CN110152737A - Zr-MOF Modified ZnCdS Nano-microsphere Composite Material and Its Application - Google Patents

Zr-MOF Modified ZnCdS Nano-microsphere Composite Material and Its Application Download PDF

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CN110152737A
CN110152737A CN201910389547.8A CN201910389547A CN110152737A CN 110152737 A CN110152737 A CN 110152737A CN 201910389547 A CN201910389547 A CN 201910389547A CN 110152737 A CN110152737 A CN 110152737A
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侯东芳
邓敏
汤凡
黄磊
乔秀清
李东升
兰亚乾
吴涛
卜贤辉
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China Three Gorges University CTGU
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Abstract

本发明公开了一种双金属硫化物基复合材料,应用一步水热法制备了一种双金属硫化物纳米微球与以Zr为金属中心的金属有机框架(MOF)的复合材料,ZnCdS纳米微球与有机框架材料形成异质结构的纳米复合催化材料的制备及其在光催化产氢中的应用,属于纳米材料制备技术及绿色能源领域。本发明首先利用氯化锆和对苯二甲酸为原料,经过溶剂热合成方块状Zr金属有机框架材料(简称UIO‑66(Zr)),然后利用乙酸镉和乙酸锌进一步合成ZnCdS纳米微球改性金属有机框架UIO‑66(Zr)的纳米复合材料。该纳米复合材料在光催化产氢中显示出优异的催化活性。

The invention discloses a bimetallic sulfide-based composite material. A composite material of bimetallic sulfide nano-microspheres and a metal-organic framework (MOF) with Zr as the metal center is prepared by applying a one-step hydrothermal method. ZnCdS nano-microspheres The preparation of nanocomposite catalytic materials with heterostructure formed by spheres and organic framework materials and its application in photocatalytic hydrogen production belong to the field of nanomaterial preparation technology and green energy. In the present invention, zirconium chloride and terephthalic acid are used as raw materials to synthesize a square Zr metal-organic framework material (referred to as UIO-66(Zr)) through solvothermal synthesis, and then ZnCdS nanospheres are further synthesized by using cadmium acetate and zinc acetate Nanocomposites of Modified Metal Organic Framework UIO‑66(Zr). The nanocomposite exhibits excellent catalytic activity in photocatalytic hydrogen production.

Description

Zr-MOF改性ZnCdS纳米微球复合材料及其应用Zr-MOF Modified ZnCdS Nano-microsphere Composite Material and Its Application

技术领域technical field

本发明属于纳米材料制备技术及绿色能源领域,具体涉及一种Zr-MOF改性ZnCdS纳米微球复合材料的制备方法及其在光催化产氢中的应用。The invention belongs to the field of nano-material preparation technology and green energy, and in particular relates to a preparation method of a Zr-MOF modified ZnCdS nano-microsphere composite material and its application in photocatalytic hydrogen production.

背景技术Background technique

能源是人类生存、生活与发展寸步难离的能量载体。化石能源的过量开发利用使得环境污染问题愈发严重,为了应对化石燃料的日益枯竭和环境状况的进一步恶化,人们对绿色和可再生能源进行了大量的研究。在可再生能源中,太阳能是最大的可开采资源,以半导体为基础的光催化制氢技术被广泛认为是将太阳能转化为化学燃料的一种有前景的途径,合理设计可持续有效的可见光响应光催化剂仍是一项具有挑战性的任务。Energy is an inseparable energy carrier for human survival, life and development. The excessive development and utilization of fossil energy has made the problem of environmental pollution more and more serious. In order to cope with the depletion of fossil fuels and the further deterioration of environmental conditions, people have conducted a lot of research on green and renewable energy. Among renewable energy sources, solar energy is the largest exploitable resource, and semiconductor-based photocatalytic hydrogen production technology is widely considered as a promising route to convert solar energy into chemical fuels, rationally designing sustainable and effective visible light responses Photocatalysis is still a challenging task.

