Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d-Band Center via Local Coordination Tuning

Xiaofeng Zhu; Xin Tan; Kuang Hsu Wu; Shu Chih Haw; Chih Wen Pao; Bing Jian Su; Junjie Jiang; Sean C. Smith; Jin Ming Chen; Rose Amal; Xunyu Lu

doi:10.1002/anie.202107790

Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d-Band Center via Local Coordination Tuning

Xiaofeng Zhu, Xin Tan, Kuang Hsu Wu, Shu Chih Haw, Chih Wen Pao, Bing Jian Su, Junjie Jiang, Sean C. Smith, Jin Ming Chen, Rose Amal^*, Xunyu Lu^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

206 Citations (SciVal)

Abstract

A considerable amount of platinum (Pt) is required to ensure an adequate rate for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Thus, the implementation of atomic Pt catalysts holds promise for minimizing the Pt content. In this contribution, atomic Pt sites with nitrogen (N) and phosphorus (P) co-coordination on a carbon matrix (PtNPC) are conceptually predicted and experimentally developed to alter the d-band center of Pt, thereby promoting the intrinsic ORR activity. PtNPC with a record-low Pt content (≈0.026 wt %) consequently shows a benchmark-comparable activity for ORR with an onset of 1.0 V_RHE and half-wave potential of 0.85 V_RHE. It also features a high stability in 15 000-cycle tests and a superior turnover frequency of 6.80 s⁻¹ at 0.9 V_RHE. Damjanovic kinetics analysis reveals a tuned ORR kinetics of PtNPC from a mixed 2/4-electron to a predominately 4-electron route. It is discovered that coordinated P species significantly shifts d-band center of Pt atoms, accounting for the exceptional performance of PtNPC.

Original language	English
Pages (from-to)	21911-21917
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	40
DOIs	https://doi.org/10.1002/anie.202107790
Publication status	Published - 27 Sept 2021

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@article{68ffd2714ff943e7b06912dc9ea9ee4e,

title = "Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d-Band Center via Local Coordination Tuning",

abstract = "A considerable amount of platinum (Pt) is required to ensure an adequate rate for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Thus, the implementation of atomic Pt catalysts holds promise for minimizing the Pt content. In this contribution, atomic Pt sites with nitrogen (N) and phosphorus (P) co-coordination on a carbon matrix (PtNPC) are conceptually predicted and experimentally developed to alter the d-band center of Pt, thereby promoting the intrinsic ORR activity. PtNPC with a record-low Pt content (≈0.026 wt \%) consequently shows a benchmark-comparable activity for ORR with an onset of 1.0 VRHE and half-wave potential of 0.85 VRHE. It also features a high stability in 15 000-cycle tests and a superior turnover frequency of 6.80 s−1 at 0.9 VRHE. Damjanovic kinetics analysis reveals a tuned ORR kinetics of PtNPC from a mixed 2/4-electron to a predominately 4-electron route. It is discovered that coordinated P species significantly shifts d-band center of Pt atoms, accounting for the exceptional performance of PtNPC.",

keywords = "atomic catalysts, d-band center, doping, intrinsic activity enhancement, oxygen reduction reaction",

author = "Xiaofeng Zhu and Xin Tan and Wu, \{Kuang Hsu\} and Haw, \{Shu Chih\} and Pao, \{Chih Wen\} and Su, \{Bing Jian\} and Junjie Jiang and Smith, \{Sean C.\} and Chen, \{Jin Ming\} and Rose Amal and Xunyu Lu",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = sep,

day = "27",

doi = "10.1002/anie.202107790",

language = "English",

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publisher = "John Wiley \& Sons Ltd.",

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T1 - Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d-Band Center via Local Coordination Tuning

AU - Zhu, Xiaofeng

AU - Tan, Xin

AU - Wu, Kuang Hsu

AU - Haw, Shu Chih

AU - Pao, Chih Wen

AU - Su, Bing Jian

AU - Jiang, Junjie

AU - Smith, Sean C.

AU - Chen, Jin Ming

AU - Amal, Rose

AU - Lu, Xunyu

PY - 2021/9/27

Y1 - 2021/9/27

N2 - A considerable amount of platinum (Pt) is required to ensure an adequate rate for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Thus, the implementation of atomic Pt catalysts holds promise for minimizing the Pt content. In this contribution, atomic Pt sites with nitrogen (N) and phosphorus (P) co-coordination on a carbon matrix (PtNPC) are conceptually predicted and experimentally developed to alter the d-band center of Pt, thereby promoting the intrinsic ORR activity. PtNPC with a record-low Pt content (≈0.026 wt %) consequently shows a benchmark-comparable activity for ORR with an onset of 1.0 VRHE and half-wave potential of 0.85 VRHE. It also features a high stability in 15 000-cycle tests and a superior turnover frequency of 6.80 s−1 at 0.9 VRHE. Damjanovic kinetics analysis reveals a tuned ORR kinetics of PtNPC from a mixed 2/4-electron to a predominately 4-electron route. It is discovered that coordinated P species significantly shifts d-band center of Pt atoms, accounting for the exceptional performance of PtNPC.

AB - A considerable amount of platinum (Pt) is required to ensure an adequate rate for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Thus, the implementation of atomic Pt catalysts holds promise for minimizing the Pt content. In this contribution, atomic Pt sites with nitrogen (N) and phosphorus (P) co-coordination on a carbon matrix (PtNPC) are conceptually predicted and experimentally developed to alter the d-band center of Pt, thereby promoting the intrinsic ORR activity. PtNPC with a record-low Pt content (≈0.026 wt %) consequently shows a benchmark-comparable activity for ORR with an onset of 1.0 VRHE and half-wave potential of 0.85 VRHE. It also features a high stability in 15 000-cycle tests and a superior turnover frequency of 6.80 s−1 at 0.9 VRHE. Damjanovic kinetics analysis reveals a tuned ORR kinetics of PtNPC from a mixed 2/4-electron to a predominately 4-electron route. It is discovered that coordinated P species significantly shifts d-band center of Pt atoms, accounting for the exceptional performance of PtNPC.

KW - atomic catalysts

KW - d-band center

KW - doping

KW - intrinsic activity enhancement

KW - oxygen reduction reaction

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U2 - 10.1002/anie.202107790

DO - 10.1002/anie.202107790

M3 - Article

SN - 1433-7851

VL - 60

SP - 21911

EP - 21917

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 40

ER -

Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d-Band Center via Local Coordination Tuning

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