A Copper(II) Molecular Catalyst for Efficient and Selective Photochemical Reduction of CO<sub>2</sub> to CO in a Water‐Containing System

Liu, Wenju; Huang, Hai‐Hua; Ouyang, Ting; Jiang, Long; Zhong, Di‐Chang; Zhang, Wen; Lu, Tong‐Bu

doi:10.1002/chem.201705566

Cited by 45 publications

(31 citation statements)

References 66 publications

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“…Similar mechanism is also proposed by Song et al . for the Ni(cyclam) CO 2 reduction system, and some other systems reported by our group ,. For comparison, the energy barriers of CO 2 reduction (17.2 kcal/mol) and C−O cleavage (13.8 kcal/mol) for 1 are much lower than those for 2 (19.52 and 18.08 kcal/mol, respectively), indicating the reduction of CO 2 to CO by 1 is more favored than the reduction by 2 .…”

Section: Figurementioning

confidence: 64%

“…The deactivation of the system is probably related to the photo‐degradation of catalyst or photosensitizer. As determined by UV‐vis spectroscopy, only about 68 % of the [Ru(phen) 3 ] 2+ remained after 10 h of photolysis (Figure S6) ,,. We speculate that the deactivation of the catalytic system can be tentatively attributed to the photo‐degradation of photosensitizer.…”

Section: Figurementioning

confidence: 89%

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Highly Efficient and Selective Visible‐Light Driven CO₂‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H₂O/CH₃CN Solution

et al. 2018

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The photochemical reduction of CO 2 to chemical resources has displayed the promise to solve energy and environmental problems. To facilitate this reaction, a considerable challenge is to design not only highly efficient and selective, but also economic catalysts. In this study, we report a homogeneous catalyst, [CoL 1 (CH 3 CN)](ClO 4 ) 2 (1, L 1 = Tris[2-(iso-propylamino) ethyl]amine) which displays high activity and selectivity for CO 2 reduction to CO driven by visible light in a water-containing system, with turnover numbers (TON CO ) and turnover frequencies (TOF), and CO selectivity values of 44800, 1.24 s À1 and 97 %, respectively. The excellent performances of 1 for the photocatalytic CO 2 -to-CO conversion is confirmed by control experiments and its catalytic mechanism is corroborated by DFT calculations.Artificial photosynthesis using solar energy and abundant resources, such as CO 2 and H 2 O, to produce renewable fuels has attracted significant attention because of two serious problems: energy shortage and global warming. [1] Sunlightdriven CO 2 reduction provides a sustainable approach to convert the greenhouse gas into more valuable molecules, like CO, CH 3 OH, etc., whereby the solar energy can be stored. Simultaneously, both the energy and environmental issues can be addressed in a carbon-neutral fashion. [2] In particular, the formation of CO is appealing as it serves as a feedstock in the production of liquid fuels via Fischer-Tropsch process. [3] Due to the inherent structural stability of CO 2 , [4] a long-standing challenge is to design efficient and selective catalysts to accelerate the CO 2 reduction.So far, much research has been devoted to exploring visible-light-driven homogeneous [2c] and heterogeneous [5] systems for CO 2 reduction. Homogeneous molecule-based catalytic systems have advantages in mechanistic analysis, as well as optimization of photocatalytic properties by choosing from a range of metals and ligands. Thus, precious-metal complexes (Re, [6] Ru, [7] Ir [8] , etc.) have been widely studied as homogeneous catalysts for solar-fuel production by the reduction of CO 2 . Considering the scarcity and the price of these precious metals, [9] a number of CO 2 reduction photocatalysts based on earth-abundant metals, Co, [10] Ni, [11] Mn, [12] Fe, [13] and Cu, [14] have been reported. However, these catalysts always display relatively low efficiency and/or selectivity, especially in watercontaining systems. [7b,11c,15] Besides, an artificial photosynthesis cycle includes not only photocatalytic CO 2 reduction but also water oxidation. Therefore, it is very significative to design photocatalysts that can display efficient and selective for CO 2 conversion in a water-containing catalytic system. Up to now, the development of earth-abundant homogeneous catalysts for efficient and selective CO 2 -to-CO conversion in water-containing systems is still a great challenge.Tripodal ligands [16] have been especially of interest for developing metal-based homogeneous catalysts, [17] a...

