CN114700095A - A kind of preparation method of one-dimensional CdS nanorod/three-dimensional multilayer Ti3C2 composite photocatalyst - Google Patents
A kind of preparation method of one-dimensional CdS nanorod/three-dimensional multilayer Ti3C2 composite photocatalyst Download PDFInfo
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Abstract
本发明公开了一种一维CdS纳米棒/三维多层Ti3C2复合光催化剂的制备方法，包括如下步骤：(1)将Ti3AlC2粉末加入到氢氟酸溶液中，在磁力搅拌下恒温反应20‑28小时；(2)将所得物料反复洗涤至pH值为7；(3)制备多层Ti3C2粉末；(4)制备Cd2+/Ti3C2混合溶液；(5)取硫脲溶于乙二胺溶液中混合均匀得到硫脲/乙二胺，再将其加入至步骤(5)中制得的Cd2+/Ti3C2混合溶液中混合均匀；(6)将步骤(5)中制得的混合溶液倒入反应器中，进行水热反应，接着依次经冷却、离心洗涤和真空干燥，得到CdS/Ti3C2催化剂。本发明通过化学刻蚀法制备三维多层Ti3C2、利用水热溶剂自组装的合成方法，使CdS纳米棒原位生长并负载于三维多层Ti3C2上，得到一维CdS纳米棒/三维多层Ti3C2复合光催化剂，制备方法操作简单，质量高、重复性好。The invention discloses a preparation method of a one-dimensional CdS nanorod/ three -dimensional multilayer Ti3C2 composite photocatalyst, comprising the following steps: ( 1 ) adding Ti3AlC2 powder into a hydrofluoric acid solution, stirring under magnetic force Under constant temperature reaction for 20-28 hours; (2) the obtained material is repeatedly washed to pH 7; (3) multi-layer Ti 3 C 2 powder is prepared; (4) Cd 2+ /Ti 3 C 2 mixed solution is prepared; ( 5) get thiourea and be dissolved in ethylenediamine solution and mix well to obtain thiourea/ethylenediamine, then add it to the Cd 2+ /Ti 3 C 2 mixed solution obtained in step (5) and mix well; ( 6) The mixed solution prepared in step (5) is poured into the reactor to carry out hydrothermal reaction, followed by cooling, centrifugal washing and vacuum drying in sequence to obtain a CdS/Ti 3 C 2 catalyst. The invention prepares three-dimensional multi-layer Ti 3 C 2 by chemical etching method, and utilizes the synthesis method of hydrothermal solvent self-assembly, so that CdS nanorods are grown in situ and supported on the three-dimensional multi-layer Ti 3 C 2 to obtain one-dimensional CdS nanometer rods. The rod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst has the advantages of simple operation, high quality and good repeatability.
Description
技术领域technical field
本发明属于光催化剂制备技术领域，具体涉及一种一维CdS纳米棒/三维多层Ti3C2复合光催化剂的制备方法。The invention belongs to the technical field of photocatalyst preparation, in particular to a preparation method of a one-dimensional CdS nanorod/ three -dimensional multilayer Ti3C2 composite photocatalyst.
背景技术Background technique
为控制污染、保护环境、实现可持续发展，清洁能源的发展近年来备受关注，而通过光催化分解水产氢是缓解能源和环境危机的一种很有前景的方法。In order to control pollution, protect the environment, and achieve sustainable development, the development of clean energy has attracted much attention in recent years, and hydrogen production through photocatalytic splitting of water is a promising method to alleviate the energy and environmental crisis.
自从石墨烯(Graphene)于2004年被成功制备以来，二维层状材料便逐步成为材料科学的研究热点之一。2011年，一类新型的二维过渡族金属碳/氮化合物，MXenes材料，被成功制备出来，并于近年来被逐步应用于锂离子电池、超级电容器、催化等领域。MXenes是一种新型的二维过渡金属碳化物家族，通过选择性剥离三元碳化物、氮化物或碳氮化物而合成，通式为Mn+1Xn，其中M代表过渡金属(如Sc、Ti、Ta、Cr、Mo等)，X是C和/或N。密度泛函理论(DFT)计算表明MXenes表现出金属导电性，已被探索用于催化、能量存储和转换等领域。其在实验表征中也被证明是析氢反应(HER)中的实现有效催化的关键，表明MXenes可能是光催化H2的良好助催化剂。Since graphene was successfully prepared in 2004, two-dimensional layered materials have gradually become one of the research hotspots in materials science. In 2011, a new type of two-dimensional transition metal carbon/nitrogen compound, MXenes, was successfully prepared, and has been gradually applied in lithium-ion batteries, supercapacitors, catalysis and other fields in recent years. MXenes are a novel family of two-dimensional transition metal carbides synthesized by selective exfoliation of ternary carbides, nitrides, or carbonitrides with the general formula Mn + 1Xn , where M represents a transition metal (such as Sc , Ti, Ta, Cr, Mo, etc.), X is C and/or N. Density functional theory (DFT) calculations show that MXenes exhibit metallic conductivity and have been explored for catalysis, energy storage, and conversion. It has also been shown in experimental characterization to be the key to achieve efficient catalysis in the hydrogen evolution reaction (HER), suggesting that MXenes may be good cocatalysts for the photocatalysis of H.
