技术领域technical field
本发明涉及环保和能源功能材料领域，特别地，涉及一种多孔ZnO复合空心球催化剂及其制备方法。The invention relates to the field of environmental protection and energy functional materials, in particular to a porous ZnO composite hollow sphere catalyst and a preparation method thereof.
背景技术Background technique
随着全球范围内环境问题的日趋严重，传统化石能源的消耗殆尽，对环境进行治理修复和寻求新的替代能源成为全世界广泛关注的焦点。由于纳米尺寸的材料在光学，电学，磁学和催化等方面具有极其特殊的性质，纳米半导体光催化技术对太阳能的转化利用成为解决这些问题的重要战略之一。在众多研究开发的氧化物半导体光催化剂中，由于TiO2和ZnO的催化活性高，成本低，稳定性高并且环境友好，它们被认为在光催化产氢，CO2还原和污染物降解等方面是绝佳的光催化剂。而其中，氧化锌(ZnO)可以很方便的构建出理想的纳米结构，是影响光催化反应活性的重要因素之一。With the increasing environmental problems around the world and the depletion of traditional fossil energy sources, the restoration of the environment and the search for new alternative energy sources have become the focus of widespread attention around the world. Because nanometer-sized materials have extremely special properties in terms of optics, electricity, magnetism and catalysis, the conversion and utilization of solar energy by nano-semiconductor photocatalysis technology has become one of the important strategies to solve these problems. Among numerous researched and developed oxide semiconductor photocatalysts, due to their high catalytic activity, low cost, high stability and environmental friendliness,TiO2 and ZnO are considered to be useful in photocatalytic hydrogen production,CO2 reduction and pollutant degradation, etc. It is an excellent photocatalyst. Among them, zinc oxide (ZnO) can easily construct an ideal nanostructure, which is one of the important factors affecting the photocatalytic activity.
纳米ZnO为直接带隙(3.32eV)半导体，光电子结合能(60meV)高，在太阳能电池，化学传感，压电及光电器件等领域都有着大量的应用。纳米材料的一些特性都相当依赖于它们非本征的特性，如形貌结构，晶粒尺寸和比表面积等。因而，许多优秀的研究工作通过纳米ZnO形貌结构的调控来提升光催化反应的活性，如纳米棒，纳米阵列，纳米微球及纳米空心球等。余等报道通过葡萄糖/ZnCl2混合溶液水热一锅法后经煅烧合成了ZnO空心球。实验合成的半导体空心球的比表面积随着葡萄糖的摩尔比重上升而增大，性能最优的样品光催化降解罗丹明B(RhB)的效率高于商业催化剂P25。李等也报道了一种一步法多金属氧酸盐(H3PW12O40)协助的无模板电化学方法合成ZnO空心球。空心球结构能够有效的增加了光催化剂的比表面积和活性位点，并且通过入射光在空心结构内的散射增加对光的吸收和利用。然而，由于高温不利于Zn2+在碳球模板上的吸附，一锅水热法产量低，大小不均匀。并且ZnO对pH敏感，电化学H2O2氧化法会使ZnO空心球结构不稳定。Nano-ZnO is a semiconductor with a direct band gap (3.32eV) and a high photoelectron binding energy (60meV). It has a large number of applications in the fields of solar cells, chemical sensing, piezoelectric and optoelectronic devices. Some properties of nanomaterials are quite dependent on their extrinsic properties, such as morphology, grain size and specific surface area. Therefore, many excellent research works have improved the activity of photocatalytic reactions by adjusting the morphology and structure of nano-ZnO, such as nano-rods, nano-arrays, nano-microspheres and nano-hollow spheres. Yu et al reported the synthesis of ZnO hollow spheres by a one-pot hydrothermal method with glucose/ZnCl mixed solution followed by calcination. The specific surface area of the experimentally synthesized semiconductor hollow spheres increases with the increase of the molar specific gravity of glucose, and the photocatalytic degradation efficiency of the sample with the best performance is higher than that of the commercial catalyst P25. Li et al. also reported a one-step polyoxometalate (H3 PW12 O40 ) assisted template-free electrochemical method for the synthesis of ZnO hollow spheres. The hollow sphere structure can effectively increase the specific surface area and active sites of the photocatalyst, and increase the absorption and utilization of light through the scattering of incident light in the hollow structure. However, the one-pot hydrothermal method has low yield and uneven size due to the high temperature is not conducive to the adsorption of Zn2+ on the carbon sphere template. And ZnO is sensitive to pH, the electrochemical H2 O2 oxidation method will destabilize the structure of ZnO hollow spheres.
发明内容Contents of the invention
本发明为了解决现有技术中存在的问题，提供了一种多孔ZnO复合空心球催化剂，包括中空的碳球和包覆在所述碳球上的ZnO颗粒。In order to solve the problems in the prior art, the present invention provides a porous ZnO composite hollow sphere catalyst, which includes hollow carbon spheres and ZnO particles coated on the carbon spheres.
本发明所述的多孔ZnO复合空心球催化剂中，所述碳球占所述多孔ZnO复合空心球催化剂的质量分数为56.4％-78.2％。In the porous ZnO composite hollow sphere catalyst of the present invention, the mass fraction of the carbon spheres in the porous ZnO composite hollow sphere catalyst is 56.4%-78.2%.
本发明所述的多孔ZnO复合空心球催化剂中，所述多孔ZnO复合空心球催化剂中复合空心球的直径尺寸为100-600纳米。In the porous ZnO composite hollow sphere catalyst of the present invention, the diameter of the composite hollow sphere in the porous ZnO composite hollow sphere catalyst is 100-600 nanometers.
