CN111545197A - Ru-ZnO photocatalyst and preparation method and application thereof - Google Patents
Ru-ZnO photocatalyst and preparation method and application thereofDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及光催化剂技术领域，尤其涉及一种Ru-ZnO光催化剂及其制备方法和应用。The invention relates to the technical field of photocatalysts, in particular to a Ru-ZnO photocatalyst and a preparation method and application thereof.
背景技术Background technique
甲烷是一种常温常压下无色无味气体，是一种典型的非极性分子。甲烷中的C-H键能高达434KJ/mol，因此甲烷在室温下非常稳定，难以吸附，难以活化降解。传统的降解甲烷的方法通常是使用贵金属催化剂在高温条件下实现甲烷的催化氧化。这种方法虽然高效，但是贵金属成本太高，而且这种高温降解甲烷的方法需要在800℃以上的温度下进行，在这种条件下，贵金属纳米催化剂容易聚集长大，从而导致催化剂失活；而贵金属催化剂在高温的条件下容易催化氧化氮气生成氮氧化合物，造成二次污染。从经济和实用的角度上看，传统热催化的方法难以用于大气中甲烷的治理。Methane is a colorless, odorless gas under normal temperature and pressure, and is a typical non-polar molecule. The C-H bond energy in methane is as high as 434KJ/mol, so methane is very stable at room temperature, difficult to adsorb, and difficult to activate and degrade. The traditional method of degrading methane usually uses noble metal catalysts to achieve catalytic oxidation of methane at high temperature. Although this method is efficient, the cost of precious metals is too high, and this method of degrading methane at high temperature needs to be carried out at temperatures above 800 °C. Under such conditions, precious metal nanocatalysts tend to aggregate and grow, resulting in catalyst deactivation; However, precious metal catalysts easily catalyze nitrogen oxides to generate nitrogen oxides under high temperature conditions, causing secondary pollution. From an economic and practical point of view, traditional thermal catalysis methods are difficult to use for the treatment of methane in the atmosphere.
自从1972年Fujishima和Honda利用TiO2单晶光电分解水以来，半导体光催化在能源和环境领域受到了广泛的关注。半导体光催化技术只需要利用太阳能便可以将大气中的污染物完全氧化分解，没有形成二次污染物，具有绿色环保的优点，因此半导体光催化技术在常温常压下催化降解大气中的低浓度甲烷具有广阔的应用前景。对于光催化降解/转化甲烷的半导体材料需要具备三个条件：(1)半导体吸收太阳光从而产生电子和空穴对；(2)电子和空穴发生分离并迁移到半导体表面；(3)迁移到半导体表面的电子和空穴与吸附在半导体表面的CH4发生氧化还原反应。所以所要求的催化剂能吸收更广的太阳光；催化剂表面的电子、空穴不易复合；并且对甲烷具有很好的吸附性。Semiconductor photocatalysis has received extensive attention in the fields of energy and environment since Fujishima and Honda in 1972 for photoelectric water splitting usingTiO2 single crystals. Semiconductor photocatalytic technology only needs to use solar energy to completely oxidize and decompose pollutants in the atmosphere, without the formation of secondary pollutants, and has the advantages of green environmental protection. Therefore, semiconductor photocatalytic technology catalyzes the degradation of low concentrations in the atmosphere at room temperature and pressure. Methane has broad application prospects. For semiconductor materials for photocatalytic degradation/conversion of methane, three conditions are required: (1) the semiconductor absorbs sunlight to generate electron and hole pairs; (2) electrons and holes are separated and migrate to the semiconductor surface; (3) migration The electrons and holes to the semiconductor surface undergo a redox reaction withCH4 adsorbed on the semiconductor surface. Therefore, the required catalyst can absorb a wider range of sunlight; the electrons and holes on the surface of the catalyst are not easy to recombine; and it has good adsorption to methane.
目前，关于甲烷C-H的活化及甲烷的氧化研究主要基于TiO2基半导体和分子筛上，主要集中于研究高浓度甲烷的光催化转化和光催化氧化，对于光催化氧化低浓度甲烷的报导很少见。而且TiO2的带隙为3.2eV，只能吸收太阳光中5％的紫外光部分，限制了对太阳能的充分利用，使光催化降解甲烷的效率降低。而其他催化剂如：CeO2，Ga2O3，MoO3，V2O5等无法在常温常压下实现对低浓度甲烷的光催化氧化。此外，甲烷C-H的活化及甲烷的氧化的催化剂还存在循环稳定性差的问题。因此，开发高效的、良好循环稳定的、可在常温常压下进行降解大气中的低浓度甲烷的光催化剂便具有重大的应用价值。At present, the research on the activation of methane CH and the oxidation of methane is mainly based onTiO2 -based semiconductors and molecular sieves, mainly focusing on the photocatalytic conversion and photocatalytic oxidation of high-concentration methane, and there are few reports on the photocatalytic oxidation of low-concentration methane. Moreover, the band gap ofTiO2 is 3.2 eV, which can only absorb 5% of the ultraviolet light in sunlight, which limits the full utilization of solar energy and reduces the efficiency of photocatalytic degradation of methane. However, other catalysts such as CeO2 , Ga2 O3 , MoO3 , V2 O5 etc. cannot realize the photocatalytic oxidation of low concentration methane at normal temperature and pressure. In addition, catalysts for methane CH activation and methane oxidation also suffer from poor cycle stability. Therefore, it is of great application value to develop photocatalysts with high efficiency, good cycle stability, and the ability to degrade low-concentration methane in the atmosphere at normal temperature and pressure.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种高效、循环稳定性好、可在常温常压下进行降解大气中的低浓度甲烷的Ru-ZnO光催化剂的制备方法。The purpose of the present invention is to provide a preparation method of Ru-ZnO photocatalyst with high efficiency and good cycle stability, which can degrade low-concentration methane in the atmosphere at normal temperature and pressure.