MXenes材料表面拥有大量的亲水功能基团(-OH、-O和-F)，这些功能基团能够使MXene材料与众多半导体材料之间构筑起牢固的连接；此外，MXenes材料具有优良的金属导电性，能够确保载流子在其表面进行有效的迁移。以上这些优良的特性，使MXenes材料作为助催化剂在光催化领域也拥有巨大的应用潜力。The surface of MXenes has a large number of hydrophilic functional groups (-OH, -O and -F), which can make MXenes build strong connections with many semiconductor materials; in addition, MXenes have excellent metal The electrical conductivity can ensure the effective migration of carriers on its surface. These excellent properties make MXenes as cocatalysts also have great application potential in the field of photocatalysis.
因此，二维石墨烯类层状材料被认为是各种催化应用中最有前途的候选材料。Ti3C2作为MXenes家族中最常用的一员，具有大量裸露的金属原子，超薄的二维层状结构，高度亲水的表面，优秀的吸光性能以及良好的导电性的优点。研究表明，将具有高导电性的Ti3C2作为助催化剂有助于构建高效的异质结从而增强载流子迁移率以提升催化性能。Therefore, 2D graphene-like layered materials are considered as the most promising candidates for various catalytic applications. As the most commonly used member of the MXenes family, Ti3C2 has the advantages of a large number of bare metal atoms, ultrathin two-dimensional layered structure, highly hydrophilic surface, excellent light absorption properties, and good electrical conductivity. Studies have shown that using Ti3C2 with high electrical conductivity as a cocatalyst can help to build efficient heterojunctions to enhance carrier mobility for improved catalytic performance.
而作为光催化主材料的CdS，本身尚存在一些弊端，这些弊端限制了CdS的进一步的应用发展。例如，CdS容易发生光腐蚀从而失去反应活性。另外，CdS纳米颗粒容易聚集是限制H2产率的另一缺点。这是由于催化剂粒子的团聚势必会造成有效催化比表面积的减少，并且会加速光催化过程中产生的光生电子-空穴的聚合泯灭，极大降低了催化活性。为了克服以上缺陷，人们提出了许多提高CdS光催化活性的方法，包括将量子点的CdS与其他化合物构成复合物、掺杂离子等。本专利的产氢实验和光电测试结果均表明，将CdS纳米粒子与导电性良好的多层Ti3C2构成复合异质结可以有效提升电子-空穴对的分离速率，提高催化剂的催化活性；并且这种紧密结合的方式有效避免了CdS纳米粒子的光腐蚀从而提高了催化剂的稳定性。However, CdS, as the main photocatalytic material, still has some drawbacks, which limit the further application and development of CdS. For example, CdS is prone to photocorrosion and thus loses its reactivity. In addition, the easy aggregation of CdS nanoparticles is another disadvantage that limits the H2 yield. This is because the agglomeration of catalyst particles will inevitably reduce the effective catalytic specific surface area, and will accelerate the polymerization and extinction of photogenerated electron-holes generated in the photocatalytic process, greatly reducing the catalytic activity. In order to overcome the above defects, many methods have been proposed to improve the photocatalytic activity of CdS, including forming complexes of CdS of quantum dots with other compounds, doping ions, etc. The hydrogen production experiments and photoelectric test results of this patent both show that the composite heterojunction composed of CdS nanoparticles and multilayer Ti 3 C 2 with good conductivity can effectively improve the separation rate of electron-hole pairs and improve the catalytic activity of the catalyst. ; And this tightly combined way effectively avoids the photocorrosion of CdS nanoparticles and improves the stability of the catalyst.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术存在的缺陷，提供一种一维CdS纳米棒/三维多层Ti3C2复合光催化剂的制备方法，通过化学刻蚀法制备三维多层Ti3C2、利用水热溶剂自组装的合成方法，使CdS纳米棒原位生长并负载于三维多层Ti3C2上，得到一维CdS纳米棒/三维多层Ti3C2复合光催化剂。The purpose of the present invention is to overcome the defects of the prior art, and to provide a preparation method of a one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst, wherein three-dimensional multilayer Ti 3 C 2 , Using the synthesis method of hydrothermal solvent self-assembly, CdS nanorods were grown in situ and supported on three-dimensional multilayer Ti 3 C 2 to obtain a one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst.
