TiO_2纳米带的制备、改性及光催化活性研究
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摘要
本文以普通的工业二氧化钛粉体为前驱体,通过水热法制备了未掺杂和银元素及氮元素掺杂的二氧化钛纳米带。用扫描电镜、X射线衍射、X光电子能谱、比表面积、红外光谱等手段对产物进行表征和分析,并在紫外-可见-甲基橙体系中研究其光催化性能。
研究表明:所制备的二氧化钛均为带状,直径多在50～300nm之间,长度可达几十微米。并且随着煅烧温度的升高,团聚现象逐渐减小,分散性越来越好。银和氮元素的引入并没有改变TiO2纳米带的整体形貌,但氮的引入对纳米带的生长有一定的抑制作用,而且银和氮元素的掺杂改性都抑制了TiO2由无定形向锐钛矿转变及由锐钛矿向金红石的相转变过程。
水热法制备的二氧化钛纳米带在一定煅烧温度范围内,随着温度的升高,其催化活性有所提高;催化活性随煅烧时间增加而增大,3h后煅烧时间对催化活性的影响不大;催化剂用量为2 g/L,甲基橙初始浓度较低时,其光催化效果较佳。通过对银元素掺杂的二氧化钛纳米带的研究,发现银元素的掺杂存在一个最佳的掺杂量,。高于或低于此掺杂量,光催化效率均下降。在最佳负载量0.1(w/w)%时,Ag/TiO2纳米带的活性比纯TiO2纳米带高22%左右。采用前期掺银方式所制得催化剂明显优于后期掺银所制得催化剂,而且掺银二氧化钛纳米带的光催化活性优于纳米粒子。
通过对氮元素掺杂的二氧化钛纳米带的研究,发现样品的晶化程度随着煅烧温度的升高而增大,而BET比表面积则随之减少。掺杂后的晶粒尺寸比不掺杂的要小,且掺杂浓度越高,晶粒越小,二氧化钛的比表面积则越大。氮元素的掺杂也存在一个最佳掺杂量,当n(N):n(Ti)=4:1时,所制得的N/TiO2纳米带的可见光活性较高。本文通过比较三种不同的氮前驱体制备的N/TiO2纳米带的可见光催化活性,发现以三乙胺为前驱体所制得的N/TiO2纳米带的活性较高。通过比较三种不同的方法制备N/ TiO2纳米带,发现在水热反应前引入氮元素所制得的催化剂可见光活性较高。虽然氮元素的引入提高了TiO2纳米带的可见光活性,但使TiO2纳米带紫外光催化活性有所下降。
In this article,both pure and Ag,N doped TiO2 nanobelts were prepared by hydrothermal method using industrial TiO2 power as precursors.The properties of products were characterized by SEM,XRD,XPS,BET and FTIR.The performance of TiO2 nanobelts promoting photodegradation of methyl orange was studied.
The results show that the diameter of nanobelt was about 50nm to 300nm with a length about dozens of micron.The higher the calcination temperatures of TiO2 nanobelt,the better was the dispersed state of TiO2 nanobelts.The shape of Ag,N doped TiO2 nanobelts was not changed.Nitrogen can control the growth of TiO2 nanobelts.Both silver and nitrogen can control the process that unformed TiO2 was changed to anatase and rutile.
In a range of calcination temperatures,The higher the calcination temperatures and the calcination time of TiO2 nanobelts,the better was the photocatalytic activity of TiO2 nanobelts.And the photocatalytic activity of TiO2 nanobelts was not changed after 3h.When the content of TiO2 nanobelt was 2g/L and the content of methyl orange was low,the photocatalytic activity of TiO2 nanobelts was the better.
The modification of Ag doped TiO2 nanobelts was studied. The results show that there was the most appropriate doping ratio of Ag for Ag-doped TiO2 nanobelts.The photocatalytic ability of Ag -doped TiO2 nanobelts for degradation of methyl orange will deteriorate when the doping level was both higher and lower than the best value. When the doping ratio was 0.1(w/w)%, the activity of Ag-doped TiO2 nanobelts was higher than pure TiO2 nanobelts around 22%. Ag-doped TiO2 nanobelts prepared by preceding type were better than by upper type. The photocatalytic properties of Ag-doped TiO2 nanobelts were better than that of nanoparticles.
The modification of N-doped TiO2 nanobelts was studied. The results show that the calcination temperature was higher,the degree of crystallization was better and the specific surface area was smaller.The size of N-doped TiO2 nanobelts was smaller than pure TiO2 nanobelts.When the doping concentration was higher,the size of samples was smaller and the specific surface area was biger. there was also the most appropriate doping ratio of N for N-doped TiO2 nanobelts.When the doping ratio was n(N):n(Ti)=4:1,The photocatalytic ability of N-doped TiO2 nanobelts was the best. N-doped TiO2 nanobelts were prepared using ammonia、triethylamineas、triethanolamine as precursors.Compared to the three samples, The photocatalytic ability of N-doped TiO2 using triethylamineas as precursors was the best. The photocatalytic ability of N-doped TiO2 was the better when N was joined before hydrothermal reaction. The photocatalytic ability of N-doped TiO2 was improved under UV light,but was receded under visible light.
