An Efficient Intercalation Supramolecular Structure for Photocatalytic CO<sub>2</sub> Reduction to Ethylene Under Visible Light

Ning, Chenjun; Yang, Jiangrong; Bai, Sha; Chen, Guangbo; Liu, Guihao; Shen, Tianyang; Zheng, Lirong; Xu, Simin; Kong, Xianggui; Liu, Bin; Zhao, Yufei; Song, Yu‐Fei

doi:10.1002/adfm.202300365

Cited by 14 publications

(4 citation statements)

References 64 publications

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“…Chemie depict that LaCu/CN displays the most quenched intensity and thus the lowest recombination of photogenerated carriers. [19] Furthermore, LaCu/CN also exhibits significantly enhanced photocurrent response compared with that of CN, La/CN, and Cu/CN, as displayed in the photocurrent-time curves (Figure 3e). In addition, electrochemical impedance spectroscopy measurements show the smallest interfacial resistance of LaCu/CN (Figure S14), suggesting its fastest interfacial charge transport.…”

Section: Methodsmentioning

confidence: 87%

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Xie,

Liu,

Zhang

et al. 2023

Angew Chem Int Ed

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Photocatalytic CO2 reduction into ideal hydrocarbon fuels, such as CH4, is a sluggish kinetic process involving adsorption of multiple intermediates and multi‐electron steps. Achieving high CH4 activity and selectivity therefore remains a great challenge, which largely depends on the efficiency of photogenerated charge separation and transfer as well as the intermediate energy levels in CO2 reduction. Herein, we construct La and Cu dual‐atom anchored carbon nitride (LaCu/CN), with La‐N4 and Cu‐N3 coordination bonds connected by Cu−N−La bridges. The asymmetric Cu−N−La species enables the establishment of an atomic‐level donor‐acceptor structure, which allows the migration of electrons from La atoms to the reactive Cu atom sites. Simultaneously, intermediates during CO2 reduction on LaCu/CN demonstrate thermodynamically more favorable process for CH4 formation based on theoretical calculations. Eventually, LaCu/CN exhibits a high selectivity (91.6 %) for CH4 formation with a yield of 125.8 μmol g−1, over ten times of that for pristine CN. This work presents a strategy for designing multi‐functional dual‐atom based photocatalysts.

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Section: Methodsmentioning

confidence: 87%

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Xie,

Liu,

Zhang

et al. 2023

Angew Chem Int Ed

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“…Doping engineering has enabled the construction of homogeneous and abundant atomic-level catalytic sites for photocatalytic CO 2 reduction with improved target product selectivity. , Cu species have been widely used as co-catalysts to improve the CO 2 reduction performance due to their special adsorption and activation ability to CO 2 . Notably, as for the aqueous photocatalytic CO 2 reduction system, proton reduction to H 2 presents a hardly avoidably competitive process. − Under such circumstances, it has been found that when Cu species are introduced to modify semiconductors, the photocatalytic CO 2 reduction performance is indeed enhanced and notably, the H 2 evolution rate is simultaneously promoted. , This is mainly ascribed to the fact that the photoelectrons with a prolonged lifetime induced by Cu doping indiscriminately reduce CO 2 molecules and protons. Such a situation limits the overall CO 2 reduction yield .…”

Section: Introductionmentioning

confidence: 99%

Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO₂ Reduction

Ma,

Zhang,

Xie

et al. 2024

ACS Catal.

