新型改性膨胀石墨的制备及其催化性能的研究
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摘要
膨胀石墨(EG)是由鳞片石墨制备成的一种疏松多孔的蠕虫状物质,具有发达的网络状孔隙结构,较大的比表面积,较高的表面活性,是一种具有较高化学稳定性的,环境友好的廉价液相吸附材料。TiO2是一种新型的廉价无毒的高效光催化材料。以膨胀石墨负载TiO2而得到的复合材料不仅具有吸附性能,而且还具有光催化性能,这为环保材料的研究提供了新的思路和热点。
本文以钛酸正四丁酯为钛源,氯化高铁为铁源,膨胀石墨(EG)为载体,以比较新颖的方法制备出TiO2/EG和TiO2/Fe/EG复合材料,用以对苯酚模拟废水的吸附和光降解研究。主要研究内容包括：
1、采用化学氧化法制备低硫膨胀石墨,研究了膨胀容积的影响因素。以鳞片石墨899为原料,运用四水平五因素正交实验确定最佳工艺条件。以溶胶-凝胶法制备TiO2溶胶以及负载三价铁离子的TiO2溶胶,分别用两种方法将溶胶负载到膨胀石墨上,制成两种不同的负载TiO2的膨胀石墨(TiO2/EG)。采用量筒法分别对膨胀石墨及其复合材料的膨胀体积进行了对比。采用SEM和XRD分别对膨胀石墨及其复合材料的微观形貌和相结构进行了分析。
2、研究了不同pH值、不同温度、不同时间下膨胀石墨对苯酚的吸附性能。对EG和两种不同负载方法制备出的TiO2/EG进行了苯酚的吸附和降解性能做了对比和研究。在各种不同条件下,如：降解时间、苯酚初始浓度、膨胀石墨用量、TiO2负载量、不同的光照条件等,对TiO2/EG去除苯酚进行了研究。对TiO2/Fe/EG去除苯酚的能力做了研究,内容有：三价铁离子的掺杂量对苯酚去除的影响、双氧水存在时,以及苯胺存在时对苯酚去除效果的影响。并初步探讨了TiO2/EG和TiO2/Fe/EG对苯酚的吸附和光降解作用的机理。
结果表明：
1、制备EG的最佳工艺条件为鳞片石墨：HNO3:H3PO4:KMnO4质量比=1：1.65：1.92：0.18；酸化温度为60℃；酸化时间为40 min,微波膨化时间20秒。这样制备出的EG膨胀体积在250 mL/g左右。用先负载后膨胀的新方法制备出来的TiO2/EG比用先膨胀后负载的方法制备出的TiO2/EG具有更大的膨胀体积,外观维持蓬松的蠕虫状态。负载TiO2的膨胀石墨已经形成,且TiO2呈锐钛型。但由于掺铁量小,图谱上显示不明显。
2、EG对苯酚的最佳吸附酸碱条件是pH为7,低温有利于苯酚的吸附。先负载后膨胀的TiO2/EG对苯酚的降解效果优于先膨胀后负载的TiO2/EG。在紫外光下TiO2/EG对苯酚的去除效果最好。掺杂Fe3+可使苯酚在可见光下也能较好地降解。负载载量为35%,Fe3+掺杂量为5%的TiO2/Fe/EG对苯酚的去除能力最强,在苯酚浓度为376.98 mg/L时,TiO2/Fe/EG投加量为3 g/L时,苯酚的去除量可达62.12 mg/g。体系中存在双氧水能促进苯酚的降解,存在苯胺则会减弱苯酚的吸附和降解。
本文选用膨胀石墨作为纳米掺铁二氧化钛催化剂的载体,结合二者的优点,发挥其协同效应,制备出的光催化材料具有成本低,吸附性好,催化活性高等优点。可以作为一种具有良好的吸附降解性能的材料在环境保护中广泛应用。
Expanded graphite(EG) is a worm-like porous material which is produced by natural squama graphite. It has evolutive network-like pore structure, big specific surface area, and high surface-active, it's a kind of cheap environment-friendly liquid phase adsorption with high chemistry stability. TiO2 is a kind of new cheap and non-toxic photochemical catalysis material. The compounds which made by EG and TiO2 not only has the adsorption performance, moreover also has the photochemical catalysis performance, which provided a new idea and a new focus of study on environmental material.
TiO2/EG and TiO2/Fe/EG were successfully prepared with a new method using exfoliated graphite as support tetrabutyl titanate as titanium source and Iron (III) chloride as Fe3+source. These compounds were used to the study of adsorption and photodegradation of phenol synthetic wastewater. The research including:
3、Lower-sulfuric expandable graphite was prepared with chemistry oxidation, and the affecting factors on expandable volume of exfoliated graphite were studied.899 flake graphite as raw material, and use the four levels of five factors in orthogonal test to determine the optimum process conditions. TiO2 and TiO2/Fe sol was prepared with sol-gel process, and then the sol was deposited on EG surface u with two different methods, and made two kind of TiO2/EG. The expansion volumes of these adsorbents were contrasted by using graduated container method. The microstructure and phase of these absorbents were studied by using SEM and XRD.
