氧化亚铜纳米结构制备及性能研究
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摘要
本论文采用液相法成功合成出不同形貌和结构的Cu2O多面体颗粒、Cu2O纳米骨架和纳米笼以及Cu2O空心纳米球。同时,对各种形貌和结构Cu2O颗粒的光催化性能、气敏特性及光学性质进行了系统深入的研究。
在80℃液相条件下,以柠檬酸铜络合物和葡萄糖为前驱物,合成具有良好单分散性的Cu2O微／纳米颗粒。调节PVP浓度和反应时间,能够调控合成出一系列不同形貌和结构Cu2O多面体颗粒。PVP选择吸附特性、奥斯特瓦尔德熟化和反应溶液的低过饱和度是形成变化形貌和结构Cu2O多面体颗粒的根本原因。
首次在室温条件下,通过原位选择氧化刻蚀Cu2O去角八面体得到外形完整、高几何对称的Cu2O纳米骨架和纳米笼。调控陈化时间,实现纳米骨架和纳米笼的壁厚和窗口尺寸可控。创造性地设计合理的实验过程,证实PVP选择吸附在Cu2O晶体的{111}面上。Cu2O纳米骨架和纳米笼的形成机理是PVP择优吸附在{111}面,起到保护{111}面的作用,仅{100}面由外向内被氧化刻蚀,从而得到完整的Cu2O空心结构。
系统研究了不同形貌的Cu2O实心颗粒、纳米骨架和纳米笼对罗丹明-B的光催化活性和对H2S的气敏特性,其中六分枝和八面体具有较好的光催化活性和气敏特性,纳米骨架和纳米笼具有更优异的光催化活性和气敏特性。其机理是{111}面为光催化和气敏活性面,空心结构提供更大比表面积和更丰富的活性点,内外表面对光催化都有重要贡献,而且光在空腔内部形成多次反射,提高了光利用率；同时,暴露的刻蚀面也具有较高的催化活性。
采用低温、无模板水热法合成出Cu2O空心纳米球。PVP不仅避免颗粒团聚,提高其单分散性,而且在奥斯特瓦尔德熟化形成空心球过程中起到稳定结晶相作用。TEA起到直接将无定形小颗粒团聚形成球状大颗粒的作用。与实心球相比,Cu2O空心球的光吸收强度显著提高并且出现蓝移,主要原因是由于球壳壁很薄而具有小尺寸效应。
Cu2O is a typical p-type direct band gap semiconductor with a band gap of 2.17 eV and has potential applications in solar energy conversion, electrode materials, sensors, and catalysts. its potential application in catalysts was demonstrated by the discovery that Cu2O could act as a stable photocatalyst for the photochemical decomposition of water into O2 and H2 under visible light irradiation. In this thesis, we report a facile solution-phase route for the mass synthesis of Cu2O crystals with different morphologies, Cu2O nanoframes and nanocages, Cu2O nanospheres. And on the basis of experiment and characterization, we also did an in-depth study on shape, structure, growth, mechanism and catalytic and gas sensor properties. Some important results are obtained.
We report a facile solution-phase route for the mass synthesis of Cu2O crystals with different morphologies in the presence of poly (vinyl pyrrolidone) (PVP) at relatively mild temperature of 80℃. In our system, the morphological evolution from cubes to truncated octahedral(R=1), runcated octahedral(R=1.15), octahedra and nanospheres has been investigated by using different amounts of PVP. As a well-known capping or stabilizing agent, PVP molecules with long chains can be adsorbed to the Cu2O particle surfaces via physical and chemical bonding. When we add PVP into reaction system, it is believed that PVP tends to suppress the growth rate of the {111} planes more than that of the {100} planes, since it interacts more strongly with the {111} facets than with the {100} facets. When the PVP concentration is 1.5 mM, this interaction strength is greatly enhanced, and it could efficiently lower the surface energies of {111} facets. The capping effect of PVP would block the growth on the {111} facets and facilitate the growth on the {100} facets. Further increasing the PVP
concentration to 4.5 mM, perfect octahedral (R=1.73) are obtained due to the further increase of the growth rate on {100} facets relative to the {111} facets. Finally, spherical particles are generated only when the PVP concentration is 9 mM, owing to the high coverage of PVP on all the planes of Cu2O nanocrystals. Presumably, the steric effect of PVP against agglomeration and growth is fulfilled and the Cu2O particles are smaller, leading to an isotropic growth mode and loose spherical particles. A time-dependent morphology evolution experiments are performed by intercepting intermediate products in different reaction stages. The Cu2O crystals including smaller octahedra, star-shaped and star-shaped with six symmetric branches are obtained. Smaller particles are dissolved again and larger particles grow more, which is typical of Ostwald ripening. This preferential growth at six equivalent {100} facets eventually leads to the formation of six symmetric branch structures on the octahedra. A cut of the unit cell over one of its (111) planes reveals the presence of surface Cu atoms with dangling bonds. Thus, this simple comparison should indicate that the {111} faces are higher in surface energy and expected to be more catalytically active than the {100} faces. This series of experiments is the exceptionally high photocatalytic performance of the extended hexapods. This result suggests that Cu2O nanocrystals with more {111} facets can serve as more efficient photocatalysts. Furthermore, Cu2O crystals bounded by the {111} faces contain positively charged copper atoms at the surfaces, which facilitates the absorption of detected gases.
