Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon

Qiaowan Chang; Pu Zhang; Amir Hassan Bagherzadeh Mostaghimi; Xueru Zhao; Steven R Denny; Ji Hoon Lee; Hongpeng Gao; Ying Zhang; Huolin L Xin; Samira Siahrostami; Jingguang G Chen; Zheng Chen

doi:10.1038/s41467-020-15843-3

Promoting H₂O₂ production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon

Nat Commun. 2020 May 1;11(1):2178. doi: 10.1038/s41467-020-15843-3.

Authors

Qiaowan Chang¹, Pu Zhang¹, Amir Hassan Bagherzadeh Mostaghimi², Xueru Zhao³, Steven R Denny⁴, Ji Hoon Lee⁴, Hongpeng Gao¹, Ying Zhang⁵, Huolin L Xin⁶, Samira Siahrostami⁷, Jingguang G Chen^{8

9}, Zheng Chen^{10

11}

Affiliations

¹ Department of NanoEngineering, University of California San Diego, La Jolla, California, 92093, USA.
² Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada, T2N 1N4.
³ Chemistry Division, Brookhaven National Laboratory, Upton, New York, 11973, USA.
⁴ Department of Chemical Engineering, Columbia University, New York, New York, 10027, USA.
⁵ School of Mineral Processing and Bioengineering, Central South University, Changsha, 410083, China.
⁶ Department of Physics and Astronomy, University of California, Irvine, California, 94720, USA. huolinx@uci.edu.
⁷ Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada, T2N 1N4. samira.siahrostami@ucalgary.ca.
⁸ Chemistry Division, Brookhaven National Laboratory, Upton, New York, 11973, USA. jgchen@columbia.edu.
⁹ Department of Chemical Engineering, Columbia University, New York, New York, 10027, USA. jgchen@columbia.edu.
¹⁰ Department of NanoEngineering, University of California San Diego, La Jolla, California, 92093, USA. zhengchen@eng.ucsd.edu.
¹¹ Program of Chemical Engineering, University of California San Diego, La Jolla, California, 92093, USA. zhengchen@eng.ucsd.edu.

Abstract

Electrochemical synthesis of H₂O₂ through a selective two-electron (2e^-) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized H₂O₂ production. Herein, we report that the synergistic interaction between partially oxidized palladium (Pd^δ+) and oxygen-functionalized carbon can promote 2e^- ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition of amorphous Pd^δ+ clusters (Pd₃^δ+ and Pd₄^δ+) onto mildly oxidized carbon nanotubes (Pd^δ+-OCNT) shows nearly 100% selectivity toward H₂O₂ and a positive shift of ORR onset potential by ~320 mV compared with the OCNT substrate. A high mass activity (1.946 A mg^-1 at 0.45 V) of Pd^δ+-OCNT is achieved. Extended X-ray absorption fine structure characterization and density functional theory calculations suggest that the interaction between Pd clusters and the nearby oxygen-containing functional groups is key for the high selectivity and activity for 2e^- ORR.

Grants and funding

59989-DNI5/ACS | American Chemical Society Petroleum Research Fund (ACS Petroleum Research Fund)