CN110624563A - Preparation method of a silver ion-doped zinc thioindate heterojunction photocatalyst - Google Patents
Preparation method of a silver ion-doped zinc thioindate heterojunction photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 10
- 239000011701 zinc Substances 0.000 title claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000004332 silver Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 10
- 239000004246 zinc acetate Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- 239000013216 MIL-68 Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 8
- 230000001965 increasing effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B2203/02—Processes for making hydrogen or synthesis gas
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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Abstract
一种银离子掺杂硫代铟酸锌异质结光催化剂制备方法，涉及一种催化剂制备方法，以硝酸银、醋酸锌、醋酸铟、硫代乙酰胺和氧化铟按照一定的比例在油浴加热条件下反应，并获得目标光催化剂。这种新型的可见光光催化剂结构清晰，组成明确，通过Ag+的掺杂可以显著增强ZnIn2S4对光子的利用率，与In2O3复合后可以使光生载流子的扩散范围增大，使电子—空穴对得到了有效的分离，抑制了光生电子—空穴对的复合，大幅度的增加了对光生电子的利用率，从而增强可见光催化活性，Ag:ZnIn2S4/In2O3复合材料由于其高可见光活性、良好的制氢能力以及良好的光催化稳定性，在清洁能源生产和能量转换方面具有广阔的前景。是一种具有很好的发展前景的催化剂。A method for preparing a silver ion-doped zinc thioindium heterojunction photocatalyst, which relates to a method for preparing a catalyst, using silver nitrate, zinc acetate, indium acetate, thioacetamide and indium oxide in an oil bath according to a certain ratio React under heating conditions, and obtain the target photocatalyst. This new type of visible light photocatalyst has a clear structure and clear composition. The utilization rate of ZnIn 2 S 4 for photons can be significantly enhanced by the doping of Ag + , and the diffusion range of photogenerated carriers can be increased after being recombined with In 2 O 3 , so that the electron-hole pairs are effectively separated, the recombination of photogenerated electron-hole pairs is inhibited, and the utilization rate of photogenerated electrons is greatly increased, thereby enhancing the catalytic activity of visible light. Ag:ZnIn 2 S 4 /In 2 O 3 composites hold great promise in clean energy production and energy conversion due to their high visible-light activity, good hydrogen production capacity, and good photocatalytic stability. It is a catalyst with good development prospects.
Description
技术领域technical field
本发明涉及一种催化剂制备方法，特别是涉及一种银离子掺杂硫代铟酸锌异质结光催化剂制备方法。The invention relates to a method for preparing a catalyst, in particular to a method for preparing a silver ion-doped zinc thioindate heterojunction photocatalyst.
背景技术Background technique
光催化技术可以在相对温和的反应条件下完成许多原先需在苛刻的人为设定条件下才能完成的化学反应，因此该技术具备了一般技术所不具备的优越性和光明的应用前景。光催化被认为是一种理想的环境处理和能源再生技术，因为太阳能可作为参与反应的驱动能源之一，而太阳能是一种清洁可再生能源，驱动过程无污染产生。同时，氢能作为一种环境友好，清洁无污染的理想新型能源之一，可以通过光催化分解水来制备，因此光催化分解水制氢得到了高度的关注。为了实现高效光催化水分解产氢，科学家已经开发出大量用于制氢的半导体光催化剂。在以往的研究中，TiO2光催化剂引起了全球环境和能源研究者的关注。TiO2是一种宽带隙半导体，其响应范围仅在紫外区域，而紫外区域仅占太阳光谱的4-5％，能量占比较少，太阳能利用率低导致水分解产氢效率低。因此，将光催化范围扩展到可见光区域，是提高光催化反应效率的关键。Photocatalytic technology can complete many chemical reactions under relatively mild reaction conditions, which can only be completed under harsh artificial setting conditions. Therefore, this technology has advantages and bright application prospects that ordinary technologies do not have. Photocatalysis is considered to be an ideal environmental treatment and energy regeneration technology, because solar energy can be used as one of the driving energy participating in the reaction, and solar energy is a clean and renewable energy, and the driving process is generated without pollution. At the same time, hydrogen energy, as one of the ideal new energy sources that are environmentally friendly, clean and pollution-free, can be produced by photocatalytic water splitting, so photocatalytic water splitting for hydrogen production has received high attention. In order to achieve efficient photocatalytic water splitting for hydrogen production, scientists have developed a large number of semiconductor photocatalysts for hydrogen production. In previous studies, TiO2 photocatalysts have attracted the attention of global environmental and energy researchers. TiO 2 is a wide bandgap semiconductor, its response range is only in the ultraviolet region, and the ultraviolet region only accounts for 4-5% of the solar spectrum, and the energy accounts for less. The low utilization rate of solar energy leads to low efficiency of water splitting and hydrogen production. Therefore, extending the photocatalytic range to the visible light region is the key to improving the photocatalytic reaction efficiency.
