Journal
JOURNAL OF CATALYSIS
Volume 418, Issue -, Pages 163-177Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2023.01.020
Keywords
N-alkyl amine; Borrowing hydrogen; Lewis acid-base pairs; CeO2; Interface
Categories
Ask authors/readers for more resources
The Lewis acid-base pairs (LPs) at the interface of Cu/CeO2 catalyst exhibit excellent catalytic performance on the hydrogen borrowing reaction. LPs consist of Lewis acidic Cu(I) and Lewis basic surface oxygen (Osurf). The Cu(I)-H and Osurf-H intermediates are generated and preferentially transfer to C@N bonds instead of forming H2 molecules, leading to outstanding selectivity towards N-alkyl amine.
The interface between metal sites and metal oxides sometimes acts as the real active site, but the iden-tification of its structure and function in catalysis is still elusive. Here, we demonstrate that Lewis acid-base pairs (LPs) at the interface of Cu/CeO2 catalyst display outstanding catalytic performance on the hydrogen borrowing reaction under base free conditions. Characterizations disclose that LPs consist of Lewis acidic Cu(I) and Lewis basic surface oxygen (Osurf), where the Cu(I) species are formed by electron transfer between the interfacial Cu and Ce {e.g., Ce(III) + Cu(II) M Ce(IV) + Cu(I)} and Osurf species are simultaneously created by surface oxygen mobility. The Cu(I)-H and Osurf-H intermediates are generated by reacting hydride (H-) and proton (H+) from C-H and O-H cleavage with Lewis acidic Cu(I) and Lewis basic Osurf, respectively. The combination of control experiments, deuterium isotope studies and DFT cal-culations reveals that the Cu(I)-H and Osurf-H intermediates are spatially isolated by LPs and prefer to transfer to C@N bonds rather than forming H2 molecules, leading to outstanding selectivity towards the desired N-alkyl amine.(c) 2023 Elsevier Inc. All rights reserved.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available