本发明还提供了一种多孔ZnO复合空心球催化剂的制备方法，包括如下步骤：The present invention also provides a preparation method of porous ZnO composite hollow sphere catalyst, comprising the following steps:
S1，合成胶质碳球；S1, synthetic colloidal carbon spheres;
S2，合成多孔ZnO复合空心球催化剂。S2, synthesis of porous ZnO composite hollow sphere catalyst.
在本发明所述的多孔ZnO复合空心球催化剂的制备方法中，步骤S1具体包括如下步骤：In the preparation method of the porous ZnO composite hollow sphere catalyst of the present invention, step S1 specifically includes the following steps:
S11，将葡萄糖溶解在纯水中，搅拌至澄清溶液，制成浓度为0.1g/ml的葡萄糖溶液；S11, dissolving glucose in pure water, stirring to a clear solution, and making a glucose solution with a concentration of 0.1g/ml;
S12，将制备好的所述葡萄糖溶液转移至反应釜中在180度下水热8小时；S12, transfer the prepared glucose solution to a reaction kettle and heat it under water at 180 degrees for 8 hours;
S13，将步骤S12中得到的产物用去离子水和乙醇洗涤，并烘干。S13, washing the product obtained in step S12 with deionized water and ethanol, and drying.
在本发明所述的多孔ZnO复合空心球催化剂的制备方法中，步骤S2具体包括如下步骤：In the preparation method of the porous ZnO composite hollow sphere catalyst of the present invention, step S2 specifically includes the following steps:
S21，将醋酸锌溶解在纯水中，搅拌至完全溶解，制成5mg/ml的醋酸锌溶液；S21, dissolving zinc acetate in pure water, stirring until completely dissolved, to make a 5mg/ml zinc acetate solution;
S22，在醋酸锌溶液中加入步骤S1中制备的所述胶质碳球，并密封超声分散10分钟，然后搅拌6小时；S22, adding the colloidal carbon spheres prepared in step S1 to the zinc acetate solution, sealing and ultrasonically dispersing for 10 minutes, and then stirring for 6 hours;
S23，将S22中得到的混合溶液在室温下静置陈化10小时制得C/ZnO复合材料；S23, standing and aging the mixed solution obtained in S22 at room temperature for 10 hours to prepare a C/ZnO composite material;
S24，将所述C/ZnO复合材料放在坩埚中加盖，在400-500摄氏度下煅烧1小时。S24, placing the C/ZnO composite material in a crucible with a cover, and calcining at 400-500 degrees Celsius for 1 hour.
在本发明所述的多孔ZnO复合空心球催化剂的制备方法中，步骤S22具体为：取60毫升的步骤S21中制备的醋酸锌溶液，加入0.3克步骤S1中制备的所述胶质碳球，并密封超声分散10分钟，然后搅拌6小时。In the preparation method of the porous ZnO composite hollow sphere catalyst of the present invention, step S22 is specifically: take 60 milliliters of the zinc acetate solution prepared in step S21, add 0.3 g of the colloidal carbon spheres prepared in step S1, Sealed and ultrasonically dispersed for 10 minutes, then stirred for 6 hours.
在本发明所述的多孔ZnO复合空心球催化剂的制备方法的一个实施例中，步骤S24具体为，将所述C/ZnO复合材料放在坩埚中加盖，在400摄氏度下煅烧1小时。In one embodiment of the preparation method of the porous ZnO composite hollow sphere catalyst of the present invention, step S24 is specifically, placing the C/ZnO composite material in a crucible with a cover, and calcining at 400 degrees Celsius for 1 hour.
在本发明所述的多孔ZnO复合空心球催化剂的制备方法的另一个实施例中，步骤S24具体为，将所述C/ZnO复合材料放在坩埚中加盖，在450摄氏度下煅烧1小时。In another embodiment of the preparation method of the porous ZnO composite hollow sphere catalyst of the present invention, step S24 specifically includes placing the C/ZnO composite material in a crucible with a cover, and calcining at 450 degrees Celsius for 1 hour.
有益效果：本发明利用简单的离子吸附原理基于碳球模板制备合成了多孔ZnO复合空心球催化剂，并通过调整煅烧温度系统性控制空心球内碳质材料的含量。实验结果发现，当碳含量为约56.4％，光催化还原CO2活性最高。碳材料的引入显著改善了复合光催化剂的可见光吸收和CO2吸附，并且会产生局部热效应，有利于电荷传输。本发明所述的多孔ZnO复合空心球催化剂具有制备方法简单，光催化效果高的有益效果。Beneficial effects: the present invention uses a simple ion adsorption principle to prepare and synthesize a porous ZnO composite hollow sphere catalyst based on a carbon sphere template, and systematically controls the content of carbonaceous materials in the hollow sphere by adjusting the calcination temperature. The experimental results found that when the carbon content was about 56.4%, the photocatalytic CO2 reduction activity was the highest. The introduction of carbon materials significantly improves the visible light absorption and CO2 adsorption of the composite photocatalyst, and produces a local thermal effect that is beneficial to charge transport. The porous ZnO composite hollow sphere catalyst of the invention has the beneficial effects of simple preparation method and high photocatalytic effect.