双金属硫化物作为一种典型的无贵金属高分子半导体光催化剂,具有良好的环境友好性、表面合成性、良好的物理化学稳定性和独特的电子特性,然而,原始双金属硫化物也存在一些局限性,如比表面积不高,在光催化反应过程中光激发产生的活性物种电子空穴分离效率低、电荷载流子迁移能力弱等,直接导致催化活性降低。为了解决这一系列问题,人们已进行了许多研究,如通过控制Cd0.5Zn0.5S的形貌,掺杂贵金属,以及与其他半导体复合,Cd0.5Zn0.5S的光催化性能得到了一定程度的提高。遗憾的是,Cd0.5Zn0.5S光催化剂的光催化活性还远远不能满足实际应用的基本要求。因此,开发Cd0.5Zn0.5S光催化剂改性的新途径是非常必要的;金属-有机骨架(MOFs)具有高的比表面积、可调谐的孔径、高暴露的活性中心和灵活的结构等特性,由此引起人们对其在光催化领域的广泛关注,然而,由于UIO-66(Zr)带隙大(3.5 eV),只能吸收紫外光,在可见光催化方面的应用受到限制。因此,我们将该Zr-MOF材料与半导体材料双金属硫化物连接起来,从而改善Zr-MOF的可见光响应,作为光催化剂具有高比表面积的MOFs不仅可以避免半导体纳米粒子的聚集,而且可以提供更多的反应中心和催化活性中心,从而提高了光催化性能。Bimetallic sulfides, as a typical noble metal-free polymer semiconductor photocatalyst, have good environmental friendliness, surface synthesis, good physicochemical stability, and unique electronic properties. However, pristine bimetallic sulfides also have some Limitations, such as low specific surface area, low electron-hole separation efficiency of active species generated by photoexcitation during photocatalytic reaction, and weak charge carrier migration ability, etc., directly lead to the reduction of catalytic activity. In order to solve this series of problems, many studies have been carried out. For example, by controlling the morphology of Cd 0.5 Zn 0.5 S, doping noble metals, and compounding with other semiconductors, the photocatalytic performance of Cd 0.5 Zn 0.5 S has been improved to a certain extent. improve. Unfortunately, the photocatalytic activity of Cd 0.5 Zn 0.5 S photocatalysts is far from meeting the basic requirements for practical applications. Therefore, it is very necessary to develop new pathways for the modification of Cd 0.5 Zn 0.5 S photocatalysts; metal-organic frameworks (MOFs) have the characteristics of high specific surface area, tunable pore size, highly exposed active centers, and flexible structure. This has attracted widespread attention in the field of photocatalysis. However, due to the large band gap (3.5 eV) of UIO-66(Zr), it can only absorb ultraviolet light, and its application in visible light catalysis is limited. Therefore, we link this Zr-MOF material with the semiconductor material bimetallic sulfide to improve the visible light response of Zr-MOF, and as a photocatalyst, MOFs with high specific surface area can not only avoid the aggregation of semiconductor nanoparticles, but also provide more There are many reaction centers and catalytic active centers, thereby improving the photocatalytic performance.

发明内容Contents of the invention

针对上述技术问题,本发明将Zr基MOF材料(以下记为UIO-66(Zr))引进入双金属硫化物纳米微球,该材料的引入,提供了更多的活性中心和有效的电荷转移,使得复合材料的催化活性得到明显提高。In view of the above technical problems, the present invention introduces Zr-based MOF material (hereinafter referred to as UIO-66(Zr)) into bimetallic sulfide nanospheres. The introduction of this material provides more active centers and effective charge transfer , so that the catalytic activity of the composite material is significantly improved.

本发明以双金属硫化物ZnCdS和金属有机框架UIO-66(Zr)为材料,合成了纳米微球生长于方块状Zr基MOF表面的特殊组成方式的ZnCdS/UIO-66 (Zr)纳米复合材料。The present invention uses bimetallic sulfide ZnCdS and metal-organic framework UIO-66 (Zr) as materials, and synthesizes a ZnCdS/UIO-66 (Zr) nanocomposite with a special composition mode in which nanospheres grow on the surface of a square Zr-based MOF Material.

