稀土掺杂氧化铋可见光响应催化剂制备及性能研究
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摘要
染料废水是工业废水的重要组成部分之一，中国是染织大国，染料废水排放量巨大，其中含有的偶氮、芳香类化合物、重金属等成分对生物体有毒害作用，并且由于其高色度、高COD，可生物降解性差等，使染料废水的处理技术普遍成本高，处理效果较差。因此，选用高效节能的污水处理方法来处理染料废水是目前的研究方向。
光催化技术就是一种先进的高级氧化技术，由于它可以受光能激发产生具有强氧化性的活性物质，因此具有可以利用太阳能这种清洁能源的优势。以目前的研究成果来看，对TiO_2的研究最多，但由于TiO_2的禁带宽度较大，对光能的利用率低，限制了它的应用。人们的研究方向转向开发新型窄带隙光催化剂和利用掺杂等方法拓宽催化剂的吸光范围。
基于以上内容，本文以铋系材料为基础，利用非晶态络合法成功的制备得到了掺杂Eu的Bi_2O_3催化剂样品。制得的催化剂样品中组成元素为Bi(III)、Eu (III)和Ce(IV)，并且都是以氧化物形式存在。对掺杂Eu的Bi_2O_3样品进行XRD分析可知，Eu的掺杂比例对样品的晶体结构有很大影响，增加Eu的掺杂比例，可以使催化剂样品的晶体结构由四角晶型的Bi_2O_3向立方晶型的Bi_(0.25)(Bi_(0.375)Eu_(0.375))O_(1.5)转变，同时掺杂Eu的Bi_2O_3催化剂样品具有较小的禁带宽度，因此能够有效地吸收可见光。其中Eu掺杂量为1:8和1:4的催化剂样品的禁带宽度都仅为2.75eV，但当掺杂量增加到1:1时，禁带宽度达到了3.3eV。根据光催化剂光催化效果确定Eu的最佳掺杂比例为1:4，在此条件下制备的催化剂光生电子-空穴对分离能力最强，对甲基橙的降解率可以达到97.6%。
通过改变灼烧温度和时间来研究灼烧过程对掺杂Eu的Bi_2O_3催化剂样品结构及性质的影响，制备过程中温度的升高会使催化剂晶体结晶度增加，同时也产生团聚现象，并且在500℃和600℃条件下产生了斜方六面体的Bi_(0.775)Eu0.225O_(1.5)，改变了催化剂的晶体结构。灼烧时间对掺杂Eu的Bi_2O_3催化剂样品的作用主要是促进晶体的形成；在不同灼烧温度及时间条件下制备的掺杂Eu的Bi_2O_3催化剂样品中，400℃灼烧5h条件下制备得到的催化剂样品带隙宽度最小，并且在550nm内光吸收性和光生电子和空穴的分离效率最高，光催化活性最好，因此确定最佳掺杂Eu的Bi_2O_3催化剂最佳灼烧过程为400℃灼烧5h。
同样采用非晶态络合法制备掺杂Ce的Bi_2O_3催化剂，在掺杂量1:1时催化剂样品为四方晶系的Bi_2O_3和立方晶系的CeO_2。并且随着稀土掺杂量的增加，结晶度降低。不同掺杂浓度下制备的样品在550nm内都有较好的光吸收性，根据催化剂光催化甲基橙效果确定Ce的最佳掺杂比例为1:1。由于在600℃时产生单斜晶型的Bi_2O_3，其光催化性能不如四角的Bi_2O_3，并且在高温下会产生团聚现象。因而在400℃灼烧5h条件下制备的催化剂样品禁带宽度最小，为2.35eV，光生载流子的分离传输能力最好，光催化性能最高，反应1h时对甲基橙的降解率可以达到99%。因此确定最佳灼烧温度为400℃。
通过比较不同稀土掺杂Bi_2O_3催化剂的性能，发现掺杂Ce的样品吸收边比掺杂Eu的样品有明显的红移，禁带宽度减小。掺杂Ce的样品光电压信号强度要高于掺杂Eu的样品，光生载流子的分离和传输能力更强。掺杂Ce的样品光照1h对甲基橙的降解效率就达到了99%，与之相比，掺杂Eu的样品反应2h的降解效果达到90%多。由此认为掺杂Ce的Bi_2O_3催化剂性能比掺杂Eu的催化剂好。
利用自制Ce掺杂Bi_2O_3催化剂进行光催化降解甲基橙研究，在光照开始阶段，甲基橙未被完全矿化，反应生成了一系列有机中间产物，而从4h后开始中间产物被逐渐的降解，产生NO_3~-、SO_4~(2-)等矿化产物。催化剂对甲基橙有一定的吸附作用，但通过UV-Vis DRS并未检测到有光敏化的现象发生。自制Ce掺杂Bi_2O_3催化剂光催化降解亚甲基蓝降解途径与甲基橙不同，但反应速率相似，并且催化剂对亚甲基蓝的吸附性要强于甲基橙。反应结束后，在UV-Vis DRS结果中发现了在575-675nm范围出现新的吸收峰，推测吸附在催化剂表面的染料及中间产物促使催化剂产生了更多的活性位点，扩展了催化剂的吸光范围，存在光敏化作用。而由于催化剂对染料的降解作用，在反应12h后催化剂在575-675nm的吸收峰减弱。
光催化反应速率随催化剂用量和光照强度的增加而增大，随反应物初始浓度增加而减小，通过相关影响因素分析，确定不同反应条件的反应速率方程式为ν=0.0113C_0~(-1.459)m~(1.3458)P~(0.3332)。此外，NaCl、NaNO_3和Na_2SO_4对光催化反应速率都有抑制作用，并且各离子的抑制作用都是随着浓度的增大而增强。
综上所述，本论文通过非晶态络合法制备的掺杂Eu和Ce的Bi_2O_3催化剂，拓宽了催化剂的光响应范围，具有较高的光生载流子分离能力，在可见光下具有较好的光催化效果。通过对催化剂光降解污染物的途径及反应条件分析，得到反应速率方程，为催化剂的应用提供了理论依据。
Dye wastewater which contains azo, aromatic compounds and heavy metals isharmful to the human and ecological environment. It has high color degree, high CODand low biodegradability, resulting in high cost and low efficiency of dye wastewatertreatment. Therefore, how to develop a cost-effective technology for the treatment ofdye wastewater has been paid a lot of attention.
