CN110787812A - A method for synergistic modification of ZnIn2S4 photocatalyst with hole promoter Ti(IV) and electron promoter Ni(OH)2 - Google Patents

A method for synergistic modification of ZnIn2S4 photocatalyst with hole promoter Ti(IV) and electron promoter Ni(OH)2 Download PDF

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CN110787812A
CN110787812A CN201910935101.0A CN201910935101A CN110787812A CN 110787812 A CN110787812 A CN 110787812A CN 201910935101 A CN201910935101 A CN 201910935101A CN 110787812 A CN110787812 A CN 110787812A
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陈�峰
周伟军
余火根
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Wuhan University of Technology WUT
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Abstract

本发明涉及空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，包括以下步骤：1)ZnIn2S4光催化材料与去离子水混合，充分搅拌形成悬浮液；2)向悬浮液加入可溶于水的钛盐；3)将悬浮液边搅拌边水浴加热一定时间；4)将沉淀过滤洗涤干燥，即为光催化剂；5)将光催化剂与去离子水混合，通过搅拌形成均匀的悬浮液；6)向悬浮液加入可溶于水的镍盐与尿素溶液；7)把悬浮液边搅拌边水浴加热一定时间；8)将沉淀过滤洗涤干燥，即为空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂。本发明合成方法操作十分简单、绿色环保、节能、无需加入任何有机表面活性剂。The invention relates to a preparation method for a ZnIn 2 S 4 photocatalyst that is synergistically modified by a hole assistant Ti(IV) and an electron assistant Ni(OH) 2 , comprising the following steps: 1) mixing the ZnIn 2 S 4 photocatalytic material with deionized water 2) Add water-soluble titanium salt to the suspension; 3) Heat the suspension in a water bath while stirring for a certain period of time; 4) Filter, wash and dry the precipitate, which is a photocatalyst; The photocatalyst is mixed with deionized water, and a uniform suspension is formed by stirring; 6) Add water-soluble nickel salt and urea solution to the suspension; 7) Heat the suspension in a water bath while stirring for a certain period of time; 8) Precipitate Filtration, washing, and drying are the synergistic modification of the ZnIn 2 S 4 photocatalyst by the hole assistant Ti(IV) and the electron assistant Ni(OH) 2 . The synthesis method of the invention has the advantages of simple operation, green environmental protection, energy saving and no need to add any organic surfactant.

Description

空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化 剂的方法Synergistic modification of ZnIn2S4 photocatalysis by hole promoter Ti(IV) and electron promoter Ni(OH)2 method of dosing

技术领域technical field

本发明涉及空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，特别是涉及到空穴助剂Ti(IV)与电子助剂Ni(OH)2的负载方法。The invention relates to a preparation method of a ZnIn 2 S 4 photocatalyst by synergistically modifying a hole assistant Ti(IV) and an electron assistant Ni(OH) 2 , in particular to a hole assistant Ti(IV) and an electron assistant Ni( OH) 2 loading method.

技术背景technical background

现在能源缺乏问题日益严重，而太阳能是清洁的可再生能源，故利用太阳能解决环境污染问题和能源问题是最有潜力的策略之一；其中光催化技术能够实现高效的太阳能捕获和转化而备受关注。而光催化技术的核心是光催化剂，但是纯相TiO2、CdS、C3N4、BiVO4等光催化剂的光催化活性都很低，需要对其进行改性，其中助剂的修饰是提高光催化剂活性的有效手段之一。因此，寻找高活性助剂修饰光催化剂的制备方法是该技术中开发的热点和重点。At present, the problem of energy shortage is becoming more and more serious, and solar energy is a clean and renewable energy source. Therefore, using solar energy to solve environmental pollution and energy problems is one of the most potential strategies. Among them, photocatalytic technology can achieve efficient solar energy capture and conversion. focus on. The core of photocatalytic technology is photocatalyst, but the photocatalytic activity of pure-phase TiO 2 , CdS, C 3 N 4 , BiVO 4 and other photocatalysts is very low and needs to be modified. The modification of additives is to improve the One of the effective means of photocatalytic activity. Therefore, finding a preparation method for high-activity co-modified photocatalysts is the focus and focus of development in this technology.

