Light‐Driven C−C Coupling for Targeted Synthesis of CH<sub>3</sub>COOH with Nearly 100 % Selectivity from CO<sub>2</sub>

Ding, Jinyu; Du, Peijin; Zhu, Juncheng; Hu, Qing; He, Dongpo; Wu, Yang; Liu, Wenxiu; Zhu, Shan; Yan, Wensheng; Hu, Jun; Zhu, Junfa; Chen, Qingxia; Jiao, Xingchen; Xie, Yi

doi:10.1002/anie.202400828

Cited by 11 publications

(1 citation statement)

References 31 publications

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“…Due to the good physicochemical property, tunable surface configuration, and electronic structure, two-dimensional (2D) nanomaterials have shown great potential in photocatalysis. − The surface characteristics of 2D nanomaterials have been proven to be easily adjustable to optimize the photocatalytic behavior . Considering the high surface atom to entire atoms ratio in 2D nanomaterials, if the entire plane is transformed into a symmetry-breaking structure on the surface of a 2D atomic layer, sufficient polarization center sites can be formed to enhance the charge separation across the entire atomic layer.…”

Section: Introductionmentioning

confidence: 99%

Amorphizing MnIn₂S₄ Atomic Layers Create an Asymmetrical InO₁S₅ Polarization Plane for Photocatalytic Ammonia Synthesis and CO₂ Reduction

Liang,

Ye,

Xiong

et al. 2024

ACS Nano

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Building a polarization center is an effective avenue to boost charge separation and molecular activation in photocatalysis. However, a limited number of polarization centers are usually created. Here, a polarization plane based on two-dimensional (2D) atomic layers is designed to maximize the surface polarization centers. The Mn in a 2D crystal lattice is etched from the MnIn 2 S 4 atomic layers to build a consecutive symmetry-breaking structure of isolated InO 1 S 5 sites. More charges aggregate around O, making the isolated InO 1 S 5 sites highly polarized. Due to the formation of the InO 1 S 5 polarization plane, an enormous polarized electric field is formed perpendicular to the 2D atomic layers and the carrier lifetime can be prolonged from 93.2 ps in MnIn 2 S 4 to 1130 ps in amorphous Mn x In 2 S y . Meantime, the formed large charge density gradient favors coupling and activation of small molecules. Benefiting from these features, a good NH 3 photosynthesis performance (515.8 μmol g −1 h −1 ) can be realized over amorphous Mn x In 2 S y , roughly 2.5 and 48.9 times higher than those of MnIn 2 S 4 atomic layers and bulk MnIn 2 S 4 , respectively. The apparent quantum yields reach 5.4 and 3.3% at 380 and 400 nm, respectively. Meanwhile, a greatly improved CO 2 reduction activity is also achieved over Mn x In 2 S y . This strategy provides an accessible pathway for designing an asymmetrical polarization plane to motivate photocatalysis optimization. KEYWORDS: isolated InO 1 S 5 sites, NH 3 photosynthesis, charge separation, polarization plane, MnIn 2 S 4 atomic layers, consecutive symmetry breaking

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Section: Introductionmentioning

confidence: 99%

Amorphizing MnIn₂S₄ Atomic Layers Create an Asymmetrical InO₁S₅ Polarization Plane for Photocatalytic Ammonia Synthesis and CO₂ Reduction

Liang,

Ye,

Xiong

et al. 2024

ACS Nano

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Induced C−C Coupling by Amorphous‐Crystalline Hybrid Structure for Selective CO₂ Photoreduction into C₂ Fuels