We report low cost, simplicity, green synthetic and efficiency route for Cu2O nanoframes and nanocages with single-crystal walls. Our synthetic strategy involves following processes. First, polyhedra Cu2O particles were prepared by adding weak reductive agent (glucose) into copper citrate complex solution with the use of PVP as capping agents, and then Cu2O nanoframes and nanocages were obtained in situ via the oxidative etching at room temperature. During the hollowing step, the truncated octahedra are selectively etched on the {100} faces. With the increasing aging time, the interior of each truncated octahedra becomes empty increasingly, while the size of the hole in the surface starts to enlarge and to form a frame with relatively thick walls. An important feature of the as-synthesized products is that most of the surface of the six {100} faces is absent. Thus, the Cu2O nanoframes are constructed of hexagonal
{111} skeletons. Our results also demonstrated that PVP has acted as a capping agent and that preferential adsorption occurred on the {111} faces of the Cu2O crystals, which'freeze'the {111} planes to facilitate the formation of hollow structure. It should be noted that, the photocatalytic activity of nanocages particles is higher than the nanoframes. This result further suggests that Cu2O particle with more {111} facets can serve as more efficient photocatalysts. Moreover, the photocatalytic activity of hollow particles is higher than the solid particles. This can be attributed to the hollow structure and higher surface area. The hollow structure can allow the appearance of multiple reflections of light within the interior hollow and lead to the more efficient use of light and improve the photocatalytic activity of Cu2O. Furthermore, the hollow structure particles result in larger surface area and much more capacious interspaces than any solid particles, which can provide sufficient space for the interaction between Cu2O and detected gases.
We demonstrate a template-free hydrothermal method to synthesize Cu2O hollow spheres at 90℃. The key points of the successful realization are that we introduce PVP to improve the stabilization of crystalline phase occurred at a rate commensurate with localized Ostawald ripening and self-transformation for producting Cu2O hollow spheres. Compared with the conventional methods, the present synthetic procedure has the advantages of simplicity, low growth temperature, and efficiency. TEA may serve as surface modifier, which plays a role of "structure directing agent" which directed the aggregation of the building blocks. Furthermore, the observation on a blue-shift of Cu2O hollow spheres can be rationalized by considering that it is largely attributed to the hollowing of the spheres structures.
在80℃液相条件下,以柠檬酸铜络合物和葡萄糖为前驱物,合成具有良好单分散性的Cu2O微／纳米颗粒。调节PVP浓度和反应时间,能够调控合成出一系列不同形貌和结构Cu2O多面体颗粒。PVP选择吸附特性、奥斯特瓦尔德熟化和反应溶液的低过饱和度是形成变化形貌和结构Cu2O多面体颗粒的根本原因。
首次在室温条件下,通过原位选择氧化刻蚀Cu2O去角八面体得到外形完整、高几何对称的Cu2O纳米骨架和纳米笼。调控陈化时间,实现纳米骨架和纳米笼的壁厚和窗口尺寸可控。创造性地设计合理的实验过程,证实PVP选择吸附在Cu2O晶体的{111}面上。Cu2O纳米骨架和纳米笼的形成机理是PVP择优吸附在{111}面,起到保护{111}面的作用,仅{100}面由外向内被氧化刻蚀,从而得到完整的Cu2O空心结构。
系统研究了不同形貌的Cu2O实心颗粒、纳米骨架和纳米笼对罗丹明-B的光催化活性和对H2S的气敏特性,其中六分枝和八面体具有较好的光催化活性和气敏特性,纳米骨架和纳米笼具有更优异的光催化活性和气敏特性。其机理是{111}面为光催化和气敏活性面,空心结构提供更大比表面积和更丰富的活性点,内外表面对光催化都有重要贡献,而且光在空腔内部形成多次反射,提高了光利用率；同时,暴露的刻蚀面也具有较高的催化活性。
采用低温、无模板水热法合成出Cu2O空心纳米球。PVP不仅避免颗粒团聚,提高其单分散性,而且在奥斯特瓦尔德熟化形成空心球过程中起到稳定结晶相作用。TEA起到直接将无定形小颗粒团聚形成球状大颗粒的作用。与实心球相比,Cu2O空心球的光吸收强度显著提高并且出现蓝移,主要原因是由于球壳壁很薄而具有小尺寸效应。
Cu2O is a typical p-type direct band gap semiconductor with a band gap of 2.17 eV and has potential applications in solar energy conversion, electrode materials, sensors, and catalysts. its potential application in catalysts was demonstrated by the discovery that Cu2O could act as a stable photocatalyst for the photochemical decomposition of water into O2 and H2 under visible light irradiation. In this thesis, we report a facile solution-phase route for the mass synthesis of Cu2O crystals with different morphologies, Cu2O nanoframes and nanocages, Cu2O nanospheres. And on the basis of experiment and characterization, we also did an in-depth study on shape, structure, growth, mechanism and catalytic and gas sensor properties. Some important results are obtained.