最近有研究表明：Ni(OH)2能作为电子助剂，快速转移光生电子，抑制了光生电子与光生空穴的复合，从而提高了ZnIn2S4的光催化性能。更重要的是，Ni(OH)2吸附光生电子后，能使Ni2+还原成Ni单质，而Ni单质能作为光催化反应的活性位点，从而加快了界面还原反应速率。众所周知，半导体光催化速率由三个重要部分决定：1)光生电子和空穴的传输速率、 2)界面还原反应速率、3)界面氧化反应速率。故为了进一步提高ZnIn2S4的光催化性能，我们同时利用空穴助剂Ti(IV)来加快界面氧化反应速率，最终达到提高ZnIn2S4的光催化性能的目的。Recent studies have shown that Ni(OH) 2 can act as an electron assistant to rapidly transfer photo-generated electrons and inhibit the recombination of photo-generated electrons and photo-generated holes, thereby improving the photocatalytic performance of ZnIn 2 S 4 . More importantly, after Ni(OH) 2 absorbs photogenerated electrons, it can reduce Ni 2+ to Ni elemental substance, which can serve as the active site of photocatalytic reaction, thus speeding up the interfacial reduction reaction rate. It is well known that the photocatalytic rate of semiconductors is determined by three important parts: 1) the transport rate of photogenerated electrons and holes, 2) the rate of the interfacial reduction reaction, and 3) the rate of the interfacial oxidation reaction. Therefore, in order to further improve the photocatalytic performance of ZnIn 2 S 4 , we also use the hole promoter Ti(IV) to speed up the interfacial oxidation reaction rate, and finally achieve the purpose of improving the photocatalytic performance of ZnIn 2 S 4 .

发明的内容content of invention

本发明所要解决的技术问题就是针对上述技术问题，提出一种操作简单、绿色环保的空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，其通过低温水浴的方法将空穴助剂Ti(IV)与电子助剂Ni(OH)2负载在ZnIn2S4表面上。The technical problem to be solved by the present invention is to solve the above-mentioned technical problems, and propose a preparation method of a ZnIn 2 S 4 photocatalyst that is simple to operate, green and environmentally friendly, and the hole assistant Ti(IV) and the electron assistant Ni(OH) 2 synergistically modify the ZnIn 2 S 4 photocatalyst , which supports the hole assistant Ti(IV) and electron assistant Ni(OH) 2 on the surface of ZnIn 2 S 4 by means of a low temperature water bath.

为了解决上述技术问题所采用的技术方案是：空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，其特征在于包括以下步骤：The technical scheme adopted in order to solve the above-mentioned technical problems is: a preparation method of a ZnIn 2 S 4 photocatalyst that is synergistically modified by a hole assistant Ti(IV) and an electron assistant Ni(OH) 2 , which is characterized by comprising the following steps:

1)ZnIn2S4光催化材料与去离子水混合，充分搅拌形成均匀的悬浮液；1) The ZnIn 2 S 4 photocatalytic material is mixed with deionized water and fully stirred to form a uniform suspension;

2)向步骤1)中的悬浮液加入可溶于水的钛盐；2) adding water-soluble titanium salt to the suspension in step 1);

3)将步骤2)中的悬浮液边搅拌边水浴加热一定时间；3) heating the suspension in step 2) in a water bath for a certain period of time while stirring;

4)将步骤3)中的沉淀过滤洗涤干燥，即为空穴助剂Ti(IV)修饰的ZnIn2S4；4) filter, wash and dry the precipitate in step 3), that is, ZnIn 2 S 4 modified by cavitation aid Ti(IV);

5)将步骤4)中的光催化剂与去离子水混合，通过搅拌形成均匀的悬浮液；5) Mix the photocatalyst in step 4) with deionized water, and form a uniform suspension by stirring;

6)向步骤5)中的悬浮液加入可溶于水的镍盐与尿素溶液；6) adding water-soluble nickel salt and urea solution to the suspension in step 5);

7)把步骤6)中的悬浮液边搅拌边水浴加热一定时间；7) heating the suspension in step 6) in a water bath while stirring for a certain period of time;

8)将步骤7)中的沉淀过滤洗涤干燥，即为空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰 ZnIn2S4光催化剂。8) Filter, wash and dry the precipitate in step 7), that is, the hole assistant Ti(IV) and the electron assistant Ni(OH) 2 synergistically modify the ZnIn 2 S 4 photocatalyst.

按上述方案，步骤3)与步骤7)所述的水浴加热反应温度为70-90℃，反应时间为4-6h。According to the above scheme, the water bath heating reaction temperature of step 3) and step 7) is 70-90°C, and the reaction time is 4-6h.

按上述方案，步骤2)所述的钛盐为氯化钛或硫酸钛。According to the above scheme, the titanium salt in step 2) is titanium chloride or titanium sulfate.

按上述方案，步骤6)所述的镍盐为硫酸镍或硝酸镍。According to the above scheme, the nickel salt described in step 6) is nickel sulfate or nickel nitrate.