目前，具有层状结构的AB2X4系列半导体因其在电荷储存和热电等不同领域的潜在应用而备受关注。ZnIn2S4作为多组分金属硫化物属于AB2X4（A = Zn，Ca，Cu，Cd; B = Al，Ga，In; X = S，Se，Te），具有独特的层状结构和窄带隙（2.34-2.48 eV），是一种光响应范围广，化学性质稳定的新型催化剂。但由于单纯的ZnIn2S4具有较高的载流子复合率，导致光催化效率低，光催化活性有待进一步提高。因此，如何增大宽带隙半导体材料的可见光光谱响应范围，同时缩短光生载流子从半导体内部转移至表面所需要的时间以及有效的将电子与空穴进行有效的分离，进而降低载流子的复合速率而增强光催化活性，已成为光催化研究领域亟待解决的问题。由于Ag+具有4d电子结构，在ZnIn2S4中掺杂少量Ag+，可在半导体中产生Ag4d施主能级，因其具有比ZnIn2S4更广的光谱响应范围，电子可以从该价带光激发到导带，因此能够提高光子的利用率，以这种方式增强了光催化活性。Currently, the AB2X4 series semiconductors with layered structures have attracted much attention for their potential applications in diverse fields such as charge storage and thermoelectricity . ZnIn2S4 as a multicomponent metal sulfide belongs to AB2X4 ( A = Zn, Ca, Cu, Cd; B = Al, Ga, In ; X = S, Se, Te), with a unique layered structure and narrow bandgap (2.34-2.48 eV), it is a new type of catalyst with wide photoresponse range and stable chemical properties. However, due to the high carrier recombination rate of pure ZnIn 2 S 4 , the photocatalytic efficiency is low, and the photocatalytic activity needs to be further improved. Therefore, how to increase the visible light spectral response range of wide-bandgap semiconductor materials, shorten the time required for photogenerated carriers to transfer from the interior of the semiconductor to the surface, and effectively separate electrons and holes, thereby reducing the carrier density. Enhancing the photocatalytic activity by increasing the recombination rate has become an urgent problem to be solved in the field of photocatalytic research. Since Ag + has a 4d electronic structure, doping a small amount of Ag + in ZnIn 2 S 4 can generate Ag4d donor energy level in the semiconductor, because it has a wider spectral response range than ZnIn 2 S 4 , and electrons can get from this valence The band is photoexcited to the conduction band, thus enabling improved utilization of photons, and in this way the photocatalytic activity is enhanced.
In2O3是重要的III-VI半导体之一。其禁带宽度约为2.73eV，具有较小的电阻率和较好的光化学稳定性，以及还具备制备条件简便、易获取、形貌可控等优点。但是，由于其禁带宽度较宽，禁带能较大，在可见光范围内的吸收效果较差，光响应范围不理想，距离达到可见光的使用效率还存在一定的距离。因此，深入研究In2O3复合材料与其他活性材料的组合延迟光生电子和空穴材料的快速复合和辅助其它半导体进行光生电子与空穴的有效分离充分发挥材料复合的协同优势。In 2 O 3 is one of the important III-VI semiconductors. Its bandgap width is about 2.73eV, it has small resistivity and good photochemical stability, and it also has the advantages of simple preparation conditions, easy acquisition, and controllable morphology. However, due to its wide bandgap width and large bandgap energy, the absorption effect in the visible light range is poor, and the photoresponse range is not ideal, and there is still a certain distance from the use efficiency of visible light. Therefore, in-depth research on the combination of In 2 O 3 composite materials and other active materials delays the rapid recombination of photogenerated electrons and holes and assists other semiconductors to effectively separate photogenerated electrons and holes to give full play to the synergistic advantages of material recombination.
