碳酸镁模板化制备复杂微纳结构及性能表征
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摘要
复杂微纳米结构材料因其独特的物理化学性质,在能量存储、药物运输、催化、传感以及污染物处理等方面具有重要的应用价值,因此制备具有可控微观尺寸与形貌的复杂微纳米结构一直是材料化学领域的研究热点。在复杂微纳米结构制备方法中,模板法被认为是最简单,最有效的合成策略,但仍存在一些难以克服的问题,如模板剂合成成本高,去除条件苛刻等。近些年来,作者所在课题组一直专注于镁资源开发与利用。在此研究期间发现和注意到：合成的碳酸镁具有可调变的微观尺寸与形貌、可控的碳酸镁—碳酸氢镁固液相转化过程、以及相对较大的溶度积常数——较高的复分解反应活性。本论文利用这些性质,在课题组已有研究工作基础上,提出一条由碳酸镁为模板制备复杂微纳米结构氧化物的新思路,使其克服传统模板法中模板成本昂贵,去除条件苛刻等不足。为了验证这一想法,本文首先以碳酸镁模板为切入点,探讨合成过程中反应条件对其微观结构的影响,调变作用及机制；然后对碳酸镁作为模板合成复杂微纳米结构氧化物,并对所得产品的吸附性能(如比表面积,孔结构,有机物染料吸附等)进行了探讨和研究。主要内容和结果如下：
碳酸镁模板的制备研究。在乙醇辅助下热解重镁水制备微纳米级棒状三水碳酸镁,并以三水碳酸镁为前驱体通过相转化合成了微纳米级分级结构碱式碳酸镁和块状无水碳酸镁。系统地研究了反应因素对制备微尺度碳酸镁的影响规律和机理。结果表明在碳酸镁形成过程中,结晶速度对产物的尺寸起着关键的作用,通过调节碳酸氢镁热解过程中的搅拌时间,MgCO3·3H2O在微纳米范围内尺寸可控；同时控制三水碳酸镁的大小,可以调变相转化后碱式碳酸镁和无水碳酸镁的微观尺寸。
碳酸镁循环模板法制备微纳米级中空氧化物的研究。采用棒状三水碳酸镁,花状分级碱式碳酸镁为模板,醇盐为原料,基于溶胶-凝胶和碳酸镁与碳酸氢镁之间相转化过程,成功地合成了SiO2, A12O3, TiO2微米管及SiO2, SiO2-TiO2中空分级结构。探讨模板循环性结果表明,收集的碳酸氢镁滤液经多次循环,仍然能够制备棒状三水碳酸镁模板和花状分级碱式碳酸镁模板。作为潜在的功能材料,合成的中空分级结构SiO2和SiO2-TiO2均展现出优秀的吸附容量和吸附速率
碳酸镁牺牲模板法合成复杂微纳米结构氧化物的研究。以NiO为模型产物,采用碳酸镁为牺牲模板,硝酸镍为原料,合成了管状NiO和复杂分级结构NiO,推测其前驱物生成机制是基于柯肯达尔效应和复分解反应。将这种方法扩展到其他氧化物,成功合成了Fe2O3,Co3O、Gd2O3微米管,和Gd2O3分级结构。合成的分级结构NiO和Fe203的展现出较高的吸附容量和优异的吸附速率,有望应用于催化、能源与环境领域。
碳酸镁为前驱体热解制备微纳米级氧化镁的研究。系统地探讨了反应条件对氧化镁结构及吸附性能的影响,结果表明煅烧微纳米级碳酸镁颗粒能够得到相应尺寸和形貌的氧化镁,碳酸镁前驱体起到了模板作用。煅烧温度、升温速率、前驱体尺寸和形貌对最终产物的结构无明显影响,但却均对氧化镁吸附性能产生影响。将氧化镁用于阴离子染料刚果红吸附,管状分级结构氧化镁表现出超强的刚果红吸附能力,其最大吸附量高达4400mg/g,是目前已报道刚果红吸附剂的数倍甚至是数十倍；对吸附刚果红的氧化镁进行循环再生处理,通过二氧化碳和水溶解氧化镁生成碳酸氢镁溶液,同时使用H202光催化处理碳酸氢镁溶液中的刚果红,脱色后的碳酸氢镁能够成功用于循环制备氧化镁纳米吸附剂。
Complex micro/nanostructures have received considerable attention due to their unique physical and chemical properties and promising applications, such as energy storage, drug delivery, catalysis, sensor and water treatment. Up to now, templating method has been proved to the most straight-forward, versatile and effective approach for fabricating complex micro-/nanostructures, but some difficulties, such as high cost and hard removal condition of template are still hardly overcome. Recently, our group has paid much attention on the development and utilization of magnesium resources. During this time, the magnesium carbonate (MC) have interested us because of its list features:tunable particle size and morphology, controllable phase transformation process (MC+CO2←→Mg(HCO3)2), higher solubility product—better chemical activity. Base on these, a new synthetic concept—MC templated method was proposed to prepare complex micro/nanostructures for avoiding high cost and hard removal condition in the traditional template method. To test this idea, we have systemically investigated the tunable influence and mechanism of reaction condition on the morphologies of MC template firstly in this doctoral dissertation. Then, employed MC as recyclable and sacrificial template for fabricating complex micro/nanostructures and relative adsorption performance (such as specific surface area, pore structure and organic dye adsorption, etc.) of the products were discussed. The main points and contents are summarized as follows:
Synthesis of the magnesium carbonates templates. MgCO3·3H2O microrods were synthesized via a thermal-decomposition process in the presence of ethanol with Mg(HCCO3)2as the reactant. Meanwhile, microscale hierarchical4MgCO3·Mg(OH)2·4H2O and cubelike MgCO3were prepared by phase transformation method using MgCO3·3H2O as precursor. And the influence rule and mechanism of reaction condition on MC were systemically investigated. The results show that the crystallization rate plays key role in the size control of product. The size of MgCO3·3H2O was determined by stirring speed, while the4MgCO3·Mg(OH)2·4H2O and MgCO3can be controlled by size of MgCO3·3H2O precursor.
