Immobilization of Mn(<scp>i</scp>) and Ru(<scp>ii</scp>) polypyridyl complexes on TiO<sub>2</sub> nanoparticles for selective photoreduction of CO<sub>2</sub> to formic acid

Le-Quang, Long; Stanbury, Matthew; Chardon‐Noblat, Sylvie; Mouesca, Jean‐Marie; Maurel, Vincent; Chauvin, Jérôme

doi:10.1039/c9cc05129e

Cited by 13 publications

(7 citation statements)

References 38 publications

(47 reference statements)

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“…Metal complexes for PCR were mainly based on bipyridine, and porphyrin units, among which the Ru−bipyridine complex has been the most popular choice to be used as the photosensitizer due to its good stability and suitable energy level. For example, TiO 2 , [ 101 ] Co 3 O 4 , [ 102 ] α‐Fe 2 O 3 , [ 103 ] NiAl‐LDH (NiAl‐LDH), [ 104 ] and Co 2 P [ 105 ] have been used as the catalysts with the combination of Ru(bpy) 3 Cl 2 ·6H 2 O as a photosensitizer to form a hybrid photocatalyst system. The photosensitizers first adsorb incident light to generate electrons, which transfer from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) of photosensitizers.…”

Section: Photocatalysismentioning

confidence: 99%

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Zhang

Pérez‐Ramírez

et al. 2021

Adv Energy and Sustain Res

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The excess depletion of carbon‐rich fossil fuels and agroforest biomass resources has aggravated the energy crisis and environmental pollution, causing increased CO2 emissions. Accordingly, the goal of “peak CO2 emissions and carbon neutrality” is proposed to alleviate global warming. CO2‐to‐fuel conversion is considered as a preferable move for reducing the atmospheric CO2 concentration and further upgrading to chemical feedstocks. However, the highly efficient CO2 conversion remains challenging due to the thermodynamic limits and kinetic barriers, which require high energy input through conventional thermocatalysis. Inspired by “artificial photosynthesis,” photocatalytic CO2 transformation has received tremendous attention and makes remarkable progress over the past decades, although it is still far from practical application. Recently, the integrated photothermocatalysis has emerged as an intelligent strategy to utilize solar energy to induce local heating and energetic hot carriers, which synergistically promote CO2‐to‐fuel conversion. The key to the success of CO2 upgradation is catalysts’ development with improved activity, selectivity, and stability. This review highlights the recent advancements in materials designing for practical CO2 conversion through thermocatalysis, photocatalysis, and photothermocatalysis during the past five years, emphasizing the reaction pathways and mechanism on the CO bond activation and intermediates formation. Finally, the current challenges and future opportunities are described.

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Section: Photocatalysismentioning

confidence: 99%

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Zhang

Pérez‐Ramírez

et al. 2021

Adv Energy and Sustain Res

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“…Similar to the previous work, Chauvin et al . immobilized the Mn(I) complex 30 b (Figure ), as catalyst, and [Ru(bpy) 3 ] 2+ , as photosensitizer, via their lateral phosphonate moieties onto TiO 2 . The co‐assembled system was found to be efficient and selective for the photoelectrochemical reduction of CO 2 to formic acid (a quantum yield ( φ ) of 0.17 % upon irradiation with visible light was reached).…”

Section: Terpyridine Complexes As Catalysts In Energy Conversion Appmentioning

confidence: 99%

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Winter

Schubert

2020

ChemCatChem

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2,2′:6′,2′′‐Terpyridine (tpy) and its derivatives represent highly versatile ligands for the complexation of transition metal ions. Today, such complexes are employed in a highly diverse fashion – including inter alia materials science, opto‐electronics, pharmacy or catalysis. Concerning the latter one, a vast development has led to new or improved applications in both “conventional” organic chemistry (i. e., catalysis of functional‐group interconversions, CH‐activation or cross‐coupling reactions) as well as energy‐related applications (e. g., CO2 reduction, artificial photosynthesis, dye degradation). In this respect, not only homogeneous catalysts (i. e., molecular complexes) but also heterogeneous and recyclable ones have moved to the focus of interest. These heterogeneous structures include 1D metallopolymers, metal‐organic frameworks (MOFs), organic‐inorganic hybrids and bio‐inspired catalysts. We gave a first overview on this topic already in 2011; in here, the methods and implementations established within the last decade as well as relevant contributions from earlier works are presented and discussed.

