摘要
TiO2 is the most photoactive material because of its superstrong photooxidizing ability,and TiO2 photocatalysis has been widely applied in sustainable water treatment and environmental remediation.However,poor sunlight or visible-light harvesting efficiency and fast recombination rate of the photogenerated charge carriers severely limit the practical applications of TiO2.To overcome these problems,the present work demonstrates a facile in-situ co-condensation method combined with hydrothermal treatment to prepare a series of graphitized carbon/TiO2 composite photocatalysts,and anatase TiO2 phase andp-p-conjugated polycyclic aromatic carbon structure are created simultaneously.As-prepared TiO2/C composites exhibit remarkably high visible-light photocatalytic activity in the degradation of aqueous emerging phenolic pollutants,acetaminophen(APAP)and methylparaben(MPB),and apparent rate constant of the TiO2/C composite with carbon doping level of 10.3%for APAP and MPB removal is 7.6 and 2.8 times higher than that of bare TiO2,and 6.2 and 2.6 times higher than that of Degussa P25 TiO2.Based on the results of photoelectrochemical experiments,indirect chemical probe measurements,and ESR spectroscopy,it is verified that doping TiO2 with graphitized carbon is responsible for this enhanced photocatalytic activity,which renders the improved visible-light harvesting ability,the accelerated separation of the photogenerated charge carriers,and enlarged BET surface areas.Through analyzing the intermediates yielded in the photodegradation process,the pathway of visible-light photocatalytic degradation of APAP and MPB over the TiO2/C composite is proposed.
绿色光催化技术在可持续水处理和环境修复领域具有广阔的应用前景.光催化效率在很大程度上取决于光催化剂,其中二氧化钛(Ti O2)因具有超强的光氧化能力、化学稳定性和低成本等优点而广泛应用于光催化降解水中各类有机污染物.然而,Ti O2的光催化效率仍然受限于其自身比表面积小、太阳光利用率低以及光生载流子复合速率快等缺点.为了克服以上缺点,进一步提高Ti O2的光催化效率,本研究采用简单易行的原位共缩合结合水热处理技术,以葡萄糖为碳源,四异丙氧基钛(TTIP)为钛源,成功制备了一系列由锐钛矿相Ti O2与石墨相碳组成的Ti O2/C复合光催化剂,它们在水中新兴酚类污染物的降解中表现出了优异的可见光光催化活性.通过X射线衍射、热重分析、X射线光电子能谱、孔隙率分析、扫描电镜、透射电镜、紫外-可见漫反射光谱等表征手段对催化剂的组成和结构、形貌、孔隙率性质及光吸收特性进行了表征.结果显示,Ti O2/C复合光催化剂具有独特的微孔/介孔结构,以及比Ti O2更大的比表面积(222-263 m^2 g^-1)和更窄的带隙能(2.50-2.77 e V).通过水中新兴酚类污染物如乙酰氨基酚(APAP)和对羟基苯甲酸甲酯(MPB)的可见光光催化降解实验研究了Ti O2/C的光催化性能.结果显示,Ti O2/C复合光催化剂表现出优于纯Ti O2和商用P25-Ti O2的可见光光催化活性.其中,性能最佳的Ti O2/C-10.3(碳掺杂量为10.3%)在可见光照射下20 min即可完全降解APAP,180 min可降解90%以上的MPB;Ti O2/C-10.3光催化降解APAP和MPB的表观速率常数分别是纯Ti O2的7.6和2.8倍,是商用P25-Ti O2的6.2和2.6倍.Ti O2/C复合光催化剂表现出良好的稳定性,能够在完成五次光催化循环实验后仍然保持其良好的光催化活性.通过光电化学实验、间接化学探针测试和电子自旋共振光谱分析并结合表征结果,揭示了Ti O2/C可见光光催化活性提高的原因.首先,石墨相碳的掺入降低了材料的带隙能,拓宽了材料的可见光吸收范围,同时石墨相碳可作为电子阱促进光生电子从Ti O2的价带转移到自身,从而有效抑制光生载流子的复合;其次,在复合催化剂中,锐钛矿相Ti O2与石墨相碳密切接触有利于光生载流子的有效分离,也可起到抑制光生载流子复合的作用;最后,复合催化剂较大的比表面积和独特的微孔/介孔双孔结构为APAP和MPB降解反应提供了充足活性位点,同时入射光在孔道内多次反射又进一步提高了催化剂对光能的利用率.在Ti O2/C光催化降解体系中检测到的主要活性物种有羟基自由基、光生空穴和超氧自由基,三者共同参与APAP和MPB的降解和矿化过程.通过对光催化降解中间产物的分析,分别提出了Ti O2/C复合光催化剂可见光催化降解APAP和MPB的路径.本研究为设计高效降解水中有机污染物的碳掺杂Ti O2光催化材料提供了新思路.
基金
国家自然科学基金(21573038,51608102).
