English

Surface Sulfur Species Influence Hydrogenation Performance of Palladium-Sulfur Nanosheets

• Weihan Zhang ^{1, †,} ,
• Menglu Wang ^{1, †,} ,
• Ankang Jia ^1, ,
• Wei Deng ^2, ,
• Shuxing Bai ^{1, ,}

• 1.

  Institute for Sustainable Energy and Resources, College of Chemistry and Chemical Engineering, Qingdao University, Qingdao 266071, Shandong Province, China

• 2.

  School of Optoelectronic Materials and Technology, Jianghan University, Wuhan 430056, China

Corresponding author: Shuxing Bai, Email: shuxbai@qdu.edu.cn; Tel.: +86-15063919273

• Received Date: 27 September 2023
  Accepted Date: 13 November 2023
  Revised Date: 10 November 2023
  Available Online: 15 November 2024
• Fund Project:

  the National Natural Science Foundation of China 

  the Natural Science Foundation of Shandong Province, China 

  the Start-up Supports from Qingdao University 

• ^†These authors contributed equally to this work.

Abstract: Olefins play a crucial role as fundamental raw materials in organic synthesis, particularly in the production of polyolefins and synthetic rubber. The conversion of alkynes to olefins is pivotal in both the polymer and fine chemical industries. However, this process faces significant challenges in terms of equilibrium selectivity and activity. The inherent low solubility of hydrogen, coupled with the thermodynamic ease of hydrogenating intermediate olefins compared to alkynes, contributes to a decline in olefin selectivity due to further hydrogenation leading to alkanes. Palladium-based catalysts, widely used for hydrogenation, exhibit robust hydrogen adsorption but lack selectivity. Researchers commonly modify catalyst structures by introducing other metals or non-metals to create intermetallic compounds, aiming to enhance olefin selectivity. This study focuses on synthesizing palladium-sulfur nanosheets (Pd-S NSs) using various sulfur sources to explore the impact of surface S species on the catalytic efficiency of selectively hydrogenating alkynes. Among these, Pd-S-PT NSs/C, utilizing 1,4-benzenedithiol (PT) as the sulfur source, demonstrated high styrene selectivity (92.3%–96.7%) following phenylacetylene hydrogenation for 2 h, showing notable selectivity for different alkynes' end-groups. Contrastingly, Pd-S-TU NSs/C, with thiourea (TU) as the sulfur source, exhibited poor olefin selectivity (72.4%). X-ray photoelectron spectroscopy (XPS) revealed that the improved olefin selectivity in Pd-S-PT NSs/C was attributed to hindered electron transfer from Pd to S, as well as the presence of surface S⁰ species, maintaining high hydrogenation activity while avoiding over-hydrogenation induced by oxidized S species (S⁴⁺). In situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) demonstrated weak styrene adsorption on Pd-S-PT NSs, inhibiting further hydrogenation to ethylbenzene. The ease of styrene desorption on Pd-S-PT NSs, indicated by reduced adsorption strength with increasing desorption temperature, highlighted high olefin selectivity. Conversely, stronger styrene adsorption on Pd-S-TU NSs facilitated additional hydrogenation to produce ethylbenzene, suggesting that the presence of additional S⁴⁺ species hindered improved styrene selectivity. This study not only introduces efficient catalysts for olefin hydrogenation but also advances fundamental research on precisely controlling catalytic processes, particularly focusing on the nuanced control of catalytic surfaces.

Key words:
• Palladium-sulfur nanosheets
•  /  Surface sulfur species
•  /  Alkyne hydrogenation
•  /  Alkene
•  /  Selectivity

• 1. [1]

     Crespo-Quesada, M.; Yarulin, A.; Jin, M. S.; Xia, Y. N.; Kiwi-Minsker, L. J. Am. Chem. Soc. 2011, 133, 12787. doi: 10.1021/ja204557m

  2. [2]

     Teschner, D.; Borsodi, J.; Wootsch, A.; Revay, Z.; Havecker, M.; Knop-Gericke, A.; Jackson, S. D.; Schlogl, R. Science 2008, 320, 86. doi: 10.1126/science.1155200

  3. [3]

     Liu, K. L.; Jiang, L. Z.; Huang, W. G.; Zhu, G. Z.; Zhang, Y. J.; Xu, C. F.; Qin, R. X.; Liu, P. X.; Hu, C. Y.; Wang, J. J.; et al. Nat. Commun. 2022, 13, 2597. doi: 10.1038/s41467-022-30327-2

  4. [4]

     Boudart, M.; Hwang, H. J. Catal. 1975, 39, 44. doi: 10.1016/0021-9517(75)90280-8

  5. [5]

