Hydrogen Peroxide Assisted Electrooxidation of Benzene to Phenol over Bifunctional Ni-(O-C2 )4 Sites

Shengbo Zhang; Meng Jin; Hui Xu; Wenyi Li; Yixing Ye; Tongfei Shi; Hongjian Zhou; Chun Chen; Guozhong Wang; Yunxia Zhang; Yue Lin; Lirong Zheng; Haimin Zhang; Huijun Zhao

doi:10.1002/advs.202204043

Hydrogen Peroxide Assisted Electrooxidation of Benzene to Phenol over Bifunctional Ni-(O-C₂ )₄ Sites

Adv Sci (Weinh). 2022 Dec;9(35):e2204043. doi: 10.1002/advs.202204043. Epub 2022 Oct 30.

Authors

Shengbo Zhang^{1

2}, Meng Jin^{1

2}, Hui Xu^{1

2}, Wenyi Li^{1

2}, Yixing Ye^{1

2}, Tongfei Shi^{1

2}, Hongjian Zhou^{1

2}, Chun Chen^{1

2}, Guozhong Wang^{1

2}, Yunxia Zhang^{1

2}, Yue Lin³, Lirong Zheng⁴, Haimin Zhang^{1

2}, Huijun Zhao⁵

Affiliations

¹ Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei, 230031, China.
² University of Science and Technology of China, Hefei, 230026, China.
³ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
⁴ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquan Road, Beijing, 100049, China.
⁵ Centre for Catalysis and Clean Energy, Griffith University, Gold Coast Campus, QLD, 4222, Australia.

Abstract

Direct electrocatalytic oxidation of benzene has been regarded as a promising approach for achieving high-value phenol product, but remaining a huge challenge. Here an oxygen-coordinated nickel single-atom catalyst (Ni-O-C) is reported with bifunctional electrocatalytic activities toward the two-electron oxygen reduction reaction (2e^- ORR) to H₂ O₂ and H₂ O₂ -assisted benzene oxidation to phenol. The Ni-(O-C₂ )₄ sites in Ni-O-C ar proven to be the catalytic active centers for bifunctional 2e^- ORR and H₂ O₂ -assisted benzene oxidation processes. As a result, Ni-O-C can afford a benzene conversion as high as 96.4 ± 3.6% with a phenol selectivity of 100% and a Faradaic efficiency (FE) of 80.2 ± 3.2% with the help of H₂ O₂ in 0.1 m KOH electrolyte at 1.5 V (vs RHE). A proof of concept experiment with Ni-O-C concurrently as cathode and anode in a single electrochemical cell demonstrates a benzene conversion of 33.4 ± 2.2% with a phenol selectivity of 100% and a FE of 44.8 ± 3.0% at 10 mA cm^-2 .

Keywords: 2e− ORR; Ni-O coordination; benzene oxidation; phenol; single-atom catalysts.

Abstract

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