Stabilizing Cu+ in Cu/SiO2 Catalysts with a Shattuckite-Like Structure Boosts CO2 Hydrogenation into Methanol

被引:181
作者
Yu, Jiafeng [1 ,4 ]
Yang, Meng [1 ,2 ]
Zhang, Jixin [1 ]
Ge, Qingjie [1 ]
Zimina, Anna [3 ,4 ]
Pruessmann, Tim [5 ]
Zheng, Lei [3 ]
Grunwaldt, Jan-Dierk [3 ,4 ]
Sun, Jian [1 ]
机构
[1] Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
[3] Karlsruhe Inst Technol, Inst Chem Technol & Polymer Chem, D-76131 Karlsruhe, Germany
[4] Karlsruhe Inst Technol, Inst Catalysis Res & Technol, D-76344 Eggenstein Leopoldshafen, Germany
[5] Karlsruhe Inst Technol, Inst Nucl Waste Disposal, D-76344 Eggenstein Leopoldshafen, Germany
关键词
Cu/SiO2; catalyst; CO2; hydrogenation; methanol synthesis; synchrotron radiation; in situ X-ray absorption spectroscopy; HETEROGENEOUS CATALYSIS; ABSORPTION-SPECTRA; COPPER-CATALYSTS; ACTIVE-SITE; PERFORMANCE; STATE; SPECTROSCOPY; ZNO; ADSORPTION; CHALLENGES;
D O I
10.1021/acscatal.0c04371
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
Cu-based catalysts are widely employed for CO or CO2 hydrogenation into methanol. However, their catalytic performance highly depends on supports, and the real evolution of Cu species is still covered by active components. Herein, we supply a Cu/SiO2 catalyst prepared by flame spray pyrolysis (FSP), showing catalytic performance comparable to that of the active Cu/ZrO2 catalyst for methanol synthesis from CO2. It reaches 79% selectivity at a CO2 conversion of 5.2%, which is an outstanding selectivity among previously reported Cu/SiO2 catalysts, considering they are generally treated as nearly inert catalysts. In situ X-ray absorption spectroscopy (XAS) analysis shows that 5 times more Cu+ species in the FSP-Cu/SiO2 are stabilized in comparison to those in the traditional ammonia evaporation (AE) made catalyst even after reduction at 350 degrees C. A unique shattuckite-like precursor with a slightly distorted Cu-O-Si texture structure formed in the FSP-made catalyst is responsible for the enriched Cu+ species. Variations of intermediate formation and methanol production are found to have a good relationship with the amount of Cu+ species. According to the results of high-pressure in situ DRIFTS, we attribute this to the promotional effect of Cu+ on the stabilization of CO* intermediates, which inhibits CO desorption and facilitates further hydrogenation to CH3OH via the RWGS + CO-Hydro pathway. These results bring insights into the Cu reduction behavior and the function of Cu+ species during methanol production on Cu-based catalysts without the assistance of active supports.
引用
收藏
页码:14694 / 14706
页数:13
相关论文
共 67 条
[1]   Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes [J].
Alvarez, Andrea ;
Bansode, Atul ;
Urakawa, Atsushi ;
Bavykina, Anastasiya V. ;
Wezendonk, Tim A. ;
Makkee, Michiel ;
Gascon, Jorge ;
Kapteijn, Freek .
CHEMICAL REVIEWS, 2017, 117 (14) :9804-9838
[2]   Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH [J].
Arena, Francesco ;
Italiano, Giuseppe ;
Barbera, Katia ;
Bordiga, Silvia ;
Bonura, Giuseppe ;
Spadaro, Lorenzo ;
Frusteri, Francesco .
APPLIED CATALYSIS A-GENERAL, 2008, 350 (01) :16-23
[3]   A DRIFTS STUDY OF THE MORPHOLOGY AND SURFACE ADSORBATE COMPOSITION OF AN OPERATING METHANOL SYNTHESIS CATALYST [J].
BAILEY, S ;
FROMENT, GF ;
SNOECK, JW ;
WAUGH, KC .
CATALYSIS LETTERS, 1995, 30 (1-4) :99-111
[4]   Heterogeneous Catalysis of CO2 Conversion to Methanol on Copper Surfaces [J].
Behrens, Malte .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (45) :12022-12024
[5]  
Behrens M, 2012, SCIENCE, V336, P893, DOI [10.1126/science.1219831, 10.1126/science.12198331]
[6]   Phosphinate stabilised ZnO and Cu colloidal nanocatalysts for CO2 hydrogenation to methanol [J].
Brown, N. J. ;
Weiner, J. ;
Hellgardt, K. ;
Shaffer, M. S. P. ;
Williams, C. K. .
CHEMICAL COMMUNICATIONS, 2013, 49 (94) :11074-11076
[7]   Methanol Synthesis from Industrial CO2 Sources: A Contribution to Chemical Energy Conversion [J].
Bukhtiyarova, Marina ;
Lunkenbein, Thomas ;
Kaehler, Kevin ;
Schloegl, Robert .
CATALYSIS LETTERS, 2017, 147 (02) :416-427
[8]   Self-consistent aspects of x-ray absorption calculations [J].
Bunau, O. ;
Joly, Y. .
JOURNAL OF PHYSICS-CONDENSED MATTER, 2009, 21 (34)
[9]   Mechanism of CO formation in reverse water-gas shift reaction over Cu/Al2O3 catalyst [J].
Chen, CS ;
Cheng, WH ;
Lin, SS .
CATALYSIS LETTERS, 2000, 68 (1-2) :45-48
[10]   Synthesis and characterization of supported copper phyllosilicate catalysts for acetic ester hydrogenation to ethanol [J].
Di, Wei ;
Cheng, Jihong ;
Tian, Shuxun ;
Li, Jing ;
Chen, Jingyun ;
Sun, Qi .
APPLIED CATALYSIS A-GENERAL, 2016, 510 :244-259