Reaction Kinetics, Mechanisms and Catalysis

, Volume 121, Issue 2, pp 523–537 | Cite as

Multilayer-stacked paper-structured catalysts for microflow Suzuki–Miyaura cross-coupling reaction

  • Yuki Ishihara
  • Kyohei Kanomata
  • Taichi Homma
  • Takuya Kitaoka


Paper-like porous composites of ceramic fibers and ZnO whiskers were prepared using a papermaking technique, followed by the in situ synthesis of a Pd catalyst on the ZnO whiskers using a facile impregnation method. The flexible Pd@ZnO papers had micrometer-sized pores of average diameter ca. 25 μm, which promoted the effective diffusion of reactants passing through an assembly of vertically stacked papers in a flow reactor. The catalytic efficiency of the stacked Pd@ZnO papers in a flow Suzuki–Miyaura cross-coupling (SMC) reaction to synthesize 4-methylbiphenyl from phenylboronic acid and 4-iodotoluene was higher than that of a bead-type Pd particulate catalyst in a reactor. Microchannels originating from the porous fiber-network microstructures in the stacked papers contributed to effective heterogeneous catalysis, possibly by enabling smooth diffusion of substrates to the surfaces of the Pd catalysts, as in a microreactor system. K2CO3, which was used as the base in the SMC reaction, was also immobilized in the paper-structured fibrous composites. Stacks of two types of paper, i.e., containing either Pd catalysts or K2CO3, significantly affected the SMC catalytic activity in a continuous microflow reaction. A combination of K2CO3 papers upstream and Pd@ZnO papers downstream in the flow system provided higher catalytic efficiency via on-site K2CO3-mediated borate formation of phenylboronic acid in the initial stage in the reactor. Tailoring of the stacking patterns of the paper-structured composites is expected to be effective for sequential SMC reaction and to improve catalytic process engineering.


Flow reactor Microchannel Paper Porous material Sequential reaction 



This research was supported by a Grant-in-Aid for Challenging Exploratory Research (16K14959) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

Compliance with ethical standards

Conflict of interest

The authors declare that there is no conflict of interest.

Supplementary material

11144_2017_1178_MOESM1_ESM.docx (2.8 mb)
Supplementary material 1 (DOCX 2879 kb)


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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2017

Authors and Affiliations

  • Yuki Ishihara
    • 1
  • Kyohei Kanomata
    • 1
  • Taichi Homma
    • 1
    • 2
  • Takuya Kitaoka
    • 1
  1. 1.Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental SciencesKyushu UniversityFukuokaJapan
  2. 2.Processing Development Research LaboratoryKao CorporationTochigiJapan

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