Effect of support morphology on the activity and reusability of Pd/SiO2 for NBR hydrogenation


Silica hollow microspheres with moonscape-like rough surface (RS) and macroporous surface (MS) have been controllably synthesized by a water–oil–water three-phase emulsion method, which are used as supports of the heterogeneous catalysts for the catalytic hydrogenation of nitrile-butadiene rubber (NBR). It is found that Pd can be uniformly dispersed on both amino-functionalized RS and MS supports and both the catalysts show high hydrogenation activity with 100% selectivity to C=C bonds. However, the reusability of Pd/N-RS is much better than that of Pd/N-MS, maintaining 92% of activity without any regeneration treatment after five times of recycling experiment. The high activity retention is because the moonscape-like surface of the RS support is favorable for the contact of NBR macromolecules with the active sites, and more importantly, the NBR macromolecules do not need to diffuse into the interior of the catalyst, leading to fast desorption of the hydrogenated NBR from the surface of catalyst and re-exposure of the active sites.

This is a preview of subscription content, log in to check access.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6


  1. 1

    Chiang C-H, Tsai J-C (2017) Hydrogenation of polystyrene-b-polybutadiene-b-polystyrene mediated by group (IV) metal metallocene complexes. J Polym Sci Pol Chem 55:2141–2149

    CAS  Article  Google Scholar 

  2. 2

    Han K-Y, Zuo H-R, Zhu Z-W, Cao G-P, Lu C, Wang Y-H (2013) High performance of palladium nanoparticles supported on carbon nanotubes for the hydrogenation of commercial polystyrene. Ind Eng Chem Res 52:17750–17759

    CAS  Article  Google Scholar 

  3. 3

    Higaki Y, Suzuki K, Kiyoshima Y et al (2017) Molecular aggregation states and physical properties of syndiotactic polystyrene/hydrogenated polyisoprene multiblock copolymers with crystalline hard domain. Macromolecules 50:6184–6191

    CAS  Article  Google Scholar 

  4. 4

    Wei L, Jiang JY, Wang YH, Jin ZL (2004) Selective hydrogenation of SBS catalyzed by Ru/TPPTS complex in polyether modified ammonium salt ionic liquid. J Mol Catal A Chem 221:47–50

    CAS  Article  Google Scholar 

  5. 5

    Wang H, Yang L, Rempel GL (2013) Homogeneous hydrogenation art of nitrile butadiene rubber: a review. Polym Rev 53:192–239

    CAS  Article  Google Scholar 

  6. 6

    Zhao J, Hahn SF, Hucul DA, Meunier DM (2001) Thermal and viscoelastic behavior of hydrogenated polystyrene. Macromolecules 34:1737–1741

    CAS  Article  Google Scholar 

  7. 7

    Ai C, Li J, Gong G, Zhao X, Liu P (2018) Preparation of hydrogenated nitrile-butadiene rubber (H-NBR) with controllable molecular weight with heterogeneous catalytic hydrogenation after degradation via olefin cross metathesis. React Funct Polym 129:53–57

    CAS  Article  Google Scholar 

  8. 8

    Kongparakul S, Prasassarakich P, Rempel GL (2008) Catalytic hydrogenation of methyl methacrylate-g-natural rubber (MMA-g-NR) in the presence of OsHCl(CO)(O-2)(PCy3)(2). Appl Catal A Gen 344:88–97

    CAS  Article  Google Scholar 

  9. 9

    Ness JS, Brodil JC, Bates FS, Hahn SF, Hucul DA, Hillmyer MA (2002) Molecular weight effects in the hydrogenation of model polystyrenes using platinum supported on wide-pore silica. Macromolecules 35:602–609

    CAS  Article  Google Scholar 

  10. 10

    Kawaguchi T, Sugimoto W, Murakami Y, Takasu Y (2005) Particle growth behavior of carbon-supported Pt, Ru, PtRu catalysts prepared by an impregnation reductive-pyrolysis method for direct methanol fuel cell anodes. J Catal 229:176–184

