聚苯胺制备和改性及其与氢相互作用研究
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摘要
有机导电聚合物具有众多优良的物理化学性能,在电化学催化、生物传感器、超级电容器、储氢等诸多领域有着广泛的应用前景。在众多的有机导电聚合物中,聚苯胺由于原料廉价易得、合成简单、电导率高、环境稳定性好等特点而备受人们的关注。本文针对聚苯胺在储氢领域的应用进行了初步研究,主要结论如下:
1.采用了合成成本低廉、所得产物更适于储氢应用的合成方法——氧化聚合,以过硫酸铵为氧化剂,采用乳液法、相转移催化以及超声化学法合成了具有不同形貌的盐酸掺杂聚苯胺;氧化剂过硫酸铵与苯胺单体物质量比为1∶1时较佳,在机械搅拌条件下,反应时间在2小时较合适,在超声波存在条件下,只需要5～10分钟反应就可以完成;盐酸浓度对反应产物形貌影响较大,在超声波条件下,合适的盐酸反应浓度(≥1mol/L)可以得到纳米棒状的盐酸掺杂聚苯胺;BET比表面积分析显示,超声化学法合成的聚苯胺具有更大的比表面积,最大可达56.3m~2/g,这与超声波所产生的微射流能够提供更大面积的相接触界面有关;以乙二醇为还原剂,以氯化钯为钯源,通过超声化学法制备了钯掺杂的聚苯胺,XRD图谱显示,超声波对聚苯胺基底没有明显改变,钯是以单质钯存在的。
2.为了研究聚苯胺与氢相互作用,根据容积法原理建立起一套氢吸附测试平台,通过不吸附气体氦气来确定参比槽体积和样品槽剩余体积,这是一种较为准确的测定体积的途径。通过分析,该系统误差主要来源于六个方面,而且都比较难于克服,但在相同条件下,其误差积累基本保持不变,因而可以通过测定一定条件下的本底并扣除之,从而得到更为准确的试验结果。该吸附试验平台适用于氢吸附量较大的样品的测试。用该平台测试聚苯胺的氢吸附量发现其吸附量与系统本底是相当,因此该平台不适于测量聚苯胺的氢吸附量。
3.利用自动吸附仪测量了不同聚苯胺在77K、0～1大气压的氢吸附/脱附等温线。聚苯胺在该条件下的氢吸附/脱附等温线和气凝胶有着很大的区别,主要是由于其吸附机理不一样、吸附能也存在较大差异造成的;市售碱基聚苯胺经盐酸掺杂处理后氢气吸附量可以提高为原来的3倍,自制盐酸掺杂聚苯胺氢吸附量比市售碱基聚苯胺要高,机械搅拌和超声化学法制备的聚苯胺氢气吸附量差别不大;钯掺杂处理能够大大提高聚苯胺的氢气吸附量,这是一条对储氢材料进行改性的很好途径。
4.聚苯胺在高压下吸氢后其电阻率会有明显降低,当置于常压环境中,吸附的氢气能够缓慢释放,电阻率会缓慢回升,十几个小时后氢气能够完全释放。测试材料和氢相互作用前后电阻变化是用来研究材料和氢相互作用机理的一条重要途径。
Organic conductive polymer, on account of their excellent physical and chemical properties, are prominsing in many fileds such as electrochemical catalysis, biosensor, electrochemical capacitor, hydrogen storage and so on. Among conductive polymers, polyaniline(PAn) has attracted considerable interesting due to its availaility, simple synthesis, high conductivity and stability. PAn used as a hydrogen storage material was investigated. The main progresses are presented as follows:
PAn which was synthesized via oxidation polymeization adapt to the application of hydrogen storage and the ammonium persulfate was used as oxidant. PAn doped by hydrochloric acid with different shapes was synthesized via many aproaches such as sono-chemical and emulsion. The oxidant dosage play a key role in the produciton to material ratio and the best ratio of oxidant to anliline monomer is 1:1. hydrochloric acid concentration can affect the polyanline shape. The specific surface area of polyanline which is fabricated by sono-chemical is bigger than the specific surface area of polyanline is bought or is synthesized via other approaches and it is 56.3m~2·g~(-1). PAn doped by palladium was synthesized via sono-chemical and the resul of XRD show palladium elementary substance.
A volumetric apparatus for hydrogen adsorption measurement and experiment methods were fabricated. The volume of comparable vessel and the residual volume of adsorption chamber were measured using helium which is not adsorbed by any materials and exact measuring result can be acquired. The apparatus produces error from six aspects and the error does not change while conditions are same. So the error can be measured and took out. The apparatus for hydrogen adsorption measurement is fit for measuring the samples which can adsorb a mass of hydrogen.
The isotherm of PAn hydrogen adsorption and desoption at low temperature (77K) and low pressure (the high limit is 1×10~6Pa) was measured by Changing the adsorbate gas of the Autosorb-1 Instrument from nitrogen to hydrogen. The isotherm of PAn is different from the isotherm of aerogel and their adsorption mechanism may not be same. After doped by hydrochloric acid the hydrogen adsorption capacity of the merchandise PAn is 3 times than primary. The hydrogen adsorption capacity of the PAn can be increased by doping with palladium.