附图说明Description of drawings
图1为本发明实施例所述的多孔ZnO复合空心球催化剂的结构及其催化原理图；Fig. 1 is the structure of the porous ZnO composite hollow sphere catalyst described in the embodiment of the present invention and its catalytic principle diagram;
图2a-2f为本发明实施例所述的多孔ZnO复合空心球催化剂制备过程中产物的扫描电镜图，其中图2a为胶质碳球的扫描电镜图，图2b为C/ZnO复合材料的扫描电镜图，图2c为本发明第一实施例中制备的多孔ZnO复合空心球催化剂的扫描电镜图，图2d为本发明第二实施例中制备的多孔ZnO复合空心球催化剂的扫描电镜图，图2e为本发明第三实施例中制备的多孔ZnO复合空心球催化剂的扫描电镜图，图2f为直接从市场购买的商业ZnO扫描电镜图。Fig. 2a-2f is the scanning electron micrograph of the product in the preparation process of the porous ZnO composite hollow sphere catalyst described in the embodiment of the present invention, wherein Fig. 2a is the scanning electron micrograph of the colloidal carbon sphere, and Fig. 2b is the scanning electron micrograph of the C/ZnO composite material Fig. 2c is a scanning electron micrograph of the porous ZnO composite hollow sphere catalyst prepared in the first embodiment of the present invention, and Fig. 2d is a scanning electron micrograph of the porous ZnO composite hollow sphere catalyst prepared in the second embodiment of the present invention, Fig. 2e is a scanning electron micrograph of the porous ZnO composite hollow sphere catalyst prepared in the third embodiment of the present invention, and FIG. 2f is a scanning electron micrograph of commercial ZnO purchased directly from the market.
图3为本发明中不同实施例中制备的多孔ZnO复合空心球催化剂的热重分析图；Fig. 3 is the thermal gravimetric analysis figure of the porous ZnO composite hollow sphere catalyst prepared in different embodiments in the present invention;
图4为本发明所述的C/ZnO复合材料的形成机理图；Fig. 4 is the formation mechanism figure of C/ZnO composite material of the present invention;
图5为本发明中不同实施例中制备的多孔ZnO复合空心球催化剂的紫外可见漫反射光谱图；Fig. 5 is the ultraviolet-visible diffuse reflection spectrogram of the porous ZnO composite hollow sphere catalyst prepared in different embodiments of the present invention;
图6为本发明中不同实施例中制备的多孔ZnO复合空心球催化剂的CO2吸附等温线图；Fig. 6 is theCO of the porous ZnO composite hollow sphere catalyst prepared in different embodiments of the present invention Adsorption isotherm diagram;
图7a为本发明第二实施例中制备的多孔ZnO复合空心球催化剂的和商业ZnO的催化结果的气相色谱图，图7b为出本发明不同实施例中制备的多孔ZnO复合空心球催化剂及商业ZnO的光催化产率对比图；Fig. 7 a is the gas chromatogram of the catalytic result of the porous ZnO composite hollow sphere catalyst prepared in the second embodiment of the present invention and commercial ZnO, and Fig. 7 b is the porous ZnO composite hollow sphere catalyst prepared in different embodiments of the present invention and commercial ZnO Comparison chart of photocatalytic yield of ZnO;
图8为本发明不同实施例中制备的多孔ZnO复合空心球催化剂的电化学阻抗谱。Fig. 8 is the electrochemical impedance spectrum of porous ZnO composite hollow sphere catalysts prepared in different embodiments of the present invention.
具体实施方式Detailed ways
下面结合附图与具体实施方式对本发明作进一步详细描述。The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
本发明为了解决现有技术中存在的问题，提供了一种多孔ZnO复合空心球催化剂，如图1所示，所述ZnO复合空心球催化剂包括中空的碳球和包覆在所述碳球上的ZnO颗粒。In order to solve the problems in the prior art, the present invention provides a porous ZnO composite hollow sphere catalyst, as shown in Figure 1, the ZnO composite hollow sphere catalyst comprises hollow carbon spheres and coated on the carbon spheres of ZnO particles.
当使用本发明所述的ZnO复合空心球催化剂催化时，CO2分子吸附与ZnO空心球表面，同时大量CO2由于π-π共轭效应吸附于空心球内部碳核上。光照时，ZnO产生大量电子空穴对。由于碳费米能级低于ZnO导带位置，电子传输到碳材料上并被局部热效应加速，促进了光生电子空穴的分离。碳材料上的具有相应还原能力电子引发了CO2和水分子的光还原反应。ZnO价带上空穴能氧化H2O，产生O2和H+离子。同时CO2同H+和电子发生还原反应生成CH3OH。When the ZnO composite hollow sphere catalyst of the present invention is used for catalysis,CO2 molecules are adsorbed on the surface of ZnO hollow spheres, and a large amount ofCO2 is adsorbed on the carbon core inside the hollow spheres due to the π-π conjugation effect. When illuminated, ZnO generates a large number of electron-hole pairs. Since the carbon Fermi level is lower than the ZnO conduction band position, electrons are transported to the carbon material and accelerated by the local thermal effect, which facilitates the separation of photogenerated electron holes. Electrons with corresponding reducing abilities on the carbon material initiate the photoreduction reaction ofCO2 and water molecules. The holes on the valence band of ZnO can oxidizeH2O to produceO2 and H+ ions. At the same time, CO2 undergoes a reduction reaction with H+ and electrons to generate CH3 OH.
碳材料和半导体ZnO的准费米能级差是光生电子发生移动(从ZnO到碳)的动力。并且，大量电子从ZnO传输到碳核上降低了ZnO晶格中的电子数量，从而能够有效抑制电子空穴发生复合，同时使得ZnO表面有更多空穴用以氧化水分子。因此，在这个过程中，光催化CO2还原全反应的效率得到显著的提升。The quasi-Fermi level difference between carbon materials and semiconductor ZnO is the driving force for the movement of photogenerated electrons (from ZnO to carbon). Moreover, the transfer of a large number of electrons from ZnO to the carbon core reduces the number of electrons in the ZnO lattice, which can effectively inhibit the recombination of electrons and holes, and at the same time make more holes on the surface of ZnO to oxidize water molecules. Therefore, in this process, the efficiency of the photocatalyticCO2 reduction overall reaction is significantly enhanced.
本发明所述的多孔ZnO复合空心球催化剂制备方法包括如下步骤：The preparation method of the porous ZnO composite hollow sphere catalyst of the present invention comprises the following steps:
S1，合成胶质碳球。S1, Synthetic colloidal carbon spheres.