    CAS  Article  Google Scholar 

  11. 11

    Zou R, Li C, Zhang LQ, Yue DM (2016) Selective hydrogenation of nitrile butadiene rubber (NBR) with rhodium nanoparticles supported on carbon nanotubes at room temperature. Catal Commun 81:4–9

    CAS  Article  Google Scholar 

  12. 12

    Chen J, Hu Y, Cai A et al (2018) The mesopore-elimination treatment and silanol-groups recovery for macroporous silica microspheres and its application as an efficient support for polystyrene hydrogenation. Catal Commun 111:75–79

    CAS  Article  Google Scholar 

  13. 13

    Cao P, Ni Y, Zou R, Zhang L, Yue D (2015) Enhanced catalytic properties of rhodium nanoparticles deposited on chemically modified SiO2 for hydrogenation of nitrile butadiene rubber. RSC Adv 5:3417–3424

    CAS  Article  Google Scholar 

  14. 14

    Ai CJ, Gong GB, Zhao XT, Liu P (2017) Macroporous hollow silica microspheres-supported palladium catalyst for selective hydrogenation of nitrile butadiene rubber. J Taiwan Inst Chem E 77:250–256

    CAS  Article  Google Scholar 

  15. 15

    Chen J, Ma L, Cheng T et al (2018) Stable and recyclable Pd catalyst supported on modified silica hollow microspheres with macroporous shells for enhanced catalytic hydrogenation of NBR. J Mater Sci 53:15064–15080. https://doi.org/10.1007/s10853-018-2698-1

    CAS  Article  Google Scholar 

  16. 16

    Wang H, Rempel GL (2015) Organic solvent-free catalytic hydrogenation of diene-based polymer nanoparticles in latex form: mass transfer of hydrogen in a semibatch process. J Ind Eng Chem 25:29–34

    Article  Google Scholar 

  17. 17

    Fujiwara M, Shiokawa K, Araki M, Nakao M, Sakakura I, Nakahara Y (2011) Preparation of silica thin films with macropore holes from sodium silicate and polymethacrylate: an approach to formation mechanism of diatomaceous earth like silica hollow particles. Chem Eng J 172:1103–1110

    CAS  Article  Google Scholar 

  18. 18

    Li H, Xu Y, Yang H, Zhang F, Li H (2009) Ni-B amorphous alloy deposited on an aminopropyl and methyl co-functionalized SBA-15 as a highly active catalyst for chloronitrobenzene hydrogenation. J Mol Catal A Chem 307:105–114

    CAS  Article  Google Scholar 

  19. 19

    Yu T, Yang R, Xia S, Li G, Hu C (2014) Direct amination of benzene to aniline with H2O2 and NH3 center dot H2O over Cu/SiO2 catalyst. Catal Sci Technol 4:3159–3167

    CAS  Article  Google Scholar 

  20. 20

    Chong ASM, Zhao XS (2003) Functionalization of SBA-15 with APTES and characterization of functionalized materials. J Phys Chem B 107:12650–12657

    CAS  Article  Google Scholar 

  21. 21

    Chen J, Wu Z, Liu H, Bao X, Yuan P (2019) A surface-cofunctionalized silica supported palladium catalyst for selective hydrogenation of nitrile butadiene rubber with enhanced catalytic activity and recycling performance. Ind Eng Chem Res 58:11821–11830

    CAS  Article  Google Scholar 

Download references


The authors gratefully acknowledge the financial supports from the National Natural Science Foundation of China (Grants 21776048 and 21576290) and Natural Science Foundation of Fujian Province (2018J06002).

Author information



Corresponding authors

Correspondence to Hongwei Zhang or Pei Yuan.

Ethics declarations

Conflict of interest

The authors declared no competing financial interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1214 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhang, P., Zhang, H., Wang, S. et al. Effect of support morphology on the activity and reusability of Pd/SiO2 for NBR hydrogenation. J Mater Sci 55, 12876–12883 (2020). https://doi.org/10.1007/s10853-020-04986-9

Download citation