本发明提供了一种Ru-ZnO光催化剂的制备方法，包括以下步骤：The invention provides a preparation method of Ru-ZnO photocatalyst, comprising the following steps:
(1)将锌盐与草酸和水混合，沉淀反应得到草酸锌；(1) zinc salt is mixed with oxalic acid and water, and precipitation reaction obtains zinc oxalate;
(2)将所述步骤(1)得到的草酸锌进行第一退火，得到ZnO；(2) first annealing the zinc oxalate obtained in the step (1) to obtain ZnO;
(3)将所述步骤(2)得到的ZnO与氯化钌和水混合，进行氧化还原反应，得到前驱体；(3) mixing the ZnO obtained in the step (2) with ruthenium chloride and water, and carrying out a redox reaction to obtain a precursor;
(4)将所述步骤(3)得到的前驱体进行第二退火，得到Ru-ZnO光催化剂。(4) Second annealing is performed on the precursor obtained in the step (3) to obtain a Ru-ZnO photocatalyst.
优选的，所述步骤(1)中的锌盐为硝酸锌和/或醋酸锌。Preferably, the zinc salt in the step (1) is zinc nitrate and/or zinc acetate.
优选的，所述步骤(1)中的锌盐与草酸的质量比为(1:1)～(1:2)。Preferably, the mass ratio of zinc salt to oxalic acid in the step (1) is (1:1)～(1:2).
优选的，所述步骤(2)中的第一退火的温度为250～550℃。Preferably, the temperature of the first annealing in the step (2) is 250-550°C.
优选的，所述步骤(2)中的第一退火的时间为1～10h。Preferably, the time of the first annealing in the step (2) is 1-10 h.
优选的，所述步骤(3)中的氯化钌中的钌元素与ZnO的质量比为(0.05:100)～(1:100)。Preferably, the mass ratio of the ruthenium element in the ruthenium chloride to ZnO in the step (3) is (0.05:100)～(1:100).
优选的，所述步骤(4)中第二退火的温度为30～350℃。Preferably, the temperature of the second annealing in the step (4) is 30-350°C.
优选的，所述步骤(4)中第二退火的时间为0～6h。Preferably, the time of the second annealing in the step (4) is 0-6h.
本发明还提供了一种上述技术方案所述的制备方法得到的Ru-ZnO光催化剂，包括ZnO基体以及负载于所述ZnO基体表面的Ru。The present invention also provides a Ru-ZnO photocatalyst obtained by the preparation method described in the above technical solution, comprising a ZnO substrate and Ru supported on the surface of the ZnO substrate.
本发明还提供了上述技术方案所述制备方法得到的Ru-ZnO光催化剂在催化净化空气中甲烷的应用，所述空气中甲烷的浓度为1ppb～10000ppm。The present invention also provides the application of the Ru-ZnO photocatalyst obtained by the preparation method described in the above technical solution in catalytic purification of methane in air, where the concentration of methane in the air is 1 ppb-10000 ppm.
本发明提供了一种Ru-ZnO光催化剂的制备方法，将锌盐与草酸和水混合，沉淀反应得到草酸锌；将所述草酸锌进行第一退火，得到ZnO；将所述ZnO与氯化钌和水混合，进行氧化还原反应，得到前驱体；将所述前驱体进行第二退火，得到Ru-ZnO光催化剂。本发明提供的制备方法得到的Ru-ZnO光催化剂有利于吸附空气中的甲烷，并且ZnO能够吸收太阳光从而产生电子和空穴对，电子和空穴发生分离并迁移到半导体表面，迁移到半导体表面的电子和空穴与吸附在ZnO表面的CH4发生氧化还原反应，从而提高光电催化效率；ZnO与Ru的复合，形成异质结构，使得Ru-ZnO光催化剂具有良好的循环稳定性。实验结果表明，本发明提供的0.1～0.5-Ru-ZnO在模拟太阳光下能够高效地催化降解甲烷，表现出优异的光催化净化空气中低浓度甲烷的性能；0.1-Ru-ZnO光催化剂在十次循环降解测试中均表现出很好的循环稳定性。因此，本发明提供的Ru-ZnO催化剂在模拟太阳光下对低浓度甲烷具有高效的催化性能和循环稳定性，即对光催化净化大气中的低浓度甲烷具有良好的光催化活性及循环稳定性。The invention provides a preparation method of a Ru-ZnO photocatalyst. The zinc salt is mixed with oxalic acid and water to obtain zinc oxalate through a precipitation reaction; the zinc oxalate is first annealed to obtain ZnO; the ZnO is mixed with chloride Ruthenium and water are mixed to carry out a redox reaction to obtain a precursor; the second annealing is performed on the precursor to obtain a Ru-ZnO photocatalyst. The Ru-ZnO photocatalyst obtained by the preparation method provided by the present invention is beneficial to adsorb methane in the air, and ZnO can absorb sunlight to generate electron and hole pairs. The electrons and holes are separated and migrate to the surface of the semiconductor and migrate to the semiconductor surface. The electrons and holes on the surface undergo redox reactions withCH4 adsorbed on the surface of ZnO, thereby improving the photocatalytic efficiency; the recombination of ZnO and Ru forms a heterostructure, which makes the Ru-ZnO photocatalyst have good cycling stability. The experimental results show that the 0.1-0.5-Ru-ZnO provided by the present invention can efficiently catalyze the degradation of methane under simulated sunlight, showing excellent performance of photocatalytic purification of low-concentration methane in the air; All ten cycle degradation tests showed good cycling stability. Therefore, the Ru-ZnO catalyst provided by the present invention has efficient catalytic performance and cycle stability for low-concentration methane under simulated sunlight, that is, it has good photocatalytic activity and cycle stability for photocatalytic purification of low-concentration methane in the atmosphere .