4、The adsorbability of phenol at different pH, at different times and for different temperatures was studied. The two kinds of TiO2/EG were used to treat phenol synthetic wastewater, and the adsorbability and photodegradation ability were contrasted and studied. The phenol removal effect of TiO2/EG was studied under different conditions, just like:degradation time, phenol initial concentration, the consumption of EG or TiO2/EG, TiO2 inserted amount, different illuminations, and so on. The phenol removal ability of TiO2/Fe/EG was studied, the research including:effects of Fe3+doped amount, the effect of H2O2 and aniline. The adsorption and photodegradation mechanism of TiO2/EG and TiO2/Fe/EG was elementary deduced.
The results showed that:
3、expanded graphite having an exfoliation volume of 250mL/g could be produced under the optimum conditions with the weight ratio of natural flake graphite:nitric acid:phosphoric acid:potassium permanganate being 1:1.65:1.92:0.18, reaction time of 40 min, reaction temperature of 60℃, and microwave expanded time of 20 second. The TiO2/EG which inserting TiO2 first has bigger expansion than the TiO2/EG which expand first, and the TiO2/EG which inserting TiO2 first can keep its appearance as worm-like. TiO2 load the expanded graphite has been formed, and was anatase TiO2. Due to the doping of smaller vanadium, it was not obvious in the map display.
4、The best pH condition of EG adsorption of phenol is 7, low temperature is beneficial to the adsorption of phenol. The TiO2/EG which inserting TiO2 first have more strong capability of adsorption and degradation than the TiO2/EG which expand first. There is good degeneration effect to the phenol by using TiO2/Fe/EG under the ultraviolet ray. Fe3+-dope can made phenol be degeneration well under visible light. It is showed that doped amount is 5%, inserted amount is 35% made TiO2/Fe/EG have the best removal ability of phenol. When phenol concentration is 376.98mg/L时, TiO2/Fe/EG dosage is 3g/L, the removal quantity of phenol is 62.12mg/g. When H2O2 in the system, it can promote the degeneration of phenol. When aniline in the system, it can weaken the adsorption and the degeneration of phenol.
In this paper, expanded graphite as a selection of Fe3+-doped titanium dioxide nano-catalyst carrier. Combined with the advantages of both, to play its synergy photocatalytic preparation of low cost materials, adsorption, and high catalytic activity. Can be used as a degradation of sound absorption properties of materials widely used in environmental protection.
本文以钛酸正四丁酯为钛源,氯化高铁为铁源,膨胀石墨(EG)为载体,以比较新颖的方法制备出TiO2/EG和TiO2/Fe/EG复合材料,用以对苯酚模拟废水的吸附和光降解研究。主要研究内容包括：
1、采用化学氧化法制备低硫膨胀石墨,研究了膨胀容积的影响因素。以鳞片石墨899为原料,运用四水平五因素正交实验确定最佳工艺条件。以溶胶-凝胶法制备TiO2溶胶以及负载三价铁离子的TiO2溶胶,分别用两种方法将溶胶负载到膨胀石墨上,制成两种不同的负载TiO2的膨胀石墨(TiO2/EG)。采用量筒法分别对膨胀石墨及其复合材料的膨胀体积进行了对比。采用SEM和XRD分别对膨胀石墨及其复合材料的微观形貌和相结构进行了分析。
2、研究了不同pH值、不同温度、不同时间下膨胀石墨对苯酚的吸附性能。对EG和两种不同负载方法制备出的TiO2/EG进行了苯酚的吸附和降解性能做了对比和研究。在各种不同条件下,如：降解时间、苯酚初始浓度、膨胀石墨用量、TiO2负载量、不同的光照条件等,对TiO2/EG去除苯酚进行了研究。对TiO2/Fe/EG去除苯酚的能力做了研究,内容有：三价铁离子的掺杂量对苯酚去除的影响、双氧水存在时,以及苯胺存在时对苯酚去除效果的影响。并初步探讨了TiO2/EG和TiO2/Fe/EG对苯酚的吸附和光降解作用的机理。
结果表明：
1、制备EG的最佳工艺条件为鳞片石墨：HNO3:H3PO4:KMnO4质量比=1：1.65：1.92：0.18；酸化温度为60℃；酸化时间为40 min,微波膨化时间20秒。这样制备出的EG膨胀体积在250 mL/g左右。用先负载后膨胀的新方法制备出来的TiO2/EG比用先膨胀后负载的方法制备出的TiO2/EG具有更大的膨胀体积,外观维持蓬松的蠕虫状态。负载TiO2的膨胀石墨已经形成,且TiO2呈锐钛型。但由于掺铁量小,图谱上显示不明显。
2、EG对苯酚的最佳吸附酸碱条件是pH为7,低温有利于苯酚的吸附。先负载后膨胀的TiO2/EG对苯酚的降解效果优于先膨胀后负载的TiO2/EG。在紫外光下TiO2/EG对苯酚的去除效果最好。掺杂Fe3+可使苯酚在可见光下也能较好地降解。负载载量为35%,Fe3+掺杂量为5%的TiO2/Fe/EG对苯酚的去除能力最强,在苯酚浓度为376.98 mg/L时,TiO2/Fe/EG投加量为3 g/L时,苯酚的去除量可达62.12 mg/g。体系中存在双氧水能促进苯酚的降解,存在苯胺则会减弱苯酚的吸附和降解。
本文选用膨胀石墨作为纳米掺铁二氧化钛催化剂的载体,结合二者的优点,发挥其协同效应,制备出的光催化材料具有成本低,吸附性好,催化活性高等优点。可以作为一种具有良好的吸附降解性能的材料在环境保护中广泛应用。
