助剂对ZnO/ZrO2物化性质及催化性能的影响
收稿日期: 2023-06-16
网络出版日期: 2024-03-14
基金资助
贵州省自然科学基金项目(黔科合基础-ZK［2023］重点004);贵州省教育厅创新群体项目(黔教合KY字［2021］010);贵州大学实验室开放项目(SYSKF2023008)
Effect of promoter on physicochemical properties and catalytic performance of ZnO/ZrO2
Received date: 2023-06-16
Online published: 2024-03-14
CO2加氢制甲醇是实现碳中和目标的有效途径。尽管已报道的ZnO/ZrO2催化剂具有高活性和稳定性，但其催化性能仍有望进一步提高。采用浸渍法制备得到一系列不同元素掺杂的Ma-ZnO x /ZrO2催化剂，并通过评价发现只有Ga促进了ZnO/ZrO2催化剂催化CO2加氢制甲醇。其中，5%Ga-ZnO x /ZrO2催化剂表现出优异的催化性能，在反应条件：P=3 MPa、T=320 ℃、V（H2）∶V（CO2）=4∶1、气体质量空速（WHSV）=24 000 mL/（g∙h）时CO2转化率为7.2%，甲醇选择性为81.0%，甲醇时空产率可达410 mg/（g∙h），是ZnO/ZrO2的1.26倍，且在反应100 h内催化性能无明显衰减。X射线光电子能谱（XPS）和电子顺磁共振（EPR）表征发现，适量Ga助剂的掺入可以促进催化剂中氧空位的形成。H2程序升温还原（H2-TPR）、CO2/H2程序升温脱附（CO2/H2-TPD）结果表明，Ga助剂的掺入增强了ZnO/ZrO2催化剂活性位点的活性，Ga-ZnO x /ZrO2催化剂表现出更强的CO2和H2吸附活化能力。原位漫反射傅里叶变换红外（in situ DRIFTS）结果表明，各催化剂合成甲醇均遵循甲酸盐-甲氧基路径，Ga助剂的掺入促进了甲醇中间体的形成，并且更有利于HCOO*物种向CH3O*物种的转化，从而提高甲醇产率。
任启霞 , 杨坤 , 刘飞 , 姚梦琴 , 曹建新 . 助剂对ZnO/ZrO2物化性质及催化性能的影响[J]. 无机盐工业, 2024 , 56(3) : 144 -154 . DOI: 10.19964/j.issn.1006-4990.2023-0333
CO2 hydrogenation to methanol is an effective way to achieve the goal of carbon neutrality.Although the reported ZnO/ZrO2 catalysts have high activity and stability，their catalytic performance are expected to be further improved.A series of Ma-ZnO x /ZrO2 catalysts with different elements doping were prepared by the impregnation method，and it was found by evaluation that only Ga promoted the catalytic CO2 hydrogenation to methanol by ZnO/ZrO2 catalyst.Among them，5%Ga-ZnO x /ZrO2 catalyst showed excellent catalytic performance.At the reaction conditions：P=3 MPa，T=320 ℃，V（H2）∶V（CO2）=4∶1 and gas weight hourly space velocity（WHSV）=24 000 mL/（g∙h），the CO2 conversion of 5%Ga-ZnO x /ZrO2 catalyst was 7.2%，the methanol selectivity was 81.0% and the methanol space-time yield was up to 410 mg/（g∙h），which was 1.26 times higher than that of the ZnO/ZrO2.And there was no significant decay in the catalytic performance within 100 h of reaction.X-ray photoelectron spectrometry（XPS） and electron paramagnetic resonance（EPR） characterization showed that doping with the appropriate amount of Ga promoter could promote the formation of oxygen vacancies in the catalyst.H2 temperature programmed reduction（H2-TPR），temperature-programmed desorption of the preabsorbed CO2/H2（CO2/H2-TPD） results showed that the doping of the Ga promoter enhanced the activity of the active sites of the ZnO/ZrO2 catalyst，and the Ga-ZnO x /ZrO2 catalyst exhibited a stronger capacity for the adsorption and activation of CO2 and H2.The in situ diffuse reflectance infrared Fourier transform spectroscopy（in situ DRIFTS） results showed that the synthesis of methanol by each catalyst followed the formate-methoxy pathway，and the incorporation of Ga promoter facilitated the formation of methanol intermediates and was favorable for the conversion of HCOO* species to CH3O* species，thus improving the methanol yield.
Key words： CO2 hydrogenation; methanol; ZnO/ZrO2; Ga promoter; oxygen vacancy
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