为了实现以上目的，本发明的技术方案之一为：一种一维CdS纳米棒/三维多层Ti3C2复合光催化剂的制备方法，以Ti3AlC2为原料，通过化学刻蚀法制备得到三维多层Ti3C2；利用水热溶剂自组装的合成方法，使CdS纳米棒原位生长并负载于三维多层Ti3C2上，得到所述一维CdS纳米棒/三维多层Ti3C2复合光催化剂。In order to achieve the above purpose, one of the technical solutions of the present invention is: a preparation method of one-dimensional CdS nanorods/three-dimensional multilayer Ti 3 C 2 composite photocatalyst, using Ti 3 AlC 2 as raw material, prepared by chemical etching method Three-dimensional multi-layer Ti 3 C 2 is obtained; using the synthesis method of hydrothermal solvent self-assembly, CdS nanorods are grown in situ and supported on the three-dimensional multi-layer Ti 3 C 2 to obtain the one-dimensional CdS nanorod/three-dimensional multi-layer Ti3C2 composite photocatalyst .
该制备方法具体包括如下步骤：The preparation method specifically includes the following steps:
(1)取氢氟酸于反应器中，将反应器置于磁力搅拌器上，称取一定量的Ti3AlC2粉末加入到氢氟酸溶液中，并恒温反应20-28h；(1) take hydrofluoric acid in the reactor, place the reactor on a magnetic stirrer, weigh a certain amount of Ti 3 AlC 2 powder and add it to the hydrofluoric acid solution, and react at a constant temperature for 20-28h;
(2)将步骤(1)中反应所得的物料反复洗涤，直至收集到的洗涤液pH为7，以除去残留的氢氟酸和Al3+离子；(2) the material obtained by the reaction in the step (1) is repeatedly washed until the pH of the collected washing solution is 7, to remove residual hydrofluoric acid and Al 3+ ions;
(3)将步骤(2)中所得的物料真空干燥20-28h，并将干燥后的样品研磨从而得到多层Ti3C2；(3) vacuum drying the material obtained in step (2) for 20-28h, and grinding the dried sample to obtain multilayer Ti 3 C 2 ;
(4)取一定质量步骤(3)制得的Ti3C2粉末，使其均匀分散于一定体积的乙二胺溶液中得到Ti3C2/乙二胺溶液中，取硝酸镉(Cd(NO3)2.4H2O)溶于一定体积的乙二胺溶液得到硝酸镉/乙二胺溶液，将二者混合均匀得到Cd2+/Ti3C2混合溶液；(4) take the Ti 3 C 2 powder obtained in step (3) of a certain quality, make it evenly dispersed in a certain volume of ethylene diamine solution to obtain Ti 3 C 2 /ethylene diamine solution, take cadmium nitrate (Cd( NO 3 ) 2 .4H 2 O) is dissolved in a certain volume of ethylene diamine solution to obtain a cadmium nitrate/ethylene diamine solution, and the two are mixed uniformly to obtain a Cd 2+ /Ti 3 C 2 mixed solution;
(5)取硫脲溶于乙二胺溶液中混合均匀得到硫脲/乙二胺，再将其加入至步骤(5)中制备得到的Cd2+/Ti3C2混合溶液，混合均匀；(5) get thiourea dissolved in ethylenediamine solution and mix uniformly to obtain thiourea/ethylenediamine, then add it to the Cd 2+ /Ti 3 C 2 mixed solution prepared in step (5), and mix uniformly;
(6)将步骤(5)中制备得到的混合溶液倒入反应器中，进行水热反应，接着依次经冷却、离心洗涤和真空干燥，得到CdS/Ti3C2催化剂。(6) Pour the mixed solution prepared in the step (5) into a reactor to carry out a hydrothermal reaction, followed by cooling, centrifugal washing and vacuum drying in sequence to obtain a CdS/Ti 3 C 2 catalyst.
在本发明的一个优选实施方案中，所述步骤(1)中氢氟酸溶液的质量分数为40％，氢氟酸溶液与Ti3AlC2体积质量比为8-12mL/g。In a preferred embodiment of the present invention, the mass fraction of the hydrofluoric acid solution in the step (1) is 40%, and the volume mass ratio of the hydrofluoric acid solution to Ti 3 AlC 2 is 8-12 mL/g.
在本发明的一个优选实施方案中，所述步骤(1)中反应器为无盖聚四氟乙烯反应釜，Ti3AlC2加入氢氟酸溶液的方式为缓慢加入，以避免反应过热和Ti3AlC2团聚，恒温反应温度为35-45℃。In a preferred embodiment of the present invention, in the step (1), the reactor is a polytetrafluoroethylene reactor without a cover, and the Ti 3 AlC 2 is added slowly to the hydrofluoric acid solution to avoid overheating of the reaction and Ti 3 AlC 2 is agglomerated, and the constant temperature reaction temperature is 35-45 °C.
在本发明的一个优选实施方案中，所述步骤(2)中的物料洗涤方式为水与酒精交替反复洗涤。In a preferred embodiment of the present invention, the material washing method in the step (2) is repeated washing alternately with water and alcohol.