具体地，取葡萄糖溶解在纯水中，搅拌溶解至澄清溶液，制成浓度为0.1g/ml的葡萄糖溶液；然后将制备好的所述葡萄糖溶液转移至反应釜中180摄氏度水热8h；然后将制备的产物用去离子水和乙醇离心洗涤，并烘干，得到胶质碳球；Specifically, take glucose and dissolve it in pure water, stir and dissolve to a clear solution to make a glucose solution with a concentration of 0.1 g/ml; then transfer the prepared glucose solution to a reaction kettle for 8 hours at 180 degrees Celsius; then The prepared product was centrifugally washed with deionized water and ethanol, and dried to obtain colloidal carbon spheres;
S2，合成多孔ZnO复合空心球催化剂。S2, synthesis of porous ZnO composite hollow sphere catalyst.
具体地，将醋酸锌溶解在纯水中，搅拌10min至完成溶解，制成5mg/ml的醋酸锌溶液，加入S1中制备的胶质碳球，并密封超声分散10min，然后搅拌6h；然后将搅拌6h后的混合溶液在室温下静置陈化10h制得C/ZnO复合材料，将所述C/ZnO复合材料放在坩埚中加盖，在400-500摄氏度下进行煅烧1h制得多孔ZnO复合空心球催化剂。Specifically, dissolve zinc acetate in pure water, stir for 10 minutes until the dissolution is complete, and prepare a 5 mg/ml zinc acetate solution, add the colloidal carbon spheres prepared in S1, and seal and ultrasonically disperse for 10 minutes, then stir for 6 hours; then After stirring for 6 hours, the mixed solution was aged at room temperature for 10 hours to obtain a C/ZnO composite material, and the C/ZnO composite material was placed in a crucible and covered, and calcined at 400-500 degrees Celsius for 1 hour to obtain porous ZnO Composite hollow sphere catalyst.
实施例一Embodiment one
在本实施例中，步骤S2中，取60ml的醋酸锌溶液，并加入0.3g步骤S1中制备的胶质碳球，并密封超声分散10min，然后搅拌6h；然后将搅拌6h后的混合溶液在室温下静置陈化10h制得C/ZnO复合材料，将所述C/ZnO复合材料放在坩埚中加盖，在400摄氏度下进行煅烧1h制得多孔ZnO复合空心球催化剂。In this example, in step S2, 60ml of zinc acetate solution was taken, and 0.3g of the colloidal carbon spheres prepared in step S1 was added, sealed and ultrasonically dispersed for 10min, and then stirred for 6h; then the mixed solution after stirring for 6h was placed in Standing and aging at room temperature for 10 h to prepare a C/ZnO composite material, put the C/ZnO composite material in a crucible and cover it, and perform calcination at 400 degrees Celsius for 1 h to prepare a porous ZnO composite hollow sphere catalyst.
实施例二Embodiment two
在本实施例中，步骤S2中，取60ml的醋酸锌溶液，并加入0.3g步骤S1中制备的胶质碳球，并密封超声分散10min，然后搅拌6h；然后将搅拌6h后的混合溶液在室温下静置陈化10h制得C/ZnO复合材料，将所述C/ZnO复合材料放在坩埚中加盖，在450摄氏度下进行煅烧1h制得多孔ZnO复合空心球催化剂。In this example, in step S2, 60ml of zinc acetate solution was taken, and 0.3g of the colloidal carbon spheres prepared in step S1 was added, sealed and ultrasonically dispersed for 10min, and then stirred for 6h; then the mixed solution after stirring for 6h was placed in Standing and aging at room temperature for 10 h to prepare a C/ZnO composite material, put the C/ZnO composite material in a crucible with a cover, and perform calcination at 450 degrees Celsius for 1 h to prepare a porous ZnO composite hollow sphere catalyst.
实施例三Embodiment Three
在本实施例中，步骤S2中，取60ml的醋酸锌溶液，并加入0.3g步骤S1中制备的胶质碳球，并密封超声分散10min，然后搅拌6h；然后将搅拌6h后的混合溶液在室温下静置陈化10h制得C/ZnO复合材料，将所述C/ZnO复合材料放在坩埚中加盖，在500摄氏度下进行煅烧1h制得多孔ZnO复合空心球催化剂。In this example, in step S2, 60ml of zinc acetate solution was taken, and 0.3g of the colloidal carbon spheres prepared in step S1 was added, sealed and ultrasonically dispersed for 10min, and then stirred for 6h; then the mixed solution after stirring for 6h was placed in Standing and aging at room temperature for 10 h to prepare a C/ZnO composite material, put the C/ZnO composite material in a crucible with a cover, and perform calcination at 500 degrees Celsius for 1 h to prepare a porous ZnO composite hollow sphere catalyst.
实验数据Experimental data
为了验证本发明中制备的多孔ZnO复合空心球催化剂的结构、性能和原理，以下将进行试验测试和验证。实施例一中制备的多孔ZnO复合空心球催化剂被标记为T400，实施例二中制备的多孔ZnO复合空心球催化剂被标记为T450，实施例三中制备的多孔ZnO复合空心球催化剂被标记为T500。步骤S1中制备的胶质碳球被标记为Csp。同时引入直接从市场购买的商业ZnO做对比，标记为c-ZnO。In order to verify the structure, performance and principle of the porous ZnO composite hollow sphere catalyst prepared in the present invention, experimental testing and verification will be carried out below. The porous ZnO composite hollow sphere catalyst prepared in embodiment one is marked as T400, the porous ZnO composite hollow sphere catalyst prepared in embodiment two is marked as T450, and the porous ZnO composite hollow sphere catalyst prepared in embodiment three is marked as T500 . The colloidal carbon spheres prepared in step S1 are labeled as Csp. At the same time, commercial ZnO purchased directly from the market was introduced for comparison, which was labeled as c-ZnO.