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Section: Figurementioning

confidence: 64%

Section: Figurementioning

confidence: 89%

Highly Efficient and Selective Visible‐Light Driven CO₂‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H₂O/CH₃CN Solution

et al. 2018

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“…Li and co‐workers reported photo‐reduction of CO 2 to CO catalyzed by molecular Co complexes immobilized on solid support . Lu and co‐workers reported several examples of Cu complexes as photoelectron‐catalysts for CO 2 reduction in aqueous solution …”

Section: Introductionmentioning

confidence: 99%

Ni^II Complexes of C‐Substituted Cyclam as Efficient Catalysts for Reduction of CO₂ to CO

2018

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Two new nickel(II) complexes of cyclams bearing C‐alkyl groups, Ni(MEC)OTf2 (1, MEC = 5,12‐diethyl‐7,14‐dimethyl‐1,4,8,11‐tetraazacyclotetradecane) and Ni(CTMC)OTf2 (2, CTMC = 5,7,12,14‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane), were prepared, and their similarity to NiII(MPC) (MPC = 5,12‐dimethyl‐7,14‐diphenyl‐1,4,8,11‐tetraazacyclotetradecane) in ring conformation was revealed through single‐crystal X‐ray diffraction studies. Solution electronic absorption spectroscopy indicates the retention of octahedral coordination mode for both 1 and 2 in 20 % aqueous acetonitrile. Cyclic voltammetry studies of 1 and 2 under CO2 in 20 % aqueous acetonitrile revealed significantly increased catalytic currents compared to previously studied NiII(cyclam) and NiII(MPC). Controlled potential electrolysis studies of 2 revealed a 250 % increase in CO turn over frequency from that of Ni(cyclam)OTf2 and a 40 % increase from that of Ni(MPC)OTf2. Such improvements establish the benefit of electronically donating substituents that minimize steric interference around the axial catalytic sites.

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“…Acting as one of low‐cost and abundance non‐Pt metal ions in nature, Cu II ion has exhibited well‐defined coordination chemistry and can undergo a variety of redox reactions from Cu II to Cu I/ Cu 0 and/or from Cu II to Cu III/ Cu IV . Thus, lots of copper‐based complexes have been widely utilized in carbon dioxide reduction,, water oxidation, and water reduction . On the other hand, to promote the charge transfer between the organic ligands and the inorganic metal ions as well as to enhance the light absorption in the visible and/or infrared regions, highly π‐conjugated organic ligands, such as polypyridine, phthalocyanine, porphyrin, and Rhodamine B (RhB) derivatives, have been becoming good choices for the CP‐based photocatalysts .…”

Section: Introductionmentioning

confidence: 99%

Two Bulky Conjugated 4′‐(4‐Hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine‐based Layered Complexes: Synthesis, Structure, and Photocatalytic Hydrogen Evolution Activity

Zhu

Dai

Wang

et al. 2019

Zeitschrift anorg allge chemie

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Two new layered complexes with the formulas of {[Cu(H 2 O)(HL) 2 Cl](NO 3 )} n (1) and {[Cu(H 2 O) 2 (HL) 2 ](NO 3 ) 2 } n (2) were solvothermally synthesized by the reactions of the bulky conjugated 4Ј-(4-hydroxyphenyl)-4,2Ј:6Ј,4ЈЈ-terpyridine ligand (HL) with different Cu II salts, which were further used as photocatalysts to achieve hydrogen production from water splitting. Single-crystal structural analyses reveal that both complexes feature coplanar (4 4) layers

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A Copper(II) Molecular Catalyst for Efficient and Selective Photochemical Reduction of CO₂ to CO in a Water‐Containing System

Cited by 45 publications

References 66 publications

Highly Efficient and Selective Visible‐Light Driven CO₂‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H₂O/CH₃CN Solution

Highly Efficient and Selective Visible‐Light Driven CO₂‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H₂O/CH₃CN Solution

Ni^II Complexes of C‐Substituted Cyclam as Efficient Catalysts for Reduction of CO₂ to CO

Two Bulky Conjugated 4′‐(4‐Hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine‐based Layered Complexes: Synthesis, Structure, and Photocatalytic Hydrogen Evolution Activity

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A Copper(II) Molecular Catalyst for Efficient and Selective Photochemical Reduction of CO2 to CO in a Water‐Containing System

Cited by 45 publications

References 66 publications

Highly Efficient and Selective Visible‐Light Driven CO2‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H2O/CH3CN Solution

Highly Efficient and Selective Visible‐Light Driven CO2‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H2O/CH3CN Solution

NiII Complexes of C‐Substituted Cyclam as Efficient Catalysts for Reduction of CO2 to CO

Two Bulky Conjugated 4′‐(4‐Hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine‐based Layered Complexes: Synthesis, Structure, and Photocatalytic Hydrogen Evolution Activity

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A Copper(II) Molecular Catalyst for Efficient and Selective Photochemical Reduction of CO₂ to CO in a Water‐Containing System

Highly Efficient and Selective Visible‐Light Driven CO₂‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H₂O/CH₃CN Solution

Highly Efficient and Selective Visible‐Light Driven CO₂‐to‐CO Conversion by a Co(II) Homogeneous Catalyst in H₂O/CH₃CN Solution

Ni^II Complexes of C‐Substituted Cyclam as Efficient Catalysts for Reduction of CO₂ to CO