English

Ir Single Atoms and Clusters Supported on α-MoC as Catalysts for Efficient Hydrogenation of CO₂ to CO

• Junwen Lu ^{1, 2,} ,
• Shunan Zhang ^{3, ,} ,
• Haozhi Zhou ^3, ,
• Chaojie Huang ^{1, 2,} ,
• Lin Xia ^1, ,
• Xiaofang Liu ^1, ,
• Hu Luo ^1, ,
• Hui Wang ^{1, 3, ,}

• 1.

  CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China

• 2.

  University of Chinese Academy of Sciences, Beijing 100049, China

• 3.

  Institute of Carbon Neutrality, ShanghaiTech University, Shanghai 201203, China

Corresponding author: Shunan Zhang, zhangshn2@shanghaitech.edu.cn Hui Wang, wanghh@sari.ac.cn

• Received Date: 14 February 2023
  Accepted Date: 21 March 2023
  Revised Date: 20 March 2023
  Available Online: 15 November 2023
• Fund Project:

Abstract: The conversion of CO₂ into CO via the reverse water gas shift (RWGS) reaction has recently attracted considerable attention owing to the increase in atmospheric CO₂ emissions. However, metal-supported catalysts easily undergo sintering and become inactive at high temperatures. To fabricate highly active and stable catalysts, molybdenum carbide (Mo_xC), with properties similar to those of precious metals, has been extensively investigated. In particular, it has been demonstrated that face-centered cubic α-MoC can strongly interact with support metals, rendering it an attractive candidate as a catalyst for the RWGS reaction. Furthermore, it has been previously demonstrated that metallic Ir, with unique electronic properties and a low CO desorption barrier, is active for the RWGS at low temperatures (250–300 ℃). Accordingly, in this study, a system of Ir species and α-MoC was constructed using a solvent evaporation self-assembly method. The catalytic performance of the Ir/MoC catalysts for the RWGS reaction was considerably superior to that of pure α-MoC over a wide temperature range (200–500 ℃) owing to the synergistic effect of Ir and α-MoC. The optimal 0.5%Ir/MoC catalyst yielded a CO₂ conversion of 48.4% at 500 ℃, 0.1 MPa, and 300000 mL·g⁻¹·h⁻¹, which was comparable to the equilibrium conversion (49.9%). The CO selectivity and space-time yield of CO over 0.5%Ir/MoC reached 94.0% and 423.1 μmol·g⁻¹·s⁻¹, respectively, which were higher than most of the previously reported values. Moreover, 0.5%Ir/MoC retained its catalytic properties over 100 h and demonstrated excellent stability at high temperatures. Several characterization methods were used to demonstrate that the Ir species supported on α-MoC substrates were highly dispersed. The strong metal-support interaction between Ir and α-MoC, which occurred via electron transfer, considerably improved the stability of the Ir/MoC catalysts. For the Ir/MoC catalysts with Ir loadings > 0.2% (mass fraction), Ir single atoms (Ir₁) and clusters (Ir_n) coexisted to create Ir_n-Ir₁-C-Mo synergistic sites between Ir and α-MoC. The number of Ir₁ species and size of Ir_n species of 0.5%Ir/MoC were higher and smaller, respectively, than those of the other Ir/MoC catalysts. This conferred 0.5%Ir/MoC an optimal electron density, which contributed to the remarkable adsorption and activation of CO₂ and H₂ during the RWGS. In situ diffuse reflectance infrared Fourier transform spectroscopy experiments revealed that the RWGS reaction mechanism occurred via a formate pathway. Although the formation of Ir_n-Ir₁-C-Mo synergistic sites did not affect the reaction mechanism, the generation and decomposition of formate intermediates were distinctly promoted. Therefore, the catalytic performance of Ir/MoC was effectively improved by the synergistic effect. This study provides a guide for designing efficient and stable catalysts for CO₂ utilization.

Key words:
• Reverse water gas shift reaction
•  /  Metal-support interaction
•  /  Synergistic effect
•  /  Molybdenum carbide
•  /  Iridium catalyst

• 1. [1]

     Su, X.; Yang, X.; Zhao, B.; Huang, Y. J. Energy Chem. 2017, 26 (5), 854. doi: 10.1016/j.jechem.2017.07.006

  2. [2]

     Chu, W.; Wang, L. -N.; Chernavskii, P. A.; Khodakov, A. Y. Angew. Chem. Int. Ed. 2008, 47 (27), 5052. doi: 10.1002/anie.200800657

  3. [3]