(1)样品晶相结构和微观形貌(1) Sample crystal phase structure and microscopic morphology
如图2a-2f所示，图2a-2f为不同实施例中制备的多孔ZnO复合空心球催化剂以及制备过程中不同阶段的产物的场发射扫描电镜图。其中，图2a为步骤S1中制备的胶质碳球的扫描电镜图，从图2a中可以看出，合成的碳球模板为直径约800nm的均匀球形，所有球体大小均匀，无明显差别。As shown in Figures 2a-2f, Figures 2a-2f are field emission scanning electron microscope images of porous ZnO composite hollow sphere catalysts prepared in different embodiments and products at different stages in the preparation process. Among them, Figure 2a is a scanning electron microscope image of the colloidal carbon spheres prepared in step S1. It can be seen from Figure 2a that the synthesized carbon sphere template is a uniform spherical shape with a diameter of about 800 nm, and all spheres are uniform in size without significant difference.
图2b为步骤S2中制备的在煅烧前C/ZnO复合材料的扫描电镜图，当碳球加到醋酸锌溶液中，经搅拌陈化处理后碳球表面出现了少许的均匀颗粒感，说明Zn2+离子吸附于碳球表面水解反应生成了氢氧化物和一些锌系物。Figure 2b is the scanning electron microscope image of the C/ZnO composite material prepared in step S2 before calcination. When the carbon spheres were added to the zinc acetate solution, a little uniform graininess appeared on the surface of the carbon spheres after stirring and aging treatment, indicating that the ZnO The2+ ion is adsorbed on the surface of carbon spheres and hydrolyzed to generate hydroxide and some zinc series.
后图2c为第一实施例中制备的多孔ZnO复合空心球催化剂的扫描电镜图，图2d为第二实施例中制备的多孔ZnO复合空心球催化剂的扫描电镜图，图2e为第三实施例中制备的多孔ZnO复合空心球催化剂的扫描电镜图。随着煅烧温度的上升，复合空心球直径尺寸不断下降，从600nm降到100nm。而且可以发现煅烧温度越高，氧化锌的晶粒尺寸增大。当煅烧温度上升到500度时，经过1h的保温内部的碳核完全消失了，这也跟XRD图谱中碳的宽峰的减弱消失相佐证，同时空心球结构变成了典型的颗粒组成的多孔疏松表面形貌。而第二实施例中制备的多孔ZnO复合空心球催化剂结构稳定，粗糙的颗粒堆积的表面非常有利于空心球的光吸收，增加了复合材料的比表面积和表面活性位点。图2f为直接从市场购买的商业ZnO扫描电镜图。Figure 2c is a scanning electron micrograph of the porous ZnO composite hollow sphere catalyst prepared in the first embodiment, and Fig. 2d is a scanning electron micrograph of the porous ZnO composite hollow sphere catalyst prepared in the second embodiment, and Fig. 2e is a third embodiment Scanning electron micrographs of porous ZnO composite hollow sphere catalysts prepared in . With the increase of calcination temperature, the diameter of composite hollow spheres decreased continuously, from 600nm to 100nm. And it can be found that the higher the calcination temperature, the larger the grain size of zinc oxide. When the calcination temperature rises to 500 degrees, the internal carbon nuclei completely disappear after 1h of heat preservation, which is also evidenced by the weakening and disappearance of the broad peak of carbon in the XRD pattern, and the hollow spherical structure becomes a typical particle composition. loose surface topography. However, the porous ZnO composite hollow sphere catalyst prepared in the second embodiment has a stable structure, and the rough particle-stacked surface is very conducive to the light absorption of the hollow sphere, which increases the specific surface area and surface active sites of the composite material. Figure 2f is the SEM image of commercial ZnO purchased directly from the market.
(2)热重分析(TGA)(2) Thermogravimetric Analysis (TGA)
如图3所示，图3示出了不同实施例的热重分析图，用以分析制备的多孔ZnO复合空心球催化剂中碳的含量。从图3中可以看出，第三实施例中制备的多孔ZnO复合空心球催化剂T500和商业c-ZnO基本无明显失重。而第一实施例和第二实施例中制备的多孔ZnO复合空心球催化剂在100-400℃范围出现第一次失重，主要是材料表面吸附的少量气体分子，水和一部分无定型碳的分解。同时说明了碳材料的引入提升了材料的吸附能力。温度进一步上升，T450和T400由于内部碳核的不断分解，在400-580℃之间出现非常明显的失重。通过计算样品的失重百分比，可以得到所有样品的碳材料含量百分比：T500和c-ZnO约为0％，而T400最多，达到了78.2％，与其他的数据一并记载入下表1。As shown in FIG. 3 , FIG. 3 shows thermogravimetric analysis diagrams of different embodiments, which are used to analyze the carbon content in the prepared porous ZnO composite hollow sphere catalyst. It can be seen from Fig. 3 that the porous ZnO composite hollow sphere catalyst T500 prepared in the third embodiment and the commercial c-ZnO have almost no obvious weight loss. However, the porous ZnO composite hollow sphere catalysts prepared in the first embodiment and the second embodiment experienced the first weight loss in the range of 100-400°C, mainly due to the decomposition of a small amount of gas molecules adsorbed on the surface of the material, water and a part of amorphous carbon. At the same time, it shows that the introduction of carbon material improves the adsorption capacity of the material. As the temperature rises further, T450 and T400 will experience very obvious weight loss between 400-580°C due to the continuous decomposition of internal carbon nuclei. By calculating the weight loss percentage of the samples, the carbon material content percentage of all samples can be obtained: T500 and c-ZnO are about 0%, while T400 is the most, reaching 78.2%, which is recorded in the following table 1 together with other data.