本发明ZnIn2S4的制备方法见文献(Z.Yan,X.Yu,A.Han,P.Xu,P.Du,Journal ofPhysical Chemistry C 118(2014)22896-22903)，其中ZnIn2S4是六方体晶形的微球结构，通过低温水浴的方法来负载一定量空穴助剂Ti(IV)与电子助剂Ni(OH)2。其光催化活性增强的基本原理是：空穴助剂Ti(IV)与电子助剂Ni(OH)2提高了ZnIn2S4内部光生载流子的分离效率，同时电子助剂Ni(OH)2加速了界面氧化反应速率，从而提高了Ni(OH)2-Ti(IV)/ZnIn2S4的光催化活性。The preparation method of ZnIn 2 S 4 of the present invention is shown in the literature (Z.Yan, X. Yu, A. Han, P. Xu, P. Du, Journal of Physical Chemistry C 118 (2014) 22896-22903), wherein ZnIn 2 S 4 It is a hexagonal microsphere structure, and a certain amount of hole assistant Ti(IV) and electron assistant Ni(OH) 2 are loaded by the method of low temperature water bath. The basic principle of its photocatalytic activity enhancement is that the hole assistant Ti(IV) and electron assistant Ni(OH) 2 improve the separation efficiency of photogenerated carriers inside ZnIn 2 S 4 , while the electron assistant Ni(OH) 2 accelerates the interfacial oxidation reaction rate, thereby enhancing the photocatalytic activity of Ni(OH) 2 -Ti(IV)/ZnIn 2 S 4 .

本发明的有益效果：本发明提出以ZnIn2S4为前驱体，通过低温水浴的方法使二价镍离子在ZnIn2S4表面生成Ni(OH)2，该合成方法操作十分简单、绿色环保、节能、无需加入任何有机表面活性剂，并且氢氧化镍具有原料来源广泛、价格低廉、无毒、无污染，化学性质稳定等优点。同时整个反应过程无需昂贵的各种加工合成设备和高温高压等反应装置，具有易于大批量合成等优点。制备的光催化材料具有高的可见光光催化活性，有望产生良好的社会和经济效益。Beneficial effects of the present invention: The present invention proposes to use ZnIn 2 S 4 as a precursor, and to generate Ni(OH) 2 from divalent nickel ions on the surface of ZnIn 2 S 4 by means of a low-temperature water bath. The synthesis method is very simple to operate and environmentally friendly. , energy saving, no need to add any organic surfactant, and nickel hydroxide has the advantages of wide source of raw materials, low price, non-toxic, non-polluting, and stable chemical properties. At the same time, the whole reaction process does not need expensive various processing synthesis equipment and reaction devices such as high temperature and high pressure, and has the advantages of being easy to synthesize in large quantities. The prepared photocatalytic material has high visible light photocatalytic activity and is expected to produce good social and economic benefits.

附图说明Description of drawings

图1为实施例1中样品(A)ZnIn2S4、(B)Ti(IV,0.5％)/ZnIn2S4、(C)Ni(OH)2(3％)/ZnIn2S4、 (D)Ni(OH)2(3％)-Ti(IV,0.5％)/ZnIn2S4的FESEM图。其中，(A)、(B)、(C)和(D)中嵌入的图分别是ZnIn2S4、Ti(IV,0.5％)/ZnIn2S4、Ni(OH)2/ZnIn2S4、Ni(OH)2-Ti(IV,0.5％)/ZnIn2S4的能量色散X射线光谱仪(EDX)谱图；Figure 1 shows the samples in Example 1 (A) ZnIn 2 S 4 , (B) Ti(IV, 0.5%)/ZnIn 2 S 4 , (C) Ni(OH) 2 (3%)/ZnIn 2 S 4 , (D) FESEM image of Ni(OH) 2 (3%)-Ti(IV, 0.5%)/ZnIn 2 S 4 . Among them, the embedded images in (A), (B), (C) and (D) are ZnIn 2 S 4 , Ti(IV, 0.5%)/ZnIn 2 S 4 , Ni(OH) 2 /ZnIn 2 S , respectively 4. The energy dispersive X-ray spectrometer (EDX) spectrum of Ni(OH) 2 -Ti(IV, 0.5%)/ZnIn 2 S 4 ;

图2为实施例1中不同样品的XRD图：(a)ZnIn2S4、(b)Ti(IV,0.5％)/ZnIn2S4、 (c)Ni(OH)2(3％)/ZnIn2S4、(d)Ni(OH)2(3％)-Ti(IV,0.5％))/ZnIn2S4；Figure 2 shows the XRD patterns of different samples in Example 1: (a) ZnIn 2 S 4 , (b) Ti(IV, 0.5%)/ZnIn 2 S 4 , (c) Ni(OH) 2 (3%)/ ZnIn 2 S 4 , (d)Ni(OH) 2 (3%)-Ti(IV, 0.5%))/ZnIn 2 S 4 ;

