A copper-phyllosilicate core-sheath nanoreactor for carbon–oxygen hydrogenolysis reactions

Hydrogenolysis of carbon-oxygen bonds is a versatile synthetic tool in organic synthesis. Copper-based catalysts have been intensively explored as the copper sites account for the highly selective hydrogenation of carbon-oxygen bonds. However, the inherent drawback of conventional copper-based catalysts is the deactivation by metal-particle growth and unstable surface Cu(0) and Cu(+) active species in the strongly reducing hydrogen and oxidizing carbon-oxygen atmosphere. Here we report the superior reactivity of a core (copper)-sheath (copper phyllosilicate) nanoreactor for carbon-oxygen hydrogenolysis of dimethyl oxalate with high efficiency (an ethanol yield of 91%) and steady performance (>300 h at 553 K). This nanoreactor, which possesses balanced and stable Cu(0) and Cu(+) active species, confinement effects, an intrinsically high surface area of Cu(0) and Cu(+) and a unique tunable tubular morphology, has potential applications in high-temperature hydrogenation reactions.

[1]  Kangnian Fan,et al.  Cu/SiO2 catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol , 2008 .

[2]  Shengping Wang,et al.  Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu‐MCM‐41 catalysts , 2013 .

[3]  Ping Liu,et al.  Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction , 2012, Nature Communications.

[4]  Jonathan W. Lekse,et al.  Active Sites and Structure−Activity Relationships of Copper-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol , 2012 .

[5]  G. Somorjai,et al.  Thermally stable Pt/mesoporous silica core-shell nanocatalysts for high-temperature reactions. , 2009, Nature materials.

[6]  C. Pham‐Huu,et al.  Selective deposition of metal nanoparticles inside or outside multiwalled carbon nanotubes. , 2009, ACS nano.

[7]  Xun Wang,et al.  Ni3Si2O5(OH)4 multi-walled nanotubes with tunable magnetic properties and their application as anode materials for lithium batteries , 2011 .

[8]  Wei Chen,et al.  Effect of confinement in carbon nanotubes on the activity of Fischer-Tropsch iron catalyst. , 2008, Journal of the American Chemical Society.

[9]  M. Comotti,et al.  High-temperature-stable catalysts by hollow sphere encapsulation. , 2006, Angewandte Chemie.

[10]  W. Cai,et al.  One-pot synthesis of nanotube-based hierarchical copper silicate hollow spheres. , 2008, Chemical communications.

[11]  Shengping Wang,et al.  Chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate on Cu/SiO2: Enhanced stability with boron dopant , 2013 .

[12]  P. Serp,et al.  An efficient strategy to drive nanoparticles into carbon nanotubes and the remarkable effect of confinement on their catalytic performance. , 2009, Angewandte Chemie.

[13]  Haihui Ye,et al.  Carbon nanotubes loaded with magnetic particles. , 2005, Nano letters.

[14]  Kangnian Fan,et al.  The Nature of Active Copper Species in Cu-HMS Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol: New Insights on the Synergetic Effect between Cu0 and Cu+ , 2009 .

[15]  F. Schüth,et al.  Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al2O3 catalysts for methanol synthesis , 2008 .

[16]  K. Schulte,et al.  Assembly of Cobalt Phthalocyanine Stacks inside Carbon Nanotubes , 2007 .

[17]  R. Baker,et al.  Carbon-supported copper catalysts. II. Crotonaldehyde hydrogenation , 1999 .

[18]  A. Cao,et al.  Exceptional high-temperature stability through distillation-like self-stabilization in bimetallic nanoparticles. , 2010, Nature materials.

[19]  B. Shanks,et al.  Active species of copper chromite catalyst in C–O hydrogenolysis of 5-methylfurfuryl alcohol , 2012 .

[20]  S. Mayo,et al.  A new method to position and functionalize metal-organic framework crystals , 2011, Nature communications.

[21]  C. Campbell,et al.  Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding , 2010, Science.

[22]  Shengping Wang,et al.  Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+ sites. , 2012, Journal of the American Chemical Society.

[23]  S. C. Parker,et al.  The Effect of Size-Dependent Nanoparticle Energetics on Catalyst Sintering , 2002, Science.

[24]  S. Tsang,et al.  Non-syngas direct steam reforming of methanol to hydrogen and carbon dioxide at low temperature , 2012, Nature Communications.

[25]  C. Louis,et al.  Metal Particle Size in Silica-Supported Copper Catalysts. Influence of the Conditions of Preparation and of Thermal Pretreatments , 2000 .

[26]  P. He,et al.  Effect of boric oxide doping on the stability and activity of a Cu-SiO2 catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol , 2011 .

[27]  Xinbin Ma,et al.  Ethylene glycol: properties, synthesis, and applications. , 2012, Chemical Society reviews.

[28]  Shengping Wang,et al.  Hydrogenation of dimethyl oxalate to ethylene glycol on a Cu/SiO2/cordierite monolithic catalyst: Enhanced internal mass transfer and stability , 2012 .

[29]  T. Agapie,et al.  Nickel-mediated hydrogenolysis of C-O bonds of aryl ethers: what is the source of the hydrogen? , 2012, Journal of the American Chemical Society.

[30]  Wei Chen,et al.  Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles. , 2007, Nature materials.

[31]  K. Tomishige,et al.  C–O bond hydrogenolysis of cyclic ethers with OH groups over rhenium-modified supported iridium catalysts , 2012 .

[32]  H. Orikasa,et al.  Template synthesis of water-dispersible and magnetically responsive carbon nano test tubes. , 2008, Chemical communications.

[33]  Xiulian Pan,et al.  The effects of confinement inside carbon nanotubes on catalysis. , 2011, Accounts of chemical research.

[34]  J. Nørskov,et al.  The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts , 2012, Science.

[35]  H. Friedrich,et al.  Towards stable catalysts by controlling collective properties of supported metal nanoparticles. , 2013, Nature materials.