Spin-Polarized Photocatalytic CO2 Reduction of Mn-Doped Perovskite Nanoplates

Cheng-Chieh Lin; Ting-Ran Liu; Sin-Rong Lin; Karunakara Moorthy Boopathi; Chun-Hao Chiang; Wen-Yen Tzeng; Wan-Hsiu Chang Chien; Hua-Shu Hsu; Chih-Wei Luo; Hui-Ying Tsai; Hsin-An Chen; Pai-Chia Kuo; Jessie Shiue; Jau-Wern Chiou; Way-Faung Pong; Chia-Chun Chen; Chun-Wei Chen

doi:10.1021/jacs.2c06060

Spin-Polarized Photocatalytic CO₂ Reduction of Mn-Doped Perovskite Nanoplates

J Am Chem Soc. 2022 Aug 31;144(34):15718-15726. doi: 10.1021/jacs.2c06060. Epub 2022 Aug 17.

Authors

Cheng-Chieh Lin^{1

2}, Ting-Ran Liu³, Sin-Rong Lin⁴, Karunakara Moorthy Boopathi³, Chun-Hao Chiang³, Wen-Yen Tzeng⁵, Wan-Hsiu Chang Chien⁶, Hua-Shu Hsu⁶, Chih-Wei Luo^{5

7

8

9}, Hui-Ying Tsai⁴, Hsin-An Chen¹⁰, Pai-Chia Kuo¹¹, Jessie Shiue^{11

12}, Jau-Wern Chiou¹³, Way-Faung Pong¹⁴, Chia-Chun Chen^{4

11}, Chun-Wei Chen^{1

3

15

16}

Affiliations

¹ International Graduate Program of Molecular Science and Technology, National Taiwan University (NTU-MST), Taipei 10617, Taiwan.
² Molecular Science and Technology Program, Taiwan International Graduate Program (TIGP), Academia Sinica, Taipei 11529, Taiwan.
³ Department of Materials Science and Engineering, National Taiwan University, Taipei 10617, Taiwan.
⁴ Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan.
⁵ Department of Electrophysics, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan.
⁶ Department of Applied Physics, National Pingtung University, Pingtung 90044, Taiwan.
⁷ Institute of Physics and Center for Emergent Functional Matter Science, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan.
⁸ National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
⁹ Taiwan Consortium of Emergent Crystalline Materials (TCECM), Ministry of Science and Technology, Taipei 10622, Taiwan.
¹⁰ Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei 10608, Taiwan.
¹¹ Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
¹² Institute of Physics, Academia Sinica, Taipei 11520, Taiwan.
¹³ Department of Applied Physics, National University of Kaohsiung, Kaohsiung 81148, Taiwan.
¹⁴ Department of Physics, Tamkang University, New Taipei City 25137, Taiwan.
¹⁵ Center of Atomic Initiative for New Materials (AI-MAT), National Taiwan University (NTU), Taipei 10617, Taiwan.
¹⁶ Center for Condensed Matter Sciences, National Taiwan University, Taipei 10617, Taiwan.

PMID: 35975916
DOI: 10.1021/jacs.2c06060

Abstract

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance of electrocatalysts and photocatalysts. This work demonstrates the manipulations of spin-polarized electrons in CsPbBr₃ halide perovskite nanoplates (NPLs) to boost the photocatalytic CO₂ reduction reaction (CO₂RR) efficiencies by doping manganese cations (Mn²⁺) and applying an external magnetic field. Mn-doped CsPbBr₃ (Mn-CsPbBr₃) NPLs exhibit an outstanding photocatalytic CO₂RR compared to pristine CsPbBr₃ NPLs due to creating spin-polarized electrons after Mn doping. Notably, the photocatalytic CO₂RR of Mn-CsPbBr₃ NPLs is significantly enhanced by applying an external magnetic field. Mn-CsPbBr₃ NPLs exhibit 5.7 times improved performance of photocatalytic CO₂RR under a magnetic field of 300 mT with a permanent magnet compared to pristine CsPbBr₃ NPLs. The corresponding mechanism is systematically investigated by magnetic circular dichroism spectroscopy, ultrafast transient absorption spectroscopy, and density functional theory simulation. The origin of enhanced photocatalytic CO₂RR efficiencies of Mn-CsPbBr₃ NPLs is due to the increased number of spin-polarized photoexcited carriers by synergistic doping of the magnetic elements and applying a magnetic field, resulting in prolonged carrier lifetime and suppressed charge recombination. Our result shows that manipulating spin-polarized electrons in photocatalytic semiconductors provides an effective strategy to boost photocatalytic CO₂RR efficiencies.