炭微球的水热制备、表征及活化
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摘要
与传统炭材料相比,球形炭材料特殊几何形状使其具有独特的优势：球形结构完整,表面光滑,粒径均一,填充密度高,耐磨性好,机械强度高等,目前已广泛用于电极、吸附剂、催化剂载体及化学防护等领域。
本论文以葡萄糖为原料,采用水热法制备炭球。并讨论了水热反应温度、反应时间、葡萄糖浓度及二次水热对炭球的影响。利用元素分析、扫描电镜(SEM)、红外光谱分析(FTIR)、X射线衍射(XRD)、光电子能谱(XPS)等方法对产物的粒径、形貌、化学结构进行分析。结果表明：以葡萄糖为原料,采用水热法,制备粒径在300-1200 nm的炭球。炭球的粒径均一、表面光滑、球形结构完整,水热制备过程中可通过改变葡萄糖的浓度,水热反应时间,温度调节炭球的形貌、粒径、均一度及化学结构。炭球的粒径随水热温度的升高而增大,球形度及粒径的均一度随之先增大后减小；反应时间对球体的粒径影响不大但对其球形度及球体间的交联现象影响较大：随反应时间的延长,球形度降低,球体间的交联现象增加；炭球的粒径随葡萄糖的浓度增大而增加,其球形度、表面光滑度及粒径的均一度变化不大。通过对炭球化学结构分析可知,炭球由C、H、O三种元素组成,其中O含量在30%以上,球体表面有大量含氧官能团(以-OH、C=O为主),含氧官能团的种类、数量均受水热反应条件影响。葡萄糖在水热过程中经羟醛缩合、芳环化反应聚合成晶核,再经炭化,陈化得到炭球。随水热温度、时间及葡萄糖浓度的增大,芳环化更加完全；葡萄糖浓度的增大有助于羟醛过程的发生。
以炭球为吸附剂,并以Pb2+为模型物,通过原子吸收光谱检测炭球的吸附性能。结果表明,炭球对Pb2+的最大饱和吸附量约为2.4 mmol/g,其表面的含氧官能团与金属离子形成化学键为吸附提供了活性点。
以炭球为前驱体,以KOH为活化剂,分别讨论了研磨法、浸渍法制备多孔炭微球。经讨论,研磨法易导致前驱体球形结构的破坏。浸渍法能得到球形结构完整、表面光滑、比表面积和孔容积较大的多孔炭微球,其孔隙结构以微孔为主。活化过程中,活化温度、活化时间、浸渍比均对产物的形貌、粒径及孔结构影响较大。经分析认为,炭球经“汽化”、“活化”得到多孔炭微球。
Compared with traditional carbon material, spherical carbonous materials with specific advantages, due to its unique geometrical structure, have good shape, smooth outer surface, monodispersed size and high dentisity, which were used in the areas of electronic, adsorbent, catalyst, chemical protection and so on.
This synthesis was focused on the preparation of carbon sphere in a glucose hydrothermal treatment. The experimental conditions (hydrothermal temperature, reaction time, glucose concentration and a second treatment) were investigated, which play the key role in the shape and chemical structural control. Scanning electron microscopy (SEM), elemental C/H/O chemical analysis, Fourier transform diffuse reflectance infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) were applied in identifying its shapes, sizes and functional groups. It can be noted that, carbon spheres with smooth outer surface, tunable and monodispersed size and perfect spherical shape were prepared in 300-1200 nm. With the increasing temperature, its diameter increase obviously, however, its morphology and monidisperity changed without a simple tendency. The reaction time plays an important role in shape-control, but has few relationships with its diameter. Extending feeding time, CS with irregular shapes (such as peanut shape, liner strucutre) appears, due to the fusion. Higher glucose concentration is available to the formation of larger spheres with good morphology. CS is consisted of C, H and O, a higher oxygen content in the core. The ratios of O/C are about 35%, indicating large numbers of functional groups in CS. The number of functional groups (mainly -OH and C=O) on the outer surface were determined by experimental factors.
The possible mechanism of CS may maintain two steps, which were "nucleation" and "growth of nuclea". A second hydrothermal treatment separating the process of "nucleation" and "the growth process" effectively is helpful to prepare a larger CS with smooth outer surface, prefect spherical morphology and a narrow size distribution. The process was named as "aging".
The maximum adsorption capacity of CS to Pb2+ was 2.4 mmol/g, which is bigger than other traditional adsorbent materials. The higher adsorption resulted from ionic bonds or covalent bonds between oxygen-containing groups on the surface and Pb2+.
Porous carbon spheres (PCS) were prepared by KOH activation. Two different methods were applied to mix KOH and CS, which were mechanical mixing and immersion method. It resulted that PCS has irregular morphologies and various sizes following the mechanical mixing, which suggested the process of mechanical mixing is unsuitable to PCS. PCS prepared after a process of immersion were discussed. CS activated at 350℃for 30 min under nitrogen enviroment were more suitable to the preparation of PCS than CS. PCS with perfect spherical structure, smooth outer-surface, small size and a narrow distribution were prepared at 700℃for 60 min under nitrogen enviroment, its BET surface areas 967.19 m2/g, pore volumes 0.453 cm3/g, whereas the ratio of micropores volume is 88.3%. The Process of KOH activation includes "gasification" and "activation".
