TY  - JOUR
A1  - Lepre, Enrico
A1  - Heske, Julian
A1  - Nowakowski, Michal
A1  - Scoppola, Ernesto
A1  - Zizak, Ivo
A1  - Heil, Tobias
A1  - Kühne, Thomas D.
A1  - Antonietti, Markus
A1  - Lopez-Salas, Nieves
A1  - Albero, Josep
T1  - Ni-based electrocatalysts for unconventional CO2 reduction reaction to formic acid
JF  - Nano energy
N2  - Electrochemical reduction stands as an alternative to revalorize CO2. Among the different alternatives, Ni single atoms supported on carbonaceous materials are an appealing catalytic solution due to the low cost and versatility of the support and the optimal usage of Ni and its predicted selectivity and efficiency (ca. 100% towards CO). Herein, we have used noble carbonaceous support derived from cytosine to load Ni subnanometric sites. The large heteroatom content of the support allows the stabilization of up to 11 wt% of Ni without the formation of nanoparticles through a simple impregnation plus calcination approach, where nickel promotes the stabilization of C3NOx frameworks and the oxidative support promotes a high oxidation state of nickel. EXAFS analysis points at nickel single atoms or subnanometric clusters coordinated by oxygen in the material surface. Unlike the wellknown N-coordinated Ni single sites selectivity towards CO2 reduction, O-coordinated-Ni single sites (ca. 7 wt% of Ni) reduced CO2 to CO, but subnanometric clusters (11 wt% of Ni) foster the unprecedented formation of HCOOH with 27% Faradaic efficiency at - 1.4 V. Larger Ni amounts ended up on the formation of NiO nanoparticles and almost 100% selectivity towards hydrogen evolution.
KW  - CO 2 reduction reaction
KW  - Noble carbon
KW  - Ni-O4 electrocatalysts
KW  - Formic acid
Y1  - 2022
U6  - https://doi.org/10.1016/j.nanoen.2022.107191
SN  - 2211-2855
SN  - 2211-3282
VL  - 97
PB  - Elsevier
CY  - Amsterdam
ER  -