图3(A)为实施例1中不同样品的XPS全谱图以及不同元素(B)Ti 2p、(C)Ni 2p、(D)In 3d、 (E)Zn 2p、(F)S 2p的高分辨XPS图：(a)ZnIn2S4、(b)Ti(IV,0.5％)ZnIn2S4、(c)Ni(OH)2(3％)/ZnIn2S4、 (d)Ni(OH)2(3％)-Ti(IV,0.5％))/ZnIn2S4；Figure 3 (A) is the XPS full spectrum of different samples in Example 1 and the different elements (B) Ti 2p, (C) Ni 2p, (D) In 3d, (E) Zn 2p, (F) S 2p High-resolution XPS images: (a) ZnIn 2 S 4 , (b) Ti(IV, 0.5%)ZnIn 2 S 4 , (c) Ni(OH) 2 (3%)/ZnIn 2 S 4 , (d) Ni (OH) 2 (3%)-Ti(IV, 0.5%))/ZnIn 2 S 4 ;

图4(A)为实施例1中不同样品产氢的速率图：(a)ZnIn2S4，(b)Ti(IV,0.5％)/ZnIn2S4，(c) Ni(OH)2(3％)-Ti(IV,0.5％)/ZnIn2S4的光催化循环图，图4(B)为 Ni(OH)2(3％)/Ti(IV,0.5％)/ZnIn2S4的光催化循环图。Figure 4(A) is a graph of the hydrogen production rate of different samples in Example 1: (a) ZnIn 2 S 4 , (b) Ti(IV, 0.5%)/ZnIn 2 S 4 , (c) Ni(OH) 2 Photocatalytic cycle diagram of (3%)-Ti(IV, 0.5%)/ZnIn 2 S 4 , Fig. 4(B) is Ni(OH) 2 (3%)/Ti(IV, 0.5%)/ZnIn 2 S The photocatalytic cycle diagram of 4 .

具体实施方式Detailed ways

下面结合实施例对本发明做进一步详细的说明，但是以下说明不会构成对本发明的限制。The present invention will be described in further detail below in conjunction with the embodiments, but the following description will not constitute a limitation to the present invention.

实施例1：Example 1:

空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备过程如下：首先把 30mL去离子水加到三口烧瓶中，然后将0.2g的ZnIn2S4粉末与上述溶液在磁力搅拌下混合，形成均匀悬浮液，接着用移液枪取526μL的TiCl4(0.01mol/L)溶液加到上述悬浮液中；然后，把三口烧瓶放在75℃下，边搅拌边水浴6h，将反应产物用水洗三遍，在40℃烘箱中干燥12h获得Ti(IV,0.5％)/ZnIn2S4光催化材料，接着把0.2g的上述的光催化材料加到含有30mL 去离子水、0.6ml的Ni(NO3)2(10g/L)溶液和5mL的尿素溶液(1mol/L)的三口烧瓶中，然后，把三口烧瓶放在75℃下，边搅拌边水浴6h，将反应产物用水洗三遍，在40℃烘箱中干燥12 h获得Ni(OH)2(3％)-Ti(IV,0.5％)/ZnIn2S4光催化材料。The preparation process of the ZnIn 2 S 4 photocatalyst modified by the hole assistant Ti(IV) and the electron assistant Ni(OH) 2 synergistically 4. The powder is mixed with the above-mentioned solution under magnetic stirring to form a uniform suspension, and then 526 μL of TiCl 4 (0.01 mol/L) solution is taken with a pipette and added to the above-mentioned suspension; then, the three-necked flask is placed at 75 ° C. , water bath for 6h while stirring, the reaction product was washed three times with water, dried in an oven at 40°C for 12h to obtain a Ti(IV, 0.5%)/ZnIn 2 S 4 photocatalytic material, and then 0.2 g of the above photocatalytic material was added into a three-necked flask containing 30 mL of deionized water, 0.6 mL of Ni(NO 3 ) 2 (10 g/L) solution and 5 mL of urea solution (1 mol/L), then put the three-necked flask at 75°C while stirring The reaction product was washed three times with water while in a water bath for 6 h, and dried in an oven at 40°C for 12 h to obtain a Ni(OH) 2 (3%)-Ti(IV, 0.5%)/ZnIn 2 S 4 photocatalytic material.