The resistivity of PAn will reduce after absorb hydrogen under high pressure an the resistivity can slow increase while the hydrogen absorbed release under low pressure.
1.采用了合成成本低廉、所得产物更适于储氢应用的合成方法——氧化聚合,以过硫酸铵为氧化剂,采用乳液法、相转移催化以及超声化学法合成了具有不同形貌的盐酸掺杂聚苯胺;氧化剂过硫酸铵与苯胺单体物质量比为1∶1时较佳,在机械搅拌条件下,反应时间在2小时较合适,在超声波存在条件下,只需要5～10分钟反应就可以完成;盐酸浓度对反应产物形貌影响较大,在超声波条件下,合适的盐酸反应浓度(≥1mol/L)可以得到纳米棒状的盐酸掺杂聚苯胺;BET比表面积分析显示,超声化学法合成的聚苯胺具有更大的比表面积,最大可达56.3m~2/g,这与超声波所产生的微射流能够提供更大面积的相接触界面有关;以乙二醇为还原剂,以氯化钯为钯源,通过超声化学法制备了钯掺杂的聚苯胺,XRD图谱显示,超声波对聚苯胺基底没有明显改变,钯是以单质钯存在的。
2.为了研究聚苯胺与氢相互作用,根据容积法原理建立起一套氢吸附测试平台,通过不吸附气体氦气来确定参比槽体积和样品槽剩余体积,这是一种较为准确的测定体积的途径。通过分析,该系统误差主要来源于六个方面,而且都比较难于克服,但在相同条件下,其误差积累基本保持不变,因而可以通过测定一定条件下的本底并扣除之,从而得到更为准确的试验结果。该吸附试验平台适用于氢吸附量较大的样品的测试。用该平台测试聚苯胺的氢吸附量发现其吸附量与系统本底是相当,因此该平台不适于测量聚苯胺的氢吸附量。
3.利用自动吸附仪测量了不同聚苯胺在77K、0～1大气压的氢吸附/脱附等温线。聚苯胺在该条件下的氢吸附/脱附等温线和气凝胶有着很大的区别,主要是由于其吸附机理不一样、吸附能也存在较大差异造成的;市售碱基聚苯胺经盐酸掺杂处理后氢气吸附量可以提高为原来的3倍,自制盐酸掺杂聚苯胺氢吸附量比市售碱基聚苯胺要高,机械搅拌和超声化学法制备的聚苯胺氢气吸附量差别不大;钯掺杂处理能够大大提高聚苯胺的氢气吸附量,这是一条对储氢材料进行改性的很好途径。
4.聚苯胺在高压下吸氢后其电阻率会有明显降低,当置于常压环境中,吸附的氢气能够缓慢释放,电阻率会缓慢回升,十几个小时后氢气能够完全释放。测试材料和氢相互作用前后电阻变化是用来研究材料和氢相互作用机理的一条重要途径。
Organic conductive polymer, on account of their excellent physical and chemical properties, are prominsing in many fileds such as electrochemical catalysis, biosensor, electrochemical capacitor, hydrogen storage and so on. Among conductive polymers, polyaniline(PAn) has attracted considerable interesting due to its availaility, simple synthesis, high conductivity and stability. PAn used as a hydrogen storage material was investigated. The main progresses are presented as follows:
PAn which was synthesized via oxidation polymeization adapt to the application of hydrogen storage and the ammonium persulfate was used as oxidant. PAn doped by hydrochloric acid with different shapes was synthesized via many aproaches such as sono-chemical and emulsion. The oxidant dosage play a key role in the produciton to material ratio and the best ratio of oxidant to anliline monomer is 1:1. hydrochloric acid concentration can affect the polyanline shape. The specific surface area of polyanline which is fabricated by sono-chemical is bigger than the specific surface area of polyanline is bought or is synthesized via other approaches and it is 56.3m~2·g~(-1). PAn doped by palladium was synthesized via sono-chemical and the resul of XRD show palladium elementary substance.
A volumetric apparatus for hydrogen adsorption measurement and experiment methods were fabricated. The volume of comparable vessel and the residual volume of adsorption chamber were measured using helium which is not adsorbed by any materials and exact measuring result can be acquired. The apparatus produces error from six aspects and the error does not change while conditions are same. So the error can be measured and took out. The apparatus for hydrogen adsorption measurement is fit for measuring the samples which can adsorb a mass of hydrogen.
The isotherm of PAn hydrogen adsorption and desoption at low temperature (77K) and low pressure (the high limit is 1×10~6Pa) was measured by Changing the adsorbate gas of the Autosorb-1 Instrument from nitrogen to hydrogen. The isotherm of PAn is different from the isotherm of aerogel and their adsorption mechanism may not be same. After doped by hydrochloric acid the hydrogen adsorption capacity of the merchandise PAn is 3 times than primary. The hydrogen adsorption capacity of the PAn can be increased by doping with palladium.
The resistivity of PAn will reduce after absorb hydrogen under high pressure an the resistivity can slow increase while the hydrogen absorbed release under low pressure.
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