Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
(C2H4O+*) on Cu+. Nucleophilic attack of C2H5O* to the
12. E. Santacesaria, G. Carotenuto, R. Tesser and M. Di Serio, Chem.
carbonyl of C2H4O+* reforms Cu2+ and
a
hemiacetal
Eng. J., 2012, 179, 209.
DOI: 10.1039/C6CC08305F
13. M. E. Sad, M. Neurock and E. Iglesia, J. Am. Chem. Soc., 2011,
133, 20384.
14. Y. Wang, Y. L. Shen, Y. J. Zhao, J. Lv, S. P. Wang and X. B. Ma, ACS
Catal., 2015, 5, 6200.
15. J. C. Kenvin, M. G. White and M. B. Mitchell, Langmuir, 1991, 7,
1198.
intermediate (1.7), which dehydrogenates to produce C4H8O2*
and H* (1.8), which desorb (1.9, 1.10). Scheme 1 shows that
Lewis acidic Cu+ sites that bind activated aldehydes
interconvert with Cu2+ sites within the redox cycle that forms
C4H8O2, as described for esterification on homogenous Cu
catalysts (e.g., CuBr18,19 and Cu(OAc)2).19
16. A. K. Agarwal, M. S. Wainwright, D. L. Trimm and N. W. Cant, J.
Mol. Catal., 1988, 45, 247.
Overall, the strong correlation between γ and the ratio of
the Cu oxidation states, together with the inhibiting effects of
pyridine on ester formation rates, provide compelling evidence
that Cuδ+ sites participate primarily in the catalytic cycle that
produces C4H8O2 from reactions of C2H4O and C2H5OH (Scheme
1) while Cu0 mainly catalyzes the intervening steps for
dehydrogenation. The number of esterification active sites
(i.e., Cuδ+ species) depends on the cluster size (i.e., number of
perimeter Cu atoms), and the identity of the support, which
affects the extent of charge transfer. This work offers insight
into possible combinations of characterization methods to
identify specific reaction centers and highlights the need to
understand and control selectivity of potential reactions of
biomass fermentation products to commodity chemicals.
We thank Pranjali Priyadarshini, Daniel T. Bregante, and
Rogan Kipp for assistance with experiments. TEM and XRD
measurements were carried out in part in the Frederick Seitz
Materials Research Laboratory Central Research Facilities,
University of Illinois. MRCAT operations are supported by the
Department of Energy and the MRCAT member institutions.
This research used resources of the Advanced Photon Source,
a U.S. Department of Energy (DOE) Office of Science User
Facility operated for the DOE Office of Science by Argonne
National Laboratory under Contract No. DE-AC02-06CH11357.
This work was funded by the Energy Biosciences Institute at
the University of Illinois. This material is based upon work
supported by the National Science Foundation Graduate
Research Fellowship Program under Grant No. DGE - 1144245.
17. I. Ro, Y. Liu, M. R. Ball, D. H. K. Jackson, J. P. Chada, C. Sener, T.
F. Kuech, R. J. Madon, G. W. Huber and J. A. Dumesic, ACS
Catal., 2016, 10, 7040.
18. W. J. Yoo and C. J. Li, Tetrahedron Lett., 2007, 48, 1033.
19. Y. Zheng, W. B. Song and L. J. Xuan, Org. Biomol. Chem., 2015,
13, 10834.
20. I. C. Freitas, S. Damyanova, D. C. Oliveira, C. M. P. Marques and
J. M. C. Bueno, J. Mol. Catal. A: Chem., 2014, 381, 26.
21. E. Geravand, Z. Shariatinia, F. Yaripour and S. Sahebdelfar,
Chem. Eng. Res. Des. 2015, 96, 63.
22. N. Iwasa and N. Takezawa, Bull. Chem. Soc. Jpn., 1991, 64, 2619.
23. G. Carotenuto, R. Tesser, M. Di Serio and E. Santacesaria, Catal.
Today, 2013, 203, 202.
24. X. Y. Liu, B. J. Xu, J. Haubrich, R. J. Madix and C. M. Friend, J. Am.
Chem. Soc., 2009, 131, 5757.
25. K. Inui, T. Kurabayashi and S. Sato, J. Catal., 2002, 212, 207.
26. K. Takeshita, S. Nakamura and K. Kawamoto, Bull. Chem. Soc.
Jpn., 1978, 51, 2622.