空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的表征方法如下：样品的形貌结构通过JSM-7500场发射扫描电子显微镜(FESEM，JEOL，Japan)观察测得，同时利用能量色散X射线光谱仪(EDX)研究样品的化学组成。样品的晶相结构及相组成采用日本Rigaku公司生产的Ultima III X射线衍射仪(Cu Kα为射线源)进行表征。样品的表面元素通过英国生产的KRATOA XSAM800 X射线光电子能谱***(靶源为Al Kα)进行分析，各样品元素的结合能都以标准碳元素峰C1s 284.8eV为参照。 The characterization of the ZnIn2S4 photocatalyst by the synergistic modification of the hole promoter Ti(IV) and the electron promoter Ni(OH) 2 is as follows: The morphology and structure of the samples were analyzed by a JSM-7500 field emission scanning electron microscope (FESEM, JEOL, Japan ) were observed and measured, and the chemical composition of the samples was studied by energy dispersive X-ray spectrometer (EDX). The crystal phase structure and phase composition of the samples were characterized by Ultima III X-ray diffractometer (Cu Kα as the ray source) produced by Rigaku Corporation of Japan. The surface elements of the samples were analyzed by KRATOA XSAM800 X-ray photoelectron spectroscopy system (target source is Al Kα) produced in the UK. The binding energy of each sample element was based on the standard carbon peak C1s 284.8eV as a reference.

图1中A为ZnIn2S4微球结构的扫描电镜(SEM)图，从图中可以看出ZnIn2S4的尺寸范围为1-2μm。图1中B为Ti(IV,0.5％)/ZnIn2S4的SEM图，由图可以看出微球结构花瓣之间有一些非晶态的物质存在，从图1中B的内嵌EDS图也证明了Ti元素的存在。图1中C为 Ni(OH)2(3％)/ZnIn2S4的SEM图，从图也可以看出微球结构花瓣之间有一些非晶态的物质存在，内嵌的能量色散X射线光谱图也证明了镍元素的存在。图1中D为空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂，EDS图也证明了镍元素和Ti元素的存在A in Figure 1 is a scanning electron microscope (SEM) image of the ZnIn 2 S 4 microsphere structure, and it can be seen from the figure that the size range of ZnIn 2 S 4 is 1-2 μm. In Figure 1, B is the SEM image of Ti(IV, 0.5%)/ZnIn 2 S 4. It can be seen from the figure that some amorphous substances exist between the petals of the microsphere structure. From the embedded EDS of B in Figure 1 The figure also proves the existence of Ti element. In Figure 1, C is the SEM image of Ni(OH) 2 (3%)/ZnIn 2 S 4 . It can also be seen from the figure that there are some amorphous substances between the petals of the microsphere structure, and the embedded energy dispersion X The ray spectrogram also proved the presence of nickel element. In Figure 1, D is the synergistic modification of ZnIn 2 S 4 photocatalyst by hole promoter Ti(IV) and electron promoter Ni(OH) 2. The EDS diagram also proves the existence of nickel and Ti elements.

图2为不同样品的X射线衍射(XRD)图。由图可知，本实验制备出的a样品都为六方晶型的ZnIn2S4(PDF卡片编号:49-1562)。样品b、c和d的XRD谱图和样品a相似，说明和 Ti(IV)与Ni(OH)2助剂修饰对ZnIn2S4样品晶相结构未造成影响。Figure 2 is an X-ray diffraction (XRD) pattern of different samples. It can be seen from the figure that the samples a prepared in this experiment are all hexagonal ZnIn 2 S 4 (PDF card number: 49-1562). The XRD patterns of samples b, c and d are similar to those of sample a, indicating that the modification with Ti(IV) and Ni(OH) 2 additives has no effect on the crystal phase structure of the ZnIn 2 S 4 sample.

图3为不同样品的X射线光电子能谱(XPS)图。从图3中A可看出，这些样品均含有Zn、 In、O、S以及C，其中Zn、S、In元素主要来自于ZnIn2S4，O可能来自样品表面吸附的水，而C元素可能来源于XPS测试仪器中外来C源。图3中B、C、D、E、F分别表示Ti 2p、 Ni 2p、In 3d、Zn 2p、S 2p的高分辨XPS，图Ti(IV,0.5％)/ZnIn2S4样品的高分辨XPS图中在 457.8和464.1eV处出现了XPS峰，这可以与Ti的2p3/2和2p1/2的特征峰相对应，故该样品的Ti的化合价为+4(如图3-B-b)。从图3中C可以看出，在856.2和873.6eV处出现了XPS 峰，这可以与Ni的2p3/2和2p1/2的特征峰一致，故该样品的Ni的化合价为+4。其Ni 2p对应的结合能可参考文献(Z.Yan,X.Yu,A.Han,P.Xu,P.Du,Journal of Physical Chemistry C 118 (2014)22896-22903)，而Ti2p对应的结合能则参考文献(P.Wang,Y.Lu,X.Wang,H.Yu, AppliedSurface Science 391(2017)259-266.)。故上述数据证明了助剂Ti(IV)与Ni(OH)2已成功的负载在ZnIn2S4的表面上了。Figure 3 is an X-ray photoelectron spectroscopy (XPS) diagram of different samples. It can be seen from A in Figure 3 that these samples all contain Zn, In, O, S and C, in which Zn, S, In elements mainly come from ZnIn 2 S 4 , O may come from the water adsorbed on the surface of the samples, and C element It may come from an external C source in the XPS test instrument. In Figure 3, B, C, D, E, and F represent the high-resolution XPS of Ti 2p, Ni 2p, In 3d, Zn 2p , and S 2p, respectively. There are XPS peaks at 457.8 and 464.1 eV in the XPS diagram, which can correspond to the characteristic peaks of 2p 3/2 and 2p 1/2 of Ti, so the valence of Ti of this sample is +4 (as shown in Figure 3-Bb ). It can be seen from C in Figure 3 that XPS peaks appear at 856.2 and 873.6 eV, which can be consistent with the characteristic peaks of 2p 3/2 and 2p 1/2 of Ni, so the valence of Ni in this sample is +4. The binding energy corresponding to Ni 2p can refer to the literature (Z.Yan, X.Yu, A.Han, P.Xu, P.Du, Journal of Physical Chemistry C 118 (2014) 22896-22903), and the corresponding binding energy of Ti2p References (P. Wang, Y. Lu, X. Wang, H. Yu, Applied Surface Science 391 (2017) 259-266.). Therefore, the above data proves that the additives Ti(IV) and Ni(OH) 2 have been successfully supported on the surface of ZnIn 2 S 4 .