     Liu, K.; Qin, R.; Zheng, N. J. Am. Chem. Soc. 2021, 143, 4483. doi: 10.1021/jacs.0c13185

  6. [6]

     Mitsudome, T.; Takahashi, Y.; Ichikawa, S.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Angew. Chem. Int. Ed. 2013, 52, 1481. doi: 10.1002/anie.201207845

  7. [7]

     Studt, F.; Abild-Pedersen, F.; Bligaard, T.; Sørensen, R. Z.; Christensen, C. H.; Nørskov, J. K. Angew. Chem. Int. Ed. 2008, 120, 9439. doi: 10.1002/ange.200802844

  8. [8]

     Slack, E. D.; Gabriel, C. M.; Lipshutz, B. H. Angew. Chem. Int. Ed. 2014, 53, 14051. doi: 10.1002/ange.201407723

  9. [9]

     Ulan, J. G.; Maier, W. F.; Smith, D. A. J. Org. Chem. 1987, 52, 3132. doi: 10.1021/jo00390a032

  10. [10]

      Teschner, D.; Vass, E.; Havecker, M.; Zafeiratos, S.; Schnorch, P.; Sauer, H.; Knop-Gericke, A.; Schloegl, R.; Chamam, M.; Wootsch, A.; et al. J. Catal. 2006, 242, 26. doi: 10.1016/j.jcat.2006.05.030

  11. [11]

      王沾祺, 周志明, 张锐, 李莉, 程振民. 物理化学学报, 2014, 30, 2315. doi: 10.3866/PKU.WHXB201410152Wang, Z.-Q.; Zhou, Z.-M.; Zhang, R.; Li, L.; Cheng, Z.-M. Acta Phys.-Chim. Sin. 2014, 30, 2315. doi: 10.3866/PKU.WHXB201410152

  12. [12]

      Feng, Q.; Zhao, S.; Wang, Y.; Dong, J.; Chen, W.; He, D.; Wang, D.; Yang, J.; Zhu, Y.; Zhu, H. J. Am. Chem. Soc. 2017, 139, 7294. doi: 10.1021/jacs.7b01471

  13. [13]

      Pachulski, A.; Schödel, R.; Claus, P. Appl. Catal. A: Gen. 2011, 400, 14. doi: 10.1016/j.apcata.2011.03.019

  14. [14]

      Vile, G.; Albani, D.; Nachtegaal, M.; Chen, Z. P.; Dontsova, D.; Antonietti, M.; Lopez, N.; Perez-Ramirez, J. Angew. Chem. Int. Ed. 2015, 54, 11265. doi: 10.1002/anie.201505073

  15. [15]

      Ravanchi, M. T.; Sahebdelfar, S.; Komeili, S. Rev. Chem. Eng. 2018, 34, 215. doi: 10.1515/revce-2016-0036

  16. [16]

      Wei, Z. Z.; Yao, Z. H.; Zhou, Q.; Zhuang, G. L.; Zhong, X.; Deng, S. W.; Li, X. N.; Wang, J. G. ACS Catal. 2019, 9, 10656. doi: 10.1021/acscatal.9b03300

  17. [17]

      Studt, F.; Abild-Pedersen, F.; Bligaard, T.; Sorensen, R. Z.; Christensen, C. H.; Norskov, J. K. Science 2008, 320, 1320. doi: 10.1126/science.1156660

  18. [18]

      Dong, M. J.; Wang, X.; Wu, C. D. Adv. Funct. Mater. 2020, 30, 1908519. doi: 10.1002/adfm.201908519

  19. [19]

      Chan, C. W. A.; Mahadi, A. H.; Li, M. M. J.; Corbos, E. C.; Tang, C.; Jones, G.; Kuo, W. C. H.; Cookson, J.; Brown, C. M.; Bishop, P. T.; Tsang, S. C. E. Nat. Commun. 2014, 5, 5787. doi: 10.1038/ncomms6787

  20. [20]

      Li, H. Z.; Gao, Y.; Wu, Y. M.; Liu, C. B.; Cheng, C. Q.; Chen, F. P.; Shi, Y. M.; Zhang, B. J. Am. Chem. Soc. 2022, 144, 19456. doi: 10.1021/jacs.2c07742

  21. [21]

      Wu, Y. M.; Liu, C. B.; Wang, C. H.; Lu, S. Y.; Zhang, B. Angew. Chem. Int. Ed. 2020, 59, 21170. doi: 10.1002/anie.202009757

  22. [22]

      Yang, Y.; Zhu, X. J.; Wang, L. L.; Lang, J. Y.; Yao, G. H.; Qin, T.; Ren, Z. H.; Chen, L. W.; Liu, X.; Li, W.; et al. Nat. Commun. 2022, 13, 2754. doi: 10.1038/s41467-022-30540-z