表1Table 1
(3)机理分析(3) Mechanism analysis
图4示出了步骤S2中C/ZnO复合材料的形成机理。葡萄糖本身有大量的羟基等含氧基团，经高温水热碳化后形成了内层为芳构化的碳核，外层为大量亲水基团的胶质碳球。羟基是一种极性基团，当连接在芳构化碳核时会容易电离出H+显弱酸性，自身表面带负电。Zeta电势的测试结果显示，碳球的表面由于-OH等基团的作用，带有大量的负电荷。因而当碳球混合在醋酸锌溶液中时，大量Zn2+阳离子会由于静电吸附作用吸附于碳球表面。另一方面，醋酸锌会与碳球表面基团相互作用发生水解反应，生成Zn(OH)2和一些锌系物。FIG. 4 shows the formation mechanism of the C/ZnO composite in step S2. Glucose itself has a large number of oxygen-containing groups such as hydroxyl groups. After high-temperature hydrothermal carbonization, colloidal carbon spheres with aromatized carbon cores in the inner layer and a large number of hydrophilic groups in the outer layer are formed. Hydroxyl is a polar group, when connected to the aromatized carbon nucleus, it will be easily ionized to produce H+, which is weakly acidic, and its surface is negatively charged. The test results of Zeta potential show that the surface of carbon spheres has a lot of negative charges due to the effect of groups such as- OH. Therefore, when carbon spheres are mixed in zinc acetate solution, a large number of Zn2+ cations will be adsorbed on the surface of carbon spheres due to electrostatic adsorption. On the other hand, zinc acetate will interact with the surface groups of carbon spheres to undergo a hydrolysis reaction to generate Zn(OH)2 and some zinc series.
(4)紫外可见漫反射光谱(DRS)(4) UV-Vis Diffuse Reflectance Spectroscopy (DRS)
材料的光吸收对光催化剂的催化效率影响非常明显。如图5所示为样品的紫外可见漫反射光谱。从图5中可以看出，碳球样品表现出从近红外波长到紫外区(800-300nm)全波段的高吸收，这是由于碳材料具有“黑体效应”，它的禁带宽度基本为零，可以吸收所有波段的光。在光催化CO2反应活性测试过程中发现，光照1h之后，整个自制耐热玻璃反应的温度特别是铺满复合催化剂的底部温度明显上升。这个现象证明了碳质材料如石墨烯等具有零禁带的特点，基本可以吸收太阳全光谱波段而造成“局部热效应”，能够增加光催化剂周围温度。因而光生电子会得到更多能量，移动速率加快从而有效地促进电子空穴分离。The light absorption of materials has a significant impact on the catalytic efficiency of photocatalysts. Figure 5 shows the UV-Vis diffuse reflectance spectrum of the sample. It can be seen from Figure 5 that the carbon sphere sample exhibits high absorption from near-infrared wavelengths to the ultraviolet region (800-300nm), which is due to the "black body effect" of carbon materials, and its forbidden band width is basically zero. , can absorb all wavelengths of light. During the photocatalytic CO2 reaction activity test, it was found that the temperature of the whole self-made heat-resistant glass reaction, especially the temperature at the bottom covered with the composite catalyst, increased significantly after 1 hour of light irradiation. This phenomenon proves that carbonaceous materials such as graphene have the characteristics of zero bandgap, which can basically absorb the full spectrum of the sun and cause "local thermal effects", which can increase the temperature around the photocatalyst. Therefore, the photogenerated electrons will get more energy, and the moving speed will be accelerated to effectively promote the separation of electrons and holes.
其他复合样品的在可见光区(800-400nm)光吸收随着煅烧温度的上升而不断下降，商业ZnO最低，规律为T400>T450>T500>c-ZnO。说明复合样品中以煅烧温度控制的碳质材料含量直接影响复合光催化剂的光吸收。而碳含量基本为零的样品T500的光吸收高于c-ZnO主要归因于ZnO空心球结构有利于入射光在球体中散射，使得光吸收有所提升。所有复合样品的谱线都显示出在400nm左右的光吸收阈值，这来源于ZnO的本征吸收。然而，可以发现所有含ZnO样品的光激发的阈值有微小差别，主要是由于煅烧温度影响了晶粒大小，纳米尺寸效应导致ZnO的禁带宽度发生了变化。实验证明，复合光催化剂的可见光吸收有明显提升，主要是来源于空心结构内部的碳材料能够高效地吸收可见光，非常有利于光催化反应效率。The light absorption of other composite samples in the visible light region (800-400nm) decreases with the increase of calcination temperature, and the commercial ZnO is the lowest, and the law is T400>T450>T500>c-ZnO. It shows that the content of carbonaceous material controlled by the calcination temperature in the composite sample directly affects the light absorption of the composite photocatalyst. The light absorption of the sample T500 with almost zero carbon content is higher than that of c-ZnO, mainly due to the fact that the hollow sphere structure of ZnO facilitates the scattering of incident light in the sphere, which improves the light absorption. The spectral lines of all composite samples show an optical absorption threshold around 400 nm, which is derived from the intrinsic absorption of ZnO. However, it can be found that the photoexcitation thresholds of all ZnO-containing samples are slightly different, mainly due to the influence of calcination temperature on the grain size, and the change of the forbidden band width of ZnO due to the nanometer size effect. Experiments have proved that the visible light absorption of the composite photocatalyst has been significantly improved, mainly because the carbon material inside the hollow structure can efficiently absorb visible light, which is very beneficial to the photocatalytic reaction efficiency.
