d, and other steps are carried out by the method of Example 1 to obtain the catalyst of the present invention. .
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所做的等效变化与修饰，皆应仍属本发明涵盖的范围。The above are only preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the description should still belong to the present invention. scope covered.
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