Photoelectrochemical hybrid cell for unbiased CO2 reduction coupled to alcohol oxidation

Antón‐García, Daniel; Moore, Elaine; Bajada, Mark A.; Eisenschmidt, Annika; Oliveira, Ana Rita; Pereira, Inês; Warnan, Julien; Reisner, Erwin

doi:10.1038/s44160-021-00003-2

Cited by 53 publications

(39 citation statements)

References 79 publications

(120 reference statements)

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“…Furthermore, the addition of 3 mol % HOOC-TEMPO could facilitate the reaction process effectively. The ratio of ρ reaches approximately 1.9, evincing that HOOC-TEMPO might play a critical role in speeding up the charge transfer, and enhancing the separation of photoexcited electrons and holes. , The effect of light intensity on this reaction was also inspected (Figure b). The photocatalytic system with the addition of HOOC-TEMPO not only maintained the linear relationship of the sulfoxide yields with an increase in light intensity but also exhibited a greater reaction order than that without HOOC-TEMPO.…”

Section: Resultsmentioning

confidence: 99%

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Sheng

Wang

et al. 2022

ACS Catal.

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Metal–organic frameworks (MOFs) are promising visible light photocatalysts due to their adaptable building blocks. In principle, further optimization of the activity could be envisaged by integrating a redox mediator into a MOF to assemble cooperative photocatalysis. Considering the abundant mesopores and the accessible hydroxyl binding sites, PCN-222, consisting of Zr6(μ-OH)8 clusters and carboxyl porphyrin ligands, was synthesized to integrate with 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxyl (HOOC-TEMPO). As a proof of concept, the selective aerobic oxidation of sulfides was selected as the model reaction. Significantly, PCN-222 exhibited a cooperative impact with HOOC-TEMPO on selective aerobic oxidation of sulfides powered by 660 nm red light. In contrast, PCN-226, devoid of accessible hydroxyl sites, only had an inconspicuous cooperation with HOOC-TEMPO. The density functional theory calculations reveal that HOOC-TEMPO could be spontaneously adsorbed on the Zr6(μ-OH)8 clusters via the bidentate model. Due to the lack of binding sites of Zr6(μ-OH)8, TEMPO was proven to be much less effective than HOOC-TEMPO in promoting the oxidation of sulfides over PCN-222. The covalent integration of HOOC-TEMPO into PCN-222 is essential for the effectiveness and durance of cooperative photocatalysis for the selective aerobic oxidation of a wide range of organic sulfides. This work suggests that MOFs, a versatile platform, could be integrated with a redox mediator to enable smooth photocatalytic selective transformations.

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Section: Resultsmentioning

confidence: 99%

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Sheng

Wang

et al. 2022

ACS Catal.

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“…Initially, it was believed that only W-containing FDHs would be capable of CO 2 reduction, due to the more negative redox potentials of W, but it is now known that Mo-FDHs can also reduce CO 2 . , The FdhAB (Fdh-1) from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough is a good example of a W-dependent FDH, showing very high activity for CO 2 reduction, which is only surpassed by more complex and very oxygen-sensitive FDHs. ,, FdhAB has the great advantage of being tolerant to oxygen exposure in the oxidized state, allowing its purification and handling in air . Moreover, its simple composition with only two subunits and structural and catalytic robustness make this FDH an excellent model system for biocatalytic applications. − The crystal structure of FdhAB was recently determined in both oxidized and formate-reduced states, providing important insights into the metal coordination in the fully reduced state. However, there is still no information on possible catalytic intermediates in this enzyme.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis

et al. 2022

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Metal-dependent formate dehydrogenases are important enzymes due to their activity of CO 2 reduction to formate. The tungstencontaining FdhAB formate dehydrogenase from Desulfovibrio vulgaris Hildenborough is a good example displaying high activity, simple composition, and a notable structural and catalytic robustness. Here, we report the first spectroscopic redox characterization of FdhAB metal centers by EPR. Titration with dithionite or formate leads to reduction of three [4Fe−4S] 1+ clusters, and full reduction requires Ti(III)−citrate. The redox potentials of the four [4Fe−4S] 1+ centers range between −250 and −530 mV. Two distinct W V signals were detected, W D V and W F V, which differ in only the g 2 -value. This difference can be explained by small variations in the twist angle of the two pyranopterins, as determined through DFT calculations of model compounds. The redox potential of W VI/V was determined to be −370 mV when reduced by dithionite and −340 mV when reduced by formate. The crystal structure of dithionitereduced FdhAB was determined at high resolution (1.5 Å), revealing the same structural alterations as reported for the formatereduced structure. These results corroborate a stable six-ligand W coordination in the catalytic intermediate W V state of FdhAB.

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“…One intriguing example is the co-electrolysis of CO 2 and organic substrates. [118][119][120] Due to the low redox potential for organic oxidation (<1.23 V RHE ), the energy requirement to drive solar CO 2 reduction in organic oxidation-paired PEC CRR cells is much lower than that in the common OER-paired cells. Gu's group [119] coupled the PEC CO 2 reduction with the oxidation of waste [20] Copyright 2019, Royal Society of Chemistry; b) Reproduced with permission.…”

Section: Self-biased Pec Co 2 Reduction Systemsmentioning

confidence: 99%

Powering the World with Solar Fuels from Photoelectrochemical CO₂ Reduction: Basic Principles and Recent Advances

Deng

Yang

Lian

et al. 2022

Advanced Energy Materials

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Carbon neutrality has become an urgent mission for the future of mankind. Powering the world with renewable energy from solar CO2 reduction represents a promising way to accomplish this target. Photoelectrochemical (PEC) CO2 reduction, integrating the merits of photocatalysis and electrocatalysis, offers an intriguing and effective approach to realizing solar fuel production and CO2 mitigation in one shot. To stimulate research efforts in PEC CO2 reduction, a comprehensive review of recent advances in this field is presented, with a special emphasis on the general design motives for the assembly of highly efficient PEC cells. First, basic principles and evaluating parameters of PEC CO2 reduction cells are introduced. Then, recent innovative PEC cells with highly active photocathodes for CO2 reduction to different target chemicals are highlighted and the material designing principles are discussed. In addition, the representative self‐biased PEC CO2 reduction cells including the tandem and artificial‐leaf configurations are also addressed. Finally, this review is concluded with remarks on the present achievements in PEC CO2 reduction to different chemicals, pointing out some effective strategies to promote the efficiencies for solar fuel production. A vision of the challenges and opportunities for how to forward PEC CO2 reduction research is further provided.

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Photoelectrochemical hybrid cell for unbiased CO2 reduction coupled to alcohol oxidation

Cited by 53 publications

References 79 publications

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis

Powering the World with Solar Fuels from Photoelectrochemical CO₂ Reduction: Basic Principles and Recent Advances

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Photoelectrochemical hybrid cell for unbiased CO2 reduction coupled to alcohol oxidation

Cited by 53 publications

References 79 publications

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Spectroscopic and Structural Characterization of Reduced Desulfovibrio vulgaris Hildenborough W-FdhAB Reveals Stable Metal Coordination during Catalysis

Powering the World with Solar Fuels from Photoelectrochemical CO2 Reduction: Basic Principles and Recent Advances

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Powering the World with Solar Fuels from Photoelectrochemical CO₂ Reduction: Basic Principles and Recent Advances