在本发明的一个优选实施方案中，所述步骤(3)中物料干燥温度为45-55℃。In a preferred embodiment of the present invention, the drying temperature of the material in the step (3) is 45-55°C.
在本发明的一个优选实施方案中，所述步骤(4)中Ti3C2粉末与乙二胺溶液质量体积比为0.3-3mg/mL，硝酸镉与乙二胺溶液摩尔体积比为0.5-1mmol/mL。In a preferred embodiment of the present invention, in the step (4), the mass volume ratio of Ti 3 C 2 powder to ethylene diamine solution is 0.3-3 mg/mL, and the molar volume ratio of cadmium nitrate to ethylene diamine solution is 0.5-3 mg/mL. 1 mmol/mL.
更进一步优选的，所述步骤(4)中Ti3C2/乙二胺溶液与硝酸镉/乙二胺溶液体积比为2-4:1-3，混合方式为将硝酸镉/乙二胺溶液缓慢滴加至Ti3C2/乙二胺溶液中，通过超声或搅拌均匀混合。Further preferably, in the step (4), the volume ratio of Ti3C2 /ethylenediamine solution to cadmium nitrate/ethylenediamine solution is 2-4 :1-3, and the mixing method is to mix cadmium nitrate/ethylenediamine. The solution was slowly added dropwise to the Ti 3 C 2 /ethylenediamine solution, and uniformly mixed by sonication or stirring.
在本发明的一个优选实施方案中，所述步骤(5)中硫脲与乙二胺摩尔体积比为1.8-2.1mmol/mL，溶液加入方式为缓慢倒入，Cd2+/Ti3C2乙二胺溶液、硫脲/乙二胺溶液体积比为4-6:1-3，均匀混合方式为搅拌混合。In a preferred embodiment of the present invention, in the step (5), the molar volume ratio of thiourea to ethylenediamine is 1.8-2.1 mmol/mL, and the solution is added by slowly pouring, Cd 2+ /Ti 3 C 2 The volume ratio of the ethylenediamine solution and the thiourea/ethylenediamine solution is 4-6:1-3, and the uniform mixing method is stirring and mixing.
在本发明的一个优选实施方案中，所述步骤(6)中水热反应温度为150-170℃，反应时间为20-26h。In a preferred embodiment of the present invention, the hydrothermal reaction temperature in the step (6) is 150-170° C., and the reaction time is 20-26 h.
与现有技术相比，本发明的有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
1.本发明利用化学刻蚀法及水热溶剂自组装法来制备一维CdS纳米棒/三维多层Ti3C2复合光催化剂，通过强酸刻蚀去除Ti3AlC2中Al3+原子以制备得到三维Ti3C2粉末；采用水热溶剂自组装的方法，以乙二胺为水热溶剂使一维CdS纳米棒生长在三维多层Ti3C2上；在反应物搅拌混合过程中，乙二胺可与Cd2+形成配合物，有助于形成规则的一维CdS纳米棒；在水热反应过程中，乙二胺既提供了碱性的反应条件，并且作为偶联剂将CdS与Ti3C2连接在一起，构成异质结，有效提高了电子传输能力，并且降低了载流子复合率；1. The present invention utilizes chemical etching method and hydrothermal solvent self-assembly method to prepare one-dimensional CdS nanorods/three-dimensional multilayer Ti 3 C 2 composite photocatalyst, and removes Al 3+ atoms in Ti 3 AlC 2 by strong acid etching. Three-dimensional Ti 3 C 2 powder is prepared; the self-assembly method of hydrothermal solvent is adopted, and one-dimensional CdS nanorods are grown on three-dimensional multilayer Ti 3 C 2 by using ethylenediamine as the hydrothermal solvent; during the stirring and mixing process of the reactants , ethylenediamine can form complexes with Cd 2+ , which helps to form regular one-dimensional CdS nanorods; during the hydrothermal reaction, ethylenediamine not only provides basic reaction conditions, and acts as a coupling agent to CdS and Ti 3 C 2 are connected together to form a heterojunction, which effectively improves the electron transport ability and reduces the carrier recombination rate;
2.本发明的制备方法操作简单，质量高，重复性好，与现有技术相比，不仅可大量制备出一种新型高效一维CdS纳米棒/三维多层Ti3C2复合光催化剂，并且操作难度不高，可行性强，制备周期短，成本低等优点。2. The preparation method of the present invention is simple in operation, high in quality and good in repeatability. Compared with the prior art, not only a new type of high-efficiency one-dimensional CdS nanorod/ three -dimensional multilayer Ti3C2 composite photocatalyst can be prepared in large quantities, And the operation difficulty is not high, the feasibility is strong, the preparation cycle is short, and the cost is low.
附图说明Description of drawings
图1为本发明实施例1中三维多层Ti3C2的X射线衍射图谱。FIG. 1 is the X-ray diffraction pattern of the three-dimensional multilayer Ti 3 C 2 in Example 1 of the present invention.
