Lee, Dong-Gyu Kim, Su Hwan Lee, Hyun Ho Shin, Seokmin Lee, Jiyun Joo, Se Hun Lee, Yeongdae Kwak, Sang Kyu Song, Hyun-Kon 2024-01-19T13:33:01Z 2024-01-19T13:33:01Z 2022-04-05 2021-10 2155-5435 https://pubs.kist.re.kr/handle/201004/116276 Theoretical computational studies have claimed that the catalytic activity of a family of heterogeneous catalysts (e.g., metal catalysts) is governed by a linear scaling relationship (LSR) between adsorption energy levels of intermediates on active sites of catalysts. The volcano shape of the activity versus the adsorption energy of one of the intermediates was obtained from the LSR and the Brensted-Evans-Polanyi relationship. An improved activity can be achieved using a catalyst having optimized adsorption energy of the volcano or alternatively by circumventing or breaking the LSR. Herein, we demonstrated that the LSR of a series of transition metal terephthalates (MTPs; M = Fe, Co, Ni, Cu, or Zn) as electrocatalysts for the oxygen reduction reaction (ORR) was broken in the presence of polypyrrole (pPy) as a proton donor. The reason for the LSR breakage was that the intermediate to which the proton of pPy was delivered was different depending on the metal of MTP. Also, pPy affected the adsorption energy of the specific intermediate (the target of the proton transfer) more strongly while the other intermediates were less affected by pPy. Experimentally as well as theoretically, pPy significantly improved the ORR activity of MTPs, altering the activity volcano plot. The most significant improvement was found on CoTP: the onset potential of ORR on CoTP was shifted toward the more easy-to-be-reduced direction from 0.7 to 0.85 V-RHE at 1 mA cm(-2). English American Chemical Society Breaking the Linear Scaling Relationship by a Proton Donor for Improving Electrocatalytic Oxygen Reduction Kinetics Article 10.1021/acscatal.1c02934 1 ACS Catalysis, v.11, no.20, pp.12712 - 12720 ACS Catalysis 11 20 12712 12720 N scie scopus 000709692900027 2-s2.0-85117175297 Chemistry, Physical Chemistry Article METAL-AIR BATTERIES POLYPYRROLE ELECTROCHEMISTRY DEPROTONATION CATALYSIS OXIDATION VOLCANO linear scaling relationship volcano plot oxygen reduction reaction proton donor polypyrrole