TY - JOUR
T1 - Alcohol oxidation with high efficiency and selectivity by nickel phosphide phases
AU - Ghosh, Sirshendu
AU - Mondal, Biswajit
AU - Roy, Shubasis
AU - Shalom, Menny
AU - Sadan, Maya Bar
N1 - Funding Information:
S. G. thanks the financial support of the Kreitman Post-Doctoral fellowship at the BGU. This center of excellence was supported by The Israel Science Foundation (grant no. 1212/21). B. M. and M. S. thank the Planning & Budgeting Committee/Israel Council for Higher Education (CHE) and Fuel Choice Initiative (Prime Minister Office of Israel), within the framework of ?Israel National Research Center for Electrochemical Propulsion? (INREP) and the Minerva Center No. 117873 for the financial support.
Funding Information:
S. G. thanks the financial support of the Kreitman Post-Doctoral fellowship at the BGU. This center of excellence was supported by The Israel Science Foundation (grant no. 1212/21). B. M. and M. S. thank the Planning & Budgeting Committee/Israel Council for Higher Education (CHE) and Fuel Choice Initiative (Prime Minister Office of Israel), within the framework of “Israel National Research Center for Electrochemical Propulsion” (INREP) and the Minerva Center No. 117873 for the financial support.
Publisher Copyright:
© 2022 The Royal Society of Chemistry.
PY - 2022/3/8
Y1 - 2022/3/8
N2 - Small aliphatic alcohols are excellent fuels that have a much higher energy density than liquid H2. It is advantageous to avoid their complete oxidation to CO2 and produce chemicals with higher commercial value along with moderate energy extraction. We explored three different phases of nickel phosphide (Ni12P5, Ni2P, and Ni5P4) for the electro-oxidation of methanol, ethanol, isopropanol, ethylene glycol, and glycerol. Ni12P5 exhibits excellent activity (210 mA cm−2 at 1.72 V vs. RHE), durability, and mass activity (∼4.2 A mg−1), outperforming the state-of-the-art catalysts. We compared the reaction mechanisms and concluded that except ethylene glycol, the various alcohols are oxidized following a similar reaction mechanism, both on Ni12P5 and on Ni2P. The high selectivity of the reaction and the large suppression of further oxidation to CO2 are a marker of a preferred bidentate adsorption configuration that conveys a specific O-H activation reaction path. The catalysts show excellent activity towards alcohol oxidation and durability, likely thanks to the mild conditions required for the process, which allow the formation of a regenerating thin active layer of oxidized nickel.
AB - Small aliphatic alcohols are excellent fuels that have a much higher energy density than liquid H2. It is advantageous to avoid their complete oxidation to CO2 and produce chemicals with higher commercial value along with moderate energy extraction. We explored three different phases of nickel phosphide (Ni12P5, Ni2P, and Ni5P4) for the electro-oxidation of methanol, ethanol, isopropanol, ethylene glycol, and glycerol. Ni12P5 exhibits excellent activity (210 mA cm−2 at 1.72 V vs. RHE), durability, and mass activity (∼4.2 A mg−1), outperforming the state-of-the-art catalysts. We compared the reaction mechanisms and concluded that except ethylene glycol, the various alcohols are oxidized following a similar reaction mechanism, both on Ni12P5 and on Ni2P. The high selectivity of the reaction and the large suppression of further oxidation to CO2 are a marker of a preferred bidentate adsorption configuration that conveys a specific O-H activation reaction path. The catalysts show excellent activity towards alcohol oxidation and durability, likely thanks to the mild conditions required for the process, which allow the formation of a regenerating thin active layer of oxidized nickel.
UR - http://www.scopus.com/inward/record.url?scp=85127850338&partnerID=8YFLogxK
U2 - 10.1039/d2ta00863g
DO - 10.1039/d2ta00863g
M3 - Article
AN - SCOPUS:85127850338
VL - 10
SP - 8238
EP - 8244
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
SN - 2050-7488
IS - 15
ER -
