Exceptionally Low-Coordinated Bismuth–Oxygen Vacancy Defect Clusters for Generating Black In<sub>2</sub>O<sub>3</sub> Photocatalysts with Superb CO<sub>2</sub> Reduction Performance

Indium oxide (In2O3) is a widely used catalyst for CO2 reduction, yet its inherent properties, such as a wide band gap and low-active surface, necessitate a modification to achieve broad-wavelength absorption and enhanced surface activity. However, simultaneously achieving these goals through a single material modulation approach remains challenging. Here, we present a simple yet innovative strategy to develop a black catalyst, BixIn2–xO3–y, comprising notably low-coordinated bismuth on oxygen-defect-laden In2O3. This approach induces local structural and charge carrier changes, resulting in remarkably high visible light absorption and preeminent surface activity. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirms the spontaneous dissociation of CO2 species into CO even in the dark on the BixIn 2–xO3–y surface, underscoring the catalyst’s enhanced activity. Compared to pristine In2O3, BixIn2–xO3–y exhibits approximately 24 times greater CO production. Characterization techniques, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) analyses, along with density functional theory (DFT) calculations, reveal that oxygen vacancies in the reduced sample decrease both the average coordination number of bismuth and its effective oxidation state. Our findings indicate that the unusually low-coordinated bismuth dopant preferably promotes the formation of oxygen vacancies close to bismuth (Bi-Vö) rather than near indium, which induces local structural and charge carrier changes. These Bi-Vö clusters enhance light harvesting, charge separation, and CO2 adsorption/activation/reduction. Importantly, our approach demonstrates promise for a wide range of applications, addressing key challenges in catalyst modification for CO2 reduction and offering opportunities for further advancement in this field.

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Publication Details

Journal
ACS Catalysis
Published
2025-01-09
DOI
https://doi.org/10.1021/acscatal.4c03491
Citations
22
Primary Topic
Advanced Photocatalysis Techniques
Type
article
Field-Weighted Citation Impact
8.00

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article

Exceptionally Low-Coordinated Bismuth–Oxygen Vacancy Defect Clusters for Generating Black In2O3 Photocatalysts with Superb CO2 Reduction Performance

Farzin Nekouei, Christopher J. Pollock, Alexey M. Glushenkov, Nicholas J. Cox et al.
22 citations
ACS Catalysis
Advanced Photocatalysis Techniques
8.00
article

Exceptionally Low-Coordinated Bismuth–Oxygen Vacancy Defect Clusters for Generating Black In2O3 Photocatalysts with Superb CO2 Reduction Performance

Farzin Nekouei, Christopher J. Pollock, Alexey M. Glushenkov, Nicholas J. Cox, Siva Krishna Karuturi, Shahram Nekouei, Huanyu Jin, Zongwen Liu, Thrinathreddy Ramireddy, Elwy H. Abdelkader, Zhong Zheng, Zelio Fusco, Julien Langley, Zongyou Yin, Hieu T. Nguyen, Farzaneh Keshtpour, Teng Lü, Ary Anggara Wibowo, Hao Li, Tianyi Wang, Wei Li, Yun Liu, Yanzhao Zhang
article en
22 citations

Abstract

Indium oxide (In2O3) is a widely used catalyst for CO2 reduction, yet its inherent properties, such as a wide band gap and low-active surface, necessitate a modification to achieve broad-wavelength absorption and enhanced surface activity. However, simultaneously achieving these goals through a single material modulation approach remains challenging. Here, we present a simple yet innovative strategy to develop a black catalyst, BixIn2–xO3–y, comprising notably low-coordinated bismuth on oxygen-defect-laden In2O3. This approach induces local structural and charge carrier changes, resulting in remarkably high visible light absorption and preeminent surface activity. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirms the spontaneous dissociation of CO2 species into CO even in the dark on the BixIn 2–xO3–y surface, underscoring the catalyst’s enhanced activity. Compared to pristine In2O3, BixIn2–xO3–y exhibits approximately 24 times greater CO production. Characterization techniques, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) analyses, along with density functional theory (DFT) calculations, reveal that oxygen vacancies in the reduced sample decrease both the average coordination number of bismuth and its effective oxidation state. Our findings indicate that the unusually low-coordinated bismuth dopant preferably promotes the formation of oxygen vacancies close to bismuth (Bi-Vö) rather than near indium, which induces local structural and charge carrier changes. These Bi-Vö clusters enhance light harvesting, charge separation, and CO2 adsorption/activation/reduction. Importantly, our approach demonstrates promise for a wide range of applications, addressing key challenges in catalyst modification for CO2 reduction and offering opportunities for further advancement in this field.

ACS CatalysisVol. 15(3)
Islamic Azad University, Tehran (IR), Australian National University (AU), The University of Sydney (AU), Islamic Azad University, Science and Research Branch (IR), Tohoku University (JP), Cornell University (US), Battery Park (US), Islamic Azad University Central Tehran Branch (IR), Advanced Institute of Materials Science (JP), Stanford Synchrotron Radiation Lightsource (US), Science Club (US), ARC Centre of Excellence for Innovations in Peptide and Protein Science (AU), Iran's National Elites Foundation (IR), Institute for Materials Research, Tohoku University, Cornell High Energy Synchrotron Source, The University of Adelaide (AU)
National Computational Infrastructure, Australian Research Council, Japan Society for the Promotion of Science
Openalex Percentile: Top 2%
Advanced Photocatalysis Techniques
8.00
DOISourceOpenAlex
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