发明内容Contents of the invention
本发明的目的在于提供一种银离子掺杂硫代铟酸锌异质结光催化剂制备方法，本发明以硝酸银、醋酸锌、醋酸铟、硫代乙酰胺和氧化铟按照一定的比例在油浴条件下反应，并获得目标光催化剂。制备的光催化剂结构清晰，组成明确，在紫外光和可见光照射下，可以进行水分解产生氢气，将其应用于光催化产氢中。The purpose of the present invention is to provide a method for preparing a silver ion-doped zinc thioindate heterojunction photocatalyst. The present invention uses silver nitrate, zinc acetate, indium acetate, thioacetamide and indium oxide in oil according to a certain ratio. bath conditions, and obtain the target photocatalyst. The prepared photocatalyst has a clear structure and a definite composition. Under the irradiation of ultraviolet light and visible light, it can decompose water to generate hydrogen, and it can be applied in photocatalytic hydrogen production.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种银离子掺杂硫代铟酸锌异质结光催化剂制备方法，所述方法制备一种银离子掺杂硫代铟酸锌复合氧化铟的异质结光催化剂，其以三元硫化物ZnIn2S4为基础，通过油浴加热的方法将Ag+均匀的掺杂于ZnIn2S4中，并且使之与In2O3复合；A method for preparing a silver ion-doped zinc thioindate heterojunction photocatalyst, the method prepares a silver ion-doped zinc thioindate composite indium oxide heterojunction photocatalyst, which uses ternary sulfide Based on ZnIn 2 S 4 , Ag + is uniformly doped in ZnIn 2 S 4 by oil bath heating method, and it is compounded with In 2 O 3 ;
包括以下制备过程：Including the following preparation process:
首先，利用溶剂热法合成In-MIL-68金属有机框架化合物，将制得的金属有机框架化合物烘干后置于坩埚中，用铝箔纸包好后放入管式炉进行退火，使其自然氧化，最终得到氧化铟空心管；其次，将氧化铟空心管均匀分散在30ml水中，向其中加入一定量的醋酸锌， 醋酸铟， 硝酸银 和L-半胱氨酸，在磁力搅拌条件下使其分散均匀，然后再加入一定量的硫代乙酰胺继续进行磁力搅拌，待其分散均匀之后，将溶液转移到100ml的圆底烧瓶中，进行油浴加热反应；油浴加热反应过后，将黄色的沉淀通过离心分离，并用去离子水依次清洗数次，烘干得到Ag:ZnIn2S4/In2O3异质结光催化剂。Firstly, the In-MIL-68 metal-organic framework was synthesized by solvothermal method. The obtained metal-organic framework was dried and placed in a crucible, wrapped with aluminum foil and placed in a tube furnace for annealing to make it naturally Oxidation finally obtains the indium oxide hollow tube; secondly, the indium oxide hollow tube is evenly dispersed in 30ml water, and a certain amount of zinc acetate, indium acetate, silver nitrate and L-cysteine are added thereto, and made under magnetic stirring conditions It is uniformly dispersed, and then a certain amount of thioacetamide is added to continue magnetic stirring. After it is uniformly dispersed, the solution is transferred to a 100ml round-bottomed flask for an oil bath heating reaction; after the oil bath heating reaction, the yellow The precipitate was separated by centrifugation, washed several times with deionized water, and dried to obtain the Ag:ZnIn 2 S 4 /In 2 O 3 heterojunction photocatalyst.