The semiconductor photocatalytic technique is an advanced oxidation technologyand can produce strong oxidizing active substances by energy excitation. So it canmake use of solar clean energy. Recently, many researches focus on the TiO_2asphotocatalyst. Due to band gap of TiO_2which results in low utilization of light energy,there is a limit of TiO_2application. Therefore, there is a need to develop a new type ofnarrow band gap and wide absorbance range of photocatalyst.
In this study, the preparation of Bi_2O_3doped with Eu was conducted by amorphouscomplexation. Thr catalysts were made up of oxide by Bi (III) and Eu (III) and Ce(Ⅳ).The results indicated that the influence of doping ratio on the crystal structure wassignificant. The crystal structure of Bi_2O_3and Bi_(0.25)(Bi_(0.375)Eu_(0.375))O_(1.5)is quadrangularpolymorph and non-stoichiometric ratio of the cubic crystal with the doping ratio of1:8, respectively. High doping ratio with more Eu can induce the Bi_2O_3transformed toBi_(0.25)(Bi_(0.375)Eu_(0.375))O_(1.5). The Europium-doped Bi_2O_3catalyst can effectively adsorbthe visible light. The band gap of catalyst was2.75eV when the doping amount of thesample1:8and1:4. But the band gap of catalyst was increased with increasing dopingamount. The band gap of catalyst was3.3eV when the doping amount was1mol/mol.The separation ability of light-generated electron-hole was strongest when Eudoping ratio was1:4, resulting that the methyl orange degradation rate can reach97.6%.
The crystallinity was increased with increasing temperature and agglomeration wasproduced. At500°C and600°C, the Bi_(0.775)Eu0.225O_(1.5)with structure of rhombichexahedron was formed. The band gap of catalyst prepared at400°C was minimumand its separation ability of light-generated electron-hole was strongest, illustratinggreat photocatalytic activity. Thus, the optimal preparation condition is temperature of400°C with5h calcinations.
The structure of Bi_2O_3doped with Ce is tetragonal and transformed to cubic crystalwhen doping amount is1:1. The crystallinity decreased with increasing dopingamount. Samples prepared under different doping levels have better light absorptionat550nm. Based on the catalyst photocatalytic ability of methyl orange, the optimumdoping ratio was1:1. The monoclinic polymorph of Bi_2O_3was formed at600℃andits photocatalytic ability was less than cubic crystal of Bi_2O_3. High temperatures led toagglomeration. The band gap of samples prepared at400℃is2.35eV and effectiveseparation of photo-generated electron-hole pairs produced, resulting that highestphotocatalytic degradation of methyl orange achieved up to99%within1hour.