  23. [23]

      Albani, D.; Shahrokhi, M.; Chen, Z.; Mitchell, S.; Hauert, R.; López, N.; Pérez-Ramírez, J. Nat. Commun. 2018, 9, 2634. doi: 10.1038/s41467-018-05052-4

  24. [24]

      Zhao, X. J.; Zhou, L. Y.; Zhang, W. Y.; Hu, C. Y.; Dai, L.; Ren, L. T.; Wu, B. H.; Fu, G.; Zheng, N. F. Chem 2018, 4, 1080. doi: 10.1016/j.chempr.2018.02.011

  25. [25]

      Wu, R. F.; Tsiakaras, P.; Shen, P. K. Appl. Catal. B 2019, 251, 49. doi: 10.1016/j.apcatb.2019.03.045

  26. [26]

      Gao, Y.; Yang, R.; Wang, C. H.; Liu, C. B.; Wu, Y. M.; Li, H. Z.; Zhang, B. Sci. Adv. 2022, 8, eabm9477. doi: 10.1126/sciadv.abm9477

  27. [27]

      Zhu, Q. J.; Wegener, S. L.; Xie, C.; Uche, O.; Neurock, M.; Marks, T. J. Nat. Chem. 2013, 5, 104. doi: 10.1038/Nchem.1527

  28. [28]

      Zhang, W. J.; Qin, R. X.; Fu, G.; Zheng, N. F. J. Am. Chem. Soc. 2021, 143, 15882. doi: 10.1021/jacs.1c08153

  29. [29]

      McCue, A. J.; Guerrero-Ruiz, A.; Ramirez-Barria, C.; Rodriguez-Ramos, I.; Anderson, J. A. J. Catal. 2017, 355, 40. doi: 10.1016/j.jcat.2017.09.004

  30. [30]

      Li, L. Y.; Yang, W. J.; Yang, Q. H.; Guan, Q. Q.; Lu, J. L.; Yu, S. H.; Jiang, H. L. ACS Catal. 2020, 10, 7753. doi: 10.1021/acscatal.0c00177

  31. [31]

      Deng, X.; Wang, J. M.; Guan, N. J.; Li, L. D. Cell Rep. Phys. Sci. 2022, 3, 101017. doi: 10.1016/j.xcrp.2022.101017

  32. [32]

      Zhang, M.; Xu, Y.; Zhang, H. G.; Duan, Z. Y.; Ren, T. L.; Wang, Z. Q.; Li, X. N. A.; Wang, L.; Wang, H. J. Chem. Eng. J. 2022, 429, 132194. doi: 10.1016/j.cej.2021.132194

  33. [33]

      Yang, T.; Yang, C. Y.; Le, J. B.; Yu, Z. Y.; Bu, L. Z.; Li, L. G.; Bai, S. X.; Shao, Q.; Hu, Z. W.; Pao, C. W.; et al. Nano Res. 2022, 15, 1861. doi: 10.1007/s12274-021-3786-0

  34. [34]

      Zhang, Q. F.; Wu, J. C.; Su, C.; Feng, F.; Ding, Q. L.; Yuan, Z. L.; Wang, H.; Ma, L.; Lu, C. S.; Li, X. N. Chin. Chem. Lett. 2012, 23, 1111. doi: 10.1016/j.cclet.2012.07.016

  35. [35]

      Luo, Z. Y.; Li, J. J.; Li, Y. L.; Wu, D. J.; Zhang, L.; Ren, X. Z.; He, C. X.; Zhang, Q. L.; Gu, M.; Sun, X. L. Adv. Energy Mater. 2022, 12, 2103823. doi: 10.1002/aenm.202103823

  36. [36]

      Yagi, S.; Nambu, M.; Tsukada, C.; Ogawa, S.; Kutluk, G.; Namatame, H.; Taniguchi, M. Appl. Surf. Sci. 2013, 267, 45. doi: 10.1016/j.apsusc.2012.05.098

  37. [37]

      Capote, A. J.; Roberts, J. T.; Madix, R. J. Surf. Sci. Lett. 1989, 209, L151. doi: 10.1016/0167-2584(89)90611-7

  38. [38]

      Zhang, Y. L.; Wang, H. X.; Li, S. N.; Lu, B.; Zhao, J. X.; Cai, Q. H. Mol. Catal. 2021, 515, 111940. doi: 10.1016/j.mcat.2021.111940

  39. [39]

      Bachiller-Baeza, B.; Anderson, J. A. J. Catal. 2002, 212, 231. doi: 10.1006/jcat.2002.3787

•