(5)CO2吸附测试分析(5) CO2 adsorption test analysis
CO2分子吸附于催化剂表面是光催化反应重要的第一个步骤。图6示出了多个样品的CO2吸附等温线。其中，样品T400，T450和碳球在低压区(P/P0<0.2)随着CO2气压上升快速上升，这主要来源于碳材料中微孔和小介孔的强吸附能力。吸附量的大小规律与比表面积相一致，也与碳含量正相关。碳核中的离域共轭π键π66与CO2中离域π键(π43)的π-π共轭效应显著提升了复合光催化剂对CO2分子的吸附量。测试结果显示，T400和T450的碳含量较高并且比表面积大，显示出较大的CO2吸附量。而纯碳球(Csp)吸附量低于T400和T450，主要是因为ZnO空心结构对CO2的吸附，同时煅烧处理也改善了碳核的孔结构。丰富的孔结构和高比表面积有利于吸附更多的CO2分子。实验结果说明：除了提升了复合材料的比表面积，ZnO空心结构中的碳核还非常有利于提升复合材料的CO2吸附量。空心球中的碳质材料显著提升了CO2的吸附，对光催化反应的进行是非常有利的。The adsorption ofCO2 molecules on the catalyst surface is an important first step in the photocatalytic reaction. Figure 6 shows theCO2 adsorption isotherms for several samples. Among them, samples T400, T450 and carbon spheres rose rapidly in the low-pressure region (P/P0 <0.2) with the increase of CO2 pressure, which was mainly due to the strong adsorption capacity of micropores and small mesopores in carbon materials. The size law of the adsorption amount is consistent with the specific surface area, and is also positively correlated with the carbon content. The π-π conjugation effect of the delocalized conjugated π bond π66 in the carbon core and the delocalized π bond (π43 ) in CO2 significantly enhanced the adsorption capacity of the composite photocatalyst for CO2 molecules. The test results show that T400 and T450 have higher carbon content and larger specific surface area, showing largerCO2 adsorption capacity. However, the adsorption capacity of pure carbon spheres (Csp) is lower than that of T400 and T450, mainly because of the adsorption ofCO2 by the hollow structure of ZnO, and the calcination treatment also improves the pore structure of the carbon core. The abundant pore structure and high specific surface area are favorable for the adsorption of moreCO2 molecules. The experimental results show that in addition to increasing the specific surface area of the composite material, the carbon core in the ZnO hollow structure is also very beneficial to improving the CO2 adsorption capacity of the composite material. The carbonaceous material in the hollow spheres significantly improves theCO2 adsorption, which is very beneficial for the photocatalytic reaction.
(6)光催化CO2还原性能(6) PhotocatalyticCO2 reduction performance
光催化还原CO2生成太阳能燃料活性测试是将制备的样品处于无氧，充满CO2气体氛围中，光源为模拟太阳光(λ>200nm)。如图7a所示为样品的色谱原图，控制实验中加入光催化剂，反应器中不加入CO2气体并光照一个小时后，发现色谱图没有检测到任何明显谱峰，从而可以排除光催化CO2还原产物的碳元素来源于除实验提供CO2外其他可能碳源。并且可以看到，样品T450和c-ZnO的色谱图出现了相同位置，保留时间约为2.91min的谱峰，指出检测到相同产物甲醇(CH3OH)。而T450色谱峰的峰面积明显大于c-ZnO，说明样品T450光催化反应能够产生更多的CH3OH。更值得注意的是，引入碳材料的T450的电子传输效率明显优于商业ZnO，导致有少量的C2H5OH的产生，如下面反应式所示。Photocatalytic reduction of CO2 to generate solar fuel activity test is to place the prepared sample in an oxygen-free, CO2 gas atmosphere, and the light source is simulated sunlight (λ>200nm). The original chromatogram of the sample is shown in Figure 7a. In the control experiment, photocatalyst was added, and CO2 gas was not added to the reactor and illuminated for one hour. It was found that no obvious peaks were detected in the chromatogram, so that photocatalytic CO could be excluded.2 The carbon element of the reduction product comes from other possible carbon sources except CO2 provided by the experiment. And it can be seen that the chromatograms of samples T450 and c-ZnO have peaks at the same position with a retention time of about 2.91 min, indicating that the same product methanol (CH3 OH) was detected. The peak area of the T450 chromatographic peak is significantly larger than that of c-ZnO, indicating that the photocatalytic reaction of the sample T450 can produce more CH3 OH. What is more noteworthy is that the electron transport efficiency of T450 introduced into carbon materials is significantly better than that of commercial ZnO, resulting in a small amount of C2 H5 OH generation, as shown in the following reaction formula.
CO2+6H++6e–→CH3OH+H2O (1)CO2 +6H+ +6e– →CH3 OH+H2 O (1)
CO2+9H++12e–→C2H5OH+12OH– (2)CO2 +9H+ +12e– → C2 H5 OH+12OH– (2)
图7b显示出复合光催化剂及商业ZnO的光催化CO2转化到CH3OH的产率对比。光催化活性最优的T450的CH3OH产率约为c-ZnO的2倍。而碳含量最多的样品T400光催化反应效率是最低的，主要是由于ZnO空心球内碳核过多，体积较大的碳材料大量吸收入射光，明显影响了半导体ZnO的光激发。碳含量基本为零的T500催化活性也优于商业ZnO的，这是因为样品T500为空心球结构，比表面积大，暴露出的活性位点多，光吸收及吸附能力均优于c-ZnO。实验结果表明：合适的含碳量的TC@ZH复合材料，既能够发挥碳材料的吸光能力，导电能力和CO2吸附位点，又能够避免由于碳过多而发生光屏蔽而影响半导体的光激发作用，对光催化反应效率非常有利。Figure 7b shows the comparison of the photocatalyticCO2 toCH3OH yields of the composite photocatalyst and commercial ZnO. The CH3 OH yield of T450 with the best photocatalytic activity is about 2 times that of c-ZnO. The photocatalytic reaction efficiency of the sample T400 with the most carbon content is the lowest, mainly because there are too many carbon nuclei in the ZnO hollow spheres, and the larger carbon material absorbs a large amount of incident light, which obviously affects the photoexcitation of the semiconductor ZnO. The catalytic activity of T500 with basically zero carbon content is also better than that of commercial ZnO. This is because the sample T500 has a hollow sphere structure with a large specific surface area, more active sites exposed, and better light absorption and adsorption capabilities than c-ZnO. The experimental results show that the TC@ZH composite material with a suitable carbon content can not only exert the light absorption ability, electrical conductivity andCO2 adsorption sites of carbon materials, but also avoid the light shielding caused by too much carbon and affect the light emission of semiconductors. The excitation effect is very beneficial to the photocatalytic reaction efficiency.