样品的光催化活性的评估依据为样品在光催化过程中的产氢速率。其测试条件为：在常温常压下，把100mL的平底三口瓶作为光催化反应容器，并且利用硅胶塞与密封膜对***开口处进行密封处理，而光催化反应的光源则采用350W并过滤掉紫外光的发光二极管(LED) 灯(λ＝420nm)，光源与三口瓶相距20cm。同时利用北京师范大学生产的FZ-A型可见光计测定出烧瓶表面上的光强为180mW cm-2。具体光催化实验过程为：把50mg的样品放到100mL 的平底三口瓶中，在向其中加入65mL的去离子水与15mL的三乙醇胺，三乙醇胺的作用为消耗掉光催化过程中产生的光生空穴，避免光生空穴与光生电子复合，从而提高样品的光催化活性。在光照之前应先往烧瓶中通大约30min的氮气，以达到除去烧瓶中的空气与溶解在水中的氧气的目的。然后对反应容器进行边搅拌边光照处理，其目的是为了使样品颗粒悬浮在溶液中，以达到充分反应的目的。在光照0.5h后，用气体进样器通过烧瓶封口处的硅胶塞抽取烧瓶内400μL的气体，然后再用日本岛津生产的型号为GC-2014C的气相色谱仪检测该气体中氢气的含量，该仪器配置的检测器为热导检测器(TCD)，载气为氮气，毛细管柱为

Figure RE-GDA0002346509460000041
的分子筛。The evaluation of the photocatalytic activity of the sample is based on the hydrogen production rate of the sample in the photocatalytic process. The test conditions are: under normal temperature and pressure, a 100mL flat-bottom three-necked flask is used as a photocatalytic reaction vessel, and the opening of the flask is sealed with a silica gel stopper and a sealing film, while the light source of the photocatalytic reaction is 350W and filtered. A light-emitting diode (LED) lamp (λ=420 nm) that emits ultraviolet light is used, and the distance between the light source and the three-necked bottle is 20 cm. At the same time, the light intensity on the surface of the flask was measured to be 180 mW cm -2 using the FZ-A visible light meter produced by Beijing Normal University. The specific photocatalytic experiment process is as follows: put 50 mg of the sample into a 100 mL flat-bottom three-necked flask, add 65 mL of deionized water and 15 mL of triethanolamine, and the role of triethanolamine is to consume the photo-generated space generated during the photocatalytic process. Holes, avoiding the recombination of photo-generated holes and photo-generated electrons, thus improving the photocatalytic activity of the samples. Before the illumination, nitrogen should be passed into the flask for about 30min to achieve the purpose of removing the air in the flask and the oxygen dissolved in the water. Then, the reaction vessel is subjected to light treatment while stirring, the purpose of which is to suspend the sample particles in the solution, so as to achieve the purpose of sufficient reaction. After 0.5h of illumination, use a gas injector to extract 400 μL of gas in the flask through the silica gel plug at the seal of the flask, and then use a gas chromatograph with a model of GC-2014C produced by Shimadzu to detect the hydrogen content in the gas. The detector of the instrument is a thermal conductivity detector (TCD), the carrier gas is nitrogen, and the capillary column is
Figure RE-GDA0002346509460000041
of molecular sieves.

