Atomic-scale facet-defect coupling enables spatially confined electron accumulation in ZnIn2S4 for reductive photocatalysis
7 affiliations
- 1Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China.
- 2Shandong Provincial Key Laboratory for Science of Material Creation and Energy Conversion, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, Shandong, China.
- 3Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, Henan, China.
- 4School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, New South Wales 2006, Australia.
- 5State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.
- 6Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, United States.
- 7Department of Earth and Environmental Science, University of Pennsylvania, Philadelphia, PA 19104-6316, United States.
Abstract
Atomic-scale regulation of photogenerated electrons remains a central challenge in reductive photocatalysis because highly reductive electrons are intrinsically prone to rapid recombination and spatial delocalization. Although crystal-facet engineering and defect modulation have independently improved photocatalytic performance, their synergistic coupling in governing electron accumulation and carrier kinetics remains poorly understood. Here, we report a facet-defect coupling strategy that enables spatially confined electron accumulation in ZnIn₂S₄ through preferential exposure of high-index {102} facets. Density functional theory calculations reveal that the {102} facets simultaneously have a more negative conduction band minimum and intrinsically lower sulfur vacancy formation energy than conventional {110} facets, thereby coupling enhanced reduction thermodynamics with spontaneous defect generation. Guided by these predictions, an ethanol-glycerol-mediated solvothermal strategy was developed to stabilize the high-energy {102} facets via surface-energy regulation. Combined crystallographic, spectroscopic, and ultrafast transient absorption analyses demonstrate that the facet-induced sulfur vacancies act as long-lived electron-trapping centers, promoting electron localization, suppressing charge recombination, and prolonging carrier lifetime. As a result, the engineered ZnIn₂S₄ exhibits substantially enhanced catalytic activity across representative multielectron transformations, including H₂O₂ photosynthesis, H₂ evolution, Cr(VI)/U(VI) reduction, and perfluoroalkyl substance defluorination. This work establishes facet-defect coupling as a general strategy for regulating electron accumulation and carrier behavior to advance reductive photocatalysis at the atomic scale.
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BibTeX
@article{shan2026atomicscale,
title = {{Atomic-scale facet-defect coupling enables spatially confined electron accumulation in ZnIn2S4 for reductive photocatalysis}},
author = {Xiangcheng Shan and Lu Qi and Xiaoyu Zhang and Zongwei Chen and Xiaoyang Song and Qiang Song and Runzeng Liu and Canzhu Gao and Yongguang Yin and Yong Cai and Patrick J. Cullen and Joseph S. Francisco and Qingzhe Zhang and Guibin Jiang},
journal = {Science Advances},
year = {2026},
month = oct,
doi = {10.1126/sciadv.aek0913},
url = {https://www.science.org/doi/abs/10.1126/sciadv.aek0913},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Atomic-scale facet-defect coupling enables spatially confined electron accumulation in ZnIn2S4 for reductive photocatalysis
AU - Xiangcheng Shan
AU - Lu Qi
AU - Xiaoyu Zhang
AU - Zongwei Chen
AU - Xiaoyang Song
AU - Qiang Song
AU - Runzeng Liu
AU - Canzhu Gao
AU - Yongguang Yin
AU - Yong Cai
AU - Patrick J. Cullen
AU - Joseph S. Francisco
AU - Qingzhe Zhang
AU - Guibin Jiang
PY - 2026
DA - 2026/10/28
JO - Science Advances
DO - 10.1126/sciadv.aek0913
UR - https://www.science.org/doi/abs/10.1126/sciadv.aek0913
AB - Atomic-scale regulation of photogenerated electrons remains a central challenge in reductive photocatalysis because highly reductive electrons are intrinsically prone to rapid recombination and spatial delocalization. Although crystal-facet engineering and defect modulation have independently improved photocatalytic performance, their synergistic coupling in governing electron accumulation and carrier kinetics remains poorly understood. Here, we report a facet-defect coupling strategy that enables spatially confined electron accumulation in ZnIn₂S₄ through preferential exposure of high-index {102} facets. Density functional theory calculations reveal that the {102} facets simultaneously have a more negative conduction band minimum and intrinsically lower sulfur vacancy formation energy than conventional {110} facets, thereby coupling enhanced reduction thermodynamics with spontaneous defect generation. Guided by these predictions, an ethanol-glycerol-mediated solvothermal strategy was developed to stabilize the high-energy {102} facets via surface-energy regulation. Combined crystallographic, spectroscopic, and ultrafast transient absorption analyses demonstrate that the facet-induced sulfur vacancies act as long-lived electron-trapping centers, promoting electron localization, suppressing charge recombination, and prolonging carrier lifetime. As a result, the engineered ZnIn₂S₄ exhibits substantially enhanced catalytic activity across representative multielectron transformations, including H₂O₂ photosynthesis, H₂ evolution, Cr(VI)/U(VI) reduction, and perfluoroalkyl substance defluorination. This work establishes facet-defect coupling as a general strategy for regulating electron accumulation and carrier behavior to advance reductive photocatalysis at the atomic scale.
SN - 2375-2548
ER -