研究表明:所制备的二氧化钛均为带状,直径多在50～300nm之间,长度可达几十微米。并且随着煅烧温度的升高,团聚现象逐渐减小,分散性越来越好。银和氮元素的引入并没有改变TiO2纳米带的整体形貌,但氮的引入对纳米带的生长有一定的抑制作用,而且银和氮元素的掺杂改性都抑制了TiO2由无定形向锐钛矿转变及由锐钛矿向金红石的相转变过程。
水热法制备的二氧化钛纳米带在一定煅烧温度范围内,随着温度的升高,其催化活性有所提高;催化活性随煅烧时间增加而增大,3h后煅烧时间对催化活性的影响不大;催化剂用量为2 g/L,甲基橙初始浓度较低时,其光催化效果较佳。通过对银元素掺杂的二氧化钛纳米带的研究,发现银元素的掺杂存在一个最佳的掺杂量,。高于或低于此掺杂量,光催化效率均下降。在最佳负载量0.1(w/w)%时,Ag/TiO2纳米带的活性比纯TiO2纳米带高22%左右。采用前期掺银方式所制得催化剂明显优于后期掺银所制得催化剂,而且掺银二氧化钛纳米带的光催化活性优于纳米粒子。
通过对氮元素掺杂的二氧化钛纳米带的研究,发现样品的晶化程度随着煅烧温度的升高而增大,而BET比表面积则随之减少。掺杂后的晶粒尺寸比不掺杂的要小,且掺杂浓度越高,晶粒越小,二氧化钛的比表面积则越大。氮元素的掺杂也存在一个最佳掺杂量,当n(N):n(Ti)=4:1时,所制得的N/TiO2纳米带的可见光活性较高。本文通过比较三种不同的氮前驱体制备的N/TiO2纳米带的可见光催化活性,发现以三乙胺为前驱体所制得的N/TiO2纳米带的活性较高。通过比较三种不同的方法制备N/ TiO2纳米带,发现在水热反应前引入氮元素所制得的催化剂可见光活性较高。虽然氮元素的引入提高了TiO2纳米带的可见光活性,但使TiO2纳米带紫外光催化活性有所下降。
In this article,both pure and Ag,N doped TiO2 nanobelts were prepared by hydrothermal method using industrial TiO2 power as precursors.The properties of products were characterized by SEM,XRD,XPS,BET and FTIR.The performance of TiO2 nanobelts promoting photodegradation of methyl orange was studied.
The results show that the diameter of nanobelt was about 50nm to 300nm with a length about dozens of micron.The higher the calcination temperatures of TiO2 nanobelt,the better was the dispersed state of TiO2 nanobelts.The shape of Ag,N doped TiO2 nanobelts was not changed.Nitrogen can control the growth of TiO2 nanobelts.Both silver and nitrogen can control the process that unformed TiO2 was changed to anatase and rutile.
In a range of calcination temperatures,The higher the calcination temperatures and the calcination time of TiO2 nanobelts,the better was the photocatalytic activity of TiO2 nanobelts.And the photocatalytic activity of TiO2 nanobelts was not changed after 3h.When the content of TiO2 nanobelt was 2g/L and the content of methyl orange was low,the photocatalytic activity of TiO2 nanobelts was the better.
The modification of Ag doped TiO2 nanobelts was studied. The results show that there was the most appropriate doping ratio of Ag for Ag-doped TiO2 nanobelts.The photocatalytic ability of Ag -doped TiO2 nanobelts for degradation of methyl orange will deteriorate when the doping level was both higher and lower than the best value. When the doping ratio was 0.1(w/w)%, the activity of Ag-doped TiO2 nanobelts was higher than pure TiO2 nanobelts around 22%. Ag-doped TiO2 nanobelts prepared by preceding type were better than by upper type. The photocatalytic properties of Ag-doped TiO2 nanobelts were better than that of nanoparticles.
The modification of N-doped TiO2 nanobelts was studied. The results show that the calcination temperature was higher,the degree of crystallization was better and the specific surface area was smaller.The size of N-doped TiO2 nanobelts was smaller than pure TiO2 nanobelts.When the doping concentration was higher,the size of samples was smaller and the specific surface area was biger. there was also the most appropriate doping ratio of N for N-doped TiO2 nanobelts.When the doping ratio was n(N):n(Ti)=4:1,The photocatalytic ability of N-doped TiO2 nanobelts was the best. N-doped TiO2 nanobelts were prepared using ammonia、triethylamineas、triethanolamine as precursors.Compared to the three samples, The photocatalytic ability of N-doped TiO2 using triethylamineas as precursors was the best. The photocatalytic ability of N-doped TiO2 was the better when N was joined before hydrothermal reaction. The photocatalytic ability of N-doped TiO2 was improved under UV light,but was receded under visible light.
引文
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