A suitable catalyst with an exact match of the acidity/basicity,
ingenious geometric structure, and proper electronic environment is
vital to the Guerbet reaction for the synthesis of C6+ higher
alcohols. Herein, we synthesized a series of Ni/MgAlO and NiSn/MgAlO
catalysts based on hydrotalcite laminate for one-pot upgrading of
aqueous bioethanol to C6+ higher alcohols. Through the
introduction of Sn to form NiSn alloys, the Ni–Ni interactions
were attenuated and the cleavage of C–C bonds was suppressed
with a yield of 21.9% of C6+ higher alcohols at 250 °C.
Meanwhile, by precisely adjusting the ratio of the metal cation Mg2+ to Al3+, the acidity and basicity of the catalysts
were optimized and Ni/(4-Mg)AlO with an optimal ratio of 4 presented
a considerable C6+ alcohol yield (25.2%) at even 220 °C,
as well as an impressive ethanol conversion of 67.7%. Such an excellent
activity achieved at lower temperature was attributed to highly dispersed
Ni metal with a Ni(Mg)O solid solution structure,
leading to the enormously inhibited aqueous ethanol reforming process
and significant increased yield of higher alcohols. The results reveal
that the electronic structure and coordination environment of metal
sites as well as higher moderately basic and strong acid sites were
demonstrated to be beneficial for carbon-chain extension of higher
alcohols and ethanol selectivity for dehydrogenation/hydrogenation.
Moreover, the number of metal, acid, and base sites should be balanced
to inhibit side reactions.