TY - JOUR
T1 - Correlating electrocatalytic oxygen reduction activity with d-band centers of metallic nanoparticles
AU - Zhou, Yao
AU - Zhou, Zhenzhen
AU - Shen, Ruxiang
AU - Ma, Ruguang
AU - Liu, Qian
AU - Cao, Guozhong
AU - Wang, Jiacheng
N1 - Publisher Copyright:
© 2018
PY - 2018/7
Y1 - 2018/7
N2 - The establishment of correlating the electronic structures with the activity of non-noble-metal electrocatalysts toward the oxygen reduction reaction (ORR) plays a pivotal role in designing high-performance cathodic electrocatalysts. Here, a procedure of metallic Fe-family nanoparticles (NPs), such as nitrides (Co5.47N, Fe4N and Ni3N) and zero-valence metals (Co and Ni) NPs encapsulated into three-dimensional porous nitrogen-doped carbon (NCC) has been successfully demonstrated by the combination of sol-gel processing and subsequent nitridation process. The density functional theory (DFT) calculations, X-ray photoelectron spectroscopy (XPS) valence band experiments, and the electrochemical measurements suggest that the ORR activities of encased Fe-family metallic NPs evidently increase as the d-band centre values move away from the Fermi level as the following order: Ni3N4N5.47N, showing that the d-band centre value can be a good criterion to screen and evaluate the electrocatalysts. The optimized Co5.47N phase leads to an exceptional ORR activity with a nearly close 4e- reaction pathway (half-wave potential (E1/2): −176 mV vs. saturated calomel electrode (SCE), n: 3.8–4.0, HO2- yields: 7.3–8.1%), comparable to those of the state-of-the-art Pt/C in alkaline medium. Moreover, the Co5.47N/NCC also has a superior long-term stability and tolerance to MeOH crossover effect to commercial Pt/C.
AB - The establishment of correlating the electronic structures with the activity of non-noble-metal electrocatalysts toward the oxygen reduction reaction (ORR) plays a pivotal role in designing high-performance cathodic electrocatalysts. Here, a procedure of metallic Fe-family nanoparticles (NPs), such as nitrides (Co5.47N, Fe4N and Ni3N) and zero-valence metals (Co and Ni) NPs encapsulated into three-dimensional porous nitrogen-doped carbon (NCC) has been successfully demonstrated by the combination of sol-gel processing and subsequent nitridation process. The density functional theory (DFT) calculations, X-ray photoelectron spectroscopy (XPS) valence band experiments, and the electrochemical measurements suggest that the ORR activities of encased Fe-family metallic NPs evidently increase as the d-band centre values move away from the Fermi level as the following order: Ni3N4N5.47N, showing that the d-band centre value can be a good criterion to screen and evaluate the electrocatalysts. The optimized Co5.47N phase leads to an exceptional ORR activity with a nearly close 4e- reaction pathway (half-wave potential (E1/2): −176 mV vs. saturated calomel electrode (SCE), n: 3.8–4.0, HO2- yields: 7.3–8.1%), comparable to those of the state-of-the-art Pt/C in alkaline medium. Moreover, the Co5.47N/NCC also has a superior long-term stability and tolerance to MeOH crossover effect to commercial Pt/C.
KW - Electrocatalysis
KW - Metallic nanoparticles
KW - Oxygen reduction reaction
KW - Porous carbon
KW - d-band centre
UR - http://www.scopus.com/inward/record.url?scp=85041420355&partnerID=8YFLogxK
U2 - 10.1016/j.ensm.2018.01.011
DO - 10.1016/j.ensm.2018.01.011
M3 - Article
AN - SCOPUS:85041420355
SN - 2405-8297
VL - 13
SP - 189
EP - 198
JO - Energy Storage Materials
JF - Energy Storage Materials
ER -