附图说明Description of drawings
图1为实施例1～6中制备的不同比例的Ru-ZnO催化剂在模拟太阳光下的光催化降解甲烷性能图；1 is a graph showing the photocatalytic degradation of methane under simulated sunlight of Ru-ZnO catalysts in different proportions prepared in Examples 1-6;
图2为实施例1中制备的0.1-Ru-ZnO催化剂在模拟太阳光下催化降解甲烷的循环稳定性图。Figure 2 is a cycle stability diagram of the 0.1-Ru-ZnO catalyst prepared in Example 1 for catalytic degradation of methane under simulated sunlight.
具体实施方式Detailed ways
本发明的目的在于提供一种高效、循环稳定性好、可在常温常压下进行降解大气中的低浓度甲烷的Ru-ZnO光催化剂的制备方法。The purpose of the present invention is to provide a preparation method of Ru-ZnO photocatalyst with high efficiency and good cycle stability, which can degrade low-concentration methane in the atmosphere at normal temperature and pressure.
为实现以上目的，本发明提供了一种Ru-ZnO光催化剂的制备方法，包括以下步骤：In order to achieve the above purpose, the present invention provides a preparation method of Ru-ZnO photocatalyst, comprising the following steps:
(1)将锌盐与草酸和水混合，沉淀反应得到草酸锌；(1) zinc salt is mixed with oxalic acid and water, and precipitation reaction obtains zinc oxalate;
(2)将所述步骤(1)得到的草酸锌进行第一退火，得到ZnO；(2) first annealing the zinc oxalate obtained in the step (1) to obtain ZnO;
(3)将所述步骤(2)得到的ZnO与氯化钌和水混合，进行氧化还原反应，得到前驱体；(3) mixing the ZnO obtained in the step (2) with ruthenium chloride and water, and carrying out a redox reaction to obtain a precursor;
(4)将所述步骤(3)得到的前驱体进行第二退火，得到Ru-ZnO光催化剂。(4) Second annealing is performed on the precursor obtained in the step (3) to obtain a Ru-ZnO photocatalyst.
本发明将锌盐与草酸和水混合，沉淀反应得到草酸锌。本发明对所述锌盐与草酸和水混合的操作没有特殊限定，采用本领域技术人员熟知的混合的技术方案即可。在本发明中，所述锌盐与草酸和水混合优选为将锌盐与水在搅拌条件下完全溶解，随后加入草酸。本发明对所述搅拌的速率和时间没有特殊限定，保证各组分混合均匀即可。In the present invention, zinc salt is mixed with oxalic acid and water, and zinc oxalate is obtained by precipitation reaction. The present invention has no particular limitation on the operation of mixing the zinc salt with oxalic acid and water, and a mixing technical solution well known to those skilled in the art can be used. In the present invention, the mixing of the zinc salt with oxalic acid and water is preferably to completely dissolve the zinc salt and water under stirring conditions, and then the oxalic acid is added. The present invention does not specifically limit the speed and time of the stirring, and it is sufficient to ensure that the components are mixed uniformly.
在本发明中，所述锌盐与草酸的质量比优选为(1:1)～(1:2)，更优选为1:2；所述锌盐的质量与水的体积比优选为10g:(80～100)mL，更优选为10g:100mL。在本发明中，所述水能够溶解锌盐，在本发明限定所述锌盐的质量与水的体积比在上述范围内能够保证沉淀反应更加充分。In the present invention, the mass ratio of the zinc salt to the oxalic acid is preferably (1:1)～(1:2), more preferably 1:2; the mass ratio of the zinc salt to the water is preferably 10g: (80 to 100) mL, more preferably 10 g:100 mL. In the present invention, the water can dissolve the zinc salt, and the present invention limits the mass ratio of the zinc salt to the volume of the water to ensure that the precipitation reaction is more sufficient.
在本发明中，所述锌盐优选为硝酸锌和/或醋酸锌，更优选为二水合乙酸锌。在本发明中，所述草酸优选为二水合草酸。本发明对所述锌盐和所述草酸的来源没有特殊限定，采用本领域技术人员熟知的市售产品即可。In the present invention, the zinc salt is preferably zinc nitrate and/or zinc acetate, more preferably zinc acetate dihydrate. In the present invention, the oxalic acid is preferably oxalic acid dihydrate. The source of the zinc salt and the oxalic acid is not particularly limited in the present invention, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述沉淀反应的温度优选为室温，更优选为23～25℃。在本发明中，所述锌盐与草酸和水混合，在室温下搅拌即可发生沉淀反应得到草酸锌。In the present invention, the temperature of the precipitation reaction is preferably room temperature, more preferably 23 to 25°C. In the present invention, the zinc salt is mixed with oxalic acid and water, and the zinc oxalate can be obtained by precipitation reaction after stirring at room temperature.