Based on the characteristics of Bi_2O_3catalyst with different doped rare earths, itwas found that the absorption edge of Bi_2O_3doped with Ce was obviously red shiftedand the band gap decreased. Compared with Bi_2O_3doped with Eu, the Bi_2O_3dopedwith Ce had a high voltage signal, photo-generated carriers separation and transportcapabilities. The degradation of methyl orange by Bi_2O_3catalyst doped with Ce was99%within1hour, while the degradation of methyl orange by Bi_2O_3catalyst dopedwith Eu was90%within2hour. This suggested that the best photocatalyst is Bi_2O_3catalyst doped with Ce.
During the photocatalytic degradation of methyl orange by Bi_2O_3catalyst dopedwith Ce, some intermediate products were produced within4hours. After that, mostof intermediate products were mineralized to NO_3~-、SO_4~(2-)and a few amounts ofintermediate products were still incompletely degraded. It was found that the catalysthad the adsorption capacity of methyl orange. But photosensitization phenomenonwas not detected by UV-Vis DRS.The photocatalytic degradation of methylene blueby Bi_2O_3catalyst doped with Ce was different with photocatalytic degradation of methyl orange, but similar to the reaction rate. The adsorption of methylene blue washigher than that of methyl orange. A new peak appeared in the range of575-675nm inthe UV-Vis DRS results. Adsorbed dyes and intermediates prompted catalyst producemore active sites and extend the scope of the absorbance of the catalyst. Thephotosensitizing effect existed. However, due to the degradation of fuel by catalyst,the absorption peak weakened at the575-675nm after12h reaction.
Photocatalytic reaction rate increased with the increasing amount of catalyst andlight intensity, while decreased with the increasing initial concentration of reactant.The reaction fitted to the first-order kinetics and their relationship can be expressed asν=0.0113C_0~(-1.459)m~(1.3458)P~(0.3332).The results showed that the reaction rate was inhibitedby Na_2SO_4, NaNO_3and NaCl, and the inhibitory effect of ions are enhanced withincreasing concentration.
In general, the Bi_2O_3catalyst doped with Eu and Ce in this study had broad lightresponse range of the catalyst and high photo-generated carrier separation ability, andgood photocatalytic ability under visible light. Through the analysis of pathway andreaction condition in the photodegradation of pollutants, the relationship between thereaction rate and the different conditions was proposed in this study, aiming toprovide a theoretical basis for the application of the catalyst in future.
光催化技术就是一种先进的高级氧化技术，由于它可以受光能激发产生具有强氧化性的活性物质，因此具有可以利用太阳能这种清洁能源的优势。以目前的研究成果来看，对TiO_2的研究最多，但由于TiO_2的禁带宽度较大，对光能的利用率低，限制了它的应用。人们的研究方向转向开发新型窄带隙光催化剂和利用掺杂等方法拓宽催化剂的吸光范围。