图2为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的X射线衍射图谱。2 is an X-ray diffraction pattern of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图3为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的扫描电镜照片。3 is a scanning electron microscope photograph of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图4为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的扫描电镜能谱照片。4 is a scanning electron microscope photo of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图5为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的透射电镜照片。5 is a transmission electron microscope photograph of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图6为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的紫外可见漫反射吸光度图谱。6 is the UV-Vis diffuse reflection absorbance spectrum of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图7为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的紫外可见漫反射带隙图。FIG. 7 is an ultraviolet-visible diffuse reflection band gap diagram of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图8为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的EIS奈奎斯特图谱。8 is the EIS Nyquist spectrum of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图9为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的瞬态光电流响应图。9 is a transient photocurrent response diagram of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图10为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的稳态荧光图谱。FIG. 10 is the steady-state fluorescence spectrum of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
图11为本发明实施例1中一维CdS纳米棒/三维多层Ti3C2复合光催化剂的产氢量对比图。11 is a comparison diagram of the hydrogen production of the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst in Example 1 of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚明白，以下结合附图和具体实施例对本发明进行更详细地描述，但本发明的保护范围并不受限于这些实施例。To make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be described in more detail below with reference to the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to these embodiments.
一种一维CdS纳米棒/三维多层Ti3C2复合光催化剂的制备方法，具体包括如下步骤：A preparation method of a one-dimensional CdS nanorod/ three -dimensional multilayer Ti3C2 composite photocatalyst, specifically comprising the following steps:
(1)取氢氟酸于反应器中，将反应器置于磁力搅拌器上，称取一定量的Ti3AlC2粉末加入到氢氟酸溶液中，并恒温反应20-28h；(1) take hydrofluoric acid in the reactor, place the reactor on a magnetic stirrer, weigh a certain amount of Ti 3 AlC 2 powder and add it to the hydrofluoric acid solution, and react at a constant temperature for 20-28h;
(2)将步骤(1)中反应所得的物料反复洗涤，直至收集到的洗涤液pH为7，以除去残留的氢氟酸和Al3+离子；(2) the material obtained by the reaction in the step (1) is repeatedly washed until the pH of the collected washing solution is 7, to remove residual hydrofluoric acid and Al 3+ ions;
(3)将步骤(2)中所得的物料真空干燥20-28h，并将干燥后的样品研磨从而得到多层Ti3C2粉末；(3) vacuum-drying the material obtained in step (2) for 20-28h, and grinding the dried sample to obtain multi-layer Ti 3 C 2 powder;
(4)取一定质量的上述Ti3C2粉末，使其均匀分散于一定体积的乙二胺溶液中得到Ti3C2/乙二胺溶液，取硝酸镉(Cd(NO3)2.4H2O)溶于一定体积的乙二胺溶液得到硝酸镉/乙二胺溶液，将硝酸镉/乙二胺溶液缓慢滴加入Ti3C2/乙二胺溶液中混合均匀得到Cd2+/Ti3C2混合溶液；(4) Take a certain mass of the above-mentioned Ti 3 C 2 powder, make it uniformly dispersed in a certain volume of ethylene diamine solution to obtain a Ti 3 C 2 /ethylene diamine solution, take cadmium nitrate (Cd(NO 3 ) 2 .4H 2 O) is dissolved in a certain volume of ethylenediamine solution to obtain a cadmium nitrate/ethylenediamine solution, and the cadmium nitrate/ethylenediamine solution is slowly added dropwise to the Ti3C2 /ethylenediamine solution and mixed uniformly to obtain Cd2+ / Ti 3 C 2 mixed solution;
(5)取硫脲溶于乙二胺溶液中混合均匀得到硫脲/乙二胺，再将其加入至步骤(5)中制备得到的Cd2+/Ti3C2混合溶液，混合均匀；(5) get thiourea dissolved in ethylenediamine solution and mix uniformly to obtain thiourea/ethylenediamine, then add it to the Cd 2+ /Ti 3 C 2 mixed solution prepared in step (5), and mix uniformly;
(6)将步骤(5)中制备得到的混合溶液倒入反应器中，进行水热反应，接着依次经冷却、离心洗涤和真空干燥，得到CdS/Ti3C2催化剂。(6) Pour the mixed solution prepared in the step (5) into a reactor to carry out a hydrothermal reaction, followed by cooling, centrifugal washing and vacuum drying in sequence to obtain a CdS/Ti 3 C 2 catalyst.
所述步骤(1)中氢氟酸溶液的质量分数为40％，氢氟酸溶液与Ti3AlC2体积质量比为8-12mL/g。In the step (1), the mass fraction of the hydrofluoric acid solution is 40%, and the volume mass ratio of the hydrofluoric acid solution to Ti 3 AlC 2 is 8-12 mL/g.