其中,Zr基MOF材料,可作为光催化分解水的半导体,其在水中具有优异的热稳定性、化学稳定性和结构稳定性,是一种很有前途的光催化剂。ZnCdS固溶体在可见光照射下,对水裂解制氢及降解有机污染物表现出很强的催化活性,具有较高的化学稳定性。但是原始ZnCdS存在一些局限性,如活性位分散差、电子空穴分离效率低、光激发电荷载流子迁移能力弱等。因此,引入高比表面积的MOF来克服ZnCdS中存在的光致电荷载流子的低比表面积和快速复合的缺点;而UIO-66(Zr)由于光吸收有限而无法获得优异的产氢活性,本发明将其与双金属硫化物进行复合,以更好地分离电荷和激活反应物。Among them, Zr-based MOF material, which can be used as a semiconductor for photocatalytic water splitting, has excellent thermal, chemical and structural stability in water, and is a promising photocatalyst. ZnCdS solid solution exhibits strong catalytic activity for hydrogen production from water splitting and degradation of organic pollutants under visible light irradiation, and has high chemical stability. However, pristine ZnCdS has some limitations, such as poor dispersion of active sites, low electron-hole separation efficiency, and weak mobility of photoexcited charge carriers. Therefore, MOF with high specific surface area was introduced to overcome the shortcomings of low specific surface area and fast recombination of photoinduced charge carriers existing in ZnCdS; while UIO-66(Zr) could not obtain excellent hydrogen production activity due to limited light absorption, this paper The invention compounded it with bimetallic sulfides to better separate charges and activate reactants.

为实现上述目的,本发明采用的技术方案为:To achieve the above object, the technical solution adopted in the present invention is:

首先通过一步溶剂热法合成方块状金属有机框架材料UIO-66(Zr),然后将UIO-66(Zr)加入到双金属硫化物的合成条件下,通过溶剂热法得到ZnCdS纳米微球生长于金属有机框架表面的新型ZnCdS/UIO-66(Zr)复合光催化剂,其中,UIO-66(Zr)保留了其高比表面的特点,当加入量为40%-70%时,得到的复合材料的比表面积范围为128.05-450.53 m2/g。First, the square metal-organic framework material UIO-66(Zr) was synthesized by a one-step solvothermal method, and then UIO-66(Zr) was added to the synthesis conditions of bimetallic sulfides to grow ZnCdS nanospheres by solvothermal method A new ZnCdS/UIO-66(Zr) composite photocatalyst on the surface of a metal organic framework, in which UIO-66(Zr) retains the characteristics of its high surface area, when the addition amount is 40%-70%, the obtained composite The specific surface area of the material ranges from 128.05 to 450.53 m 2 /g.

本发明所述的UIO-66(Zr)改性ZnCdS纳米微球复合材料的制备方法包括以下几个步骤:The preparation method of UIO-66 (Zr) modified ZnCdS nano-microsphere composite material of the present invention comprises the following steps:

(1)称取氯化锆和对苯二甲酸溶解于DMF中,超声至完全溶解后,转移至50mL(1) Weigh zirconium chloride and terephthalic acid and dissolve them in DMF, sonicate until completely dissolved, then transfer to 50mL

的聚四氟乙烯反应釜内衬中,加盖密封加热,产物用DMF和甲醇洗涤多次,于真空干燥箱中干燥处理,得到UIO-66(Zr)。In a polytetrafluoroethylene reaction kettle lined with a cover, sealed and heated, the product was washed with DMF and methanol several times, and dried in a vacuum oven to obtain UIO-66(Zr).

(2)将步骤(1)中得到的UIO-66(Zr)溶解于水中,超声处理得悬浮液A;称取乙酸镉和乙酸锌,分散于水中,搅拌至均匀分散得悬浮液B,后将悬浮液B加入到悬浮液A中,搅拌一段时间,再逐滴滴加硫化钠溶液,继续搅拌处理以形成均匀混合溶液。(2) Dissolve the UIO-66(Zr) obtained in step (1) in water, and ultrasonically treat it to obtain suspension A; weigh cadmium acetate and zinc acetate, disperse them in water, stir until uniformly dispersed to obtain suspension B, and then Add suspension B to suspension A, stir for a period of time, then add sodium sulfide solution drop by drop, and continue stirring to form a uniform mixed solution.