He,

Huang,

et al. 2024

Advanced Energy Materials

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Selective photoreduction of carbon dioxide (CO2) into high‐value C2 products remains a formidable challenge due to the elusive C−C coupling step. Herein, the novel concept is first introduced that an amorphous‐crystalline hybrid structure can galvanize previously inert metal atoms, thereby establishing highly active dual sites. This ingenious configuration promotes the C−C coupling, paving the way for CO2 photoreduction into C2 products. Taking the Bi2MoO6 nanosheets anchored by amorphous FeOOH species as an example, X‐ray photoelectron spectroscopy (XPS) spectra and X‐ray absorption near edge structure spectra and density functional theoretical (DFT) calculations confirm the electron transfer from FeOOH to Bi2MoO6 nanosheets. Thus, the introduction of FeOOH activates the nonoperative Bi sites for the construction of Bi−Mo dual sites, verified by the in situ XPS spectra and DFT calculations. Gibbs free energy calculations revealed the formation energy barrier of C−C coupling is hugely lowed from 3.41 to 0.45 eV thanks to the presence of FeOOH species. Therefore, the FeOOHBi2MoO6 nanosheets are a game changer, delivering the sole liquid product, acetic acid, with an impressive electron selectivity of ≈86.9%. In contrast, the Bi2MoO6 nanosheets lag behind, only capable of producing carbon monoxide from CO2 photoreduction.

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Recent Advances of In Situ Insights into CO₂ Reduction toward Fuels

Chen,

Zhang,

Jiao

2024

ChemCatChem

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The conversion of CO2 into valuable chemical fuels addresses both environmental pollution and energy scarcity. However, understanding reaction mechanisms and the dynamic catalyst evolution during CO2 reduction remains a challenge to data. In this review, we present a detailed description of recent advanced in situ characterization techniques, which provide a reliable means of monitoring the intermediate evolution during CO2 reduction and the dynamic evolution of the catalyst, respectively. Finally, we provide an outlook on the development of in situ characterization techniques.

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Light‐Driven C−C Coupling for Targeted Synthesis of CH₃COOH with Nearly 100 % Selectivity from CO₂

Cited by 11 publications

References 31 publications

Amorphizing MnIn₂S₄ Atomic Layers Create an Asymmetrical InO₁S₅ Polarization Plane for Photocatalytic Ammonia Synthesis and CO₂ Reduction

Amorphizing MnIn₂S₄ Atomic Layers Create an Asymmetrical InO₁S₅ Polarization Plane for Photocatalytic Ammonia Synthesis and CO₂ Reduction

Induced C−C Coupling by Amorphous‐Crystalline Hybrid Structure for Selective CO₂ Photoreduction into C₂ Fuels

Recent Advances of In Situ Insights into CO₂ Reduction toward Fuels

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Light‐Driven C−C Coupling for Targeted Synthesis of CH3COOH with Nearly 100 % Selectivity from CO2

Cited by 11 publications

References 31 publications

Amorphizing MnIn2S4 Atomic Layers Create an Asymmetrical InO1S5 Polarization Plane for Photocatalytic Ammonia Synthesis and CO2 Reduction

Amorphizing MnIn2S4 Atomic Layers Create an Asymmetrical InO1S5 Polarization Plane for Photocatalytic Ammonia Synthesis and CO2 Reduction

Induced C−C Coupling by Amorphous‐Crystalline Hybrid Structure for Selective CO2 Photoreduction into C2 Fuels

Recent Advances of In Situ Insights into CO2 Reduction toward Fuels

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Light‐Driven C−C Coupling for Targeted Synthesis of CH₃COOH with Nearly 100 % Selectivity from CO₂

Amorphizing MnIn₂S₄ Atomic Layers Create an Asymmetrical InO₁S₅ Polarization Plane for Photocatalytic Ammonia Synthesis and CO₂ Reduction

Amorphizing MnIn₂S₄ Atomic Layers Create an Asymmetrical InO₁S₅ Polarization Plane for Photocatalytic Ammonia Synthesis and CO₂ Reduction

Induced C−C Coupling by Amorphous‐Crystalline Hybrid Structure for Selective CO₂ Photoreduction into C₂ Fuels

Recent Advances of In Situ Insights into CO₂ Reduction toward Fuels