Roles of nitrogen species on nitrogen-doped CNTs supported Cu-ZrO2 system for carbon dioxide hydrogenation to methanol
Roles of nitrogen species on nitrogen-doped CNTs supported Cu-ZrO2 system for carbon dioxide hydrogenation to methanol
复制标题
氮物种对氮掺杂碳纳米管支持的 Cu-ZrO2 体系二氧化碳加氢制甲醇的作用
DOI：
10.1016/j.cattod.2017.04.017
复制
发表时间：
2018-06-01
期刊：
影响因子：
5.3
通讯作者：
Ye, Daiqi
中科院分区：
文献类型：
--
作者：
Sun, Yuhai;Chen, Limin;Ye, Daiqi
以掺氮碳纳米管为载体，在固定床推流反应器中进行了CO_2加氢制甲醇反应。表征结果表明，吡啶氮的存在增加了铜氧化物的分散度，促进了铜氧化物的还原，减小了铜粉的粒径，提高了氢气的吸附能力；活化的CO2吸附主要控制了CO2的转化。此外，吡啶氮有助于CO2的强吸附，促进甲醇的生成，而吡咯氮有助于CO2的中等吸附，主要促进CO的生成。因此，吡啶氮占主导地位的碳纳米管负载催化剂(CZ/CNT-N)与其他三种催化剂相比具有更多的活性中心，从而获得最高的甲醇产率(8.64%)和最高的时空产率(102.21 mg g(CAT)(-1)h(-1))，而吡咯氮占主导地位的碳纳米管(CZ/CNT-NH2)具有更高的活性结构，具有最高的本征活性(TOF值)。
Cu-ZrO2 catalysts supported on nitrogen-doped CNTs were tested for CO2 hydrogenation to methanol in a fixedbed plug flow reactor. The characterization results indicate that the presence of pyridinic nitrogen increases the copper oxide dispersion, promotes their reduction, decreases the Cu particle size and enhances H-2 adsorption capability; the activated CO2 adsorption predominantly controls CO2 conversion. In addition, pyridinic nitrogen contributes to the strong adsorption of CO2, stimulating methanol formation, while pyrrolic nitrogen contributes to the medium adsorption of CO2, mainly boosting CO formation. Thus, pyridinic nitrogen dominant CNTs supported catalyst (CZ/CNT-N) possesses more active sites compared with the other three catalysts, leading to maximum methanol yield (8.64%) and space time yield (102.21 mg g(cat)(-1) h(-1)); pyrrolic nitrogen dominant CNTs supported catalyst (CZ/CNT-NH2) obtains more highly active structure, giving the highest intrinsic activity (TOF values).