Single and dual metal atom catalysts for enhanced singlet oxygen generation and oxygen reduction reaction

Mohsen Tamtaji; Songhhua Cai; Wenting Wu; Tongchao Liu; Zhimin Li; Hsun-Yun Chang; Patrick Ryan Galligan; Shin-ichi Iida; Xiangrong Li; Faisal Rehman; Khalil Amine; William A. Goddard; Zhengtang Luo

doi:10.1039/D2TA08240C

Single and dual metal atom catalysts for enhanced singlet oxygen generation and oxygen reduction reaction†

Mohsen Tamtaji,^a Songhhua Cai,^b Wenting Wu,

^c Tongchao Liu,^d Zhimin Li,^b Hsun-Yun Chang,

^e Patrick Ryan Galligan,^a Shin-ichi Iida,

^e Xiangrong Li,^a Faisal Rehman,

^af Khalil Amine,

*^d William A. Goddard, III

*^f and Zhengtang Luo

*^a

Author affiliations

* Corresponding authors

^a Department of Chemical and Biological Engineering, Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology, William Mong Institute of Nano Science and Technology, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China
E-mail: keztluo@ust.hk

^b Department of Applied Physics, The Hong Kong Polytechnic University, Hunghom, Kowloon 999077, Hong Kong

^c State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, Institute of New Energy, China University of Petroleum (East China), Qingdao 266580, P. R. China

^d Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 Cass Ave, Lemont, IL 60439, USA
E-mail: amine@anl.gov

^e ULVAC-PHI, Inc., Analytical Laboratory, 2500 Hagisono, Chigasaki, Kanagawa 253-8522, Japan

^f Materials and Process Simulation Center (MSC), MC 139-74, California Institute of Technology, Pasadena, CA, USA
E-mail: wag@caltech.edu

Abstract

We demonstrate rational design of graphene-supported single and dual metal atom catalysts (SACs and DACs) for photocatalytic applications, such as singlet oxygen (¹O₂) sensitization and H₂O₂ production. Here we combine density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations with experimental verifications. We found a synergistic effect between triplet sensitization and triplet–triplet (Dexter) energy transfer; both play a role in the photocatalytic activity through the volcano plot of 3d transition metal SACs. More specifically, FeN₄-SAC exhibits a low ISC energy gap (ΔE_ISC) of 0.039 eV, compared with 0.108 eV for FeNiN8-DACs, both possessing a high Bader charge transfer of 0.366 e⁻ and 0.405 e⁻, respectively. Guided by these computational results, we synthesized a series of SACs and a DAC and confirmed their structures with scanning transmission electron microscopy (STEM) along with the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). We then confirm their band structures with low-energy inverse photoemission spectroscopy (LEIPS) and UV-vis-NIR. Subsequently, we synthesized the catalysts for the photooxygenation of anthracene and two-electron oxygen reduction reaction (ORR) to measure their photocatalytic activity. We found that H₂O₂ production through the two-electron ORR competes with the ¹O₂ generation through Dexter energy transfer. FeN₄-SAC demonstrates a high photooxygenation conversion of 86% and a high ¹O₂ quantum yield of 1.04, obtained from electron spin resonance (ESR) spectroscopy, with low H₂O₂ production. In contrast, NiN₄-SAC exhibits a low ¹O₂ generation and a high H₂O₂ production mainly because of the high Gibbs free energy of the OOH* intermediate. This work proposes an effective DFT-guided strategy for designing SACs and DACs for various photocatalytic applications.

Journal of Materials Chemistry A

Single and dual metal atom catalysts for enhanced singlet oxygen generation and oxygen reduction reaction†

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