3D graphene/nylon rope as a skeleton for noble metal nanocatalysts for highly efficient heterogeneous continuous-flow reactions

Continuous-flow catalytic systems represent a highly efficient approach towards scalable synthesis with features of time and energy saving, easy operation, and improved safety. Herein, we rationally design a novel 3D noble metal/graphene/nylon rope to act as a highly efficient catalyst for continuous-flow organic reactions. We show that different noble metal (Pd, Pt, Au and Ag) nanocatalysts and graphene can be readily assembled with the chemically inert nylon rope by a one-step hydrothermal method. Graphene, acting as the interconnector for noble metal nanoparticles and the nylon rope, increases the flexibility and mechanical strength of rope-like catalysts and improves the catalytic activity and stability of the noble metal species. The large voids within the noble metal/graphene/nylon rope catalysts, under optimized reaction conditions, ensure the sufficient chemical transfer for the continuous-flow system. The high catalytic activity and stability of rope catalysts are demonstrated by the Suzuki–Miyaura cross-coupling reaction (SMC) and 4-nitrophenol reduction reaction. Pd/graphene/nylon rope catalysts show a high turnover number of 965 mol h−1 molPd−1, a large productivity of 1385 mg h−1 mgPd−1 at a flow rate of 70 mL h−1, and a remarkable stability for continuous-flow SMC reactions. Such a novel minifluidic system integrated with 3D noble metal/graphene/nylon rope catalysts can be extended to many important chemical reactions.

[1]  C. Porco,et al.  Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide-Alkyne Cycloadditions , 2013, Science.

[2]  Steven V Ley,et al.  Flow chemistry syntheses of natural products. , 2013, Chemical Society reviews.

[3]  Timothy F. Jamison,et al.  Continuous flow multi-step organic synthesis , 2010 .

[4]  Hua Zhang,et al.  Graphene-based composites. , 2012, Chemical Society reviews.

[5]  Guoliang Zhang,et al.  Palladium nanoparticle-graphene hybrids as active catalysts for the Suzuki reaction , 2010 .

[6]  M. El-Sayed,et al.  Effect of catalysis on the stability of metallic nanoparticles: Suzuki reaction catalyzed by PVP-palladium nanoparticles. , 2003, Journal of the American Chemical Society.

[7]  K. Jensen,et al.  Synthesis of micro and nanostructures in microfluidic systems. , 2010, Chemical Society reviews.

[8]  J. Zink,et al.  Integration of molecular and enzymatic catalysts on graphene for biomimetic generation of antithrombotic species , 2014, Nature Communications.

[9]  Jing Zhuang,et al.  Noble-metal-promoted three-dimensional macroassembly of single-layered graphene oxide. , 2010, Angewandte Chemie.

[10]  Younan Xia,et al.  Scaling up the Production of Colloidal Nanocrystals: Should We Increase or Decrease the Reaction Volume? , 2014, Advanced materials.

[11]  Qingshan Lu,et al.  In situ Formation of Palladium Nanoparticles Inside the Pore Channels of Ordered Mesoporous Silica , 2009 .

[12]  R. Mülhaupt,et al.  Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction. , 2009, Journal of the American Chemical Society.

[13]  F. Glorius,et al.  Comparison of Superparamagnetic Fe3O4‐Supported N‐Heterocyclic Carbene‐Based Catalysts for Enantioselective Allylation , 2011 .

[14]  Andreas Kirschning,et al.  Inductive heating for organic synthesis by using functionalized magnetic nanoparticles inside microreactors. , 2008, Angewandte Chemie.

[15]  Ryan L. Hartman,et al.  Deciding whether to go with the flow: evaluating the merits of flow reactors for synthesis. , 2011, Angewandte Chemie.

[16]  Timothy Noël,et al.  Cross-coupling in flow. , 2011, Chemical Society reviews.

