Strain-Induced Surface Interface Dual Polarization Constructs PML-Cu/Bi12O17Br2 High-Density Active Sites for CO2 Photoreduction

Yi Zhang; Fangyu Guo; Jun Di; Keke Wang; Molly Meng-Jung Li; Jiayu Dai; Yuanbin She; Jiexiang Xia; Huaming Li

doi:10.1007/s40820-023-01309-w

Strain-Induced Surface Interface Dual Polarization Constructs PML-Cu/Bi₁₂O₁₇Br₂ High-Density Active Sites for CO₂ Photoreduction

Nanomicro Lett. 2024 Jan 16;16(1):90. doi: 10.1007/s40820-023-01309-w.

Authors

Yi Zhang^#^{1

2}, Fangyu Guo^#³, Jun Di^{4

5}, Keke Wang⁶, Molly Meng-Jung Li², Jiayu Dai⁷, Yuanbin She⁸, Jiexiang Xia⁹, Huaming Li¹

Affiliations

¹ School of Chemistry and Chemical Engineering, Institute for Energy Research, School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang, 212013, People's Republic of China.
² Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, People's Republic of China.
³ College of Science, and Hunan Key Laboratory of Extreme Matter and Applications, National University of Defense Technology, Changsha, 410073, People's Republic of China.
⁴ School of Chemistry and Chemical Engineering, National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing, 210094, People's Republic of China. dijun@njust.edu.cn.
⁵ Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, People's Republic of China. dijun@njust.edu.cn.
⁶ State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, People's Republic of China.
⁷ College of Science, and Hunan Key Laboratory of Extreme Matter and Applications, National University of Defense Technology, Changsha, 410073, People's Republic of China. jydai@nudt.edu.cn.
⁸ State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, People's Republic of China. sheyb@zjut.edu.cn.
⁹ School of Chemistry and Chemical Engineering, Institute for Energy Research, School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang, 212013, People's Republic of China. xjx@ujs.edu.cn.

^# Contributed equally.

Abstract

The insufficient active sites and slow interfacial charge transfer of photocatalysts restrict the efficiency of CO₂ photoreduction. The synchronized modulation of the above key issues is demanding and challenging. Herein, strain-induced strategy is developed to construct the Bi-O-bonded interface in Cu porphyrin-based monoatomic layer (PML-Cu) and Bi₁₂O₁₇Br₂ (BOB), which triggers the surface interface dual polarization of PML-Cu/BOB (PBOB). In this multi-step polarization, the built-in electric field formed between the interfaces induces the electron transfer from conduction band (CB) of BOB to CB of PML-Cu and suppresses its reverse migration. Moreover, the surface polarization of PML-Cu further promotes the electron converge in Cu atoms. The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB, significantly promoting the adsorption and activation of CO₂ and CO desorption. The conversion rate of CO₂ photoreduction to CO for PBOB can reach 584.3 μmol g^-1, which is 7.83 times higher than BOB and 20.01 times than PML-Cu. This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.

Keywords: Active sites; Bi12O17Br2; CO2 photoreduction; Polarization; Porphyrin.