本发明的优点与效果是：Advantage and effect of the present invention are:
本发明一种银离子掺杂硫代铟酸锌复合氧化铟(Ag:ZnIn2S4/In2O3)异质结光催化剂的制备方法，以硝酸银、醋酸锌、醋酸铟、硫代乙酰胺和氧化铟按照一定的比例在油浴条件下反应，并获得目标光催化剂。制备的光催化剂结构清晰，组成明确，在紫外光和可见光照射下，可以进行水分解产生氢气，将其应用于光催化产氢中，是一种有前途的光催化材料。The present invention relates to a preparation method of silver ion-doped zinc thioindium oxide composite indium oxide (Ag:ZnIn 2 S 4 /In 2 O 3 ) heterojunction photocatalyst, using silver nitrate, zinc acetate, indium acetate, sulfide Acetamide and indium oxide were reacted in an oil bath according to a certain ratio, and the target photocatalyst was obtained. The prepared photocatalyst has a clear structure and clear composition. Under the irradiation of ultraviolet light and visible light, it can decompose water to generate hydrogen. It is a promising photocatalytic material to be used in photocatalytic hydrogen production.
（1）本发明通过油浴加热法可以将Ag+均匀而稳定的掺杂到ZnIn2S4中，可在半导体中产生Ag4d施主能级,所形成的新的掺杂能级更容易被可见光激发，从而提高光子的利用率，促进可见光催化反应。(1) The present invention can uniformly and stably dope Ag + into ZnIn 2 S 4 through the oil bath heating method, and can generate Ag4d donor energy levels in semiconductors, and the formed new doping energy levels are more easily detected by visible light Excitation, thereby improving the utilization rate of photons and promoting visible light catalytic reactions.
（2）本发明所制备的Ag:ZnIn2S4/In2O3双异质结光催化剂，由于与In2O3进行复合之后导致光生载流子的扩散范围增大，在电位差的影响下，电子会大量的从Ag:ZnIn2S4向In2O3方向进行转移而空穴则会由In2O3向Ag:ZnIn2S4进行转移，进而实现了光生电子—空穴对的有效分离，从而有效的抑制电子与空穴的复合，延长寿命，使半导体的光催化性能得到显著的优化。(2) The Ag:ZnIn 2 S 4 /In 2 O 3 double-heterojunction photocatalyst prepared by the present invention, due to the recombination with In 2 O 3 , the diffusion range of photogenerated carriers increases, and the potential difference Under the influence, electrons will be transferred from Ag:ZnIn 2 S 4 to In 2 O 3 in a large amount, and holes will be transferred from In 2 O 3 to Ag:ZnIn 2 S 4 , thereby realizing the photogenerated electron-hole The effective separation of pairs can effectively inhibit the recombination of electrons and holes, prolong the lifetime, and significantly optimize the photocatalytic performance of semiconductors.
（3）本发明所制备半导体的形貌较为独特，由于所制备的管为空心管，材料的表面积得到大幅度的增加，暴露出的活性位点数量也相应的得到大幅度的增加，同时电子从材料内部转移到表面的距离在很大程度上得到了缩短，有效的减缓了电子与空穴在转移过程中的复合，从而提高了光生载流子的利用率，使光催化的性能得到了进一步的提升。(3) The morphology of the semiconductor prepared by the present invention is relatively unique. Since the prepared tube is a hollow tube, the surface area of the material is greatly increased, and the number of exposed active sites is also greatly increased correspondingly. At the same time, the electron The distance transferred from the inside of the material to the surface has been shortened to a large extent, which effectively slows down the recombination of electrons and holes during the transfer process, thereby improving the utilization rate of photogenerated carriers and improving the photocatalytic performance. further improvement.
（4）本发明由于In2O3具有相对较小的电阻率，进而使电子的转移速度加快，为电子到达表面参与催化反应节省了更多的时间，这在一定程度上提升了光催化性能。(4) In the present invention, due to the relatively small resistivity of In 2 O 3 , the transfer speed of electrons is accelerated, which saves more time for electrons to reach the surface to participate in catalytic reactions, which improves the photocatalytic performance to a certain extent .
（5）本发明采用常见的油浴加热的合成方法，所合成的Ag:ZnIn2S4/In2O3异质结光催化剂的结晶度、分散性好、形状可控，且原料常见，工艺可控，易于实施，符合环境友好的要求。(5) The present invention adopts the common oil bath heating synthesis method, and the synthesized Ag:ZnIn 2 S 4 /In 2 O 3 heterojunction photocatalyst has good crystallinity, good dispersion, controllable shape, and common raw materials, The process is controllable, easy to implement, and meets the requirements of environmental friendliness.