所述步骤(1)中反应器为无盖聚四氟乙烯反应釜，Ti3AlC2加入氢氟酸溶液的方式为缓慢加入，以避免反应过热和Ti3AlC2团聚，恒温反应温度为35-40℃。In the step (1), the reactor is a polytetrafluoroethylene reactor without a cover, and the way of adding Ti 3 AlC 2 into the hydrofluoric acid solution is to add slowly, so as to avoid overheating of the reaction and Ti 3 AlC 2 agglomeration, and the constant temperature reaction temperature is 35 ℃. -40°C.
所述步骤(2)中的物料洗涤方式为水与酒精交替反复洗涤。The material washing method in the step (2) is to alternately and repeatedly wash with water and alcohol.
所述步骤(3)中物料干燥温度为45-55℃。In the step (3), the drying temperature of the material is 45-55°C.
所述步骤(4)中Ti3C2粉末与乙二胺溶液质量体积比为0.3-3mg/mL，硝酸镉与乙二胺溶液摩尔体积比为0.5-1mmol/mL。In the step (4), the mass volume ratio of Ti 3 C 2 powder to ethylene diamine solution is 0.3-3 mg/mL, and the molar volume ratio of cadmium nitrate to ethylene diamine solution is 0.5-1 mmol/mL.
所述步骤(4)中Ti3C2/乙二胺溶液与硝酸镉/乙二胺溶液体积比为2-4:1-3，混合方式为将硝酸镉/乙二胺溶液缓慢滴加至Ti3C2/乙二胺溶液中，通过超声或搅拌均匀混合。In the step (4), the volume ratio of Ti3C2 /ethylenediamine solution and cadmium nitrate/ethylenediamine solution is 2-4 :1-3, and the mixing mode is to slowly add cadmium nitrate/ethylenediamine solution dropwise to the solution. Ti 3 C 2 /ethylenediamine solution, mix uniformly by ultrasonication or stirring.
所述步骤(5)中硫脲与乙二胺摩尔体积比为1.8-2.1mmol/mL，溶液加入方式为缓慢倒入，Cd2+/Ti3C2乙二胺溶液、硫脲/乙二胺溶液体积比为4-6:1-3，均匀混合方式为搅拌混合。In the described step (5), the molar volume ratio of thiourea and ethylenediamine is 1.8-2.1mmol/mL, and the solution adding mode is to pour slowly, Cd 2+ /Ti 3 C 2 ethylenediamine solution, thiourea/ethylene diamine The volume ratio of the amine solution is 4-6:1-3, and the uniform mixing method is stirring mixing.
所述步骤(6)中水热反应温度为150-170℃，反应时间为20-26h。In the step (6), the hydrothermal reaction temperature is 150-170° C., and the reaction time is 20-26 h.
实施例1Example 1
(1)取20mL质量分数为40wt％的氢氟酸于聚四氟乙烯杯中，置于磁力搅拌器上搅拌，称取2g Ti3AlC2粉末持续10分钟缓慢加入到氢氟酸溶液中，并在40℃、搅拌条件下恒温反应24小时；(1) Take 20mL of hydrofluoric acid whose mass fraction is 40wt% in a polytetrafluoroethylene cup, place it on a magnetic stirrer and stir, weigh 2g of Ti3AlC2 powder and slowly add it to the hydrofluoric acid solution for 10 minutes, And at 40 ℃, constant temperature reaction under stirring conditions for 24 hours;
(2)将步骤(1)中反应所得的物料用水与酒精交替反复洗涤，直到洗涤液的pH为7，以除去残留的氢氟酸和Al3+离子；(2) the material obtained by the reaction in the step (1) is washed alternately with water and alcohol, until the pH of the washing solution is 7, to remove residual hydrofluoric acid and Al ions ;
(3)将步骤(2)中所得的物料真空干燥24小时，并将干燥后的样品研磨从而得到多层Ti3C2粉末；(3) vacuum drying the material obtained in step (2) for 24 hours, and grinding the dried sample to obtain multi-layer Ti 3 C 2 powder;
(4)取步骤(3)制得的50mg Ti3C2粉末，加入至30mL的乙二胺溶液中，超声2小时使其分散均匀；取15mmol的硝酸镉(Cd(NO)3.4H2O)，加入至20mL的乙二胺溶液中，搅拌使其混合均匀；将硝酸镉/乙二胺溶液倒入不断搅拌的Ti3C2/乙二胺溶液中，室温下搅拌12小时使其混合均匀，得到Cd2+/Ti3C2混合溶液；(4) Take 50 mg of Ti 3 C 2 powder obtained in step (3), add it to 30 mL of ethylenediamine solution, ultrasonicate for 2 hours to make it disperse uniformly; take 15 mmol of cadmium nitrate (Cd(NO) 3 .4H 2 ) O), add it to 20mL of ethylenediamine solution, stir to make it evenly mixed; pour the cadmium nitrate/ethylenediamine solution into the constantly stirring Ti3C2 /ethylenediamine solution, stir at room temperature for 12 hours to make it Mix evenly to obtain a Cd 2+ /Ti 3 C 2 mixed solution;
(5)取45mmol硫脲溶于20mL乙二胺溶液中搅拌使其混合均匀；将硫脲/乙二胺溶液倒入Cd2+/Ti3C2混合溶液，搅拌3小时使其混合均匀，得到混合溶液；(5) get 45mmol thiourea and be dissolved in 20mL ethylenediamine solution and stir to mix it uniformly; Pour thiourea/ethylenediamine solution into Cd 2+ /Ti 3 C 2 mixed solution, stir for 3 hours to make it mix well, to obtain a mixed solution;
(6)将步骤(5)中所得混合溶液转移至100mL聚四氟乙烯高压反应釜，在160℃条件下反应2天；接着依次经冷却、离心洗涤和真空干燥，得到CdS/Ti3C2催化剂产品。(6) The mixed solution obtained in step (5) was transferred to a 100 mL polytetrafluoroethylene autoclave, and reacted at 160° C. for 2 days; then cooling, centrifugal washing and vacuum drying were performed successively to obtain CdS/Ti 3 C 2 catalyst product.
