English

Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst

• Feifei Yang ^{1, ,} ,
• Wei Zhou ^1, ,
• Chaoran Yang ^{2, 3,} ,
• Tianyu Zhang ^{2, 3, ,} ,
• Yanqiang Huang ^4,

• 1.

  School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu Province, China

• 2.

  Beijing Key Lab for Source Control Technology of Water Pollution, College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China

• 3.

  Engineering Research Center for Water Pollution Source Control & Eco-Remediation, College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China

• 4.

  CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

Corresponding author: Emails: feiyang@cumt.edu.cn (F.Y.); Tel.: +86-18222577901 (F.Y.); Emails: tzhang@bjfu.edu.cn (T.Z.); +86-18811622063 (T.Z.)

• Received Date: 12 August 2023
  Accepted Date: 08 September 2023
  Revised Date: 07 September 2023
  Available Online: 15 July 2024
• Fund Project:

  the National Key Research and Development Program of China 

  National Natural Science Foundation of China 

  Natural Science Foundation of Jiangsu Province, China 

  the Safety Discipline Group Project of China University of Mining and Technology, China 

  the Carbon Peak Carbon Neutrality Technology Innovation Special Fund Project of Jiangsu Province, China 

  China National Postdoctoral Program for Innovative Talents 

Abstract: Selective hydrogenation of CO₂ to methanol with renewable H₂ is a promising approach to effectively utilize the anthropogenic greenhouse gas CO₂ in response to the growing environmental and energy challenges. Recently, MoS₂ has gained attention as an attractive catalyst for CO₂ hydrogenation due to its tunable S vacancy sites. However, its catalytic reactivity towards methanol production is still unsatisfactory because the general edge S vacancy site tends to favor CH₄ formation. Herein, we report that the alkali K decorated MoS₂ catalyst enables a dramatically enhancement in selective hydrogenation of CO₂ to methanol, in contrast to the pristine MoS₂ nanosheets that produce mainly CH₄. We incorporated the K promoter into MoS₂ using a simple physical mixture method, and we found that the loading of K has a crucial impact on the catalytic performance. The K-MoS₂ catalyst with an appropriate K loading of 0.5 wt.% (mass fraction) delivers an optimized methanol selectivity of 81% and a methanol space time yield of 3.6 mmol·g^-1·h^-1 at mild reaction conditions of 220 ℃ and 5 MPa, which greatly outperforms the bare MoS₂. Higher K loading would lead CO as the dominating product, while lower K loading is insufficient to tune the selectivity. Detailed characterization techniques, including X-ray diffraction (XRD), Raman, H₂-temperature programmed reduction (TPR), electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), CO-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and H₂-D₂-temperature programmed surface reaction (TPSR), reveal that K atoms tend to occupy the edge sites on MoS₂ and serve as electron donators, which enhance the density of states at the Fermi surface and the basicity of the edge active sites, while preventing H₂ dissociation on the edge S vacancy. The reaction mechanism, as studied by CO₂-temperature programmed desorption (TPD) and CO₂ + H₂ DRIFTS, suggests a reverse water-gas shift route for CO₂hydrogenation to methanol. The increased basicity at the edge active site has therefore facilitates CO₂ adsorption and lowers the activation barrier for CO₂ dissociation to CO. It also restrains the methanation activity of intermediate CO and directs the reaction path toward CO hydrogenation to methanol. However, the excessive inhibition of H₂ dissociation at higher K loading levels causes the facile desorption of CO, resulting in high CO selectivity. These results highlight the appearing effect of K promoter on modulating the edge active sites of MoS₂ to favor methanol formation over CH₄, and provide a simple yet effective strategy for tuning the structure and catalytic performance of MoS₂. This extends the application of MoS₂-based catalysts in methanol synthesis via CO₂ hydrogenation.

Key words:
• CO₂ hydrogenation
•  /  Methanol
•  /  CH₄
•  /  Selectivity tuning
•  /  K-MoS₂

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