Designing Heteroatom‐Codoped Iron Metal–Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene

Guo, Fan; Li, Ruixia; Yang, Shaohua; Zhang, Xiaoyu; Yu, Hao; Urban, Jeffrey J.; Sun, Wei‐Yin

doi:10.1002/anie.202216232

Cited by 65 publications

(20 citation statements)

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“…Solar driven conversion of CO 2 into chemical fuels and feedstocks is considered as a sustainable strategy for dealing with the crisis of energy shortages and climate change. [ 1‐4 ] Transition metal catalysts, such as Co, [ 5‐9 ] Ni, [ 10‐12 ] Cu, [ 13‐16 ] Fe, [ 17‐19 ] etc ., catalysts have been successfully used to photoreduce CO 2 . During the development of catalysts, researchers have found that altering the coordination microenvironment of metal center may impact on the activity of the active sites, which can affect the energy barrier of CO 2 activation and open up new prospects for designing CO 2 reduction catalysts.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO₂ Reduction

et al. 2023

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Comprehensive SummaryThe creation of effective and inexpensive catalysts is essential for photocatalytic CO2 reduction. Homogeneous molecular catalysts, possessing definite crystal structures, are desirable to study the relationship between catalytic performance and coordination microenvironment around catalytic center. In this report, we elaborately developed three Co(II)‐based molecular catalysts with different coordination microenvironments for CO2 reduction, which named with [CoN3O]ClO4, [CoN4]ClO4, and [CoN3S]ClO4, respectively. The optimal [CoN3O]ClO4 photocatalyst has a maximum TON of 5652 in photocatalytic reduced CO2 reduction, which is 1.28 and 1.65 times greater than [CoN4]ClO4 and [CoN3S]ClO4, respectively. The high electronegativity of oxygen in L1 (N,N‐Bis(2‐pyridylmethyl)‐N‐(2‐hydroxybenzyl)amine) provides the Co(II) catalytic centers with low reduction potentials and a more stable *COOH intermediate, which facilitates the CO2 to CO conversion and accounts for the high photocatalytic activity of [CoN3O]ClO4. This work provides researchers new insights in development of catalysts for photocatalytic CO2 reduction.This article is protected by copyright. All rights reserved.

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Section: Background and Originality Contentmentioning

confidence: 99%

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO₂ Reduction

et al. 2023

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“…As an example, we have designed charge polarized triatomic sites to realize CO 2 photoreduction into C 2 H 4 (Figure b), wherein the reactive intermediates have been detected by in situ FTIR. As an example, the peaks of surface-absorbed carbonate, COOH*, CHO*, HOOC–COH*, and *C 2 H 4 groups were detected during CO 2 photoreduction on the mildly and poorly oxidized FeCoS 2 nanosheets (Figure c). , Based on the above results, the CO 2 -to-C 2 H 4 process for the two catalysts may include the C–C coupling of two COOH* intermediates, the progressive protonation of the HOOC–COOH* to form *C 2 H 4 intermediates, and their desorption to produce C 2 H 4 . Similarly, Shen et al have designed charge polarized Au–O–Ce sites in a Au–CeO 2 composite to obtain C 2 H 6 by solar-driven CO 2 reduction, in which the reactive intermediates have been monitored via in situ FTIR.…”

Section: Investigation Into the Mechanism Of The Co2-to-c2 Pathway En...mentioning

confidence: 99%

Fundamentals and Challenges of Engineering Charge Polarized Active Sites for CO₂ Photoreduction toward C₂ Products

Wu,

Hu,

Chen

et al. 2023

Acc. Chem. Res.

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Conspectus Global warming and climatic deterioration are partly caused by carbon dioxide (CO2) emission. Given this, CO2 reduction into valuable carbonaceous fuels is a win–win route to simultaneously alleviate the greenhouse effect and the energy crisis, where CO2 reduction into hydrocarbon fuels by solar energy may be a potential strategy. Up to now, most of the current photocatalysts photoconvert CO2 to C1 products. It is extremely difficult to achieve production of C2 products, which have higher economic value and energy density, due to the kinetic challenge of C–C coupling of the C1 intermediates. Therefore, to realize CO2 photoreduction to C2 fuels, design of high-activity photocatalysts to expedite the C–C coupling is significant. Besides, the current mechanism for CO2 photoreduction toward C2 fuels is usually uncertain, which is possibly attributed to the following two reasons: (1) It is arduous to determine the actual catalytic sites for the C–C coupling step. (2) It is hard to monitor the low-concentration active intermediates during the multielectron transfer step. Most traditional metal-based photocatalysts usually possess charge balanced active sites that have the same charge density. In this aspect, the neighboring C1 intermediates may also show the same charge distribution, which would lead to dipole–dipole repulsion, thus preventing C–C coupling for producing C2 fuels. By contrast, photocatalysts with charge polarized active sites possess obviously different charge distributions in the adjacent C1 intermediates, which can effectively suppress the electrostatic repulsion to steer the C–C coupling. Based on this analysis, higher asymmetric charge density on the active sites would be more beneficial to anchoring between the adjacent intermediates and active atoms in catalysts, which can boost C–C coupling. In this Account, we summarize various strategies, including vacancy engineering, doping engineering, loading engineering, and heterojunction engineering, for tailoring charge polarized active sites to boost the C–C coupling for the first time. Also, we overview diverse in situ characterization technologies, such as in situ X-ray photoelectron spectroscopy, in situ Raman spectroscopy, and in situ Fourier transform infrared spectroscopy, for determining charge polarized active sites and monitoring reaction intermediates, helping to reveal the internal catalytic mechanism of CO2 photoreduction toward C2 products. We hope this Account may help readers to understand the crucial function of charge polarized active sites during CO2 photoreduction toward C2 products and provide guidance for designing and preparing highly active catalysts for photocatalytic CO2 reduction.

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“…Notably, the co-doped potassium (K) in CN-KRb promoted ethanol adsorption, activation, and oxidation to give H + spillover, which participated in the CO 2 reduction process. 128,129 Moreover, the precious metal Au was also reportedly effective for the photoreduction of CO 2 and the subsequent C-C coupling to C 2 H 6 . 130…”

Section: Photocatalysis For Co 2 Rr Into Multicarbonsmentioning

confidence: 99%

Intermediates and their conversion into highly selective multicarbons in photo/electrocatalytic CO₂ reduction reactions

Yang,

Pawar,

Sivasankaran

et al. 2023

J. Mater. Chem. A

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Designing Heteroatom‐Codoped Iron Metal–Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene

Cited by 65 publications

References 63 publications

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO₂ Reduction

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO₂ Reduction

Fundamentals and Challenges of Engineering Charge Polarized Active Sites for CO₂ Photoreduction toward C₂ Products

Intermediates and their conversion into highly selective multicarbons in photo/electrocatalytic CO₂ reduction reactions

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Designing Heteroatom‐Codoped Iron Metal–Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene

Cited by 65 publications

References 63 publications

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO2 Reduction

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO2 Reduction

Fundamentals and Challenges of Engineering Charge Polarized Active Sites for CO2 Photoreduction toward C2 Products

Intermediates and their conversion into highly selective multicarbons in photo/electrocatalytic CO2 reduction reactions

Contact Info

Product

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Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO₂ Reduction

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO₂ Reduction

Fundamentals and Challenges of Engineering Charge Polarized Active Sites for CO₂ Photoreduction toward C₂ Products

Intermediates and their conversion into highly selective multicarbons in photo/electrocatalytic CO₂ reduction reactions