[17]  H. Miyamura,et al.  Polymer-incarcerated chiral Rh/Ag nanoparticles for asymmetric 1,4-addition reactions of arylboronic acids to enones: remarkable effects of bimetallic structure on activity and metal leaching. , 2012, Journal of the American Chemical Society.

[18]  Andreas Kirschning,et al.  Ten key issues in modern flow chemistry. , 2011, Chemical communications.

[19]  Jun-ichi Yoshida,et al.  A flow-microreactor approach to protecting-group-free synthesis using organolithium compounds. , 2011, Nature communications.

[20]  G. Shi,et al.  Three-dimensional graphene architectures. , 2012, Nanoscale.

[21]  J. Tour,et al.  Decoration, Migration, and Aggregation of Palladium Nanoparticles on Graphene Sheets , 2010 .

[22]  C. Li,et al.  Ultralight, flexible, and fire-resistant carbon nanofiber aerogels from bacterial cellulose. , 2013, Angewandte Chemie.

[23]  M. Otyepka,et al.  Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. , 2012, Chemical reviews.

[24]  Mostafa A. El-Sayed,et al.  Size effects of PVP-Pd nanoparticles on the catalytic Suzuki reactions in aqueous solution , 2002 .

[25]  Yong Wang,et al.  Solvent-free aerobic oxidation of hydrocarbons and alcohols with Pd@N-doped carbon from glucose , 2013, Nature Communications.

[26]  M. Zawadzki,et al.  Palladium nanoparticles supported on alumina-based oxides as heterogeneous catalysts of the Suzuki–Miyaura reaction , 2008 .

[27]  Ping Wang,et al.  Macroscopic multifunctional graphene-based hydrogels and aerogels by a metal ion induced self-assembly process. , 2012, ACS nano.

[28]  Esther Alza,et al.  A solid-supported organocatalyst for highly stereoselective, batch, and continuous-flow Mannich reactions. , 2009, Chemistry.

[29]  Chunhua Yan,et al.  Double shelled hollow nanospheres with dual noble metal nanoparticle encapsulation for enhanced catalytic application. , 2013, Nanoscale.

[30]  Paul Watts,et al.  Recent advances in micro reaction technology. , 2011, Chemical communications.

[31]  Francisco del Monte,et al.  Three dimensional macroporous architectures and aerogels built of carbon nanotubes and/or graphene: synthesis and applications. , 2013, Chemical Society reviews.

[32]  Lunxiang Yin,et al.  Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts. , 2007, Chemical reviews.

[33]  G. J. Gabriel,et al.  Facile synthesis of silver nanoparticles stabilized by cationic polynorbornenes and their catalytic activity in 4-nitrophenol reduction. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[34]  Ja Hun Kwak,et al.  Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction , 2009 .

[35]  Peter H Seeberger,et al.  Continuous-flow synthesis of the anti-malaria drug artemisinin. , 2012, Angewandte Chemie.

[36]  A. Rao,et al.  Catalytic reduction of 4-nitrophenol using biogenic gold and silver nanoparticles derived from Breynia rhamnoides. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[37]  A. Sayari,et al.  Applications of pore-expanded mesoporous silica 6. Novel synthesis of monodispersed supported palladium nanoparticles and their catalytic activity for suzuki reaction , 2007 .

[38]  Shū Kobayashi,et al.  Asymmetric carbon-carbon bond formation under continuous-flow conditions with chiral heterogeneous catalysts. , 2013, Angewandte Chemie.

[39]  Á. Molnár Efficient, selective, and recyclable palladium catalysts in carbon-carbon coupling reactions. , 2011, Chemical reviews.

[40]  Luis M. Fidalgo,et al.  Suzuki-Miyaura coupling reactions in aqueous microdroplets with catalytically active fluorous interfaces. , 2009, Chemical communications.

[41]  Kazuma Gotoh,et al.  Recyclable Pd–graphene catalyst: mechanistic insights into heterogeneous and homogeneous catalysis , 2012 .