(3)将步骤(2)得到的混合溶液转移到聚四氟乙烯反应釜内衬中,于烘箱中加(3) Transfer the mixed solution obtained in step (2) to the lining of the polytetrafluoroethylene reactor, and add

热处理。冷却至室温,用纯水和乙醇洗涤多次,然后在烘箱中干燥。heat treatment. Cool to room temperature, wash with pure water and ethanol several times, and then dry in an oven.

本发明还提供一种将UIO-66(Zr)改性ZnCdS纳米微球复合材料应用在光催化产氢上的应用。具体步骤包括如下:在可见光照射下,在封闭石英反应***中进行了制氢,通过冷却循环水将反应体系的温度保持在5-8℃,将UIO-66(Zr)改性ZnCdS纳米微球复合材料催化剂分散在硫化钠和亚硫酸钠的水溶液中,其中硫化钠和亚硫酸钠作为牺牲剂,在连续搅拌下将其完全除去空气,以420 nm滤光片(CEL-HXF300)的300W Xe弧光灯为光源,采用在线气相色谱法(FULI,GC-7920)进行析氢分析,结果显示UIO-66(Zr)改性ZnCdS纳米微球复合材料呈现优异的光催化产氢活性。The invention also provides an application of UIO-66 (Zr) modified ZnCdS nano microsphere composite material in photocatalytic hydrogen production. The specific steps include the following: Under visible light irradiation, hydrogen production was carried out in a closed quartz reaction system, and the temperature of the reaction system was kept at 5-8 ° C by cooling circulating water, and UIO-66 (Zr) modified ZnCdS nanospheres The composite catalyst was dispersed in an aqueous solution of sodium sulfide and sodium sulfite as a sacrificial agent, which was completely deaired under continuous stirring, using a 300 W Xe arc lamp with a 420 nm filter (CEL-HXF300) as the light source , using online gas chromatography (FULI, GC-7920) for hydrogen evolution analysis, the results showed that UIO-66(Zr) modified ZnCdS nanosphere composites exhibited excellent photocatalytic hydrogen production activity.

本发明提供了一种光催化产氢的新型复合材料及其制备方法,并将其应用于光催化产氢,其制备方法合理简单,产氢性能提高明显,具有优异的光催化产氢活性。The invention provides a novel composite material for photocatalytic hydrogen production and a preparation method thereof, and applies it to photocatalytic hydrogen production. The preparation method is reasonable and simple, the hydrogen production performance is obviously improved, and the photocatalytic hydrogen production activity is excellent.

本发明采用简单的溶剂热法合成一种方块状UIO-66(Zr)改性ZnCdS纳米微球复合光催化剂,具有高的比表面积和更多的活性位点,合成的复合材料在可见光下具有的优异的产氢性能,可广泛地应用于绿色能源领域。The invention adopts a simple solvothermal method to synthesize a block-like UIO-66 (Zr) modified ZnCdS nano-microsphere composite photocatalyst, which has a high specific surface area and more active sites, and the synthesized composite material is stable under visible light. It has excellent hydrogen production performance and can be widely used in the field of green energy.

反应机理:本专利制备的方块状UIO-66(Zr)改性ZnCdS纳米微球复合光催化剂在光催化产氢中表现出极其优异的催化活性,主要是由于UIO-66(Zr)和ZnCdS 之间构成了异质结构,即在光照反应过程中,UIO-66(Zr)和ZnCdS的导带和价带均产生电子和空穴,由于UIO-66(Zr)导带的电极电势理更负,其导带上的电子直接传输到ZnCdS的导带,而价带上产生的空穴与加入的牺牲剂复合。即在光照反应过程中光催化活性的显著提高可归因于ZnCdS与UIO-66(Zr)界面上电荷的有效分离和转移及光诱导电荷载流子寿命的延长。Reaction mechanism: The block-like UIO-66(Zr) modified ZnCdS nano-microsphere composite photocatalyst prepared by this patent shows excellent catalytic activity in photocatalytic hydrogen production, mainly due to UIO-66(Zr) and ZnCdS A heterogeneous structure is formed between them, that is, during the photoreaction process, the conduction band and valence band of UIO-66(Zr) and ZnCdS both generate electrons and holes, because the electrode potential of UIO-66(Zr) conduction band is more Negative, the electrons on its conduction band are directly transferred to the conduction band of ZnCdS, while the holes generated on the valence band recombine with the added sacrificial agent. That is, the significant enhancement of photocatalytic activity during the light reaction process can be attributed to the effective separation and transfer of charges on the interface between ZnCdS and UIO-66(Zr) and the prolongation of the lifetime of photoinduced charge carriers.