本发明为开发可见光半导体光催化领域提供一种新的技术路径，对于解决日益严重的能源问题具有重要意义。The invention provides a new technical path for developing the field of visible light semiconductor photocatalysis, and is of great significance for solving increasingly serious energy problems.
附图说明Description of drawings
图1为In2O3空心管的透射电镜照片；Figure 1 is a transmission electron micrograph of In 2 O 3 hollow tube;
图2为Ag:ZnIn2S4/In2O3异质结光催化剂的透射电镜照片。Fig. 2 is a transmission electron micrograph of Ag:ZnIn 2 S 4 /In 2 O 3 heterojunction photocatalyst.
具体实施方式Detailed ways
下面结合实施例对本发明进行详细说明，进一步阐明本发明的内容，但其并不限制本发明的保护范围。The present invention will be described in detail below in conjunction with the examples to further clarify the content of the present invention, but it does not limit the protection scope of the present invention.
实施例1Example 1
（1）利用溶剂热法制备In-MIL-68。首先，在磁力搅拌处理下，将对苯二甲酸和In(NO3)3·xH2O分别分散在100 mL DMF中，并继续进行磁力搅拌。待到反应物质全部溶于DMF之后，将混合物转移到150 mL圆底烧瓶中，置于油浴当中100℃保持12min。在自然冷却至室温后，手动收集固体产物并通过乙醇离心，彻底洗涤并在60℃下干燥12小时， 获得In-MIL-68。(1) Prepare In-MIL-68 by solvothermal method. First, under magnetic stirring treatment, disperse terephthalic acid and In(NO 3 ) 3 ·xH 2 O in 100 mL DMF respectively, and continue magnetic stirring. After all the reaction substances were dissolved in DMF, the mixture was transferred to a 150 mL round bottom flask and placed in an oil bath at 100°C for 12 min. After natural cooling to room temperature, the solid product was collected manually and centrifuged by ethanol, washed thoroughly and dried at 60 °C for 12 hours to obtain In-MIL-68.
（2）取出90mg In-MIL-68置入坩埚当中，用铝箔纸包好之后放入管式炉，温度升到500℃进行退火，升温速率为1℃/min并且在500℃保温2h。在自然冷却至室温之后即可获得淡黄色In2O3空心管。(2) Take out 90mg of In-MIL-68 and put it into a crucible, wrap it with aluminum foil and put it into a tube furnace. The temperature is raised to 500°C for annealing. The heating rate is 1°C/min and the temperature is kept at 500°C for 2h. The pale yellow In 2 O 3 hollow tubes were obtained after natural cooling to room temperature.
（3）Ag:ZnIn2S4/In2O3异质结光催化剂的合成。在磁力搅拌条件下将100mg In2O3分散于50mL去离子水中，然后加入141μL 0.05 mmol/mL醋酸锌溶液，141μL 0.1 mmol/mL醋酸铟溶液，52μL 0.8 mmol/L硝酸银溶液，85μL的0.01 mmol/mL L-半胱氨酸并继续磁力搅拌处理10 min。将混合物转移至100mL 圆底烧瓶中，并加入284μL 0.01mmol/mL 硫代乙酰胺溶液磁力搅拌30 min。将圆底烧瓶在90℃下保持8小时。在自然冷却至室温后，手动收集固体产物并用去离子水彻底洗涤，并在50℃下干燥12小时，得到1wt％ Ag:ZnIn2S4/In2O3异质结光催化剂。(3) Synthesis of Ag:ZnIn 2 S 4 /In 2 O 3 heterojunction photocatalyst. Disperse 100 mg of In2O3 in 50 mL of deionized water under magnetic stirring conditions, then add 141 μL of 0.05 mmol/mL zinc acetate solution, 141 μL of 0.1 mmol/mL indium acetate solution, 52 μL of 0.8 mmol/L silver nitrate solution, and 85 μL of 0.01 mmol/mL L-cysteine and continue the magnetic stirring treatment for 10 min. The mixture was transferred to a 100 mL round bottom flask, and 284 μL of 0.01 mmol/mL thioacetamide solution was added and magnetically stirred for 30 min. The round bottom flask was kept at 90°C for 8 hours. After natural cooling to room temperature, the solid product was manually collected and thoroughly washed with deionized water, and dried at 50°C for 12 hours to obtain a 1 wt% Ag:ZnIn 2 S 4 /In 2 O 3 heterojunction photocatalyst.
