Bandgap Funneling in Bismuth-Based Hybrid Perovskite Photocatalyst with Efficient Visible-Light-Driven Hydrogen Evolution

Yunqi Tang; Chun Hong Mak; Chen Wang; Yu Fu; Fang-Fang Li; Guohua Jia; Chang-Wei Hsieh; Hsin-Hui Shen; Juan Carlos Colmenares; Haisheng Song; Mingjian Yuan; Yue Chen; Hsien-Yi Hsu

doi:10.1002/smtd.202200326

Bandgap Funneling in Bismuth-Based Hybrid Perovskite Photocatalyst with Efficient Visible-Light-Driven Hydrogen Evolution

Small Methods. 2022 Aug;6(8):e2200326. doi: 10.1002/smtd.202200326. Epub 2022 Jun 22.

Authors

Yunqi Tang^{1

2}, Chun Hong Mak^{1

2}, Chen Wang³, Yu Fu^{1

4}, Fang-Fang Li⁵, Guohua Jia⁶, Chang-Wei Hsieh^{7

8}, Hsin-Hui Shen⁹, Juan Carlos Colmenares^{1

10}, Haisheng Song¹¹, Mingjian Yuan¹², Yue Chen³, Hsien-Yi Hsu^{1

2}

Affiliations

¹ School of Energy and Environment, Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, 999077, China.
² Shenzhen Research Institute of City University of Hong Kong, Shenzhen, 518057, P. R. China.
³ Department of Mechanical Engineering, The University of Hong Kong, Hong Kong SAR, 999077, China.
⁴ Department of Electronic and Computer Engineering, The Hong Kong University of Science and Technology, Hong Kong SAR, 999077, China.
⁵ Huazhong University of Science and Technology, Wuhan, 430074, China.
⁶ Curtin Institute of Functional Molecules and Interfaces, School of Molecular and Life Sciences, Curtin University GPO Box U1987, Perth, WA, 6845, Australia.
⁷ Department of Food Science and Biotechnology, National Chung Hsing University, Taichung City, 402, Taiwan.
⁸ Department of Medical Research, China Medical University Hospital, Taichung City, 404, Taiwan.
⁹ Department of Materials Science and Engineering, Faculty of Engineering, Monash University, Clayton, VIC, 3800, Australia.
¹⁰ Institute of Physical Chemistry, Polish Academy of Sciences, 01-224, Warsaw, Poland.
¹¹ Wuhan National Laboratory for Optoelectronics (WNLO), School of Optical and Electronic Information, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, P. R. China.
¹² Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.

PMID: 35733072
DOI: 10.1002/smtd.202200326

Abstract

The photocatalytic system using hydrohalic acid (HX) for hydrogen production is a promising strategy to generate clean and renewable fuels as well as value-added chemicals (such as X₂ /X₃ ^- ). However, it is still challenging to develop a visible-light active and strong-acid resistive photocatalyst. Hybrid perovskites have been recognized as a potential photocatalyst for photovoltaic HX splitting. Herein, a novel environmentally friendly mixed halide perovskite MA₃ Bi₂ Cl_9-x I_x with a bandgap funnel structure is developed, i.e., confirmed by energy dispersive X-ray analysis and density functional theory calculations. Due to gradient neutral formation energy within iodine-doped MA₃ Bi₂ Cl₉ , the concentration of iodide element decreases from the surface to the interior across the MA₃ Bi₂ Cl_9-x I_x perovskite. Because of the aligned energy levels of iodide/chloride-mixed MA₃ Bi₂ Cl_9-x I_x , a graded bandgap funnel structure is therefore formed, leading to the promotion of photoinduced charge transfer from the interior to the surface for efficient photocatalytic redox reaction. As a result, the hydrogen generation rate of the optimized MA₃ Bi₂ Cl_9-x I_x is enhanced up to ≈341 ± 61.7 µmol h^-1 with a Pt co-catalyst under visible light irradiation.

Keywords: bandgap funneling; hydrogen evolution; lead-free hybrid perovskites; photocatalysis.

Abstract

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