Ru Single Atom Dispersed Cu Nanoparticle with Dual Sites Enables Outstanding Photocatalytic CO2 Reduction

Lizhen Liu; Jingcong Hu; Yuan Sheng; Hossein Akhoundzadeh; Wenguang Tu; Wei Jian Samuel Siow; Jia Hui Ong; Hongwei Huang; Rong Xu

doi:10.1021/acsnano.4c08303

Ru Single Atom Dispersed Cu Nanoparticle with Dual Sites Enables Outstanding Photocatalytic CO₂ Reduction

ACS Nano. 2024 Sep 13. doi: 10.1021/acsnano.4c08303. Online ahead of print.

Authors

Lizhen Liu^{1

2}, Jingcong Hu³, Yuan Sheng⁴, Hossein Akhoundzadeh², Wenguang Tu⁵, Wei Jian Samuel Siow^{2

6}, Jia Hui Ong², Hongwei Huang¹, Rong Xu^{2

7}

Affiliations

¹ Engineering Research Center of Ministry of Education for Geological Carbon Storage and Low Carbon Utilization of Resources, Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, China.
² School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore 637459, Singapore.
³ Beijing Key Laboratory of Microstructure and Properties of Solids, Faculty of Materials and Manufacturing, Beijing University of Technology, Beijing 100124, China.
⁴ College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
⁵ School of Science and Engineering, The Chinese University of Hong Kong, Shenzhen, Shenzhen, Guangdong 518172, China.
⁶ Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore 637141, Singapore.
⁷ C4T CREATE, National Research Foundation, CREATE Tower 1 Create Way, Singapore 138602, Singapore.

PMID: 39270050
DOI: 10.1021/acsnano.4c08303

Abstract

Cu-based catalysts are promising candidates for CO₂ reduction owing to the favorable energetics of Cu sites for CO₂ adsorption and transformation. However, CO₂ reduction involving insurmountable activation barriers and various byproducts remains a significant challenge to achieve high activity and selectivity. Herein, a photocatalyst constructed with single-Ru-site-on-Cu-nanoparticle on Bi₄Ti₃O₁₂ exhibits exceptional activity and selectivity for CO₂ conversion to CO. The experimental and theoretical results consistently reveal that the Ru-Cu dual sites allow the rapid transfer of photogenerated carriers for closely interacting with CO₂ molecules. Importantly, the Ru-Cu dual sites exhibit extremely strong CO₂ adsorption ability, and the Gibbs free energy of the rate-determining step (*CO₂ to *COOH) has been significantly reduced, synergistically enhancing the entire CO₂ conversion process. The optimal BTOCu₂Ru_0.5 photocatalyst manifests a high performance for selective reduction of CO₂ to CO, yielding 10.84 μmol over 15 mg of photocatalyst in 4 h (180.67 μmol·g^-1·h^-1) under a 300 W Xe lamp without any photosensitizer and sacrificial reagent, outperforming all bismuth-based materials and being one of the best photocatalysts ever reported under similar reaction conditions. This work presents a strategy for the rational design of multiple metal sites toward efficient photocatalytic reduction of CO₂.

Keywords: CO2 reduction; dual catalytic sites; nanoparticles; photocatalysis; single atom.