本论文以葡萄糖为原料,采用水热法制备炭球。并讨论了水热反应温度、反应时间、葡萄糖浓度及二次水热对炭球的影响。利用元素分析、扫描电镜(SEM)、红外光谱分析(FTIR)、X射线衍射(XRD)、光电子能谱(XPS)等方法对产物的粒径、形貌、化学结构进行分析。结果表明：以葡萄糖为原料,采用水热法,制备粒径在300-1200 nm的炭球。炭球的粒径均一、表面光滑、球形结构完整,水热制备过程中可通过改变葡萄糖的浓度,水热反应时间,温度调节炭球的形貌、粒径、均一度及化学结构。炭球的粒径随水热温度的升高而增大,球形度及粒径的均一度随之先增大后减小；反应时间对球体的粒径影响不大但对其球形度及球体间的交联现象影响较大：随反应时间的延长,球形度降低,球体间的交联现象增加；炭球的粒径随葡萄糖的浓度增大而增加,其球形度、表面光滑度及粒径的均一度变化不大。通过对炭球化学结构分析可知,炭球由C、H、O三种元素组成,其中O含量在30%以上,球体表面有大量含氧官能团(以-OH、C=O为主),含氧官能团的种类、数量均受水热反应条件影响。葡萄糖在水热过程中经羟醛缩合、芳环化反应聚合成晶核,再经炭化,陈化得到炭球。随水热温度、时间及葡萄糖浓度的增大,芳环化更加完全；葡萄糖浓度的增大有助于羟醛过程的发生。
以炭球为吸附剂,并以Pb2+为模型物,通过原子吸收光谱检测炭球的吸附性能。结果表明,炭球对Pb2+的最大饱和吸附量约为2.4 mmol/g,其表面的含氧官能团与金属离子形成化学键为吸附提供了活性点。
以炭球为前驱体,以KOH为活化剂,分别讨论了研磨法、浸渍法制备多孔炭微球。经讨论,研磨法易导致前驱体球形结构的破坏。浸渍法能得到球形结构完整、表面光滑、比表面积和孔容积较大的多孔炭微球,其孔隙结构以微孔为主。活化过程中,活化温度、活化时间、浸渍比均对产物的形貌、粒径及孔结构影响较大。经分析认为,炭球经“汽化”、“活化”得到多孔炭微球。
Compared with traditional carbon material, spherical carbonous materials with specific advantages, due to its unique geometrical structure, have good shape, smooth outer surface, monodispersed size and high dentisity, which were used in the areas of electronic, adsorbent, catalyst, chemical protection and so on.
This synthesis was focused on the preparation of carbon sphere in a glucose hydrothermal treatment. The experimental conditions (hydrothermal temperature, reaction time, glucose concentration and a second treatment) were investigated, which play the key role in the shape and chemical structural control. Scanning electron microscopy (SEM), elemental C/H/O chemical analysis, Fourier transform diffuse reflectance infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) were applied in identifying its shapes, sizes and functional groups. It can be noted that, carbon spheres with smooth outer surface, tunable and monodispersed size and perfect spherical shape were prepared in 300-1200 nm. With the increasing temperature, its diameter increase obviously, however, its morphology and monidisperity changed without a simple tendency. The reaction time plays an important role in shape-control, but has few relationships with its diameter. Extending feeding time, CS with irregular shapes (such as peanut shape, liner strucutre) appears, due to the fusion. Higher glucose concentration is available to the formation of larger spheres with good morphology. CS is consisted of C, H and O, a higher oxygen content in the core. The ratios of O/C are about 35%, indicating large numbers of functional groups in CS. The number of functional groups (mainly -OH and C=O) on the outer surface were determined by experimental factors.
The possible mechanism of CS may maintain two steps, which were "nucleation" and "growth of nuclea". A second hydrothermal treatment separating the process of "nucleation" and "the growth process" effectively is helpful to prepare a larger CS with smooth outer surface, prefect spherical morphology and a narrow size distribution. The process was named as "aging".
The maximum adsorption capacity of CS to Pb2+ was 2.4 mmol/g, which is bigger than other traditional adsorbent materials. The higher adsorption resulted from ionic bonds or covalent bonds between oxygen-containing groups on the surface and Pb2+.
Porous carbon spheres (PCS) were prepared by KOH activation. Two different methods were applied to mix KOH and CS, which were mechanical mixing and immersion method. It resulted that PCS has irregular morphologies and various sizes following the mechanical mixing, which suggested the process of mechanical mixing is unsuitable to PCS. PCS prepared after a process of immersion were discussed. CS activated at 350℃for 30 min under nitrogen enviroment were more suitable to the preparation of PCS than CS. PCS with perfect spherical structure, smooth outer-surface, small size and a narrow distribution were prepared at 700℃for 60 min under nitrogen enviroment, its BET surface areas 967.19 m2/g, pore volumes 0.453 cm3/g, whereas the ratio of micropores volume is 88.3%. The Process of KOH activation includes "gasification" and "activation".
引文
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