Mechanism and kinetics for methanol synthesis from CO<sub>2</sub>/H<sub>2</sub> over Cu and Cu/oxide surfaces: Recent investigations by first-principles-based simulation

doi:10.1007/s11458-011-0250-9

Front Chem Chin

2011, Vol. 6

Issue (3) : 164-172 https://doi.org/10.1007/s11458-011-0250-9

REVIEW ARTICLE

Mechanism and kinetics for methanol synthesis from CO₂/H₂ over Cu and Cu/oxide surfaces: Recent investigations by first-principles-based simulation

Qiuyang SUN, Zhipan LIU(

)

Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Key Laboratory of Computational Physical Science (Ministry of Education), Fudan University, Shanghai 200433, China

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Abstract

The efficient fixation and utilization of CO₂ has been consistently pursued by chemists for decades. Although Cu-based catalysts, e.g., Cu/ZnO/Al₂O₃, have been widely used in industry for methanol synthesis from CO₂ hydrogenation (CO₂ + 3H₂→H₃COH+ H₂O), many issues on the mechanism and the kinetics remain largely uncertain. For example, the surface site for CO₂ activation and the synergetic effect between Cu and oxide have been hotly debated in literature. In the past few years, theoretical modeling on pure Cu surfaces and Cu/oxide interfaces has been utilized to provide insight into these important questions. Here we will review the recent theoretical advances on simulating this complex heterogeneous catalytic process with first principles density functional theory (DFT) calculations and kinetics modeling. The theoretical results on the mechanism and the kinetics are compared and summarized.

Keywords density functional theory calculation CO₂ hydrogenation methanol synthesis Cu-based catalysts review

Corresponding Author(s): LIU Zhipan,Email:zpliu@fudan.edu.cn

Issue Date: 05 September 2011

Cite this article:

Qiuyang SUN,Zhipan LIU. Mechanism and kinetics for methanol synthesis from CO₂/H₂ over Cu and Cu/oxide surfaces: Recent investigations by first-principles-based simulation[J]. Front Chem Chin, 2011, 6(3): 164-172.

URL:

https://academic.hep.com.cn/fcc/EN/10.1007/s11458-011-0250-9
https://academic.hep.com.cn/fcc/EN/Y2011/V6/I3/164

Fig.1 (a) A model adcluster for Cu(100); (b) a Cu nanoparticle; (c) Cu(111) surface; (d) Cu strip at the stepped m-ZrO(12). Reprinted from Refs. [,,,] respectively.

Tab.1 Mechanisms of methanol synthesis from CO/H determined on different Cu-based model systems

Fig.2 Potential Energy Surface (PES) of methanol synthesis on Cu (111) from CO through competing pathways. The black line indicates the lowest energy pathway through the: HCOO*, HCOOH*, CHO*, CHO* and CHO* intermediates. The main intermediates along the red path are: HCOO*, HCO*, CHO*, and CHOH*. The two dashed horizontal lines indicate the desorption barriers of HCOOH and CHO. Reprinted from Ref. [].

Fig.3 Potential energy diagram for the methanol synthesis reaction on the Cu(111) surface and Cu nanoparticle, where the thin bar represents the intermediates and the thick bar represents the transition states. The upper diagram corresponds to Cu(111) and the lower diagram corresponds to Cu. Reprinted from Ref. []

Fig.4 Proposed reaction mechanism of CO hydrogenation over Cu/ZrO according to kMC simulation results. Solid and broken lines are the major and minor routes, respectively. The percentage labeled on the arrows show contributions of elementary steps. Reprinted from Ref. []

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