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“… Minor amounts of HCOO – were produced by a few examples of Mn catalysts with proton-responsive diimine ligands as well as by some bpy-based Mn derivatives heterogenized on carbon electrodes in aqueous electrodes . However, a predominant HCOO – formation was usually observed under pure photochemical conditions. , Such a change of selectivity from CO to HCOO – was attributed to the competitive protonation of the anionic Mn catalyst to form a reactive Mn(I) hydride, which rapidly reacts with CO 2 (see Scheme ). However, there is still a need to directly clarify the involvement and the role of Mn(I) hydrides in the HCOO – pathway.…”

Section: Introductionmentioning

confidence: 99%

Decoding the CO₂ Reduction Mechanism of a Highly Active Organometallic Manganese Electrocatalyst: Direct Observation of a Hydride Intermediate and Its Implications

et al. 2023

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A detailed mechanistic study of the electrochemical CO 2 reduction catalyzed by the fac-[Mn I (CO) 3 (bis-Me NHC)MeCN] + complex (1-MeCN + ) is reported herein by combining in situ FTIR spectroelectrochemistry (SEC), synthesis and characterization of catalytic intermediates, and DFT calculations. Under low proton concentrations, 1-MeCN + efficiently catalyzes CO 2 electroreduction with long catalyst durability and selectivity toward CO (ca. 100%). The [Mn -I (CO) 3 (bis-Me NHC)] − anion (1 − ) and the tetracarbonyl [Mn I (CO) 4 (bis-Me NHC)] + complex (1-CO + ) are key intermediates of the catalytic CO 2 -to-CO mechanism due to their impact on the selectivity and the reaction rate, respectively. Increasing the proton concentration increases formate production (up to 15% FE), although CO remains the major product. The origin of formate is ascribed to the competitive protonation of 1 − to form a Mn(I) hydride (1-H), detected by SEC in the absence of CO 2 . 1-H was also synthesized and thoroughly characterized, including by X-ray diffraction analysis. Stoichiometric reactivity studies of 1-H with CO 2 and labeled 13 CO 2 indicate a fast formation of the corresponding neutral Mn(I) formate species (1-OCOH) at room temperature. DFT modeling confirms the intrinsic capability of 1-H to undergo hydride transfer to CO 2 due to the strong σ-donor properties of the bis-Me NHC moiety. However, the large potential required for the HCOO − release from 1-OCOH limits the overall catalytic CO 2 -to-HCOO − cycle. Moreover, the experimentally observed preferential selectivity for CO over formate is dictated by the shallow kinetic barrier for CO 2 binding to 1 − compared to the Mn−H bond formation. The detailed mechanistic study highlights the reduction potential, pK a , and hydricity of the metal hydride intermediate as crucial factors affecting the CO 2 RR selectivity in molecular systems.

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Immobilization of Mn(i) and Ru(ii) polypyridyl complexes on TiO₂ nanoparticles for selective photoreduction of CO₂ to formic acid

Abstract: Under visible irradiation in DMF/TEOA, the hybrid nanomaterial Ru(ii)/TiO2/Mn(i), lead to the selective reduction of CO2 into HCOO−.

Cited by 13 publications

References 38 publications

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Decoding the CO₂ Reduction Mechanism of a Highly Active Organometallic Manganese Electrocatalyst: Direct Observation of a Hydride Intermediate and Its Implications

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Immobilization of Mn(i) and Ru(ii) polypyridyl complexes on TiO2 nanoparticles for selective photoreduction of CO2 to formic acid

Abstract: Under visible irradiation in DMF/TEOA, the hybrid nanomaterial Ru(ii)/TiO2/Mn(i), lead to the selective reduction of CO2 into HCOO−.

Cited by 13 publications

References 38 publications

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO2‐to‐Fuel Conversion

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO2‐to‐Fuel Conversion

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Decoding the CO2 Reduction Mechanism of a Highly Active Organometallic Manganese Electrocatalyst: Direct Observation of a Hydride Intermediate and Its Implications

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Immobilization of Mn(i) and Ru(ii) polypyridyl complexes on TiO₂ nanoparticles for selective photoreduction of CO₂ to formic acid

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Decoding the CO₂ Reduction Mechanism of a Highly Active Organometallic Manganese Electrocatalyst: Direct Observation of a Hydride Intermediate and Its Implications