     Zhang, D.; Luo, J.; Wang, J.; Xiao, X.; Liu, Y.; Qi, W.; Su, D. S.; Chu, W. Chin. J. Catal. 2018, 39 (1), 157. doi: 10.1016/S1872-2067(17)62967-X

  4. [4]

     Varvoutis, G.; Lykaki, M.; Papista, E.; Carabineiro, S. A. C.; Psarras, A. C.; Marnellos, G. E.; Konsolakis, M. J. CO₂ Util. 2021, 44, 101408. doi: 10.1016/j.jcou.2020.101408

  5. [5]

     Loiland, J. A.; Wulfers, M. J.; Marinkovic, N. S.; Lobo, R. F. Catal. Sci. Technol. 2016, 6 (14), 5267. doi: 10.1039/C5CY02111A

  6. [6]

     Lu, B.; Kawamoto, K. J. Environ. Chem. Eng. 2013, 1 (3), 300. doi: 10.1016/j.jece.2013.05.008

  7. [7]

     Vovchok, D.; Zhang, C.; Hwang, S.; Jiao, L.; Zhang, F.; Liu, Z.; Senanayake, S. D.; Rodriguez, J. A. ACS Catal. 2020, 10 (17), 10216. doi: 10.1021/acscatal.0c01584

  8. [8]

     Jung, H.S.; Zafar, F.; Wang, X.; Nguyen, T. X.; Hong, C. H.; Hur, Y. G.; Choung, J. W.; Park, M. -J.; Bae, J. W. ACS Catal. 2021, 11 (22), 14210. doi: 10.1021/acscatal.1c04451

  9. [9]

     Liu, H. -X.; Li, S. -Q.; Wang, W. -W.; Yu, W. -Z.; Zhang, W. -J.; Ma, C.; Jia, C. J. Nat. Commun. 2022, 13 (1), 867. doi: 10.1038/s41467-022-28476-5

  10. [10]

      Morse, J. R.; Juneau, M.; Baldwin, J. W.; Porosoff, M. D.; Willauer, H. D. J. CO₂ Util. 2020, 35, 38. doi: 10.1016/j.jcou.2019.08.024

  11. [11]

      Rodriguez, J. A.; Evans, J.; Feria, L.; Vidal, A. B.; Liu, P.; Nakamura, K.; Illas, F. J. Catal. 2013, 307, 162. doi: 10.1016/j.jcat.2013.07.023

  12. [12]

      Porosoff, M. D.; Yan, B.; Chen, J. G. Energ Environ. Sci. 2016, 9 (1), 62. doi: 10.1039/C5EE02657A

  13. [13]

      Li, J.; Liu, L.; Liu, Y.; Li, M.; Zhu, Y.; Liu, H.; Kou, Y.; Zhang, J.; Han, Y.; Ma, D. Energ Environ. Sci. 2014, 7 (1), 393. doi: 10.1039/C3EE41945B

  14. [14]

      Ma, Y.; Guo, Z.; Jiang, Q.; Wu, K. -H.; Gong, H.; Liu, Y. J. Energy Chem. 2020, 50, 37. doi: 10.1016/j.jechem.2020.03.012

  15. [15]

      Zhang, X.; Zhu, X.; Lin, L.; Yao, S.; Zhang, M.; Liu, X.; Wang, X.; Li, Y. -W.; Shi, C.; Ma, D. ACS Catal. 2016, 7 (1), 912. doi: 10.1021/acscatal.6b02991

  16. [16]

      Li, S.; Cao, R.; Xu, M.; Deng, Y.; Lin, L.; Yao, S.; Liang, X.; Peng, M.; Gao, Z.; Ge, Y. Nat. Sci. Rev. 2021, 9 (1), 2095. doi: 10.1093/nsr/nwab026

  17. [17]

      Lin, L.; Zhou, W.; Gao, R.; Yao, S.; Zhang, X.; Xu, W.; Zheng, S.; Jiang, Z.; Yu, Q.; Li, Y. -W. Nature 2017, 544 (7648), 80. doi: 10.1038/nature21672

  18. [18]

      Ge, Y.; Qin, X.; Li, A.; Deng, Y.; Lin, L.; Zhang, M.; Yu, Q.; Li, S.; Peng, M.; Xu, Y. J. Am. Chem. Soc. 2021, 143 (2), 628. doi: 10.1021/jacs.0c11285

  19. [19]

      Fan, X.; Liu, C.; Wu, M.; Gao, B.; Zheng, L.; Zhang, Y.; Zhang, H.; Gao, Q.; Cao, X.; Tang, Y. Appl. Catal. B 2022, 318, 121867. doi: 10.1016/j.apcatb.2022.121867

