SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2022, Vol. 43 ›› Issue (3): 248-254.DOI: 10.1016/j.cjche.2021.12.022

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The highly selective catalytic hydrogenation of CO2 to CO over transition metal nitrides

Yichao Wu1, Zhiwei Xie1, Xiaofeng Gao2, Xian Zhou2, Yangzhi Xu1, Shurui Fan1, Siyu Yao2, Xiaonian Li1, Lili Lin1   

  1. 1. Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China;
    2. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2021-08-31 Revised:2021-12-21 Online:2022-04-28 Published:2022-03-28
  • Contact: Lili Lin,E-mail:linll@zjut.edu.cn
  • Supported by:
    This work was financially supported by the National Natural Science Foundation of China (22002140), Zhejiang Provincial Natural Science Foundation of China (Nos. LR21B030001 and LR22b030003), Young Elite Scientist Sponsorship Program by CAST (No. 2019QNRC001). Use of the Advanced Photon Source (beamlines 17-BM, for in-situ XRD characterization) was supported by the U.S. DOE under contract no. DE-AC02-06CH11357.

The highly selective catalytic hydrogenation of CO2 to CO over transition metal nitrides

Yichao Wu1, Zhiwei Xie1, Xiaofeng Gao2, Xian Zhou2, Yangzhi Xu1, Shurui Fan1, Siyu Yao2, Xiaonian Li1, Lili Lin1   

  1. 1. Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China;
    2. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
  • 通讯作者: Lili Lin,E-mail:linll@zjut.edu.cn
  • 基金资助:
    This work was financially supported by the National Natural Science Foundation of China (22002140), Zhejiang Provincial Natural Science Foundation of China (Nos. LR21B030001 and LR22b030003), Young Elite Scientist Sponsorship Program by CAST (No. 2019QNRC001). Use of the Advanced Photon Source (beamlines 17-BM, for in-situ XRD characterization) was supported by the U.S. DOE under contract no. DE-AC02-06CH11357.

Abstract: Three transition metal-like facet centered cubic structured transition metal nitrides, γ-Mo2N, β-W2N and δ-NbN, are synthesized and applied in the reaction of CO2 hydrogenation to CO. Among the three nitride catalysts, the γ-Mo2N exhibits superior activity to target product CO, which is 4.6 and 76 times higher than the other two counterparts of β-W2N and δ-NbN at 600 ℃, respectively. Additionally, γ-Mo2N exhibits excellent stability on both cyclic heating–cooling and high space velocity steady state operation. The deactivation degree of cyclic heating–cooling evaluation after 5 cycles and long-term stability performance at 773 and 873 K in 50 h are all less than 10%. In-situ XRD and kinetic studies suggest that the γ-Mo2N itself is able to activate both of the reactants CO2 and H2. Below 400 ℃, the reaction mainly occurs at the surface of γ-Mo2N catalyst. CO2 and H2 competitively adsorbe on the surface of catalyst and CO2 is the relatively stronger surface adsorbate. At a higher temperature, the interstitial vacancies of the γ-Mo2N can be reversibly filled with the oxygen from CO2 dissociation. Both of the surface and bulk phase sites of γ-Mo2N participate in the high temperature CO2 hydrogenation pathway.

Key words: Carbon dioxide, Chemical reaction, Catalysis, Reverse water gas shift (RWGS) reaction, Transition metal nitride, In-situ X-ray diffraction characterization

摘要: Three transition metal-like facet centered cubic structured transition metal nitrides, γ-Mo2N, β-W2N and δ-NbN, are synthesized and applied in the reaction of CO2 hydrogenation to CO. Among the three nitride catalysts, the γ-Mo2N exhibits superior activity to target product CO, which is 4.6 and 76 times higher than the other two counterparts of β-W2N and δ-NbN at 600 ℃, respectively. Additionally, γ-Mo2N exhibits excellent stability on both cyclic heating–cooling and high space velocity steady state operation. The deactivation degree of cyclic heating–cooling evaluation after 5 cycles and long-term stability performance at 773 and 873 K in 50 h are all less than 10%. In-situ XRD and kinetic studies suggest that the γ-Mo2N itself is able to activate both of the reactants CO2 and H2. Below 400 ℃, the reaction mainly occurs at the surface of γ-Mo2N catalyst. CO2 and H2 competitively adsorbe on the surface of catalyst and CO2 is the relatively stronger surface adsorbate. At a higher temperature, the interstitial vacancies of the γ-Mo2N can be reversibly filled with the oxygen from CO2 dissociation. Both of the surface and bulk phase sites of γ-Mo2N participate in the high temperature CO2 hydrogenation pathway.

关键词: Carbon dioxide, Chemical reaction, Catalysis, Reverse water gas shift (RWGS) reaction, Transition metal nitride, In-situ X-ray diffraction characterization