在本发明中，所述沉淀反应优选为在搅拌条件下进行，所述搅拌的时间优选为0～60min，更优选为20～40min，最优选为30min。本发明对所述搅拌的速率没有特殊的限定，能够保证各组分混合均匀即可。在本发明中，由于沉淀反应伴随着沉淀的生成，随着沉淀的生成，扩散和传质会越来越慢，所述搅拌可以促进各组分混合均匀，并促进反应物更加充分反应。In the present invention, the precipitation reaction is preferably carried out under stirring conditions, and the stirring time is preferably 0-60 minutes, more preferably 20-40 minutes, and most preferably 30 minutes. The present invention has no special limitation on the stirring speed, as long as it can ensure that the components are evenly mixed. In the present invention, since the precipitation reaction is accompanied by the formation of the precipitation, the diffusion and mass transfer will become slower and slower with the formation of the precipitation, and the stirring can promote the uniform mixing of the components and promote the reaction of the reactants more fully.
沉淀反应完成后，本发明优选将所述沉淀反应得到的产物依次进行洗涤、干燥、研磨，得到草酸锌。本发明对所述洗涤、干燥、研磨的操作没有特殊限定，采用本领域技术人员所熟知的洗涤、干燥、研磨的方案即可。After the precipitation reaction is completed, in the present invention, the product obtained by the precipitation reaction is preferably washed, dried and ground in sequence to obtain zinc oxalate. The present invention does not have a special limitation on the washing, drying and grinding operations, and the washing, drying and grinding solutions well known to those skilled in the art can be used.
在本发明中，所述洗涤的洗涤剂优选为去离子水或乙醇，更优选为去离子水。在本发明中，所述干燥优选为恒温干燥；所述干燥温度优选为40～100℃，更优选为60～90℃；所述干燥时间优选为2～5h。本发明对所述干燥的设备没有特殊的限定，采用本领域技术人员熟知的恒温干燥箱即可。In the present invention, the washing detergent is preferably deionized water or ethanol, more preferably deionized water. In the present invention, the drying is preferably constant temperature drying; the drying temperature is preferably 40-100°C, more preferably 60-90°C; the drying time is preferably 2-5h. The present invention does not have a special limitation on the drying equipment, and a constant temperature drying oven well known to those skilled in the art can be used.
在本发明中，所述研磨优选为研钵研磨，本发明对所述研磨的时间没有特殊限定，使所述沉淀反应得到的草酸锌在经过洗涤、干燥后的草酸锌分散即可。在本发明中，由于沉淀经过洗涤、干燥会出现聚集，所述研磨能够将聚集的草酸锌分散。In the present invention, the grinding is preferably mortar grinding, and the grinding time is not particularly limited in the present invention, and the zinc oxalate obtained by the precipitation reaction may be dispersed in the washed and dried zinc oxalate. In the present invention, since the precipitate may aggregate after washing and drying, the grinding can disperse the aggregated zinc oxalate.
得到草酸锌后，本发明对所述草酸锌进行第一退火，得到ZnO。在本发明中，所述第一退火过程中草酸锌转变为氧化锌。After the zinc oxalate is obtained, the present invention performs first annealing on the zinc oxalate to obtain ZnO. In the present invention, zinc oxalate is converted into zinc oxide during the first annealing process.
在本发明中，所述第一退火的温度优选为250～550℃，更优选为300～400℃，最优选为350℃；所述第一退火的时间优选为1～10h，更优选为5～7h，最优选为6h。本发明对所述第一退火的设备没有特殊的限定，采用本领域技术人员熟知的退火设备即可。In the present invention, the temperature of the first annealing is preferably 250-550°C, more preferably 300-400°C, and most preferably 350°C; the time of the first annealing is preferably 1-10 hours, more preferably 5 hours ~7h, most preferably 6h. The present invention has no special limitation on the equipment for the first annealing, and an annealing equipment well-known to those skilled in the art may be used.
得到ZnO后，本发明将所述ZnO与氯化钌和水混合，进行氧化还原反应，得到前驱体。本发明对所述ZnO与氯化钌和水混合的操作没有特殊限定，采用本领域技术人员熟知的混合的技术方案即可。在本发明中，所述ZnO与氯化钌和水混合优选为：在搅拌下将氧化锌在水中分散均匀，然后加入氯化钌。本发明对所述搅拌的速率和时间没有特殊限定，保证各组分混合均匀即可。After the ZnO is obtained, in the present invention, the ZnO is mixed with ruthenium chloride and water, and a redox reaction is carried out to obtain a precursor. The present invention does not specifically limit the operation of mixing the ZnO with ruthenium chloride and water, and the technical solution of mixing well known to those skilled in the art can be used. In the present invention, the mixing of the ZnO with ruthenium chloride and water is preferably as follows: under stirring, the zinc oxide is uniformly dispersed in the water, and then the ruthenium chloride is added. The present invention does not specifically limit the speed and time of the stirring, as long as each component is uniformly mixed.
在本发明中，所述氯化钌中钌元素与所述ZnO的质量比优选为(0.05:100)～(1:100)，更优选为(0.1:100)～(0.5:100)。在本发明中，所述氯化钌中钌元素与所述ZnO的质量比为上述范围内时所得的催化剂催化降解甲烷的效率更高、稳定循环性更好。本发明对所述氯化钌的来源没有特殊限定，采用本领域技术人员熟知的市售产品即可。In the present invention, the mass ratio of ruthenium element in the ruthenium chloride to the ZnO is preferably (0.05:100)～(1:100), more preferably (0.1:100)～(0.5:100). In the present invention, when the mass ratio of the ruthenium element in the ruthenium chloride to the ZnO is within the above-mentioned range, the catalyst obtained has a higher efficiency in catalyzing the degradation of methane, and a better stable cycle. The source of the ruthenium chloride is not particularly limited in the present invention, and a commercially available product well known to those skilled in the art can be used.