  20. [20]

      Reddy, K. P.; Dama, S.; Mhamane, N. B.; Ghosalya, M. K.; Raja, T.; Satyanarayana, C. V.; Gopinath, C. S. Dalton Trans. 2019, 48 (32), 12199. doi: 10.1039/C9DT01774G

  21. [21]

      Gao, J.; Wu, Y.; Jia, C.; Zhong, Z.; Gao, F.; Yang, Y.; Liu, B. Catal. Commun. 2016, 84, 147. doi: 10.1016/j.catcom.2016.06.026

  22. [22]

      马丁. 物理化学学报, 2019, 35 (8), 794. doi: 10.3866/PKU.WHXB201810033Ma, D. Acta Phys. -Chim. Sin. 2019, 35 (8), 794. doi: 10.3866/PKU.WHXB201810033

  23. [23]

      Deng, Y.; Ge, Y.; Xu, M.; Yu, Q.; Xiao, D.; Yao, S.; Ma, D. Acc. Chem. Res. 2019, 52 (12), 3372. doi: 10.1021/acs.accounts.9b00182

  24. [24]

      Yao, S.; Zhang, X.; Zhou, W.; Gao, R.; Xu, W.; Ye, Y.; Lin, L.; Wen, X.; Liu, P.; Chen, B. Science 2017, 357 (6349), 389. doi: 10.1126/science.aah4321

  25. [25]

      Lin, L.; Yao, S.; Gao, R.; Liang, X.; Yu, Q.; Deng, Y.; Liu, J.; Peng, M.; Jiang, Z.; Li, S. Nat. Nanotechnol. 2019, 14 (4), 354. doi: 10.1038/s41565-019-0366-5

  26. [26]

      吴凯, 物理化学学报, 2017, 33 (6), 1073. doi: 10.3866/PKU.WHXB201704122Wu, K. Acta Phys. -Chim. Sin. 2017, 33 (6), 1073. doi: 10.3866/PKU.WHXB201704122

  27. [27]

      Jin, C.; Wang, B.; Zhou, Y.; Yang, F.; Guo, P.; Liu, Z.; Shen, W. Chem. Commun. 2022, 58 (52), 7313. doi: 10.1039/D2CC02478K

  28. [28]

      Guo, Y.; Wang, M.; Zhu, Q.; Xiao, D.; Ma, D. Nat. Catal. 2022, 5 (9), 766. doi: 10.1038/s41929-022-00839-7

  29. [29]

      Chen, X.; Su, X.; Su, H. -Y.; Liu, X.; Miao, S.; Zhao, Y.; Sun, K.; Huang, Y.; Zhang, T. ACS Catal. 2017, 7 (7), 4613. doi: 10.1021/acscatal.7b00903

  30. [30]

      Perumal, S.; Lim, T.; Seenivasan, S.; Seo, J. Appl. Surf. Sci. 2022, 604, 154553. doi: 10.1016/j.apsusc.2022.154553

  31. [31]

      Zhang, Y.; Zhang, Z.; Yang, X.; Wang, R.; Duan, H.; Shen, Z.; Li, L.; Su, Y.; Yang, R.; Zhang, Y. Green Chem. 2020, 22 (20), 6855. doi: 10.1039/D0GC02302G

  32. [32]

      Li, S.; Xu, Y.; Chen, Y.; Li, W.; Lin, L.; Li, M.; Deng, Y.; Wang, X.; Ge, B.; Yang, C. Angew. Chem. Int. Ed. 2017, 56 (36), 10761. doi: 10.1002/anie.201705002

  33. [33]

      Lin, L.; Yu, Q.; Peng, M.; Li, A.; Yao, S.; Tian, S.; Liu, X.; Li, A.; Jiang, Z.; Gao, R. J. Am. Chem. Soc. 2021, 143 (1), 309. doi: 10.1021/jacs.0c10776

  34. [34]

      Zuo, J.; Na, W.; Zhang, P.; Yang, X.; Wen, J.; Zheng, M.; Wang, H. Mol. Catal. 2022, 526, 112357. doi: 10.1016/j.mcat.2022.112357

  35. [35]

      Pahija, E.; Panaritis, C.; Gusarov, S.; Shadbahr, J.; Bensebaa, F.; Patience, G.; Boffito, D. C. ACS Catal. 2022, 12 (12), 6887. doi: 10.1021/acscatal.2c01099

  36. [36]

      Zhang, Q.; Pastor-Pérez, L.; Jin, W.; Gu, S.; Reina, T. R. Appl. Catal. B. 2019, 244, 889. doi: 10.1016/j.apcatb.2018.12.023