此外,ZnCdS@UIO-66(Zr)光催化剂在可见光照射下具有很好的稳定性和良好的可回收性。MOF基复合纳米材料在环境修复和新型光催化材料的设计等方面有着广阔的应用前景。In addition, the ZnCdS@UIO-66(Zr) photocatalyst has good stability and good recyclability under visible light irradiation. MOF-based composite nanomaterials have broad application prospects in environmental restoration and the design of new photocatalytic materials.

附图说明Description of drawings

图1:为实施例1制得的催化剂ZnCdS、UIO-66(Zr)、UIO-66(Zr)改性ZnCdS纳米微球复合材料的X射线衍射图。Fig. 1: is the X-ray diffraction pattern of catalyst ZnCdS, UIO-66 (Zr), UIO-66 (Zr) modified ZnCdS nano-microsphere composite material that embodiment 1 makes.

图2:为实施例1制得的UIO-66(Zr)改性ZnCdS纳米微球复合材料ZU-50的扫描电镜图。Fig. 2: is the scanning electron micrograph of the UIO-66 (Zr) modified ZnCdS nano-microsphere composite material ZU-50 prepared in Example 1.

图3:为实施例1制得的UIO-66(Zr)改性ZnCdS纳米微球复合材料ZU-50的透射电镜图。Fig. 3: is the transmission electron micrograph of the UIO-66 (Zr) modified ZnCdS nano-microsphere composite material ZU-50 prepared in Example 1.

图4:为实施例1制得的UIO-66(Zr)改性ZnCdS纳米微球复合材料的N2吸附-脱附曲线。Fig. 4 : is the N adsorption-desorption curve of the UIO-66 (Zr) modified ZnCdS nano-microsphere composite material prepared in Example 1.

图5:为实施例1制得的UIO-66(Zr)改性ZnCdS纳米微球复合材料的紫外-可见漫反射光谱图。Fig. 5: is the ultraviolet-visible diffuse reflectance spectrogram of the UIO-66 (Zr) modified ZnCdS nano-microsphere composite material prepared in Example 1.

图6:为实施例1制得的催化剂ZnCdS,UIO-66(Zr),UIO-66(Zr)改性ZnCdS纳米微球复合材料ZU-50的红外图谱。Fig. 6: is the infrared spectrum of the catalyst ZnCdS prepared in Example 1, UIO-66 (Zr), UIO-66 (Zr) modified ZnCdS nano-microsphere composite material ZU-50.

图7:为实施例1制得的催化剂ZnCdS,UIO-66(Zr),UIO-66(Zr)改性ZnCdS纳米微球复合材料的光电流图。Fig. 7: is the photocurrent diagram of the catalyst ZnCdS prepared in Example 1, UIO-66(Zr), UIO-66(Zr) modified ZnCdS nano-microsphere composite material.

图8:为实施例1制得的催化剂ZnCdS,UIO-66(Zr),UIO-66(Zr)改性ZnCdS纳米微球复合材料的交流-阻抗图。Fig. 8: It is the AC-impedance diagram of the catalyst ZnCdS prepared in Example 1, UIO-66(Zr), UIO-66(Zr) modified ZnCdS nano-microsphere composite material.

图9:为实施例2制得的催化剂ZnCdS,UIO-66(Zr),UIO-66(Zr)改性ZnCdS纳米微球复合材料的产氢性能柱状图。Fig. 9: The catalyst ZnCdS that is prepared in embodiment 2, UIO-66 (Zr), UIO-66 (Zr) The bar graph of the hydrogen production property of modified ZnCdS nano microsphere composite material.