在本发明中，所述氧化还原反应的温度优选为室温，更优选为23～25℃。在本发明中，所述氧化还原反应的条件优选为先搅拌、后静置。在本发明中，所述搅拌的时间优选为1～6h，更优选为3～4h，最优选为3h；所述静置时间优选为1～2h，更优选为1h。在本发明中，所述搅拌优选为机械搅拌。本发明对所述搅拌的速率没有特殊的限定，保证各组分混合均匀即可。本发明对所述搅拌的装置没有特殊限定，采用本领域技术人员熟知的搅拌装置即可。在本发明中，所述先搅拌、后静置是为了保证反应体系均匀，促进氯化钌中的钌与ZnO反应，使氧化还原反应能够充分进行。In the present invention, the temperature of the redox reaction is preferably room temperature, more preferably 23 to 25°C. In the present invention, the conditions of the redox reaction are preferably stirring first and then standing. In the present invention, the stirring time is preferably 1-6h, more preferably 3-4h, and most preferably 3h; the standing time is preferably 1-2h, more preferably 1h. In the present invention, the stirring is preferably mechanical stirring. The present invention does not have a special limitation on the stirring speed, as long as each component is uniformly mixed. The present invention does not specifically limit the stirring device, and a stirring device well known to those skilled in the art can be used. In the present invention, the first stirring and then standing is to ensure the uniformity of the reaction system, promote the reaction of ruthenium and ZnO in the ruthenium chloride, and enable the redox reaction to proceed fully.
氧化还原反应完成后，本发明优选对所述氧化还原反应的产物依次进行过滤和干燥，得到前驱体。本发明对所述过滤、干燥的操作没有特殊限定，采用本领域技术人员所熟知的过滤、干燥的方案即可。在本发明中，所述过滤优选为抽滤。在本发明中，所述干燥的温度优选为40～70℃，更优选为50～60℃；所述干燥的时间优选为8～10h。After the redox reaction is completed, in the present invention, the product of the redox reaction is preferably filtered and dried in sequence to obtain a precursor. The present invention does not have a special limitation on the filtering and drying operations, and the filtering and drying solutions well known to those skilled in the art may be adopted. In the present invention, the filtration is preferably suction filtration. In the present invention, the drying temperature is preferably 40-70°C, more preferably 50-60°C; the drying time is preferably 8-10 h.
得到前驱体后，本发明对所述前驱体进行第二退火，得到Ru-ZnO光催化剂。在本发明中，所述第二退火温度优选为30～350℃，更优选为150～250℃，最优选为200℃；所述第二退火的时间优选为0～6h，更优选为0.5h。在本发明中，所述第二退火的作用是将钌稳定在ZnO上得到结构稳定的Ru-ZnO光催化剂。After the precursor is obtained, the present invention performs second annealing on the precursor to obtain a Ru-ZnO photocatalyst. In the present invention, the second annealing temperature is preferably 30-350°C, more preferably 150-250°C, and most preferably 200°C; the second annealing time is preferably 0-6h, more preferably 0.5h . In the present invention, the function of the second annealing is to stabilize Ru on ZnO to obtain a Ru-ZnO photocatalyst with stable structure.
本发明提供的制备方法得到的Ru-ZnO光催化剂有利于吸附空气中的甲烷，并且ZnO能够吸收太阳光从而产生电子和空穴对，电子和空穴发生分离并迁移到半导体表面，迁移到半导体表面的电子和空穴与吸附在ZnO表面的CH4发生氧化还原反应，从而提高光电催化效率；ZnO与Ru的复合，形成异质结构，使得Ru-ZnO光催化剂具有良好的循环稳定性。The Ru-ZnO photocatalyst obtained by the preparation method provided by the present invention is beneficial to adsorb methane in the air, and ZnO can absorb sunlight to generate electron and hole pairs. The electrons and holes are separated and migrate to the surface of the semiconductor and migrate to the semiconductor surface. The electrons and holes on the surface undergo redox reactions withCH4 adsorbed on the surface of ZnO, thereby improving the photocatalytic efficiency; the recombination of ZnO and Ru forms a heterostructure, which makes the Ru-ZnO photocatalyst have good cycling stability.
本发明还提供了上述技术方案制备的Ru-ZnO光催化剂，所述Ru-ZnO光催化剂包括ZnO基体以及负载于所述ZnO基体表面的Ru。The present invention also provides the Ru-ZnO photocatalyst prepared by the above technical solution, the Ru-ZnO photocatalyst comprises a ZnO matrix and Ru supported on the surface of the ZnO matrix.
在本发明中，所述Ru-ZnO光催化剂的比表面积优选为30～55m2/g，更优选为45～55m2/g；所述Ru-ZnO光催化剂的粒径优选为14～100nm，更优选为14～20nm。In the present invention, the specific surface area of the Ru-ZnO photocatalyst is preferably 30-55 m2 /g, more preferably 45-55 m2 /g; the particle size of the Ru-ZnO photocatalyst is preferably 14-100 nm, More preferably, it is 14 to 20 nm.
本发明还提供了上述技术方案所述制备方法制备得到的Ru-ZnO光催化剂或上述技术方案所述Ru-ZnO光催化剂在催化净化空气中甲烷的应用。在本发明中，所述空气中甲烷的浓度优选为1ppb～10000ppm，更优选为100ppb～1000ppm。The present invention also provides the Ru-ZnO photocatalyst prepared by the preparation method described in the above technical solution or the application of the Ru-ZnO photocatalyst described in the above technical solution in catalytic purification of methane in air. In the present invention, the concentration of methane in the air is preferably 1 ppb to 10000 ppm, more preferably 100 ppb to 1000 ppm.