  37. [37]

      Wang, L. -X.; Guan, E.; Wang, Z.; Wang, L.; Gong, Z.; Cui, Y.; Yang, Z.; Wang, C.; Zhang, J.; Meng, X. ACS Catal. 2020, 10 (16), 9261. doi: 10.1021/acscatal.0c00907

  38. [38]

      Xu, J.; Gong, X.; Hu, R.; Liu, Z. -W.; Liu, Z. -T. Mol. Catal. 2021, 516, 111954. doi: 10.1016/j.mcat.2021.111954

  39. [39]

      Ma, Y.; Ren, Y.; Zhou, Y.; Liu, W.; Baaziz, W.; Ersen, O.; Cuong, P.; Greiner, M.; Chu, W.; Wang, A. Angew. Chem. Int. Ed. 2020, 59 (48), 21613. doi: 10.1002/anie.202007707

  40. [40]

      Gu, F.; Zheng, L.; Wei, H.; Mi, W.; Zhang, C.; Su, Q.; Zhu, W.; Lin, W. Appl. Surf. Sci. 2022, 606, 155008. doi: 10.1016/j.apsusc.2022.155008

  41. [41]

      Tang, Y.; Yang, Z.; Guo, C.; Han, H.; Jiang, Y.; Wang, Z.; Liu, J.; Wu, L.; Wang, F. J. Mater. Chem. A 2022, 10 (22), 12157. doi: 10.1039/D2TA00933A

  42. [42]

      Yang, Q.; Sun, K.; Xu, Y.; Ding, Z.; Hou, R. Appl. Catal. A-Gen. 2022, 630, 118455. doi: 10.1016/j.apcata.2021.118455

  43. [43]

      Chen, J. G. Chem. Rev. 1996, 96 (4), 1477. doi: 10.1021/cr950232u

  44. [44]

      Xia, Z.; Zhang, H.; Shen, K.; Qu, Y.; Jiang, Z. Phys. B Condens. Matter. 2018, 542, 12. doi: 10.1016/j.physb.2018.04.039

  45. [45]

      Ravel, B.; Newville, M. J. Synchrot. Radiat. 2005, 12 (4), 537. doi: 10.1107/S0909049505012719

  46. [46]

      Wang, S. -G.; Liao, X. -Y.; Cao, D. -B.; Huo, C. -F.; Li, Y. -W.; Wang, J.; Jiao, H. J. Phys. Chem. 2007, 111 (45), 16934. doi: 10.1021/jp074570y

  47. [47]

      Liu, H. -X.; Li, J. -Y.; Qin, X.; Ma, C.; Wang, W. -W.; Xu, K.; Yan, H.; Xiao, D.; Jia, C. -J.; Fu, Q. Nat. Commun. 2022, 13 (1), 5800. doi: 10.1038/s41467-022-33308-7

  48. [48]

      Alvarez-Galvan, C.; Lustemberg, P. G.; Oropeza, F. E.; Bachiller-Baeza, B.; Dapena Ospina, M.; Herranz, M.; Cebollada, J.; Collado, L.; Campos-Martin, J. M.; de la Peña-O'Shea, V. A. ACS Appl. Mater. Interfaces 2022, 14 (45), 50739. doi: 10.1021/acsami.2c11248

  49. [49]

      Zhang, Y.; Liang, L.; Chen, Z.; Wen, J.; Zhong, W.; Zou, S.; Fu, M.; Chen, L.; Ye, D. Appl. Surf. Sci. 2020, 516, 146035. doi: 10.1016/j.apsusc.2020.146035

  50. [50]

      Zhang, X.; Liu, Y.; Zhang, M.; Yu, T.; Chen, B.; Xu, Y.; Crocker, M.; Zhu, X.; Zhu, Y.; Wang, R. Chem 2020, 6 (12), 3312. doi: 10.1016/j.chempr.2020.09.016

  51. [51]

      Xu, D.; Ding, M.; Hong, X.; Liu, G. ACS Catal. 2020, 10 (24), 14516. doi: 10.1021/acscatal.0c03575

  52. [52]

      Zheng, H.; Liao, W.; Ding, J.; Xu, F.; Jia, A.; Huang, W.; Zhang, Z. ACS Catal. 2022, 12 (24), 15451. doi: 10.1021/acscatal.2c04437

  53. [53]

      Bobadilla, L. F.; Santos, J. L.; Ivanova, S.; Odriozola, J. A.; Urakawa, A. ACS Catal. 2018, 8 (8), 7455. doi: 10.1021/acscatal.8b02121

•