基于以上内容，本文以铋系材料为基础，利用非晶态络合法成功的制备得到了掺杂Eu的Bi_2O_3催化剂样品。制得的催化剂样品中组成元素为Bi(III)、Eu (III)和Ce(IV)，并且都是以氧化物形式存在。对掺杂Eu的Bi_2O_3样品进行XRD分析可知，Eu的掺杂比例对样品的晶体结构有很大影响，增加Eu的掺杂比例，可以使催化剂样品的晶体结构由四角晶型的Bi_2O_3向立方晶型的Bi_(0.25)(Bi_(0.375)Eu_(0.375))O_(1.5)转变，同时掺杂Eu的Bi_2O_3催化剂样品具有较小的禁带宽度，因此能够有效地吸收可见光。其中Eu掺杂量为1:8和1:4的催化剂样品的禁带宽度都仅为2.75eV，但当掺杂量增加到1:1时，禁带宽度达到了3.3eV。根据光催化剂光催化效果确定Eu的最佳掺杂比例为1:4，在此条件下制备的催化剂光生电子-空穴对分离能力最强，对甲基橙的降解率可以达到97.6%。
通过改变灼烧温度和时间来研究灼烧过程对掺杂Eu的Bi_2O_3催化剂样品结构及性质的影响，制备过程中温度的升高会使催化剂晶体结晶度增加，同时也产生团聚现象，并且在500℃和600℃条件下产生了斜方六面体的Bi_(0.775)Eu0.225O_(1.5)，改变了催化剂的晶体结构。灼烧时间对掺杂Eu的Bi_2O_3催化剂样品的作用主要是促进晶体的形成；在不同灼烧温度及时间条件下制备的掺杂Eu的Bi_2O_3催化剂样品中，400℃灼烧5h条件下制备得到的催化剂样品带隙宽度最小，并且在550nm内光吸收性和光生电子和空穴的分离效率最高，光催化活性最好，因此确定最佳掺杂Eu的Bi_2O_3催化剂最佳灼烧过程为400℃灼烧5h。
同样采用非晶态络合法制备掺杂Ce的Bi_2O_3催化剂，在掺杂量1:1时催化剂样品为四方晶系的Bi_2O_3和立方晶系的CeO_2。并且随着稀土掺杂量的增加，结晶度降低。不同掺杂浓度下制备的样品在550nm内都有较好的光吸收性，根据催化剂光催化甲基橙效果确定Ce的最佳掺杂比例为1:1。由于在600℃时产生单斜晶型的Bi_2O_3，其光催化性能不如四角的Bi_2O_3，并且在高温下会产生团聚现象。因而在400℃灼烧5h条件下制备的催化剂样品禁带宽度最小，为2.35eV，光生载流子的分离传输能力最好，光催化性能最高，反应1h时对甲基橙的降解率可以达到99%。因此确定最佳灼烧温度为400℃。
通过比较不同稀土掺杂Bi_2O_3催化剂的性能，发现掺杂Ce的样品吸收边比掺杂Eu的样品有明显的红移，禁带宽度减小。掺杂Ce的样品光电压信号强度要高于掺杂Eu的样品，光生载流子的分离和传输能力更强。掺杂Ce的样品光照1h对甲基橙的降解效率就达到了99%，与之相比，掺杂Eu的样品反应2h的降解效果达到90%多。由此认为掺杂Ce的Bi_2O_3催化剂性能比掺杂Eu的催化剂好。
利用自制Ce掺杂Bi_2O_3催化剂进行光催化降解甲基橙研究，在光照开始阶段，甲基橙未被完全矿化，反应生成了一系列有机中间产物，而从4h后开始中间产物被逐渐的降解，产生NO_3~-、SO_4~(2-)等矿化产物。催化剂对甲基橙有一定的吸附作用，但通过UV-Vis DRS并未检测到有光敏化的现象发生。自制Ce掺杂Bi_2O_3催化剂光催化降解亚甲基蓝降解途径与甲基橙不同，但反应速率相似，并且催化剂对亚甲基蓝的吸附性要强于甲基橙。反应结束后，在UV-Vis DRS结果中发现了在575-675nm范围出现新的吸收峰，推测吸附在催化剂表面的染料及中间产物促使催化剂产生了更多的活性位点，扩展了催化剂的吸光范围，存在光敏化作用。而由于催化剂对染料的降解作用，在反应12h后催化剂在575-675nm的吸收峰减弱。
光催化反应速率随催化剂用量和光照强度的增加而增大，随反应物初始浓度增加而减小，通过相关影响因素分析，确定不同反应条件的反应速率方程式为ν=0.0113C_0~(-1.459)m~(1.3458)P~(0.3332)。此外，NaCl、NaNO_3和Na_2SO_4对光催化反应速率都有抑制作用，并且各离子的抑制作用都是随着浓度的增大而增强。
综上所述，本论文通过非晶态络合法制备的掺杂Eu和Ce的Bi_2O_3催化剂，拓宽了催化剂的光响应范围，具有较高的光生载流子分离能力，在可见光下具有较好的光催化效果。通过对催化剂光降解污染物的途径及反应条件分析，得到反应速率方程，为催化剂的应用提供了理论依据。
Dye wastewater which contains azo, aromatic compounds and heavy metals isharmful to the human and ecological environment. It has high color degree, high CODand low biodegradability, resulting in high cost and low efficiency of dye wastewatertreatment. Therefore, how to develop a cost-effective technology for the treatment ofdye wastewater has been paid a lot of attention.
The semiconductor photocatalytic technique is an advanced oxidation technologyand can produce strong oxidizing active substances by energy excitation. So it canmake use of solar clean energy. Recently, many researches focus on the TiO_2asphotocatalyst. Due to band gap of TiO_2which results in low utilization of light energy,there is a limit of TiO_2application. Therefore, there is a need to develop a new type ofnarrow band gap and wide absorbance range of photocatalyst.