本发明对所述Ru-ZnO催化剂在催化净化空气中甲烷的应用的方法没有特殊的限定，选用本领域熟知的方法即可。在本发明中，所述Ru-ZnO催化剂在催化净化空气中甲烷的应用的方法优选为在模拟太阳光下用Ru-ZnO催化剂进行光催化降解大气中微量甲烷气体的催化性能测试。In the present invention, there is no special limitation on the application method of the Ru-ZnO catalyst in the catalytic purification of methane in the air, and a method well known in the art can be selected. In the present invention, the method for the application of the Ru-ZnO catalyst in catalytic purification of methane in air is preferably a catalytic performance test of photocatalytic degradation of trace methane gas in the atmosphere with Ru-ZnO catalyst under simulated sunlight.
在本发明实施例中，所述在模拟太阳光下用Ru-ZnO催化剂进行光催化降解大气中微量甲烷气体的催化性能测试的实施过程如下：将Ru-ZnO催化剂平铺于石英反应器的底部，将反应器进行密封；然后采用阀门型微量注射器注入甲烷气体，将该反应器避光放置，以使甲烷气体在光催化剂表面达到吸附-脱附平衡；随后打开氙灯的模拟太阳光光源进行光照，每隔1分钟进行一次取样，并利用气相色谱随时检测反应器中甲烷的浓度。In the embodiment of the present invention, the implementation process of the catalytic performance test of photocatalytic degradation of trace methane gas in the atmosphere with Ru-ZnO catalyst under simulated sunlight is as follows: The Ru-ZnO catalyst is spread on the bottom of the quartz reactor , seal the reactor; then inject methane gas with a valve-type micro-injector, and place the reactor away from light, so that the methane gas reaches the adsorption-desorption equilibrium on the surface of the photocatalyst; then turn on the simulated sunlight light source of the xenon lamp to illuminate , sampling every 1 minute, and using gas chromatography to detect the concentration of methane in the reactor at any time.
本发明提供的Ru-ZnO光催化剂应用于催化净化空气中甲烷，在模拟太阳光、常温常压下能够高效地催化降解空气中低浓度甲烷，表现出优异的光催化净化空气中低浓度甲烷的性能，并表现出很好的循环稳定性。The Ru-ZnO photocatalyst provided by the invention is applied to catalytic purification of methane in the air, can efficiently catalyze the degradation of low-concentration methane in the air under simulated sunlight and normal temperature and pressure, and exhibits excellent photocatalytic purification of low-concentration methane in the air. performance, and showed good cycle stability.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
将10g二水合乙酸锌加入到100mL去离子水中，搅拌至完全溶解，在搅拌的条件下将20g二水合草酸加入至上述溶液中(其中二水合乙酸锌与二水合草酸的重量比是1:2，搅拌30min，得到草酸锌沉淀。随后将草酸锌沉淀进行抽滤，并用足量的水进行洗涤，将草酸锌在100℃下干燥5h。将草酸锌研磨成粉末，在350℃下于空气中退火6h，得到ZnO粉末。10g of zinc acetate dihydrate was added to 100mL of deionized water, stirred until completely dissolved, and 20g of oxalic acid dihydrate was added to the above solution under stirring (wherein the weight ratio of zinc acetate dihydrate and oxalic acid dihydrate was 1:2 , and stirred for 30 min to obtain zinc oxalate precipitate. Then, the zinc oxalate precipitate was suction filtered, washed with sufficient water, and dried at 100°C for 5h. The zinc oxalate was ground into powder, and the zinc oxalate was ground into powder at 350°C in air. Annealed for 6h to obtain ZnO powder.
将1g上述ZnO粉末超声分散于75mL去离子水中，并搅拌直至形成分散均匀的悬浊液。随后加入配置好的氯化钌溶液(0.0964mol/L)，加入的氯化钌的量为102.69μL(加入的氯化钌中Ru元素与ZnO的重量比为0.1:100)。加入氯化钌溶液后，搅拌3h，随后静置1h，将所得的沉淀物进行抽滤，并在60℃下干燥10h。将烘干后的产物研磨成粉末，在200℃下于空气中退火30min，即可得到0.1-Ru-ZnO。1 g of the above ZnO powder was ultrasonically dispersed in 75 mL of deionized water, and stirred until a uniformly dispersed suspension was formed. Subsequently, the prepared ruthenium chloride solution (0.0964 mol/L) was added, and the amount of the added ruthenium chloride was 102.69 μL (the weight ratio of Ru element and ZnO in the added ruthenium chloride was 0.1:100). After adding the ruthenium chloride solution, the mixture was stirred for 3 hours, and then allowed to stand for 1 hour. The obtained precipitate was filtered with suction and dried at 60° C. for 10 hours. The dried product was ground into powder and annealed in air at 200 °C for 30 min to obtain 0.1-Ru-ZnO.
实施例2Example 2
利用实施例1的方法制备ZnO。ZnO was prepared by the method of Example 1.
将1g上述ZnO粉末超声分散于75mL去离子水中，并搅拌直至形成分散均匀的悬浊液。随后加入配置好的氯化钌溶液(0.0964mol/L)，加入的氯化钌的量为51.34μL(加入的氯化钌中Ru元素与ZnO的重量比为0.05:100)。加入氯化钌溶液后，搅拌3h，随后静置1h，将所得的沉淀物进行抽滤，并在60℃下干燥10h。将烘干后的产物研磨成粉末，在200℃下于空气中退火30min，即可得到0.05-Ru-ZnO。1 g of the above ZnO powder was ultrasonically dispersed in 75 mL of deionized water, and stirred until a uniformly dispersed suspension was formed. Subsequently, the prepared ruthenium chloride solution (0.0964mol/L) was added, and the amount of the added ruthenium chloride was 51.34 μL (the weight ratio of Ru element and ZnO in the added ruthenium chloride was 0.05:100). After adding the ruthenium chloride solution, the mixture was stirred for 3 hours, and then allowed to stand for 1 hour. The obtained precipitate was filtered with suction and dried at 60° C. for 10 hours. The dried product was ground into powder and annealed in air at 200 °C for 30 min to obtain 0.05-Ru-ZnO.