图4中A为实施例1中不同样品产氢速率图：(a)ZnIn2S4，(b)Ti(IV,0.5％)/ZnIn2S4，(c) Ni(OH)2(3％)/ZnIn2S4，(d-g)Ni(OH)2(1％,3％,5％,8％)/Ti(IV,0.5％)/ZnIn2S4。从图中可看出，光催化剂Ni(OH)2(3％)/Ti(IV,0.5％)/ZnIn2S4的产氢速率是115.51μmol h-1，它的活性明显高于 ZnIn2S4，Ti(IV,0.5％)/ZnIn2S4，和Ni(OH)2(3％)/ZnIn2S4光催化剂。图4中B为 Ni(OH)2(3％)/Ti(IV,0.5％)/ZnIn2S4的光催化循环图，说明该催化剂稳定性良好。A in Figure 4 is the hydrogen production rate diagram of different samples in Example 1: (a) ZnIn 2 S 4 , (b) Ti(IV, 0.5%)/ZnIn 2 S 4 , (c) Ni(OH) 2 (3 %)/ZnIn 2 S 4 , (dg)Ni(OH) 2 (1%, 3%, 5%, 8%)/Ti(IV, 0.5%)/ZnIn 2 S 4 . It can be seen from the figure that the hydrogen production rate of the photocatalyst Ni(OH) 2 (3%)/Ti(IV, 0.5%)/ZnIn 2 S 4 is 115.51 μmol h -1 , and its activity is significantly higher than that of ZnIn 2 S 4 , Ti(IV, 0.5%)/ZnIn 2 S 4 , and Ni(OH) 2 (3%)/ZnIn 2 S 4 photocatalysts. In Fig. 4, B is the photocatalytic cycle diagram of Ni(OH) 2 (3%)/Ti(IV, 0.5%)/ZnIn 2 S 4 , indicating that the catalyst has good stability.

实验例2：Experimental example 2:

为了检验不同可溶于水的Ti盐溶液(硫酸钛或氯化钛)对Ti负载在ZnIn2S4的影响，除可溶于水的Ti盐溶液不同以外，其它条件如水浴温度，水浴时间等均与实施例1相同。实验结果表明分别使用硫酸钛或氯化钛做Ti源时，都能使Ti较好的负载在ZnIn2S4的表面上。In order to examine the effect of different water-soluble Ti salt solutions (titanium sulfate or titanium chloride) on the loading of Ti on ZnIn 2 S 4 , in addition to the different water-soluble Ti salt solutions, other conditions such as water bath temperature, water bath time and the like are the same as in Example 1. The experimental results show that when titanium sulfate or titanium chloride is used as the source of Ti, Ti can be better supported on the surface of ZnIn 2 S 4 .

实验例3：Experimental example 3:

为了检验水浴温度对助剂Ti与Ni(OH)2负载的影响，除水浴温度不同以外，其它反应条件如水浴时间和所用的Ti、Ni源等均与实施例1相同。实验结果表明水浴温度低于65℃时，助剂Ti与Ni(OH)2没有负载在ZnIn2S4的表面上。因为过低的温度环境不能以为助剂Ti与Ni(OH)2的负载提供足够的能量，不利于助剂Ti与Ni(OH)2的负载。当水浴温度大于90℃时，负载在ZnIn2S4表面上Ti与Ni(OH)2将会有晶型。因此，在Ti(IV)/ZnIn2S4与Ni(OH)2/ZnIn2S4光催化剂的制备过程中，水浴温度最佳为70-90℃。In order to examine the effect of water bath temperature on the loading of additives Ti and Ni(OH) 2 , other reaction conditions such as water bath time and Ti and Ni sources used are the same as those in Example 1 except for different water bath temperatures. The experimental results show that when the temperature of the water bath is lower than 65 °C, the additives Ti and Ni(OH) 2 are not supported on the surface of ZnIn 2 S 4 . Because the too low temperature environment cannot provide enough energy for the loading of the auxiliary agents Ti and Ni(OH) 2 , it is not conducive to the loading of the auxiliary agents Ti and Ni(OH) 2 . When the temperature of the water bath is greater than 90℃, Ti and Ni(OH) 2 supported on the surface of ZnIn 2 S 4 will have crystal forms. Therefore, in the preparation process of Ti(IV)/ZnIn 2 S 4 and Ni(OH) 2 /ZnIn 2 S 4 photocatalysts, the optimum temperature of the water bath is 70-90℃.

实验例4：Experimental example 4:

为了检验可溶于水的镍盐对助剂Ni(OH)2负载的影响，除溶于水的镍盐不同以外，其它条件如水浴温度，水浴时间等均与实施例1相同。实验结果表明当分别使用硫酸镍或硝酸镍等作为镍源时，助剂Ni(OH)2都可以很好的负载在ZnIn2S4的表面上。In order to examine the influence of water-soluble nickel salts on the loading of auxiliary Ni(OH) 2 , other conditions such as water bath temperature and water bath time are the same as those in Example 1 except for different water-soluble nickel salts. The experimental results show that when nickel sulfate or nickel nitrate is used as the nickel source, the auxiliary Ni(OH) 2 can be well supported on the surface of ZnIn 2 S 4 .

