Partially Nitrided Ni Nanoclusters Achieve Energy-Efficient Electrocatalytic CO2 Reduction to CO at Ultralow Overpotential

Runyao Zhao; Yiding Wang; Guipeng Ji; Jiajun Zhong; Fengtao Zhang; Meifang Chen; Shengrui Tong; Peng Wang; Zhonghua Wu; Buxing Han; Zhimin Liu

doi:10.1002/adma.202205262

Partially Nitrided Ni Nanoclusters Achieve Energy-Efficient Electrocatalytic CO₂ Reduction to CO at Ultralow Overpotential

Adv Mater. 2023 Feb;35(5):e2205262. doi: 10.1002/adma.202205262. Epub 2022 Dec 19.

Authors

Runyao Zhao^{1

2}, Yiding Wang^{1

2}, Guipeng Ji^{1

2}, Jiajun Zhong³, Fengtao Zhang^{1

2}, Meifang Chen^{1

2}, Shengrui Tong¹, Peng Wang^{1

4}, Zhonghua Wu³, Buxing Han^{1

2}, Zhimin Liu^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
² University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
³ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, P. R. China.
⁴ Henan Key Laboratory of Green Chemistry, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007, P. R. China.

PMID: 36413020
DOI: 10.1002/adma.202205262

Abstract

Electrocatalytic CO₂ reduction reaction (CO₂ RR) offers a promising strategy to lower CO₂ emission while producing value-added chemicals. A great challenge facing CO₂ RR is how to improve energy efficiency by reducing overpotentials. Herein, partially nitrided Ni nanoclusters (NiN_x ) immobilized on N-doped carbon nanotubes (NCNT) for CO₂ RR are reported, which achieves the lowest onset overpotential of 16 mV for CO₂ -to-CO and the highest cathode energy efficiency of 86.9% with CO Faraday efficiency >99.0% to date. Interestingly, NiN_x /NCNT affords a CO generation rate of 43.0 mol g^-1 h^-1 at a low potential of -0.572 V (vs RHE). DFT calculations reveal that the NiN_x nanoclusters favor *COOH formation with lower Gibbs free energy than isolated Ni single-atom, hence lowering CO₂ RR overpotential. As NiN_x /NCNT is applied to a membrane electrode assembly system coupled with oxygen evolution reaction, a cell voltage of only 2.13 V is required to reach 100 mA cm^-2 , with total energy efficiency of 62.2%.

Keywords: CO; Ni nanoclusters catalysts; electrocatalytic CO 2 reduction reaction; energy efficiency; low overpotential.

Abstract

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