实施例3Example 3
利用实施例1的方法制备ZnO。ZnO was prepared by the method of Example 1.
将1g上述ZnO粉末超声分散于75mL去离子水中，并搅拌直至形成分散均匀的悬浊液。随后加入配置好的氯化钌溶液(0.0964mol/L)，加入的氯化钌的量为205.38μL(加入的氯化钌中Ru元素与ZnO的重量比为0.2:100)。加入氯化钌溶液后，搅拌3h，随后静置1h，将所得的沉淀物进行抽滤，并在60℃下干燥10h。将烘干后的产物研磨成粉末，在200℃下于空气中退火30min，即可得到0.2-Ru-ZnO。1 g of the above ZnO powder was ultrasonically dispersed in 75 mL of deionized water, and stirred until a uniformly dispersed suspension was formed. Subsequently, the prepared ruthenium chloride solution (0.0964 mol/L) was added, and the amount of the added ruthenium chloride was 205.38 μL (the weight ratio of Ru element and ZnO in the added ruthenium chloride was 0.2:100). After adding the ruthenium chloride solution, the mixture was stirred for 3 hours, and then allowed to stand for 1 hour. The obtained precipitate was filtered with suction and dried at 60° C. for 10 hours. The dried product was ground into powder and annealed in air at 200 °C for 30 min to obtain 0.2-Ru-ZnO.
实施例4Example 4
利用实施例1的方法制备ZnO。ZnO was prepared by the method of Example 1.
将1g上述ZnO粉末超声分散于75mL去离子水中，并搅拌直至形成分散均匀的悬浊液。随后加入配置好的氯化钌溶液(0.0964mol/L)，加入的氯化钌的量为308.07μL(加入的氯化钌中Ru元素与ZnO的重量比为0.3:100)。加入氯化钌溶液后，搅拌3h，随后静置1h，将所得的沉淀物进行抽滤，并在60℃下干燥10h。将烘干后的产物研磨成粉末，在200℃下于空气中退火30min，即可得到0.3-Ru-ZnO。1 g of the above ZnO powder was ultrasonically dispersed in 75 mL of deionized water, and stirred until a uniformly dispersed suspension was formed. Subsequently, the prepared ruthenium chloride solution (0.0964 mol/L) was added, and the amount of the added ruthenium chloride was 308.07 μL (the weight ratio of Ru element and ZnO in the added ruthenium chloride was 0.3:100). After adding the ruthenium chloride solution, the mixture was stirred for 3 hours, and then allowed to stand for 1 hour. The obtained precipitate was filtered with suction and dried at 60° C. for 10 hours. The dried product was ground into powder and annealed in air at 200 °C for 30 min to obtain 0.3-Ru-ZnO.
实施例5Example 5
利用实施例1的方法制备ZnO。ZnO was prepared by the method of Example 1.
将1g上述ZnO粉末超声分散于75mL去离子水中，并搅拌直至形成分散均匀的悬浊液。随后加入配置好的氯化钌溶液(0.0964mol/L)，加入的氯化钌的量为410.76μL(加入的氯化钌中Ru元素与ZnO的重量比为0.4:100)。加入氯化钌溶液后，搅拌3h，随后静置1h，将所得的沉淀物进行抽滤，并在60℃下干燥10h。将烘干后的产物研磨成粉末，在200℃下于空气中退火30min，即可得到0.4-Ru-ZnO。1 g of the above ZnO powder was ultrasonically dispersed in 75 mL of deionized water, and stirred until a uniformly dispersed suspension was formed. Subsequently, the prepared ruthenium chloride solution (0.0964mol/L) was added, and the amount of the added ruthenium chloride was 410.76 μL (the weight ratio of Ru element and ZnO in the added ruthenium chloride was 0.4:100). After adding the ruthenium chloride solution, the mixture was stirred for 3 hours, and then allowed to stand for 1 hour. The obtained precipitate was filtered with suction and dried at 60° C. for 10 hours. The dried product was ground into powder and annealed in air at 200 °C for 30 min to obtain 0.4-Ru-ZnO.
实施例6Example 6
利用实施例1的方法制备ZnO。ZnO was prepared by the method of Example 1.
将1g上述ZnO粉末超声分散于75mL去离子水中，并搅拌直至形成分散均匀的悬浊液。随后加入配置好的氯化钌溶液(0.0964mol/L)，加入的氯化钌的量为513.45μL(加入的氯化钌中Ru元素与ZnO的重量比为0.5:100)。加入氯化钌溶液后，搅拌3h，随后静置1h，将所得的沉淀物进行抽滤，并在60℃下干燥10h。将烘干后的产物研磨成粉末，在200℃下于空气中退火30min，即可得到0.5-Ru-ZnO。1 g of the above ZnO powder was ultrasonically dispersed in 75 mL of deionized water, and stirred until a uniformly dispersed suspension was formed. Subsequently, the prepared ruthenium chloride solution (0.0964 mol/L) was added, and the amount of the added ruthenium chloride was 513.45 μL (the weight ratio of Ru element and ZnO in the added ruthenium chloride was 0.5:100). After adding the ruthenium chloride solution, the mixture was stirred for 3 hours, and then allowed to stand for 1 hour. The obtained precipitate was filtered with suction and dried at 60° C. for 10 hours. The dried product was ground into powder and annealed in air at 200 °C for 30 min to obtain 0.5-Ru-ZnO.
