TY - JOUR

T1 - Acetaldehyde Production via Photocatalytic Heterolytic Dehydrogenation of Ethanol Accelerated by Tuning Lewis Acid–Base Pairs over CsGeX3 (X = Cl, Br, I) Halide Perovskites

AU - Li, Yan Jie

AU - Tang, Shuang Chao

AU - Zhao, Ting

AU - Tian, Jie

AU - He, Tao

AU - Wang, Yanjie

AU - Ji, Zhuoyu

AU - Li, Yu

AU - Dai, Yitao

AU - Lee, Wan In

AU - Bahnemann, Detlef W.

AU - Pan, Jia Hong

PY - 2025/7/7

Y1 - 2025/7/7

N2 - Photocatalytic hydrogen (H2) production fromethanol offers the dual advantages of low energy consumptionand the cogeneration of high-value chemicals. However, challengesremain in enhancing product selectivity and elucidating the precisereaction pathway. In this study, lead-free halide perovskites CsGeX3(X = Cl, Br, I) were synthesized and utilized for the simultaneousgeneration of H2 and acetaldehyde via photocatalytic ethanoloxidation under UV and visible light irradiation. Among them,CsGeI3 is reported for the first time as a highly effectivephotocatalyst, exhibiting the highest activity for both the hydrogenevolution reaction (HER) and the ethanol oxidation reaction(EOR). Under UV light irradiation for 3 h, CsGeI3 achieves H2 andacetaldehyde yields of 97.74 and 92.08 μmol g− 1, respectively, withan apparent quantum yield (AQY) of 2.31% for H2. Optical characterization and density functional theory (DFT) calculationsrevealed that the Lewis acid−base properties of CsGeI3 are mainly governed by the halogen component, enabling the selectiveactivation and cleavage of the α-C−H and O−H bonds in ethanol, promoting heterolytic reactions that enhance the formation ofboth H2 and acetaldehyde. This study provides new insights into the application of lead-free halide perovskites in tunable solar fuelgeneration and selective value-added chemical synthesis.

AB - Photocatalytic hydrogen (H2) production fromethanol offers the dual advantages of low energy consumptionand the cogeneration of high-value chemicals. However, challengesremain in enhancing product selectivity and elucidating the precisereaction pathway. In this study, lead-free halide perovskites CsGeX3(X = Cl, Br, I) were synthesized and utilized for the simultaneousgeneration of H2 and acetaldehyde via photocatalytic ethanoloxidation under UV and visible light irradiation. Among them,CsGeI3 is reported for the first time as a highly effectivephotocatalyst, exhibiting the highest activity for both the hydrogenevolution reaction (HER) and the ethanol oxidation reaction(EOR). Under UV light irradiation for 3 h, CsGeI3 achieves H2 andacetaldehyde yields of 97.74 and 92.08 μmol g− 1, respectively, withan apparent quantum yield (AQY) of 2.31% for H2. Optical characterization and density functional theory (DFT) calculationsrevealed that the Lewis acid−base properties of CsGeI3 are mainly governed by the halogen component, enabling the selectiveactivation and cleavage of the α-C−H and O−H bonds in ethanol, promoting heterolytic reactions that enhance the formation ofboth H2 and acetaldehyde. This study provides new insights into the application of lead-free halide perovskites in tunable solar fuelgeneration and selective value-added chemical synthesis.

KW - CsGeX3

KW - ethanol oxidation reaction (EOR)

KW - lead-free perovskites

KW - photocatalytic hydrogen evolution

KW - semiconductor photocatalysts

KW - solar fuel generation

UR - https://www.mendeley.com/catalogue/f1018c7c-7ea1-3d62-990b-fb4651f35d2b/

U2 - 10.1021/acssuschemeng.5c00309

DO - 10.1021/acssuschemeng.5c00309

M3 - Article

VL - 13

SP - 9941

EP - 9950

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

SN - 2168-0485

IS - 26

ER -