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Peer-reviewedCC BYJournal of the American Chemical Society

Potential Driven Spin-Crossover Synergized with Hydrogen-Bond Engineering in a Molecular Catalyst for Selective H2O2 Electrosynthesis.

  • Libo Sun1
  • Yanjie Zhai1
  • Zhiying Wu1
  • Dongxue Yu1
  • Zhiqiang Liang2
  • Zhen-An Qiao2
  • Hua Zhang1,3,4,5
  • Xin Wang1,5
5 affiliations
  1. 1Department of Chemistry, City University of Hong Kong, Kowloon999077, Hong Kong SAR, P. R. China.
  2. 2State Key Lab of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun130012, P. R. China.
  3. 3Hong Kong Institute for Clean Energy, City University of Hong Kong, Kowloon999077, Hong Kong SAR, P. R. China.
  4. 4Shenzhen Research Institute, City University of Hong Kong, Shenzhen518057, P. R. China.
  5. 5Hong Kong Branch of National Precious Metals Materials Engineering Research Center, City University of Hong Kong, Kowloon999077, Hong Kong SAR, P. R. China.
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Abstract

The electrochemical two-electron oxygen reduction reaction (2e- ORR) provides a sustainable route for hydrogen peroxide (H2O2) production. However, its efficiency is fundamentally constrained by the spin-forbidden activation of triplet O2 and the subsequent proton-coupled electron-transfer steps required to form singlet H2O2. Herein, we report a pyrazine-functionalized nickel phthalocyanine catalyst (NiPNPC) that overcomes these constraints and achieves exceptional selectivity for H2O2 (up to 97.15%). In situ spectroscopic and computational studies reveal that the pyrazine units within the macrocyclic ligand promote a dynamic spin-crossover at the Ni center from a low-spin to a high-spin under cathodic polarization for O2 activation, thereby resolving the intrinsic spin mismatch. Concurrently, the pyrazine units facilitate the reorganization of a well-defined hydrogen-bonding network at the electrolyte-catalyst interface. This network ensures efficient proton delivery to the active center and thereby efficient H2O2 formation. The synergy between dynamic spin-state modulation and interfacial hydrogen-bond engineering provides a mechanistic understanding for selective H2O2 formation and establishes a new design paradigm for advanced molecular electrocatalysts in sustainable synthesis.

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Cite

BibTeXRIS
BibTeX
@article{sun2026potential,
  title = {{Potential Driven Spin-Crossover Synergized with Hydrogen-Bond Engineering in a Molecular Catalyst for Selective H2O2 Electrosynthesis.}},
  author = {Libo Sun and Yanjie Zhai and Zhiying Wu and Dongxue Yu and Zhiqiang Liang and Zhen-An Qiao and Hua Zhang and Xin Wang},
  journal = {Journal of the American Chemical Society},
  year = {2026},
  month = sep,
  doi = {10.1021/jacs.6c16940},
  url = {https://europepmc.org/article/MED/42937837},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Potential Driven Spin-Crossover Synergized with Hydrogen-Bond Engineering in a Molecular Catalyst for Selective H2O2 Electrosynthesis.
AU  - Libo Sun
AU  - Yanjie Zhai
AU  - Zhiying Wu
AU  - Dongxue Yu
AU  - Zhiqiang Liang
AU  - Zhen-An Qiao
AU  - Hua Zhang
AU  - Xin Wang
PY  - 2026
DA  - 2026/09/01
JO  - Journal of the American Chemical Society
DO  - 10.1021/jacs.6c16940
UR  - https://europepmc.org/article/MED/42937837
AB  - The electrochemical two-electron oxygen reduction reaction (2e- ORR) provides a sustainable route for hydrogen peroxide (H2O2) production. However, its efficiency is fundamentally constrained by the spin-forbidden activation of triplet O2 and the subsequent proton-coupled electron-transfer steps required to form singlet H2O2. Herein, we report a pyrazine-functionalized nickel phthalocyanine catalyst (NiPNPC) that overcomes these constraints and achieves exceptional selectivity for H2O2 (up to 97.15%). In situ spectroscopic and computational studies reveal that the pyrazine units within the macrocyclic ligand promote a dynamic spin-crossover at the Ni center from a low-spin to a high-spin under cathodic polarization for O2 activation, thereby resolving the intrinsic spin mismatch. Concurrently, the pyrazine units facilitate the reorganization of a well-defined hydrogen-bonding network at the electrolyte-catalyst interface. This network ensures efficient proton delivery to the active center and thereby efficient H2O2 formation. The synergy between dynamic spin-state modulation and interfacial hydrogen-bond engineering provides a mechanistic understanding for selective H2O2 formation and establishes a new design paradigm for advanced molecular electrocatalysts in sustainable synthesis.
SN  - 0002-7863
SN  - 1520-5126
ER  -