Use of magnesium carbonates as recycle template for fabricating hollow structures. The SiO2, TiO2, Al2O3microtubes and SiO2, TiO2-SiO2hierarchical structures were successfully synthesized via sol-gel and phase transformation process with the MC as template and alkoxide as raw materials. The Mg(HCO3)2filtrate was used for recycling MC template, in which the reborn templates have similar morphology and size with the initial one. The as-prepared SiO2, TiO2-SiO2hierarchical structures exhibit high adsorption capacity and rate, which can be candidate for potential functional absorption materials.
Use of magnesium carbonates as sacrificial template for fabricating complex structures. NiO microtube and hierarchical structure as a representative was synthesized by using MC as template and Ni(NO3)2as raw materials. The formation mechanism of hollow and hierarchical structure is based on kirkendall effect and replacement reaction. Besides, Fe2O3, CO3O4, Gd2O3microtubes and Fe2O3, Gd2O3hierarchical structures were also synthesized via this similar route. Hierarchical Fe2O3and NiO show high adsorption capacity and rate when applied as adsorption materials.
Use of magnesium carbonates precursors as templates for preparing MgO. The influence of reaction conditions on the morphologies of MgO and adsorption performance were systemically investigated. The result shows that the MgO micro/nanostructures can be obtained through calcining MC and keep the template morphology, what's more, the calcination temperature, heating rate, size and morphology of MC have no evident effect on the morphology of MgO but its adsorption properties. Tubular hierarchical MgO shows superior adsorption capacity of Congo red (up to4400mg/g), which is much higher than the reported adsorbents. After adsorption, the material was dissolved by CO2-H2O acid into Mg(HCO3)2for achieving recycling MgO nanoadsorbent while the Congo red was treated through H2O2photocatalytic oxidation.
碳酸镁模板的制备研究。在乙醇辅助下热解重镁水制备微纳米级棒状三水碳酸镁,并以三水碳酸镁为前驱体通过相转化合成了微纳米级分级结构碱式碳酸镁和块状无水碳酸镁。系统地研究了反应因素对制备微尺度碳酸镁的影响规律和机理。结果表明在碳酸镁形成过程中,结晶速度对产物的尺寸起着关键的作用,通过调节碳酸氢镁热解过程中的搅拌时间,MgCO3·3H2O在微纳米范围内尺寸可控；同时控制三水碳酸镁的大小,可以调变相转化后碱式碳酸镁和无水碳酸镁的微观尺寸。
碳酸镁循环模板法制备微纳米级中空氧化物的研究。采用棒状三水碳酸镁,花状分级碱式碳酸镁为模板,醇盐为原料,基于溶胶-凝胶和碳酸镁与碳酸氢镁之间相转化过程,成功地合成了SiO2, A12O3, TiO2微米管及SiO2, SiO2-TiO2中空分级结构。探讨模板循环性结果表明,收集的碳酸氢镁滤液经多次循环,仍然能够制备棒状三水碳酸镁模板和花状分级碱式碳酸镁模板。作为潜在的功能材料,合成的中空分级结构SiO2和SiO2-TiO2均展现出优秀的吸附容量和吸附速率
碳酸镁牺牲模板法合成复杂微纳米结构氧化物的研究。以NiO为模型产物,采用碳酸镁为牺牲模板,硝酸镍为原料,合成了管状NiO和复杂分级结构NiO,推测其前驱物生成机制是基于柯肯达尔效应和复分解反应。将这种方法扩展到其他氧化物,成功合成了Fe2O3,Co3O、Gd2O3微米管,和Gd2O3分级结构。合成的分级结构NiO和Fe203的展现出较高的吸附容量和优异的吸附速率,有望应用于催化、能源与环境领域。
碳酸镁为前驱体热解制备微纳米级氧化镁的研究。系统地探讨了反应条件对氧化镁结构及吸附性能的影响,结果表明煅烧微纳米级碳酸镁颗粒能够得到相应尺寸和形貌的氧化镁,碳酸镁前驱体起到了模板作用。煅烧温度、升温速率、前驱体尺寸和形貌对最终产物的结构无明显影响,但却均对氧化镁吸附性能产生影响。将氧化镁用于阴离子染料刚果红吸附,管状分级结构氧化镁表现出超强的刚果红吸附能力,其最大吸附量高达4400mg/g,是目前已报道刚果红吸附剂的数倍甚至是数十倍；对吸附刚果红的氧化镁进行循环再生处理,通过二氧化碳和水溶解氧化镁生成碳酸氢镁溶液,同时使用H202光催化处理碳酸氢镁溶液中的刚果红,脱色后的碳酸氢镁能够成功用于循环制备氧化镁纳米吸附剂。
Complex micro/nanostructures have received considerable attention due to their unique physical and chemical properties and promising applications, such as energy storage, drug delivery, catalysis, sensor and water treatment. Up to now, templating method has been proved to the most straight-forward, versatile and effective approach for fabricating complex micro-/nanostructures, but some difficulties, such as high cost and hard removal condition of template are still hardly overcome. Recently, our group has paid much attention on the development and utilization of magnesium resources. During this time, the magnesium carbonate (MC) have