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Green Chemistry
Page 10 of 12
DOI: 10.1039/C7GC01387F
ARTICLE
Journal Name
exhibited good catalytic activity and chemoselectivity for the
dehydrogenation of various substituted CHLs and the
hydrogenation of HMF, with high yields of substituted phenols
and DMF. Compared with those for monomethylꢀsubstituted
CHLs (entries 1ꢀ3), dehydrogenationꢀaromatization activities
for dimethylꢀsubstituted CHLs (entries 4ꢀ6) are lower due to the
steric effect, along with higher reaction temperatures and (or)
lower LHSV values required. Furthermore, selective
dehydrogenations of substituted ethylꢀ and phenyl CHLs can
successfully proceed (entries 7ꢀ9). Meanwhile, the DMF
selectivities maintain above 94 % in all cases. The above results
clearly verify the extensive applicability of the present coupling
process between the dehydrogenation of substituted CHLs and
the hydrogenation of HMF for the highly efficient synchronized
production of DMF and various substituted phenols.
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Conclusions
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In summary, we developed a highly efficient vaporꢀphase
coupling process between the CHL dehydrogenation and the
HMF hydrogenation to simultaneously produce phenol and
DMF with high yields (> 97%), over the noble metalꢀfree Niꢀ
Cu alloy nanocatalyst with the Ni/Cu molar ratio of 2:1 in the
absence of any external hydrogen and oxygen supply.
Systematic catalytic tests revealed that CHL could be
dehydrogenated into phenol via CHN and CHO intermediates.
Meanwhile, in situ produced active hydrogen species from the
dehydrogenation of CHL, CHN, or CHO could react with HMF
to generate DMF. Furthermore, HMF as hydrogen acceptor
derived the reaction equilibrium of the CHL dehydrogenation
toward the generation of phenol in the coupling process. It was
found that the NiꢀCu alloy nanostructure substantially
facilitated the coupling process along with high yields of both
phenol and DMF, due to the fact that the electronic effect in the
NiꢀCu alloy structure benefited the βꢀhydride elimination in the
dehydrogenation and effectively restrained the aromatic
hydrogenation. Besides, a variety of substituted phenols also
could be produced through the present coupling system. Asꢀ
developed coupling process provides a promising and simple
avenue for the green production of industrial chemicals and
biofuels from fundamental raw materials, which highlights the
idea of green chemistry and sustainable development greatly.
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Conflicts of interest
a) G. H. Wang, J. Hilgert, F. H. Richter, F. Wang, H. J.
Bongard, B. Spliethoff, C. Weidenthaler and F. Schuth, Nat.
Mater., 2014, 13, 293–300; b) M. Chatterjee, T. Ishizaka
and H. Kawanami, Green Chem., 2014, 16, 1543–1551; c)
There are no conflicts of interest to declare.
Acknowledgements
M. Y. Chen, C. B. Chen, B. Zada and Y. Fu, Green Chem.
2016, 18, 3858–3866; d) Y. B. Huang, M. Y. Chen, L. Yan,
Q. X. Guo and Y. Fu, ChemSusChem, 2014, , 1068–1072;
,
This study was funded through National Natural Science
Foundation of China (21325624; 21521005) and Fundamental
Research Funds for the Central Universities (buctrc201528).
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e) Y. H. Zu, P. P. Yang, J. J. Wang, X. H. Liu, J. W. Ren, G.
Z. Lu and Y. Q. Wang, Appl. Catal., B, 2014, 146, 244–248;
f) J. Luo, H. Yun, A. V. Mironenko, K. Goulas, J. D. Lee,
M. Monai, C. Wang, V. Vorotnikov, C. B. Murray, D. G.
Notes and references
Vlachos, P. Fornasiero and R. J. Gorte, ACS Catal., 2016, 6,
10 | J. Name., 2012, 00, 1-3
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