Atomic Cobalt-Silver Dual-Metal Sites Confined on Carbon Nitride with Synergistic Ag Nanoparticles for Enhanced CO2 Photoreduction

Aixin Deng; En Zhao; Qi Li; Yue Sun; Yazi Liu; Shaogui Yang; Huan He; Yan Xu; Wei Zhao; Haiou Song; Zhe Xu; Zupeng Chen

doi:10.1021/acsnano.3c03176

Atomic Cobalt-Silver Dual-Metal Sites Confined on Carbon Nitride with Synergistic Ag Nanoparticles for Enhanced CO₂ Photoreduction

ACS Nano. 2023 Jun 27;17(12):11869-11881. doi: 10.1021/acsnano.3c03176. Epub 2023 Jun 8.

Authors

Aixin Deng^{1

2}, En Zhao³, Qi Li⁴, Yue Sun¹, Yazi Liu^{1

5}, Shaogui Yang¹, Huan He¹, Yan Xu², Wei Zhao⁶, Haiou Song¹, Zhe Xu¹, Zupeng Chen³

Affiliations

¹ School of Environment, Nanjing Normal University, Jiangsu Engineering Lab of Water and Soil Eco-Remediation, Nanjing 210023, People's Republic of China.
² Department of Municipal Engineering, School of Civil Engineering, Southeast University, Nanjing 210096, People's Republic of China.
³ Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, People's Republic of China.
⁴ Jiangsu Key Laboratory of Construction Materials, College of Materials Science and Engineering, Southeast University, Nanjing 211189, People's Republic of China.
⁵ Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia.
⁶ School of Materials Engineering, Changshu Institute of Technology, Changshu 215500, People's Republic of China.

PMID: 37289089
DOI: 10.1021/acsnano.3c03176

Abstract

Photocatalytic reduction of CO₂ to value-added solar fuels is of great significance to alleviate the severe environmental and energy crisis. Herein, we report the construction of a synergistic silver nanoparticle catalyst with adjacent atomic cobalt-silver dual-metal sites on P-doped carbon nitride (Co₁Ag_(1+n)-PCN) for photocatalytic CO₂ reduction. The optimized photocatalyst achieves a high CO formation rate of 46.82 μmol g_cat^-1 with 70.1% selectivity in solid-liquid mode without sacrificial agents, which is 2.68 and 2.18-fold compared to that of exclusive silver single-atom (Ag₁-CN) and cobalt-silver dual-metal site (Co₁Ag₁-PCN) photocatalysts, respectively. The closely integrated in situ experiments and density functional theory calculations unravel that the electronic metal-support interactions (EMSIs) of Ag nanoparticles with adjacent Ag-N₂C₂ and Co-N₆-P single-atom sites promote the adsorption of CO₂* and COOH* intermediates to form CO and CH₄, as well as boost the enrichment and transfer of photoexcited electrons. Moreover, the atomically dispersed dual-metal Co-Ag SA sites serve as the fast-electron-transfer channel while Ag nanoparticles act as the electron acceptor to enrich and separate more photogenerated electrons. This work provides a general platform to delicately design high-performance synergistic catalysts for highly efficient solar energy conversion.

Keywords: Ag nanoparticles; dual-metal sites; photocatalytic CO2 reduction; single-atom catalysts; synergistic effects.