interested us because of its list features:tunable particle size and morphology, controllable phase transformation process (MC+CO2←→Mg(HCO3)2), higher solubility product—better chemical activity. Base on these, a new synthetic concept—MC templated method was proposed to prepare complex micro/nanostructures for avoiding high cost and hard removal condition in the traditional template method. To test this idea, we have systemically investigated the tunable influence and mechanism of reaction condition on the morphologies of MC template firstly in this doctoral dissertation. Then, employed MC as recyclable and sacrificial template for fabricating complex micro/nanostructures and relative adsorption performance (such as specific surface area, pore structure and organic dye adsorption, etc.) of the products were discussed. The main points and contents are summarized as follows:
Synthesis of the magnesium carbonates templates. MgCO3·3H2O microrods were synthesized via a thermal-decomposition process in the presence of ethanol with Mg(HCCO3)2as the reactant. Meanwhile, microscale hierarchical4MgCO3·Mg(OH)2·4H2O and cubelike MgCO3were prepared by phase transformation method using MgCO3·3H2O as precursor. And the influence rule and mechanism of reaction condition on MC were systemically investigated. The results show that the crystallization rate plays key role in the size control of product. The size of MgCO3·3H2O was determined by stirring speed, while the4MgCO3·Mg(OH)2·4H2O and MgCO3can be controlled by size of MgCO3·3H2O precursor.
Use of magnesium carbonates as recycle template for fabricating hollow structures. The SiO2, TiO2, Al2O3microtubes and SiO2, TiO2-SiO2hierarchical structures were successfully synthesized via sol-gel and phase transformation process with the MC as template and alkoxide as raw materials. The Mg(HCO3)2filtrate was used for recycling MC template, in which the reborn templates have similar morphology and size with the initial one. The as-prepared SiO2, TiO2-SiO2hierarchical structures exhibit high adsorption capacity and rate, which can be candidate for potential functional absorption materials.
Use of magnesium carbonates as sacrificial template for fabricating complex structures. NiO microtube and hierarchical structure as a representative was synthesized by using MC as template and Ni(NO3)2as raw materials. The formation mechanism of hollow and hierarchical structure is based on kirkendall effect and replacement reaction. Besides, Fe2O3, CO3O4, Gd2O3microtubes and Fe2O3, Gd2O3hierarchical structures were also synthesized via this similar route. Hierarchical Fe2O3and NiO show high adsorption capacity and rate when applied as adsorption materials.
Use of magnesium carbonates precursors as templates for preparing MgO. The influence of reaction conditions on the morphologies of MgO and adsorption performance were systemically investigated. The result shows that the MgO micro/nanostructures can be obtained through calcining MC and keep the template morphology, what's more, the calcination temperature, heating rate, size and morphology of MC have no evident effect on the morphology of MgO but its adsorption properties. Tubular hierarchical MgO shows superior adsorption capacity of Congo red (up to4400mg/g), which is much higher than the reported adsorbents. After adsorption, the material was dissolved by CO2-H2O acid into Mg(HCO3)2for achieving recycling MgO nanoadsorbent while the Congo red was treated through H2O2photocatalytic oxidation.
引文
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