27. S. W. Colley, J. Tabatabaei, K. C. Waugh and M. A. Wood, J.
Catal., 2005, 236, 21.
28. T. Seki and H. Hattori, Catal. Surv. Asia, 2003, 7, 145.
29. L. Kürti and B. Czakó, Strategic applications of named reactions
in organic synthesis : background and detailed mechanisms,
Elsevier Academic, Burlington, MA, 2005.
30. T. Seki, H. Kabashima, K. Akutsu, H. Tachikawa and H. Hattori, J.
Catal., 2001, 204, 393.
31. S. K. Moromi, S. M. A. H. Siddiki, M. A. Ali, K. Kon and K. Shimizu,
Catal. Sci. Technol., 2014, 4, 3631.
32. E. K. Poels and D. S. Brands, Appl. Catal., A, 2000, 191, 83.
33. M. Shekhar, J. Wang, W. S. Lee, W. D. Williams, S. M. Kim, E. A.
Stach, J. T. Miller, W. N. Delgass and F. H. Ribeiro, J. Am. Chem.
Soc., 2012, 134, 4700.
Notes and references
1. R. D. Perlack and B. J. Stokes, U.S. Billion-Ton Update, 2011.
2. Y. N. Zeng, S. Zhao, S. H. Yang and S. Y. Ding, Curr. Opin.
Biotechnol., 2014, 27, 38.
3. J. T. Kozlowski and R. J. Davis, ACS Catal., 2013, 3, 1588.
4. P. Anbarasan, Z. C. Baer, S. Sreekumar, E. Gross, J. B. Binder, H.
W. Blanch, D. S. Clark and F. D. Toste, Nature, 2012, 491, 235.
5. T. Moteki and D. W. Flaherty, ACS Catal., 2016, 6, 4170.
6. T. Moteki, A. T. Rowley and D. W. Flaherty, ACS Catal., 2016, 6,
7278.
7. M. Eckert, G. Fleischmann, R. Jira, H. M. Bolt and K. Golka, in
Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH
Verlag GmbH & Co. KGaA, 2000.
8. L. Wu, T. Moteki, A. A. Gokhale, D. W. Flaherty and F. D. Toste,
Chem, 2016, 1, 32.
9. V. L. Sushkevich, I. I. Ivanova and E. Taarning, ChemCatChem,
2013, 5, 2367.
10. M. Y. S. Ibrahim, MS thesis, University of Illinois at Urbana-
Champaign, 2015.
11. S. Sitthisa and D. E. Resasco, Catal. Lett., 2011, 141, 784.
34. T. E. James, S. L. Hemmingson and C. T. Campbell, ACS Catal.,
2015, 5, 5673.
35. C. S. Ewing, G. Veser, J. J. McCarthy, J. K. Johnson and D. S.
Lambrecht, J. Phys. Chem. C, 2015, 119, 19934.
36. J. Saavedra, H. A. Doan, C. J. Pursell, L. C. Grabow and B. D.
Chandler, Science, 2014, 345, 1599.
37. S. Wang, K. Goulas and E. Iglesia, J. Catal., 2016, 340, 302.
38. J. Fang, F. C. Shi, J. Bu, J. J. Ding, S. T. Xu, J. Bao, Y. S. Ma, Z. Q.
Jiang, W. P. Zhang, C. Gao and W. X. Huang, J. Phys. Chem. C,
2010, 114, 7940.
39. K. T. Li and C. K. Wang, Appl. Catal., A, 2012, 433, 275.
40. L. Jun-Cheng, X. Lan, X. Feng, W. Zhan-Wen and W. Fei, Appl.
Surf. Sci., 2006, 253, 766.
41. J. Prasad and P. G. Menon, J. Catal., 1972, 26, 477.
42. P. Claus, M. Lucas, B. Lucke, T. Berndt and P. Birke, Appl. Catal.,
A, 1991, 79, 1.
43. C. Ammon, A. Bayer, G. Held, B. Richter, T. Schmidt and H. P.
Steinruck, Surf. Sci., 2002, 507, 845.
44. M. Bowker and R. J. Madix, Appl. Surf. Sci., 1981, 8, 299.
45. M. Bowker and R. J. Madix, Surf. Sci., 1982, 116, 549.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins