Heterogenization of molecular cobalt catalysts in robust metal–organic frameworks for efficient photocatalytic CO<sub>2</sub> reduction

Parshamoni, Srinivasulu; Viravaux, Cédric; Robert, Marc; Mellot‐Draznieks, Caroline; Chen, Gui; Dolbecq, Anne; Bonin, Julien

doi:10.1039/d2cy01147f

Cited by 6 publications

(3 citation statements)

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“…Molecular assembly could have similar photocatalytic activities as that of their metal complex ensembles, but with advantages in surface immobilization due to solid‐state nature and in high surface area that exposes abundant active sites. [ 15 , 16 , 17 , 18 ] Organizing photosensitizers in high‐density molecular assembly could, in principle, overcome limitations in insufficient charge‐separation states of current catalytic photoelectrodes. As chromophore assembly being integrated directly in photoelectrodes, a limitation exists in low injection efficiency due to ineffective contact between chromophore and the electrode substrate.…”

Section: Introductionmentioning

confidence: 99%

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia

He,

Wen,

Fang

et al. 2024

Advanced Science

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In the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron‐hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high‐performance photocathode for multi‐electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high‐throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly‐functionalized covalent networks for boosting eight‐electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo‐accumulating assembly and multi‐electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems.

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Section: Introductionmentioning

confidence: 99%

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia

He,

Wen,

Fang

et al. 2024

Advanced Science

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“…16−18 Heterogenization is emerging as a powerful strategy to optimize photocatalytic performances of transition metal complexes in CO 2 photoreduction. 19,20 Heterogeneous photocatalysts consisting of transition metal complexes with different sizes ranging from nanometers to micrometers have been established. Knowing more about the impact of morphology on CO 2 photoreduction is beneficial to designing superior heterogeneous molecular catalysts.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Light-driven utilization of CO 2 as a feedstock to synthesize value-added chemical fuels is promising from the perspective of sustainability. , Numerous catalysts including molecular metal complexes and inorganic and organic semiconductors have been developed to realize efficient CO 2 photoreduction. − In particular, molecular metal complexes play versatile roles in photocatalytic CO 2 reduction. They can be not only used as homogeneous photocatalysts but also integrated with various solid supporters to construct heterogeneous hybrid photocatalysts. ,− Moreover, transition metal complexes can be heterogenized by forming coordination polymers. − The durability, efficiency, and recyclability of photocatalysts can be improved after heterogenization of molecular catalysts. − Heterogenization is emerging as a powerful strategy to optimize photocatalytic performances of transition metal complexes in CO 2 photoreduction. , Heterogeneous photocatalysts consisting of transition metal complexes with different sizes ranging from nanometers to micrometers have been established. Knowing more about the impact of morphology on CO 2 photoreduction is beneficial to designing superior heterogeneous molecular catalysts.…”

Section: Introductionmentioning

confidence: 99%

Morphology Control of Supramolecular Assembly for Superior CO₂Photoreduction

et al. 2023

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Coordination-driven metallo-supramolecular assemblies are potentially efficient catalysts in photocatalytic CO2 reduction. However, the relationship between morphology and photocatalytic performance remains barely explored. In this work, three metallo-supramolecular assemblies composed of Zn2+ and a flexible tris(terpyridine) ligand have been prepared for noble metal-free CO2 photoreduction on the basis of metal–ligand coordination, hydrogen bonding, and π–π stacking. The three assemblies possess distinct self-assembled morphologies including spherical particle, fibrous-like gel, and microrod. It has been found that the fibrous-like gel exhibits the best catalytic performance in photoreduction of CO2 to CO with a yield of 6.3 mmol g–1 h–1 and 94.7% selectivity over H2 generation. Photoelectrochemical measurements, photoluminescence quenching experiments, and UV–vis absorption spectroscopy studies have demonstrated that the ligand-based electron transfer of the gel is more efficient compared with the other two assemblies.

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Progress in design and applications of supramolecular assembly of 2,2′:6′,2″-terpyridine-based first row d-block elements

Momeni,

Davarzani,

Janczak

et al. 2024

Coordination Chemistry Reviews

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Heterogenization of molecular cobalt catalysts in robust metal–organic frameworks for efficient photocatalytic CO₂ reduction

Abstract: Efficient, selective and recyclable heterogeneous catalysts for photocatalytic CO2 reduction to CO under visible light irradiation are readily prepared by immobilization of cobalt molecular catalysts into Zr(iv)-based MOFs.

Cited by 6 publications

References 35 publications

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia

Morphology Control of Supramolecular Assembly for Superior CO₂Photoreduction

Progress in design and applications of supramolecular assembly of 2,2′:6′,2″-terpyridine-based first row d-block elements

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Heterogenization of molecular cobalt catalysts in robust metal–organic frameworks for efficient photocatalytic CO2 reduction

Abstract: Efficient, selective and recyclable heterogeneous catalysts for photocatalytic CO2 reduction to CO under visible light irradiation are readily prepared by immobilization of cobalt molecular catalysts into Zr(iv)-based MOFs.

Cited by 6 publications

References 35 publications

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia

Morphology Control of Supramolecular Assembly for Superior CO2Photoreduction

Progress in design and applications of supramolecular assembly of 2,2′:6′,2″-terpyridine-based first row d-block elements

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Heterogenization of molecular cobalt catalysts in robust metal–organic frameworks for efficient photocatalytic CO₂ reduction

Morphology Control of Supramolecular Assembly for Superior CO₂Photoreduction