上述多层Ti3C2粉末其X射线衍射图如图1所示，其衍射特征峰为Ti3C2峰，尖锐的峰说明其具有良好的结晶性与纯度；其对应的透射电镜照片见图5(b)，可以看出该Ti3C2的多层片状结构。The X-ray diffraction pattern of the above-mentioned multilayer Ti 3 C 2 powder is shown in Figure 1, and its diffraction characteristic peak is the Ti 3 C 2 peak, and the sharp peak indicates that it has good crystallinity and purity; its corresponding transmission electron microscope photo is shown in Figure 5(b), it can be seen that the multi - layer sheet structure of Ti3C2 .
制备得到的CdS/Ti3C2催化剂其X射线衍射图如图2所示，由于与Ti3C2的复合，其CdS的衍射峰强度相对于纯的CdS粉末有所降低；其扫描电镜图如图3(b)(图3(a)为纯的CdS的扫描电镜图)，对于水热溶剂自组装得到的CdS/Ti3C2催化剂，其中一维CdS纳米棒均匀附着生长在三维Ti3C2表面和层间；其扫描电镜能谱照片如图4所示，从图上可知对于CdS/Ti3C2催化剂，其中Cd元素(图4(b))、S元素(图4(c))在催化剂中均匀分布。The X-ray diffraction pattern of the prepared CdS/Ti 3 C 2 catalyst is shown in Figure 2. Due to the compounding with Ti 3 C 2 , the diffraction peak intensity of CdS is lower than that of pure CdS powder; its scanning electron microscope image As shown in Figure 3(b) (Figure 3(a) is the SEM image of pure CdS), for the CdS/Ti 3 C 2 catalyst obtained by hydrothermal solvent self-assembly, one-dimensional CdS nanorods are uniformly attached and grown on the three-dimensional Ti 3 C 2 surface and interlayer; its scanning electron microscope energy spectrum photo is shown in Figure 4. It can be seen from the figure that for the CdS/Ti 3 C 2 catalyst, Cd element (Fig. 4(b)), S element (Fig. 4( c)) Uniform distribution in the catalyst.
对CdS/Ti3C2催化剂进行透射电子显微镜观察，结果如图5所示，图5(a)、图5(b)、图5(c)分别对应纯的CdS、Ti3C2、CdS/Ti3C2的透射电子显微镜照片，也证明了一维CdS纳米棒是生长在多层Ti3C2表面和层间；其紫外可见漫反射吸光度图谱如图6所示，说明CdS/Ti3C2催化剂的对光的吸收性能更好；其紫外可见漫反射带隙图如图7所示，一维CdS与三维Ti3C2的复合有效的降低了CdS催化剂的带隙，说明一维CdS与三维Ti3C2的复合可以提高电子传输能力，提升光催化性能；其EIS奈奎斯特图谱如图8所示，说明复合材料的电荷转移电阻更小，利于载流子的传输分离；其瞬态光电流响应图如图9所示，光电流密度提升至近CdS的5倍，说明复合Ti3C2后对光的响应增强，Ti3C2促使更多载流子产生和分离；其稳态荧光图谱如图10所示，也证明载流子分离效果提升。The CdS/Ti 3 C 2 catalyst was observed by transmission electron microscope, and the results are shown in Fig. 5. Fig. 5(a), Fig. 5(b), Fig. 5(c) correspond to pure CdS, Ti 3 C 2 and CdS, respectively. The transmission electron microscope photo of /Ti 3 C 2 also proves that one-dimensional CdS nanorods are grown on the surface and between layers of multilayer Ti 3 C 2 ; its UV-visible diffuse reflectance absorbance spectrum is shown in Figure 6, indicating that CdS/Ti The 3 C 2 catalyst has better light absorption performance; its UV-vis diffuse reflection band gap diagram is shown in Figure 7. The composite of one-dimensional CdS and three-dimensional Ti 3 C 2 effectively reduces the band gap of the CdS catalyst, indicating that one The composite of 3D CdS and 3D Ti 3 C 2 can improve the electron transport ability and enhance the photocatalytic performance; its EIS Nyquist spectrum is shown in Figure 8, indicating that the charge transfer resistance of the composite material is smaller, which is conducive to the transport of carriers The transient photocurrent response diagram is shown in Figure 9, the photocurrent density is increased to nearly 5 times that of CdS, indicating that the response to light is enhanced after the composite Ti 3 C 2 , and Ti 3 C 2 promotes the generation of more carriers and separation; its steady-state fluorescence spectrum is shown in Figure 10, which also proves that the carrier separation effect is improved.