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Doping engineering has enabled the construction of homogeneous and abundant atomic-level catalytic sites for photocatalytic CO 2 reduction with improved selectivity for the target product. However, little is known about the effect of the spatial position of the heteroatoms on the photocatalytic activity of the semiconductors toward CO 2 reduction. Herein, uniform Cu doping into the bulk phase of hollow CdS cubes (HCC) and Cu doping onto the surface of HCC, denoted as Cu/HCC and HCC@ Cu, respectively, are prepared by tuning the introduction order of Cu sources. Experimental analysis shows that the introduction of Cu by both methods can promote the separation and migration of photoinduced charge carriers in CdS. Notably, Cu doping onto the surface of CdS in HCC@Cu leads to much better proton reduction to H 2 production performance but lower CO 2 reduction efficiency as compared to bare CdS. In sharp contrast, Cu doping into the bulk phase of CdS enhances the CO 2 -to-CO conversion while mitigating H 2 evolution. This should be ascribed to the smaller overpotential of Cu/HCC in the CO 2 saturated system than that in the Ar system. In addition, doping Cu atoms into the bulk phase of CdS shifts the d band center of Cu/HCC upward to near the Fermi energy level, which promotes the adsorption and activation of CO 2 on CdS. These results indicate that the photoelectrons with a prolonged lifetime in Cu/HCC preferably reduce CO 2 molecules rather than protons. The density functional theory (DFT) calculation results show that the introduction of Cu heteroatoms can promote the desorption of CO*, and the adaptable sulfur vacancies (Vs) produced by in situ doping techniques can stimulate the formation of CO* intermediates, resulting in the high performance of photocatalytic CO 2 reduction to CO. This work reveals the effect of different heteroatom doping locations on the catalytic activity and will provide a reference for the design of efficient photocatalysts with atomic-level fine structure.

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“…Intercalation of guest anions into two-dimensional (2D) layered hosts is a promising method for developing 2D layered intercalation hybrids. − The layered hosts provide a rigid and constrained interlayer space that can reinforce the host–guest and guest–guest interactions, thereby enhancing the chemical and thermal stability of intercalated guests as well as their functional applications. Even more appealing, the intercalated guests afford the hybrids desirable properties and added value that otherwise may not be available for both the hosts and the guests, thus greatly expanding their application in photocatalysis, electrocatalysis, energy storage, , contaminant remediation, , etc.…”

Section: Introductionmentioning

confidence: 99%

Insight into Multiphase Interlayer Molecular Packing and Stepwise Phase Transition in 4-(Phenylazo)benzoate Anion-Intercalated Layered Zinc Hydroxide

Zhang,

Mo,

Fang

et al. 2024

Inorg. Chem.

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The properties of layered intercalation hybrids are closely related to interlayer molecular packing. To develop functional intercalation hybrids, it is essential to gain deep insights into interlayer molecular packing. This work reports a new comprehensive insight into the controllable multiphase interlayer molecular packing in 4-(phenylazo)benzoate anion-intercalated layered zinc hydroxide (LZH-4-PAB intercalation hybrids). The new insight breaks up the general understanding that the interlayer molecular packing of anions is usually single-phase, lacking diversity and controllability. Furthermore, it uncovers an interesting stepwise rather than the generally expected continuous phase transition of the interlayer molecular packing. The intercalated 4-PAB anions initially organize into the horizontal monolayer packing (θ = 0°, Phase I), which stepwise transforms to the tilted interdigitated antiparallel bilayer packing (θ ≈ 50°, Phase II) along with an increased intercalation loading and eventually to the vertical interdigitated antiparallel bilayer packing (θ = 90°, Phase III). The LZH-4-PAB hybrids exhibited a greatly enhanced interlayer molecular packing-dependent UV−vis absorption. This study provides helpful guidance for developing property-tailored intercalation hybrids. It may attract new interest in more layered intercalation hybrids. New and rich intercalation chemistry might be discovered in more functional intercalation hybrids beyond the 4-PAB anion-intercalated layered zinc hydroxide.

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An Efficient Intercalation Supramolecular Structure for Photocatalytic CO₂ Reduction to Ethylene Under Visible Light

Cited by 14 publications

References 64 publications

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO₂ Reduction

Insight into Multiphase Interlayer Molecular Packing and Stepwise Phase Transition in 4-(Phenylazo)benzoate Anion-Intercalated Layered Zinc Hydroxide

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An Efficient Intercalation Supramolecular Structure for Photocatalytic CO2 Reduction to Ethylene Under Visible Light

Cited by 14 publications

References 64 publications

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO2 Photoreduction to CH4

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO2 Photoreduction to CH4

Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO2 Reduction

Insight into Multiphase Interlayer Molecular Packing and Stepwise Phase Transition in 4-(Phenylazo)benzoate Anion-Intercalated Layered Zinc Hydroxide

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An Efficient Intercalation Supramolecular Structure for Photocatalytic CO₂ Reduction to Ethylene Under Visible Light

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO₂ Reduction