Citation: Jiarui Gao, Jia-Wei Yang, Tenglin Ma, Jia Wang, Dan Xia, Bin Du, Yan Cui, Chengwu Yang. Mechanism study on direct synthesis of glycerol carbonate from CO₂ and glycerol over shaped CeO₂ model catalysts[J]. Chinese Chemical Letters, ;2023, 34(12): 108395. doi: 10.1016/j.cclet.2023.108395 shu

Mechanism study on direct synthesis of glycerol carbonate from CO₂ and glycerol over shaped CeO₂ model catalysts

Jiarui Gao ^{a, 1} ,
Jia-Wei Yang ^{b, 1} ,
Tenglin Ma ^a ,
Jia Wang ^a ,
Dan Xia ^a ,
Bin Du ^c ,
Yan Cui ^c ,
Chengwu Yang ^{a, *,}

a.
School of Space and Environment, Beihang University, Beijing 100191, China
b.
The Future Laboratory, Tsinghua University, Beijing 100084, China
c.
PetroChina Petrochemical Research Institute, Beijing 100195, China

yangcw@buaa.edu.cn

Received Date: 19 February 2023
Revised Date: 11 March 2023
Accepted Date: 27 March 2023
Available Online: 2 April 2023

Figures(6)

Direct synthesis of glycerol carbonate (GC) from CO₂ and glycerol (a byproduct of biodiesel production) is a route to obtain a high-value chemical from waste and low-cost byproducts but has not yet industrialized due to the lack of efficient catalysts. Ceria (CeO₂) exhibits the highest catalytic activity and GC selectivity among the heterogeneous catalysts studied so far. However, the mechanism of this reaction over CeO₂ catalysts has not been studied in detail. Herein, we synthesized CeO₂ nanocrystals with different morphologies as model catalysts that can predominantly expose {111}, {110}, and {100} facets, and their surface acid-base properties were characterized using high-sensitivity temperature-programmed desorption of NH₃ and CO₂ with quadrupole mass spectrometry as detector (NH₃-TPD-QMS and CO₂-TPD-QMS). We found that the catalytic performance (GC formation rate) is strictly linearly dependent on the density of basic sites, which is relevant to the adsorption and activation of CO₂. In addition, to illustrate a more microscopic reaction mechanisms underlying the formation of GC from CO₂ and glycerol on all three low-index surfaces (111), (110) and (100), we also performed comprehensive first principles calculations. A three-step Langmuir–Hinshelwood (LH) mechanism was identified in which the annulation reaction is the rate-limiting step. The CeO₂ (111) surface exhibits the lowest overall activation energy, which agrees well with the catalytic performance that the CeO₂ nano-octahedra, predominantly exposing {111} facets, have the highest GC formation rate. This work is the first to combine experiments on shaped CeO₂ model catalysts with first-principles calculations to gain insight into the mechanism of direct synthesis of GC from CO₂ and glycerol, and will aid in the development of catalysts with improved performance.
- CO₂ conversion,
- Glycerol carbonate,
- CeO₂,
- Acid-base properties,
- Reaction mechanism
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Mechanism study on direct synthesis of glycerol carbonate from CO2 and glycerol over shaped CeO2 model catalysts

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通讯作者: 陈斌, bchen63@163.com

Mechanism study on direct synthesis of glycerol carbonate from CO₂ and glycerol over shaped CeO₂ model catalysts