Expanded graphite(EG) is a worm-like porous material which is produced by natural squama graphite. It has evolutive network-like pore structure, big specific surface area, and high surface-active, it's a kind of cheap environment-friendly liquid phase adsorption with high chemistry stability. TiO2 is a kind of new cheap and non-toxic photochemical catalysis material. The compounds which made by EG and TiO2 not only has the adsorption performance, moreover also has the photochemical catalysis performance, which provided a new idea and a new focus of study on environmental material.
TiO2/EG and TiO2/Fe/EG were successfully prepared with a new method using exfoliated graphite as support tetrabutyl titanate as titanium source and Iron (III) chloride as Fe3+source. These compounds were used to the study of adsorption and photodegradation of phenol synthetic wastewater. The research including:
3、Lower-sulfuric expandable graphite was prepared with chemistry oxidation, and the affecting factors on expandable volume of exfoliated graphite were studied.899 flake graphite as raw material, and use the four levels of five factors in orthogonal test to determine the optimum process conditions. TiO2 and TiO2/Fe sol was prepared with sol-gel process, and then the sol was deposited on EG surface u with two different methods, and made two kind of TiO2/EG. The expansion volumes of these adsorbents were contrasted by using graduated container method. The microstructure and phase of these absorbents were studied by using SEM and XRD.
4、The adsorbability of phenol at different pH, at different times and for different temperatures was studied. The two kinds of TiO2/EG were used to treat phenol synthetic wastewater, and the adsorbability and photodegradation ability were contrasted and studied. The phenol removal effect of TiO2/EG was studied under different conditions, just like:degradation time, phenol initial concentration, the consumption of EG or TiO2/EG, TiO2 inserted amount, different illuminations, and so on. The phenol removal ability of TiO2/Fe/EG was studied, the research including:effects of Fe3+doped amount, the effect of H2O2 and aniline. The adsorption and photodegradation mechanism of TiO2/EG and TiO2/Fe/EG was elementary deduced.
The results showed that:
3、expanded graphite having an exfoliation volume of 250mL/g could be produced under the optimum conditions with the weight ratio of natural flake graphite:nitric acid:phosphoric acid:potassium permanganate being 1:1.65:1.92:0.18, reaction time of 40 min, reaction temperature of 60℃, and microwave expanded time of 20 second. The TiO2/EG which inserting TiO2 first has bigger expansion than the TiO2/EG which expand first, and the TiO2/EG which inserting TiO2 first can keep its appearance as worm-like. TiO2 load the expanded graphite has been formed, and was anatase TiO2. Due to the doping of smaller vanadium, it was not obvious in the map display.
4、The best pH condition of EG adsorption of phenol is 7, low temperature is beneficial to the adsorption of phenol. The TiO2/EG which inserting TiO2 first have more strong capability of adsorption and degradation than the TiO2/EG which expand first. There is good degeneration effect to the phenol by using TiO2/Fe/EG under the ultraviolet ray. Fe3+-dope can made phenol be degeneration well under visible light. It is showed that doped amount is 5%, inserted amount is 35% made TiO2/Fe/EG have the best removal ability of phenol. When phenol concentration is 376.98mg/L时, TiO2/Fe/EG dosage is 3g/L, the removal quantity of phenol is 62.12mg/g. When H2O2 in the system, it can promote the degeneration of phenol. When aniline in the system, it can weaken the adsorption and the degeneration of phenol.
In this paper, expanded graphite as a selection of Fe3+-doped titanium dioxide nano-catalyst carrier. Combined with the advantages of both, to play its synergy photocatalytic preparation of low cost materials, adsorption, and high catalytic activity. Can be used as a degradation of sound absorption properties of materials widely used in environmental protection.
引文
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