Cu、N共掺杂TiO_(2)纳米管光催化重整甘油制备合成气  

Preparation and photocatalytic properties of Cu,N co-doped TiO_(2)nanotubes for glycerol reforming to syngas

作　　者：侯浩强 徐俪菲 徐州 杨峥 李伟[1] 马春慧 罗沙 刘守新[1] HOU Hao-Qiang;XU Li-Fei;XU Zhou;YANG Zheng;LI Wei;MA Chun-Hui;LUO Sha;LIU Shou-Xin(Material Science and Engineering College,Northeast Forestry University,Key Laboratory of Bio-based Material Science&Technology of Ministry of Education,Harbin 150040,China)

机构地区：[1]东北林业大学材料科学与工程学院,生物质材料科学与技术教育部重点实验室,哈尔滨150040

出　　处：《无机化学学报》2023年第11期2103-2112,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.31890773,31971601);中央高校基本科研业务费专项资金(No.2572021BB12)资助。

摘　　要：通过碱性水热-离子交换法制备了Cu、N共掺杂TiO_(2)纳米管(Cu/N-TNT),对其光催化重整甘油制备合成气性能进行了研究。结果表明,Cu/N-TNT具有富含氧空位(O_(v))的管状结构,N以Ti-N形式取代部分O形成杂质能级,Cu以Cu^(2+)形式掺杂在催化剂晶格间隙和表面,Cu、N共掺杂促进TiO_(2)表面电荷有效分离,有利于其光催化重整甘油制备合成气活性和选择性的提高。紫外光照射8h时,掺Cu量为0.15%的Cu/N-TNT催化剂上CO和H_(2)产量分别为7.3和8.5 mmol·g^(-1),是原始TiO_(2)的9.1和70.8倍,nH_(2)/nCO从0.52提高为1.18,nCO/nCO_(2)从0.21提高至0.42。Cu/N-TNT表面N和OV为醛类脱羰和甲酸脱水生成CO提供反应活性位点,Cu作为浅势阱提高光生电子-空穴分离效率。光生空穴(h+)是光催化重整甘油制备合成气过程中的主要活性物种,大量经基自由基(·OH)和超氧自由基(·O_(2)-)会导致甘油过度氧化,使CO选择性降低。Cu,N co-doped TiO_(2)nanotubes(Cu/N-TNT)were prepared by alkaline hydrothermal-ion exchange method,and the photocatalytic properties for glycerol reforming to syngas(H_(2)and CO)were studied.The results show that Cu/N-TNT catalyst has tubular structures with abundant oxygen vacancies(O_(V)).N forms the impurity energy level by substituting the partial O in the form of Ti-N.Cu is doped into the crystal lattice gap and surface of the catalyst in the form of Cu^(2+).Cu,N co-doping promotes the effective surface charge separation on the TiO_(2),and improves the photocatalytic activity and selectivity for glycerol reforming to syngas.CO and H_(2)yields were 7.3 and 8.5 mmol·g^(-1)on Cu/N-TNT catalyst doped with 0.15%Cu,which were 9.1 and 70.8 times those on the original TiO_(2).The molar ratio of H_(2)/CO was increased from 0.52 to 1.18,and the molar ratio of CO/CO_(2)was raised from 0.21 to 0.42 after 8 h of UV irradiation.N and OV on Cu/N-TNT surface provide the active sites for the decarbonylation of aldehydes and dehydration of formic acid to produce CO.Cu acts as the shallow potential traps to inhibit the electronhole recombination.Photogenerated holes(h+)play vital roles on the syngas generation during the photocatalytic reforming of glycerol,and excessive hydroxyl radical(·OH)and superoxide radical(·O_(2)^(-))favor the deep oxidation of glycerol and decrease the selectivity of CO.

关 键 词：Cu、N共掺杂TiO_(2) 合成气 光催化重整 甘油 

分 类 号：O643.36[理学—物理化学]