具体实施方式Detailed ways

实施例1Example 1

1)称取1 mmol氯化锆和1 mmol对苯二甲酸溶解于30 mL DMF中,超声至完1) Dissolve 1 mmol of zirconium chloride and 1 mmol of terephthalic acid in 30 mL of DMF and sonicate until complete

全溶解后,转移至50 mL的聚四氟乙烯反应釜内衬中,加盖密封,放入烘箱中,120℃加热24 h,降至室温后,产物分别用DMF和甲醇洗涤多次,于80 ℃真空干燥,得到金属有机框架Zr-MOF,命名为UIO-66(Zr)。After completely dissolving, transfer it to a 50 mL polytetrafluoroethylene reactor liner, cover and seal it, put it in an oven, heat at 120 °C for 24 h, and after cooling down to room temperature, the product is washed several times with DMF and methanol respectively, and the After vacuum drying at 80 ℃, the metal-organic framework Zr-MOF was obtained, which was named UIO-66(Zr).

2)分别称取80.7 mg,121 mg,181.5 mg,282.3 mg步骤(1)中得到的UIO-66(Zr)于四个烧杯中(分别代表UIO-66(Zr)加入量占复合材料的摩尔比为40%,50%,60%,70%),加入5mL水,超声处理得分散均匀的悬浮液A1,A2,A3,A4,另取四个烧杯,分别称取0.5 mmol乙酸镉和0.5 mmol乙酸锌,量取15 mL水,搅拌30 min至分散均匀得悬浮液B1,B2,B3,B4,然后将B1,B2,B3,B4分别对应加入到对应的A1,A2,A3,A4中搅拌1 h,后分别逐滴滴加5 mL硫化钠溶液(0.3M),继续搅拌处理2 h以形成均匀的混合溶液。2) Weigh 80.7 mg, 121 mg, 181.5 mg, 282.3 mg of UIO-66(Zr) obtained in step (1) into four beakers (representing the moles of UIO-66(Zr) added to the composite material 40%, 50%, 60%, 70%), add 5mL of water, ultrasonic treatment to obtain uniformly dispersed suspensions A1, A2, A3, A4, take four other beakers, respectively weigh 0.5 mmol cadmium acetate and 0.5 Mmol zinc acetate, measure 15 mL of water, stir for 30 min until uniformly dispersed to obtain suspensions B1, B2, B3, B4, then add B1, B2, B3, B4 to corresponding A1, A2, A3, A4 respectively After stirring for 1 h, 5 mL of sodium sulfide solution (0.3 M) was added dropwise, and stirring was continued for 2 h to form a uniform mixed solution.

3)将步骤(2)得到的均匀的混合溶液转移到50 mL的聚四氟乙烯反应釜内衬3) Transfer the homogeneous mixed solution obtained in step (2) to a 50 mL polytetrafluoroethylene reactor liner

中,于160 ℃烘箱中加热处理4 h。冷却至室温,用纯水和乙醇洗涤多次,然后在80 ℃真空烘箱中干燥一夜。样品标记为ZU-40,ZU-50,ZU-60,ZU-70,分别表示UIO-66(Zr)加入量在复合材料中摩尔比为40%,50%,60%,70%。另外,在不加入金属有机框架材料UIO-66(Zr)时合成原始双金属硫化物Zn0.5Cd0.5S。heat treatment in an oven at 160 °C for 4 h. Cool to room temperature, wash with pure water and ethanol several times, and then dry in a vacuum oven at 80 °C overnight. The samples are labeled ZU-40, ZU-50, ZU-60, and ZU-70, respectively indicating that the molar ratio of UIO-66 (Zr) in the composite material is 40%, 50%, 60%, and 70%. In addition, pristine bimetallic sulfides Zn 0.5 Cd 0.5 S were synthesized without the addition of metal-organic framework material UIO-66(Zr).