将本实施例制得的催化剂产品与使用相同方法制备得到的纯CdS催化进行光催化性能测试，在模拟太阳光条件下，以乳酸为牺牲剂，与水混合均匀在光解水制氢系统中检测评价，其光催化产氢图谱如图11所示，复合后的CdS/Ti3C2催化剂其光催化产氢性能远高于纯的CdS催化剂，产氢速率高达6.67mmol·h-1·g-1，为纯CdS样品的4倍；说明本实施例制得的催化剂产品——一维CdS纳米棒/三维多层Ti3C2复合光催化剂具有优异的光催化活性，可实现在太阳光下高效分解水产氢，高效节能。The photocatalytic performance of the catalyst product prepared in this example and the pure CdS catalysis prepared by the same method were tested for photocatalytic performance. Under simulated sunlight conditions, lactic acid was used as a sacrificial agent and mixed with water uniformly in the photolysis water hydrogen production system. The photocatalytic hydrogen production spectrum is shown in Figure 11. The photocatalytic hydrogen production performance of the composite CdS/Ti 3 C 2 catalyst is much higher than that of the pure CdS catalyst, and the hydrogen production rate is as high as 6.67 mmol·h -1 · g -1 , which is 4 times that of the pure CdS sample; it shows that the catalyst product prepared in this example, the one-dimensional CdS nanorod/three-dimensional multilayer Ti 3 C 2 composite photocatalyst, has excellent photocatalytic activity, and can achieve high photocatalytic activity in the sun. Efficiently decompose water to produce hydrogen under light, which is highly efficient and energy-saving.
上述实施例仅是本发明的优化实施方法，用以例示性说明本发明的原理及其功效，而非用于限制本发明。应当指出，对于任何熟习此项技艺的人士在不违背本发明的精神及范畴下，对上述实施例进行修改，这些修改也应视为本发明的保护范畴。The above-mentioned embodiments are only optimized implementation methods of the present invention, and are used to illustrate the principles and effects of the present invention, but not to limit the present invention. It should be pointed out that any person skilled in the art can make modifications to the above-mentioned embodiments without departing from the spirit and scope of the present invention, and these modifications should also be regarded as the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773213A (en) * | 2019-11-11 | 2020-02-11 | 福州大学 | One-dimensional cadmium sulfide/two-dimensional titanium carbide composite photocatalyst and preparation method and application thereof |
| CN111957331A (en) * | 2020-07-14 | 2020-11-20 | 广东工业大学 | TiO for water treatment2-MXene composite catalyst and preparation method thereof |
| US20200368731A1 (en) * | 2019-05-23 | 2020-11-26 | Soochow University | Titanium carbide nanosheet/layered indium sulfide heterojunction and application thereof in degrading and removing water pollutants |
| CN113441160A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | Nickel hydroxide/titanium carbide photo-thermal catalytic material and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200368731A1 (en) * | 2019-05-23 | 2020-11-26 | Soochow University | Titanium carbide nanosheet/layered indium sulfide heterojunction and application thereof in degrading and removing water pollutants |
| CN110773213A (en) * | 2019-11-11 | 2020-02-11 | 福州大学 | One-dimensional cadmium sulfide/two-dimensional titanium carbide composite photocatalyst and preparation method and application thereof |
| CN111957331A (en) * | 2020-07-14 | 2020-11-20 | 广东工业大学 | TiO for water treatment2-MXene composite catalyst and preparation method thereof |
| CN113441160A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | Nickel hydroxide/titanium carbide photo-thermal catalytic material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BENTENG SUNA等: ""The fabrication of 1D/2D CdS nanorod@Ti3C2 MXene composites for good photocatalytic activity of hydrogen generation and ammonia synthesis"" * |
| XIAO RONG等: ""In situ fabrication of 1D CdS nanorod/2D Ti3C2 MXene nanosheet Schottky heterojunction toward enhanced photocatalytic hydrogen evolution"" * |
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