Effect of Reflux Time on the Performance of the Cu/ZrO2 Catalyst for CO2 Hydrogenation to Methanol

被引:12
作者
Dai, Wenhua [1 ]
Meng, Xin [1 ]
Xu, Bowen [1 ]
Zhao, Rui [1 ]
Jin, Daoming [1 ]
Xu, Fan [1 ]
Yang, Dandan [1 ]
Xin, Zhong [1 ]
机构
[1] East China Univ Sci & Technol, Sch Chem Engn, Shanghai Key Lab Multiphase Mat Chem Engn, Shanghai 200237, Peoples R China
基金
中国国家自然科学基金;
关键词
CO2; hydrogenation; reflux; Cu/ZrO2; catalysts; basic site; oxygen vacancy; AMORPHOUS ZRO2; STATE; CU; ADSORPTION; INSIGHTS; SITES; ACID;
D O I
10.1021/acsaem.3c01373
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The hydrogenation of CO2 into methanol was investigated by means of the Cu/ZrO2 catalyst to analyze the effect of reflux time on catalytic performance. A series of high-activity Cu/ZrO2 catalysts were prepared by introducing the support pretreated with ammonia reflux. The effect of reflux time on the structure and performance of all catalysts was systematically studied. Combined with various characterizations such as X-ray diffraction (XRD), N-2 physisorption, temperature-programmed reduction by H2 (H2-TPR), temperature-programmed desorption of H-2 and CO2, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), it can be seen that the catalysts after reflux exhibited a stable amorphous structure with more medium and strong basic sites. Moreover, the proportion of defect oxygen and surface Cu+ species for Cu/ZrO2 catalysts increased, and the metal-support interaction was strengthened, which effectively increased active sites and promoted CO2 activation, and thus, the catalyst with stronger activity and better stability was obtained. The CO2 conversion dramatically increased by 4-5 times (from 5.4 to 22.1%) after reflux treatment, and the Cu/ZrO2-18h catalyst had the highest catalytic activity and a methanol space time yield of 394 g(MeOH) h-1 kg(cat)( -1) at 260 ?.
引用
收藏
页码:9417 / 9426
页数:10
相关论文
共 41 条
[11]   Effect of aging temperature during refluxing on the textural and surface acidic properties of zirconia catalysts [J].
Hong, Eunpyo ;
Baek, Sung Woo ;
Shin, Mi ;
Suh, Young-Woong ;
Shin, Chae-Ho .
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, 2017, 54 :137-145
[12]   Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis [J].
Jiang, Xiao ;
Nie, Xiaowa ;
Guo, Xinwen ;
Song, Chunshan ;
Chen, Jingguang G. .
CHEMICAL REVIEWS, 2020, 120 (15) :7984-8034
[13]   CO2-to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface [J].
Larmier, Kim ;
Liao, Wei-Chih ;
Tada, Shohei ;
Lam, Erwin ;
Verel, Rene ;
Bansode, Atul ;
Urakawa, Atsushi ;
Comas-Vives, Aleix ;
Coperet, Christophe .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (09) :2318-2323
[14]   CO2 Hydrogenation to Methanol over ZrO2-Containing Catalysts: Insights into ZrO2 Induced Synergy [J].
Li, Kongzhai ;
Chen, Jingguang G. .
ACS CATALYSIS, 2019, 9 (09) :7840-7861
[15]   Role of the Cu-ZrO2 interface in the hydrogenation of levulinic acid to c-valerolactone [J].
Li, Ziyi ;
Hao, Haigang ;
Lu, Jingjing ;
Wu, Chengming ;
Gao, Rui ;
Li, Jifan ;
Liu, Chun-Ling ;
Dong, Wen-Sheng .
JOURNAL OF ENERGY CHEMISTRY, 2021, 61 :446-458
[16]   Surface interaction of CO2/H2 mixture on mesoporous ZrO2: Effect of crystalline polymorph phases [J].
Marcos, Francielle C. F. ;
Assaf, Jose M. ;
Giudici, Reinaldo ;
Assaf, Elisabete M. .
APPLIED SURFACE SCIENCE, 2019, 496
[17]   Unifying views on catalyst deactivation [J].
Martin, Antonio J. ;
Mitchell, Sharon ;
Mondelli, Cecilia ;
Jaydev, Shibashish ;
Perez-Ramirez, Javier .
NATURE CATALYSIS, 2022, 5 (10) :854-866
[18]   Tuning electron density of metal nickel by support defects in Ni/ZrO2 for selective hydrogenation of fatty acids to alkanes and alcohols [J].
Ni, Jun ;
Leng, Wenhua ;
Mao, Jun ;
Wang, Jianguo ;
Lin, Jianyi ;
Jiang, Dahao ;
Li, Xiaonian .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2019, 253 :170-178
[19]   Comprehensive review of Cu-based CO2 hydrogenation to CH3OH: Insights from experimental work and theoretical analysis [J].
Niu, Juntian ;
Liu, Haiyu ;
Jin, Yan ;
Fan, Baoguo ;
Qi, Wenjie ;
Ran, Jingyu .
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 2022, 47 (15) :9183-9200
[20]   Acidity of co-precipitated SiO2-ZrO2 mixed oxides in the acid-catalyzed dehydrations of iso-propanol and formic acid [J].
Pyen, Seunghee ;
Hong, Eunpyo ;
Shin, Mi ;
Suh, Young-Woong ;
Shin, Chae-Ho .
MOLECULAR CATALYSIS, 2018, 448 :71-77