TY - JOUR
T1 - Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation
AU - Zhang, Ning
AU - Feng, Xiaobin
AU - Rao, Dewei
AU - Deng, Xi
AU - Cai, Lejuan
AU - Qiu, Bocheng
AU - Long, Ran
AU - Xiong, Yujie
AU - Lu, Yang
AU - Chai, Yang
N1 - Funding Information:
This work was supported by Research Grant Council of Hong Kong (Grant No. N_PolyU540/17), the Hong Kong Polytechnic University (Grant No. G-YW2A), and Science, Technology and Innovation Commission of Shenzhen (JCYJ20180507183424383). X.F. and Y.L. are grateful to the support from City University of Hong Kong (Grant No. 9610461) and the funding supporting from Shenzhen Science and Technology Innovation Committee (JCYJ20170413141157573). Theoretical simulation was supported by the National Natural Science Foundation of China (Grant No. 51801075) and performed on TianHe-2 at Lvliang Cloud Computing Center of China. D.R. gratefully acknowledge the support of Jiangsu Overseas Visiting Scholar Program for University Prominent Young and Mid-aged Teachers and Presidents. We also thank the beamline BL12B-a in the National Synchrotron Radiation Laboratory (NSRL) in Hefei, China for the support of sXAS measurements.
Publisher Copyright:
© 2020, The Author(s).
PY - 2020/8/13
Y1 - 2020/8/13
N2 - Anodic oxygen evolution reaction (OER) is recognized as kinetic bottleneck in water electrolysis. Transition metal sites with high valence states can accelerate the reaction kinetics to offer highly intrinsic activity, but suffer from thermodynamic formation barrier. Here, we show subtle engineering of highly oxidized Ni4+ species in surface reconstructed (oxy)hydroxides on multicomponent FeCoCrNi alloy film through interatomically electronic interplay. Our spectroscopic investigations with theoretical studies uncover that Fe component enables the formation of Ni4+ species, which is energetically favored by the multistep evolution of Ni2+→Ni3+→Ni4+. The dynamically constructed Ni4+ species drives holes into oxygen ligands to facilitate intramolecular oxygen coupling, triggering lattice oxygen activation to form Fe-Ni dual-sites as ultimate catalytic center with highly intrinsic activity. As a result, the surface reconstructed FeCoCrNi OER catalyst delivers outstanding mass activity and turnover frequency of 3601 A gmetal−1 and 0.483 s−1 at an overpotential of 300 mV in alkaline electrolyte, respectively.
AB - Anodic oxygen evolution reaction (OER) is recognized as kinetic bottleneck in water electrolysis. Transition metal sites with high valence states can accelerate the reaction kinetics to offer highly intrinsic activity, but suffer from thermodynamic formation barrier. Here, we show subtle engineering of highly oxidized Ni4+ species in surface reconstructed (oxy)hydroxides on multicomponent FeCoCrNi alloy film through interatomically electronic interplay. Our spectroscopic investigations with theoretical studies uncover that Fe component enables the formation of Ni4+ species, which is energetically favored by the multistep evolution of Ni2+→Ni3+→Ni4+. The dynamically constructed Ni4+ species drives holes into oxygen ligands to facilitate intramolecular oxygen coupling, triggering lattice oxygen activation to form Fe-Ni dual-sites as ultimate catalytic center with highly intrinsic activity. As a result, the surface reconstructed FeCoCrNi OER catalyst delivers outstanding mass activity and turnover frequency of 3601 A gmetal−1 and 0.483 s−1 at an overpotential of 300 mV in alkaline electrolyte, respectively.
UR - http://www.scopus.com/inward/record.url?scp=85089365394&partnerID=8YFLogxK
U2 - 10.1038/s41467-020-17934-7
DO - 10.1038/s41467-020-17934-7
M3 - Journal article
C2 - 32792524
AN - SCOPUS:85089365394
SN - 2041-1723
VL - 11
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 4066
ER -