Citation: Jun-Kang Li, Pei-Yao Wang, Jia-Lin Zhang, Shu-Na Zhao, Bo Li, Shuang-Quan Zang. Sulfur-engineered Ni single-atom catalysts for sustainable tandem CO₂-to-chemicals conversion across pH-universal windows[J]. Chinese Chemical Letters, ;2026, 37(7): 112150. doi: 10.1016/j.cclet.2025.112150 shu

Sulfur-engineered Ni single-atom catalysts for sustainable tandem CO₂-to-chemicals conversion across pH-universal windows

Jun-Kang Li ^a ,
Pei-Yao Wang ^a ,
Jia-Lin Zhang ^a ,
Shu-Na Zhao ^{a, *,} ,
Bo Li ^{b, *,} ,
Shuang-Quan Zang ^{a, *,}

a.
Henan Key Laboratory of Crystalline Molecular Functional Materials, College of Chemistry and Pingyuan Laboratory, Key Laboratory of Special Functional Molecular Materials (Zhengzhou University), Ministry of Education, Zhengzhou University, Zhengzhou 450001, China
b.
College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, China

zhaosn@zzu.edu.cn

libony0107@nynu.edu.cn

zangsqzg@zzu.edu.cn

Received Date: 30 September 2025
Revised Date: 18 November 2025
Accepted Date: 21 November 2025
Available Online: 22 November 2025

Figures(4)

Tandem CO₂ electroreduction integrated with carbonylation reactions offers a promising pathway for transforming greenhouse gases into valuable chemical products. The development of efficient CO₂–to–CO electrocatalysts operational across wide potential ranges is crucial to address renewable energy fluctuations and facilitate integrated cascade systems. Herein, a Ni single–atom catalyst (SAC) with sulfur doping in the second shell of Ni–N₄ is reported. In situ measurements and theoretical calculations demonstrate that the incorporation S atoms not only modulates the electronic configuration of Ni active sites but also enhances H₂O adsorption, enabling rapid CO₂ hydrogenation into *COOH intermediates even at high potentials. Consequently, the Ni–N–S/CNS catalyst achieves a Faradaic efficiency for CO₂–to–CO (FE_CO) of 99.3% at –0.7 V_RHE and maintains over 90% across pH–universal conditions with ultrawide potential windows: 1400 mV (from –0.3 V_RHE to –1.7 V_RHE) in alkaline media, 1200 mV (from –0.7 V_RHE to –1.9 V_RHE) in neutral conditions, and 1000 mV (from –1.3 V_RHE to –2.3 V_RHE) in acidic environments. Remarkably, this catalyst enables the tandem CO₂RR and N–alkylaniline carbonylation process for synthesizing o–aminobenzoates and isatoic anhydrides with high yield. Our findings demonstrate an electrothermo–catalytic tandem strategy for cost–effective CO₂ conversion and synthesis of high valuable fine chemicals, thereby broadening the scope of its utilization.
- Tandem system,
- CO₂ electroreduction,
- Carbonylation reaction,
- Single atom catalyst,
- Ultrawide potential window
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Sulfur-engineered Ni single-atom catalysts for sustainable tandem CO2-to-chemicals conversion across pH-universal windows

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通讯作者: 陈斌, bchen63@163.com

Sulfur-engineered Ni single-atom catalysts for sustainable tandem CO₂-to-chemicals conversion across pH-universal windows