应用例1～6Application examples 1 to 6
1)在模拟太阳光下，对实施例1～6所制备的Ru-ZnO催化剂(0.05-Ru-ZnO、0.1-Ru-ZnO、0.2-Ru-ZnO、0.3-Ru-ZnO、0.4-Ru-ZnO、0.5-Ru-ZnO)进行光催化降解大气中的微量甲烷气体的催化性能测试：1) Under simulated sunlight, the Ru-ZnO catalysts (0.05-Ru-ZnO, 0.1-Ru-ZnO, 0.2-Ru-ZnO, 0.3-Ru-ZnO, 0.4-Ru- ZnO, 0.5-Ru-ZnO) for photocatalytic degradation of trace methane gas in the atmosphere. Catalytic performance test:
实施过程如下：分别称取0.3g实施例1～6所制备Ru-ZnO催化剂，平铺于体积为240mL的石英反应器的底部，将反应器进行密封；然后，采用阀门型微量注射器注入24μL甲烷气体，使反应器中甲烷的浓度为100ppm。将该反应器避光放置1小时，以使甲烷气体在光催化剂表面达到吸附-脱附平衡；随后打开300W氙灯的模拟太阳光光源进行光照，每隔1分钟进行一次取样，并利用气相色谱随时检测反应器中甲烷的浓度。The implementation process is as follows: respectively weigh 0.3 g of the Ru-ZnO catalyst prepared in Examples 1 to 6, spread it on the bottom of a quartz reactor with a volume of 240 mL, and seal the reactor; then, inject 24 μL of methane with a valve-type micro-syringe gas so that the concentration of methane in the reactor is 100 ppm. The reactor was placed in the dark for 1 hour, so that the methane gas reached the adsorption-desorption equilibrium on the surface of the photocatalyst; then the simulated sunlight light source of the 300W xenon lamp was turned on for illumination, sampling was carried out every 1 minute, and the gas chromatography was used at any time. The concentration of methane in the reactor was measured.
测试结果如图1所示，其中，曲线0.05-Ru、0.1-Ru、0.2-Ru、0.3-Ru、0.4-Ru、0.5-Ru分别代表实施例1～6中制备得到的催化剂0.05-Ru-ZnO、0.1-Ru-ZnO、0.2-Ru-ZnO、0.3-Ru-ZnO、0.4-Ru-ZnO、0.5-Ru-ZnO。由图可知，在模拟太阳光照射下，对于曲线0.05-Ru，5分钟后反应器中的甲烷浓度已经低于1％，可认为降解完；而对于曲线0.1-Ru、0.2-Ru、0.3-Ru、0.4-Ru、0.5-Ru仅仅需要4分钟就可以降解完反应器中的甲烷，这个浓度范围内的光催化剂表现出了优异的光催化降解甲烷性能。由此可知，0.1～0.5-Ru-ZnO在模拟太阳光下表现出优异的光催化净化空气中低浓度甲烷的性能，具有很强的实际应用价值。The test results are shown in Figure 1, wherein the curves 0.05-Ru, 0.1-Ru, 0.2-Ru, 0.3-Ru, 0.4-Ru, and 0.5-Ru represent the catalysts 0.05-Ru- ZnO, 0.1-Ru-ZnO, 0.2-Ru-ZnO, 0.3-Ru-ZnO, 0.4-Ru-ZnO, 0.5-Ru-ZnO. It can be seen from the figure that under the simulated sunlight, for the curve 0.05-Ru, the methane concentration in the reactor has been lower than 1% after 5 minutes, and the degradation can be considered complete; while for the curves 0.1-Ru, 0.2-Ru, 0.3-Ru Ru, 0.4-Ru, and 0.5-Ru can degrade methane in the reactor in only 4 minutes, and the photocatalysts in this concentration range show excellent photocatalytic methane degradation performance. It can be seen that 0.1-0.5-Ru-ZnO exhibits excellent photocatalytic performance for purifying low-concentration methane in the air under simulated sunlight, and has strong practical application value.
2)循环稳定性测试：2) Cycle stability test:
按照应用例1中的实施过程，将实施例1中制备的0.1-Ru-ZnO光催化剂在上述相同条件下连续进行十次光催化降解实验，而且进行一次测试之后无需进行任何处理直接将0.1-Ru-ZnO光催化剂用于下一测试。其循环稳定性结果如图2所示，由图2可知，0.1-Ru-ZnO光催化剂在十次循环降解测试中均表现出很好的稳定性，为其实际应用提供了良好的保障。According to the implementation process in Application Example 1, the 0.1-Ru-ZnO photocatalyst prepared in Example 1 was continuously subjected to ten times of photocatalytic degradation experiments under the same conditions as above, and after one test, the The Ru-ZnO photocatalyst was used for the next test. The cycle stability results are shown in Figure 2. It can be seen from Figure 2 that the 0.1-Ru-ZnO photocatalyst shows good stability in ten cycle degradation tests, which provides a good guarantee for its practical application.
由上述实施例可知，本发明提供的Ru-ZnO催化剂模拟太阳光的条件下对甲烷具有高效的催化性能和稳定性，即在常温常压下对光催化净化甲烷具有良好的光催化活性及稳定性。It can be seen from the above examples that the Ru-ZnO catalyst provided by the present invention has efficient catalytic performance and stability for methane under the condition of simulating sunlight, that is, it has good photocatalytic activity and stability for photocatalytic purification of methane under normal temperature and pressure. sex.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
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