We report a facile solution-phase route for the mass synthesis of Cu2O crystals with different morphologies in the presence of poly (vinyl pyrrolidone) (PVP) at relatively mild temperature of 80℃. In our system, the morphological evolution from cubes to truncated octahedral(R=1), runcated octahedral(R=1.15), octahedra and nanospheres has been investigated by using different amounts of PVP. As a well-known capping or stabilizing agent, PVP molecules with long chains can be adsorbed to the Cu2O particle surfaces via physical and chemical bonding. When we add PVP into reaction system, it is believed that PVP tends to suppress the growth rate of the {111} planes more than that of the {100} planes, since it interacts more strongly with the {111} facets than with the {100} facets. When the PVP concentration is 1.5 mM, this interaction strength is greatly enhanced, and it could efficiently lower the surface energies of {111} facets. The capping effect of PVP would block the growth on the {111} facets and facilitate the growth on the {100} facets. Further increasing the PVP
concentration to 4.5 mM, perfect octahedral (R=1.73) are obtained due to the further increase of the growth rate on {100} facets relative to the {111} facets. Finally, spherical particles are generated only when the PVP concentration is 9 mM, owing to the high coverage of PVP on all the planes of Cu2O nanocrystals. Presumably, the steric effect of PVP against agglomeration and growth is fulfilled and the Cu2O particles are smaller, leading to an isotropic growth mode and loose spherical particles. A time-dependent morphology evolution experiments are performed by intercepting intermediate products in different reaction stages. The Cu2O crystals including smaller octahedra, star-shaped and star-shaped with six symmetric branches are obtained. Smaller particles are dissolved again and larger particles grow more, which is typical of Ostwald ripening. This preferential growth at six equivalent {100} facets eventually leads to the formation of six symmetric branch structures on the octahedra. A cut of the unit cell over one of its (111) planes reveals the presence of surface Cu atoms with dangling bonds. Thus, this simple comparison should indicate that the {111} faces are higher in surface energy and expected to be more catalytically active than the {100} faces. This series of experiments is the exceptionally high photocatalytic performance of the extended hexapods. This result suggests that Cu2O nanocrystals with more {111} facets can serve as more efficient photocatalysts. Furthermore, Cu2O crystals bounded by the {111} faces contain positively charged copper atoms at the surfaces, which facilitates the absorption of detected gases.
We report low cost, simplicity, green synthetic and efficiency route for Cu2O nanoframes and nanocages with single-crystal walls. Our synthetic strategy involves following processes. First, polyhedra Cu2O particles were prepared by adding weak reductive agent (glucose) into copper citrate complex solution with the use of PVP as capping agents, and then Cu2O nanoframes and nanocages were obtained in situ via the oxidative etching at room temperature. During the hollowing step, the truncated octahedra are selectively etched on the {100} faces. With the increasing aging time, the interior of each truncated octahedra becomes empty increasingly, while the size of the hole in the surface starts to enlarge and to form a frame with relatively thick walls. An important feature of the as-synthesized products is that most of the surface of the six {100} faces is absent. Thus, the Cu2O nanoframes are constructed of hexagonal
{111} skeletons. Our results also demonstrated that PVP has acted as a capping agent and that preferential adsorption occurred on the {111} faces of the Cu2O crystals, which'freeze'the {111} planes to facilitate the formation of hollow structure. It should be noted that, the photocatalytic activity of nanocages particles is higher than the nanoframes. This result further suggests that Cu2O particle with more {111} facets can serve as more efficient photocatalysts. Moreover, the photocatalytic activity of hollow particles is higher than the solid particles. This can be attributed to the hollow structure and higher surface area. The hollow structure can allow the appearance of multiple reflections of light within the interior hollow and lead to the more efficient use of light and improve the photocatalytic activity of Cu2O. Furthermore, the hollow structure particles result in larger surface area and much more capacious interspaces than any solid particles, which can provide sufficient space for the interaction between Cu2O and detected gases.
We demonstrate a template-free hydrothermal method to synthesize Cu2O hollow spheres at 90℃. The key points of the successful realization are that we introduce PVP to improve the stabilization of crystalline phase occurred at a rate commensurate with localized Ostawald ripening and self-transformation for producting Cu2O hollow spheres. Compared with the conventional methods, the present synthetic procedure has the advantages of simplicity, low growth temperature, and efficiency. TEA may serve as surface modifier, which plays a role of "structure directing agent" which directed the aggregation of the building blocks. Furthermore, the observation on a blue-shift of Cu2O hollow spheres can be rationalized by considering that it is largely attributed to the hollowing of the spheres structures.
引文
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