实施例2Example 2
如实施例1所述，所不同的是将步骤（3）中加入282μL 0.05 mmol/mL醋酸锌溶液，282μL0.1 mmol/mL醋酸铟溶液，104μL 0.8 mmol/L硝酸银溶液，170μL的0.01 mmol/mL L-半胱氨酸，568μL 0.01 mmol/mL 硫代乙酰胺溶液，则最终的催化剂为2wt％ Ag:ZnIn2S4/In2O3。As described in Example 1, the difference is that 282 μL of 0.05 mmol/mL zinc acetate solution, 282 μL of 0.1 mmol/mL indium acetate solution, 104 μL of 0.8 mmol/L silver nitrate solution, and 170 μL of 0.01 mmol /mL L-cysteine, 568 μL 0.01 mmol/mL thioacetamide solution, the final catalyst is 2wt% Ag:ZnIn 2 S 4 /In 2 O 3 .
实施例3Example 3
如实施例1所述，所不同的是将步骤（3）中加入423μL 0.05 mmol/mL醋酸锌溶液，423μL0.1 mmol/mL醋酸铟溶液，216μL 0.8 mmol/L硝酸银溶液，255μL的0.01 mmol/mL L-半胱氨酸，852μL 0.01 mmol/mL 硫代乙酰胺溶液，则最终的催化剂为3wt％ Ag:ZnIn2S4/In2O3。As described in Example 1, the difference is that 423 μL of 0.05 mmol/mL zinc acetate solution, 423 μL of 0.1 mmol/mL indium acetate solution, 216 μL of 0.8 mmol/L silver nitrate solution, and 255 μL of 0.01 mmol /mL L-cysteine, 852 μL 0.01 mmol/mL thioacetamide solution, the final catalyst is 3wt% Ag:ZnIn 2 S 4 /In 2 O 3 .
实施例4Example 4
如实施例1所述，所不同的是将步骤（3）中加入564μL 0.05 mmol/mL醋酸锌溶液，564μL0.1 mmol/mL醋酸铟溶液，208μL 0.8 mmol/L硝酸银溶液，340μL的0.01 mmol/mL L-半胱氨酸，1136μL 0.01 mmol/mL 硫代乙酰胺溶液，则最终的催化剂为4wt％ Ag:ZnIn2S4/In2O3。As described in Example 1, the difference is that 564 μL of 0.05 mmol/mL zinc acetate solution, 564 μL of 0.1 mmol/mL indium acetate solution, 208 μL of 0.8 mmol/L silver nitrate solution, and 340 μL of 0.01 mmol /mL L-cysteine, 1136 μL 0.01 mmol/mL thioacetamide solution, the final catalyst is 4wt% Ag:ZnIn 2 S 4 /In 2 O 3 .
实施例5Example 5
如实施例1所述，所不同的是将步骤（3）中加入705μL 0.05 mmol/mL醋酸锌溶液，705μL0.1 mmol/mL醋酸铟溶液，260μL 0.8 mmol/L硝酸银溶液，425μL的0.01 mmol/mL L-半胱氨酸，1420μL 0.01 mmol/mL 硫代乙酰胺溶液，则最终的催化剂为5wt％ Ag:ZnIn2S4/In2O3。As described in Example 1, the difference is that 705 μL of 0.05 mmol/mL zinc acetate solution, 705 μL of 0.1 mmol/mL indium acetate solution, 260 μL of 0.8 mmol/L silver nitrate solution, and 425 μL of 0.01 mmol /mL L-cysteine, 1420 μL 0.01 mmol/mL thioacetamide solution, the final catalyst is 5wt% Ag:ZnIn 2 S 4 /In 2 O 3 .
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Application publication date: 20191231 |