实验例5：Experimental example 5:

为了检验水浴时间对助剂Ti与Ni(OH)2负载的影响，除了水浴的时间以外，其它反应条件如水浴温度和所用的Ti、Ni源等均与实施例1相同。当水浴时间低于4h，ZnIn2S4的光催化产氢速率没有明显提升，说明溶液中只有少量的镍离子参与了反应。当水浴时间大于6h 时，ZnIn2S4的光催化产氢速率提升程度与水浴时间在4-6h的差不多。因此，从节能角度考虑，在Ni(OH)2-Ti(IV)/ZnIn2S4光催化剂的制备过程中，最佳水浴时间为4-6h。In order to examine the effect of water bath time on the loading of auxiliary Ti and Ni(OH) 2 , other reaction conditions such as water bath temperature and Ti and Ni sources used are the same as those in Example 1 except for water bath time. When the water bath time was less than 4 h, the photocatalytic hydrogen production rate of ZnIn 2 S 4 did not increase significantly, indicating that only a small amount of nickel ions in the solution participated in the reaction. When the water bath time is greater than 6h, the photocatalytic hydrogen production rate of ZnIn 2 S 4 is improved to a similar extent as that of the water bath time of 4-6h. Therefore, from the perspective of energy saving, in the preparation process of Ni(OH) 2 -Ti(IV)/ZnIn 2 S 4 photocatalyst, the optimal water bath time is 4-6h.

Claims (4)

1.空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，其特征在于包括以下步骤：1. The preparation method of hole assistant Ti(IV) and electron assistant Ni(OH) 2 synergistically modifying ZnIn 2 S 4 photocatalyst is characterized in that comprising the following steps: 1)ZnIn2S4光催化材料与去离子水混合，充分搅拌形成均匀的悬浮液；1) The ZnIn 2 S 4 photocatalytic material is mixed with deionized water and fully stirred to form a uniform suspension; 2)向步骤1)中的悬浮液加入可溶于水的钛盐；2) adding water-soluble titanium salt to the suspension in step 1); 3)将步骤2)中的悬浮液边搅拌边水浴加热一定时间；3) heating the suspension in step 2) in a water bath for a certain period of time while stirring; 4)将步骤3)中的沉淀过滤洗涤干燥，即为空穴助剂Ti(IV)修饰的ZnIn2S4；4) filter, wash and dry the precipitate in step 3), that is, ZnIn 2 S 4 modified by cavitation aid Ti(IV); 5)将步骤4)中的光催化剂与去离子水混合，通过搅拌形成均匀的悬浮液；5) Mix the photocatalyst in step 4) with deionized water, and form a uniform suspension by stirring; 6)向步骤5)中的悬浮液加入可溶于水的镍盐与尿素溶液；6) adding water-soluble nickel salt and urea solution to the suspension in step 5); 7)把步骤6)中的悬浮液边搅拌边水浴加热一定时间；7) heating the suspension in step 6) in a water bath while stirring for a certain period of time; 8)将步骤7)中的沉淀过滤洗涤干燥，即为空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂。8) Filter, wash and dry the precipitate in step 7), that is, the hole assistant Ti(IV) and the electron assistant Ni(OH) 2 synergistically modify the ZnIn 2 S 4 photocatalyst. 2.根据权利要求1所述的空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，其特征在于步骤3)与步骤7)所述的水浴加热反应温度为70-90℃，反应时间为4-6h。2. The preparation method of hole promoter Ti(IV) and electron promoter Ni(OH) 2 synergistically modifying ZnIn 2 S 4 photocatalyst according to claim 1, characterized in that step 3) and step 7) described The water bath heating reaction temperature is 70-90 ℃, and the reaction time is 4-6h. 3.根据权利要求1所述的空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，其特征在于步骤2)所述的钛盐为氯化钛或硫酸钛。3. The preparation method of hole assistant Ti(IV) and electron assistant Ni(OH) 2 according to claim 1 for synergistically modifying ZnIn 2 S 4 photocatalyst, wherein the titanium salt in step 2) is: Titanium chloride or titanium sulfate. 4.根据权利要求1所述的空穴助剂Ti(IV)与电子助剂Ni(OH)2协同修饰ZnIn2S4光催化剂的制备方法，其特征在于步骤6)所述的镍盐为硫酸镍或硝酸镍。4. The preparation method of hole promoter Ti(IV) and electron promoter Ni(OH) 2 synergistically modifying ZnIn 2 S 4 photocatalyst according to claim 1, wherein the nickel salt described in step 6) is Nickel sulfate or nickel nitrate.
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