(7)电化学阻抗谱(EIS)(7) Electrochemical Impedance Spectroscopy (EIS)
碳材料的独特电子富集和传输能力使得碳基光催化材料材料能够有效地抑制光生电子空穴复合，提升光催化反应效率。电化学阻抗谱用于分析样品的电荷传输效率。如图8所示，示出了样品的电化学阻抗谱。含碳的样品T450和T400的半圆形曲线直径明显小于c-ZnO和T500，说明含碳的复合样品的电荷传输阻抗低于纯ZnO空心球和商业ZnO，电荷传输效率明显上升。并且发现T400的阻抗高于T450，这主要是由于水热碳球本身为无定型碳，高温度的煅烧处理改善了碳材料的结晶性，更加利于电荷的传输。并且高温度煅烧使得碳核在空心结构内部分散得更加均匀，与ZnO球壳内表面接触更加紧密，同样有利提升T450的电荷传输效率。另外，实验结果显示：c-ZnO的电荷传输效率略高于样品T500，这是因为商业ZnO是气相烘烧法合成，结晶度高于500度煅烧制备的T500，高结晶性更有利于电荷的传输。虽然c-ZnO的光生载流子的传输效率高于T500，但T500的空心球结构提供了更多的吸附和反应活性位点，并利于光的散射，所以T500的光催化CO2还原效率更高。复合光催化剂提升的导电性对于光催化反应有着显著的积极影响，基本与光催化CO2还原活性相一致。The unique electron enrichment and transport capabilities of carbon materials enable carbon-based photocatalytic materials to effectively inhibit the recombination of photogenerated electrons and holes and improve the efficiency of photocatalytic reactions. Electrochemical impedance spectroscopy was used to analyze the charge transport efficiency of the samples. As shown in Fig. 8, the electrochemical impedance spectrum of the sample is shown. The diameters of the semicircular curves of carbon-containing samples T450 and T400 are significantly smaller than c-ZnO and T500, indicating that the charge transfer impedance of carbon-containing composite samples is lower than that of pure ZnO hollow spheres and commercial ZnO, and the charge transfer efficiency is significantly increased. It is also found that the impedance of T400 is higher than that of T450, which is mainly due to the fact that the hydrothermal carbon sphere itself is amorphous carbon, and the high-temperature calcination treatment improves the crystallinity of the carbon material, which is more conducive to the transmission of charges. In addition, high-temperature calcination makes the carbon nuclei more uniformly dispersed in the hollow structure and makes closer contact with the inner surface of the ZnO spherical shell, which is also beneficial to improve the charge transport efficiency of T450. In addition, the experimental results show that the charge transport efficiency of c-ZnO is slightly higher than that of the sample T500. This is because the commercial ZnO is synthesized by gas-phase calcination, and the crystallinity is higher than that of T500 prepared by calcination at 500 degrees. High crystallinity is more conducive to charge transfer. transmission. Although the transport efficiency of photogenerated carriers of c-ZnO is higher than that of T500, the hollow sphere structure of T500 provides more active sites for adsorption and reaction, and facilitates the scattering of light, so the photocatalyticCO2 reduction efficiency of T500 is higher high. The enhanced electrical conductivity of the composite photocatalyst has a significant positive effect on the photocatalytic reaction, which is basically consistent with the photocatalyticCO2 reduction activity.
本发明利用简单的离子吸附原理基于碳球模板制备合成了多孔ZnO复合空心球催化剂，并通过调整煅烧温度系统性控制空心球内碳质材料的含量。实验结果发现，当碳含量为约56.4％，光催化还原CO2活性最高。碳材料的引入显著改善了复合光催化剂的可见光吸收和CO2吸附，并且会产生局部热效应，有利于电荷传输。本发明所述的多孔ZnO复合空心球催化剂具有制备方法简单，光催化效果高的有益效果。The invention utilizes a simple ion adsorption principle to prepare and synthesize a porous ZnO composite hollow sphere catalyst based on a carbon sphere template, and systematically controls the content of carbonaceous materials in the hollow sphere by adjusting the calcination temperature. The experimental results found that when the carbon content was about 56.4%, the photocatalyticCO2 reduction activity was the highest. The introduction of carbon materials significantly improves the visible light absorption andCO2 adsorption of the composite photocatalyst, and will generate a local thermal effect, which is beneficial to the charge transport. The porous ZnO composite hollow sphere catalyst of the invention has the beneficial effects of simple preparation method and high photocatalytic effect.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the present invention. within the scope of protection.
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| CN201810117012.0ACN108295832A (en) | 2018-02-06 | 2018-02-06 | A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof |
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| CN201810117012.0ACN108295832A (en) | 2018-02-06 | 2018-02-06 | A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof |
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| CN201810117012.0APendingCN108295832A (en) | 2018-02-06 | 2018-02-06 | A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof |
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