图1为实施例1制得的催化剂ZnCdS、UIO-66(Zr)、UIO-66(Zr)改性ZnCdS纳米微球复合材料的X射线衍射图。(从图中可知,复合材料中有明显UIO-66和ZnCdS的特征峰存在,说明二者复合后并未破坏原本的结构,且随着UIO-66摩尔量的增加,其在复合材料中特征峰也越明显)。Fig. 1 is the X-ray diffraction pattern of catalyst ZnCdS, UIO-66 (Zr), UIO-66 (Zr) modified ZnCdS nano-microsphere composite material prepared in Example 1. (It can be seen from the figure that there are obvious characteristic peaks of UIO-66 and ZnCdS in the composite material, indicating that the original structure is not destroyed after the two are combined, and with the increase of the molar amount of UIO-66, its characteristic peaks in the composite material The peak is also more obvious).

图3:为实施例1制得的UIO-66(Zr)改性ZnCdS纳米微球复合材料的透射电镜图。(从透射图中可以明显看出方块状UIO-66和ZnCdS纳米微球,mapping图分别为所选区域中Cd, S, Zn, Zr各种元素的分布情况,ZnCdS纳米微球主要分布于所选区域四周,故Cd, S,Zn三种元素在区域四周分布比较集中,而方块状UIO-66主要在所选区域的中部,故Zr元素集中分布于区域中部)。Fig. 3: is the transmission electron micrograph of the UIO-66 (Zr) modified ZnCdS nano-microsphere composite material prepared in Example 1. (It can be clearly seen from the transmission diagram that UIO-66 and ZnCdS nanospheres are square, and the mapping diagram shows the distribution of Cd, S, Zn, and Zr elements in the selected area, and ZnCdS nanospheres are mainly distributed in Around the selected area, the three elements of Cd, S, and Zn are relatively concentrated around the area, while the square UIO-66 is mainly in the middle of the selected area, so the Zr element is concentrated in the middle of the area).

实施例2Example 2

1)将实施例1中得到的复合材料催化剂进行可见光的光催化产氢。1) The composite material catalyst obtained in Example 1 is subjected to photocatalytic hydrogen production with visible light.

2)在可见光照射下,在封闭石英反应***中进行了制氢实验,通过冷却循环水将反应体系的温度保持在6℃,将50 mg催化剂分散在0.25 M硫化钠和0.35 M亚硫酸钠的水溶液(80mL)中,其中硫化钠和亚硫酸钠作为牺牲剂,在连续搅拌下将其完全除去空气,以420nm滤光片(CEL-HXF300)的300W Xe弧光灯为光源,采用在线气相色谱法(FULI,GC-7920)进行析氢分析。光照开始后,每隔1小时取样一次,得到图5所示产氢柱状图。可以得出,UIO-66(Zr)加入重量为50%时的产物ZU-50产氢量为4333.93μmol·h-1·g-12) Under the irradiation of visible light, the hydrogen production experiment was carried out in a closed quartz reaction system. The temperature of the reaction system was kept at 6 °C by cooling circulating water, and 50 mg of catalyst was dispersed in an aqueous solution of 0.25 M sodium sulfide and 0.35 M sodium sulfite ( 80mL), in which sodium sulfide and sodium sulfite were used as sacrificial agents, the air was completely removed under continuous stirring, and a 300W Xe arc lamp with a 420nm filter (CEL-HXF300) was used as a light source, and online gas chromatography (FULI, GC -7920) for hydrogen evolution analysis. After the illumination started, samples were taken every 1 hour, and the hydrogen production histogram shown in Figure 5 was obtained. It can be concluded that when the weight of UIO-66(Zr) is 50%, the hydrogen production of product ZU-50 is 4333.93μmol·h -1 ·g -1 .