In this study, the preparation of Bi_2O_3doped with Eu was conducted by amorphouscomplexation. Thr catalysts were made up of oxide by Bi (III) and Eu (III) and Ce(Ⅳ).The results indicated that the influence of doping ratio on the crystal structure wassignificant. The crystal structure of Bi_2O_3and Bi_(0.25)(Bi_(0.375)Eu_(0.375))O_(1.5)is quadrangularpolymorph and non-stoichiometric ratio of the cubic crystal with the doping ratio of1:8, respectively. High doping ratio with more Eu can induce the Bi_2O_3transformed toBi_(0.25)(Bi_(0.375)Eu_(0.375))O_(1.5). The Europium-doped Bi_2O_3catalyst can effectively adsorbthe visible light. The band gap of catalyst was2.75eV when the doping amount of thesample1:8and1:4. But the band gap of catalyst was increased with increasing dopingamount. The band gap of catalyst was3.3eV when the doping amount was1mol/mol.The separation ability of light-generated electron-hole was strongest when Eudoping ratio was1:4, resulting that the methyl orange degradation rate can reach97.6%.
The crystallinity was increased with increasing temperature and agglomeration wasproduced. At500°C and600°C, the Bi_(0.775)Eu0.225O_(1.5)with structure of rhombichexahedron was formed. The band gap of catalyst prepared at400°C was minimumand its separation ability of light-generated electron-hole was strongest, illustratinggreat photocatalytic activity. Thus, the optimal preparation condition is temperature of400°C with5h calcinations.
The structure of Bi_2O_3doped with Ce is tetragonal and transformed to cubic crystalwhen doping amount is1:1. The crystallinity decreased with increasing dopingamount. Samples prepared under different doping levels have better light absorptionat550nm. Based on the catalyst photocatalytic ability of methyl orange, the optimumdoping ratio was1:1. The monoclinic polymorph of Bi_2O_3was formed at600℃andits photocatalytic ability was less than cubic crystal of Bi_2O_3. High temperatures led toagglomeration. The band gap of samples prepared at400℃is2.35eV and effectiveseparation of photo-generated electron-hole pairs produced, resulting that highestphotocatalytic degradation of methyl orange achieved up to99%within1hour.
Based on the characteristics of Bi_2O_3catalyst with different doped rare earths, itwas found that the absorption edge of Bi_2O_3doped with Ce was obviously red shiftedand the band gap decreased. Compared with Bi_2O_3doped with Eu, the Bi_2O_3dopedwith Ce had a high voltage signal, photo-generated carriers separation and transportcapabilities. The degradation of methyl orange by Bi_2O_3catalyst doped with Ce was99%within1hour, while the degradation of methyl orange by Bi_2O_3catalyst dopedwith Eu was90%within2hour. This suggested that the best photocatalyst is Bi_2O_3catalyst doped with Ce.
During the photocatalytic degradation of methyl orange by Bi_2O_3catalyst dopedwith Ce, some intermediate products were produced within4hours. After that, mostof intermediate products were mineralized to NO_3~-、SO_4~(2-)and a few amounts ofintermediate products were still incompletely degraded. It was found that the catalysthad the adsorption capacity of methyl orange. But photosensitization phenomenonwas not detected by UV-Vis DRS.The photocatalytic degradation of methylene blueby Bi_2O_3catalyst doped with Ce was different with photocatalytic degradation of methyl orange, but similar to the reaction rate. The adsorption of methylene blue washigher than that of methyl orange. A new peak appeared in the range of575-675nm inthe UV-Vis DRS results. Adsorbed dyes and intermediates prompted catalyst producemore active sites and extend the scope of the absorbance of the catalyst. Thephotosensitizing effect existed. However, due to the degradation of fuel by catalyst,the absorption peak weakened at the575-675nm after12h reaction.
Photocatalytic reaction rate increased with the increasing amount of catalyst andlight intensity, while decreased with the increasing initial concentration of reactant.The reaction fitted to the first-order kinetics and their relationship can be expressed asν=0.0113C_0~(-1.459)m~(1.3458)P~(0.3332).The results showed that the reaction rate was inhibitedby Na_2SO_4, NaNO_3and NaCl, and the inhibitory effect of ions are enhanced withincreasing concentration.
In general, the Bi_2O_3catalyst doped with Eu and Ce in this study had broad lightresponse range of the catalyst and high photo-generated carrier separation ability, andgood photocatalytic ability under visible light. Through the analysis of pathway andreaction condition in the photodegradation of pollutants, the relationship between thereaction rate and the different conditions was proposed in this study, aiming toprovide a theoretical basis for the application of the catalyst in future.
引文
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