Claims (9)

1.一种Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,该复合材料为双金属硫化物纳米微球与金属有机框架Zr-MOF异质结结构的复合材料。1. A ZnCdS nano-microsphere composite material modified by Zr-MOF, characterized in that, the composite material is a composite material of bimetallic sulfide nano-microsphere and metal organic framework Zr-MOF heterojunction structure. 2.根据权利要求1所述的Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,所述的双金属硫化物纳米微球为双金属硫化物ZnCdS纳米微球,尺寸为10 nm - 15nm。2. the ZnCdS nano-microsphere composite material of Zr-MOF modification according to claim 1, is characterized in that, described bimetallic sulfide nano-microsphere is bimetallic sulfide ZnCdS nano-microsphere, and size is 10 nm - 15nm. 3.根据权利要求1所述的Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,金属有机框架Zr-MOF为Zr为金属中心的金属有机框架材料。3. The ZnCdS nano-microsphere composite material modified by Zr-MOF according to claim 1, wherein the metal-organic framework Zr-MOF is a metal-organic framework material in which Zr is a metal center. 4.根据权利要求3所述的Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,所述的金属有机框架Zr-MOF为多孔的方块结构,其孔径大小为2 nm - 50 nm,比表面积为550-570m2/g。4. The ZnCdS nano-microsphere composite material modified by Zr-MOF according to claim 3, wherein the metal-organic framework Zr-MOF is a porous box structure, and its pore size is 2 nm-50 nm , the specific surface area is 550-570m 2 /g. 5.根据权利要求1所述的Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,金属有机框架Zr-MOF在复合材料中所占摩尔比分别为0-70%。5. The ZnCdS nano-microsphere composite material modified by Zr-MOF according to claim 1, wherein the molar ratio of metal-organic framework Zr-MOF in the composite material is 0-70% respectively. 6.根据权利要求1所述的Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,金属有机框架Zr-MOF是将氯化锆与对苯二甲酸在溶剂DMF中溶解,再在反应釜内100-130℃下水热反应20-25h所得。6. the ZnCdS nano-microsphere composite material modified by Zr-MOF according to claim 1, is characterized in that, metal organic framework Zr-MOF is that zirconium chloride and terephthalic acid are dissolved in solvent DMF, then in It is obtained by hydrothermal reaction at 100-130°C in the reactor for 20-25h. 7.根据权利要求1所述的Zr-MOF改性的ZnCdS纳米微球复合材料,其特征在于,双金属硫化物纳米微球金属有机框架Zr-MOF异质结结构的复合材料的制备方法是将乙酸镉与乙酸锌的水溶液加入到金属有机框架Zr-MOF材料中,搅拌得悬乳液后滴加硫化钠,得到均匀的溶液;将均匀的溶液转移到聚四氟乙烯中,在150-180℃下水热3-5h得到双金属硫化物纳米微球与金属有机框架Zr-MOF异质结结构的复合材料。7. the ZnCdS nano-microsphere composite material modified by Zr-MOF according to claim 1, is characterized in that, the preparation method of the composite material of bimetallic sulfide nano-microsphere metal-organic framework Zr-MOF heterojunction structure is Add the aqueous solution of cadmium acetate and zinc acetate to the metal-organic framework Zr-MOF material, stir to obtain a suspoemulsion, and then add sodium sulfide dropwise to obtain a uniform solution; transfer the uniform solution to polytetrafluoroethylene at 150-180 The composite material of bimetallic sulfide nano-microspheres and metal-organic framework Zr-MOF heterojunction structure was obtained by hydrothermal heating at ℃ for 3-5 hours. 8.根据权利要求1-7任一项所述的Zr-MOF改性的ZnCdS纳米微球复合材料在光催化产氢上的应用。8. The application of the ZnCdS nano-microsphere composite material modified by Zr-MOF according to any one of claims 1-7 in photocatalytic hydrogen production. 9.根据权利要求8所述的应用,其特征在于,在可见光照射下,通过冷却循环水将反应体系的温度保持在5-8℃,将双金属硫化物基复合材料分散在硫化钠和亚硫酸钠的水溶液中,在连续搅拌及可见光下产氢。9. The application according to claim 8, characterized in that, under visible light irradiation, the temperature of the reaction system is kept at 5-8°C by cooling circulating water, and the bimetallic sulfide-based composite material is dispersed in sodium sulfide and sodium sulfite Hydrogen is produced under continuous stirring and visible light in an aqueous solution.
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CN110918125A (en) * 2019-12-23 2020-03-27 西北师范大学 Preparation method of UiO-66 supported tin sulfide nanoparticle photocatalyst
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Application publication date: 20190823