Heterobimetallic NiFe Complex for Photocatalytic CO₂ Reduction: United Efforts of NiFe Dual Sites

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 28832 - 28844

Published: Oct. 8, 2024

Catalytic CO

Language: Английский

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Electrostatic Confinement‐Induced Excited Charge Transfer in Ionic Covalent Organic Framework Promoting CO2 Reduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 4, 2024

Abstract We demonstrate an electrostatic confinement‐induced charge transfer pathway in a supramolecular photocatalyst comprising of ionic covalent organic framework (COF) and cationic metal complexes. The dynamic interactions not only attract cations around the COF to accept photogenerated electrons, but also allow for retention homogeneous catalytic characters complexes, making subtle balance. Accordingly, confinement effect facilitates forward electron from photoexcited Co complex, realizing remarkable photocatalytic CO 2 reduction performance. Its efficiency is far superior counterparts with Van‐der‐Waals or hydrogen bonding interactions. This work presents insight enhancing systems, provides effective approach construction highly efficient photocatalysts.

Language: Английский

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Theoretical design of dual-site metallo-covalent organic frameworks for efficient CO2 photoreduction into C2H4

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 365, P. 124933 - 124933

Published: Dec. 11, 2024

Language: Английский

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Synergistic Effect Promotes Visible‐Light–Driven CO₂‐To‐CO Conversion by Macrocyclic Dinuclear Mixed‐Valence Co (II)/Co (III) Complexes

Applied Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 39(2)

Published: Jan. 12, 2025

ABSTRACT The catalytic conversion of carbon dioxide (CO 2 ) into valuable energy under light sources is one the effective ways to achieve cycle. reported nonprecious metal complex catalysts still show shortcomings low activity and selectivity in visible‐light–driven CO reduction, especially aqueous systems. Herein, we report three dinuclear mixed‐valence Co (II)/Co (III) complexes 1 – 3 bearing macrocyclic ligands that exhibit high for photocatalytic reduction an system. Moreover, TON reach as 4100 96%, respectively, which about 4.9 times higher than mononuclear (II) 4 . Through electrochemical DFT calculations, found increase due synergistic effect between two centers, site stabilizes *COOH intermediate reduces barrier rate‐determining step, thereby increasing activity.

Language: Английский

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Development of a Highly Durable Photocatalytic CO₂ Reduction Using a Mn-Complex Catalyst: Application of Selective Photosplitting of a Mn(0)–Mn(0) Bond

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

fac-[MnI(diimine)(CO)3(L)]0/+ has attracted significant attention as a catalyst for the photocatalytic reduction of CO2. However, in such systems, photoexcitation Mn complexes and reaction intermediates induces their decomposition, which lowers durability these systems. In this study, we clarified primary process whereby complex decomposes during reaction. Based thereupon, successfully constructed highly durable system, turnover number formate (TONHCOO–) exceeded 1700 when fac-[MnI(bpy)(CO)3((OC(O)OC2H5N(C2H5OH)2) (Mn-CO2-TEOA) catalyst, [OsII(4,4′-dimethyl-bpy)(5,5′-dimethyl-bpy)2]2+ (Os) photosensitizer, 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) reductant were used conjunction with irradiation at λex ≥ 620 nm. contrast, same 480 nm lowered TONHCOO– to less than 60. The difference system arises from dependence Mn(0)–Mn(0) dimer [Mn02(bpy)2(CO)6] (Dim-Mn), an intermediate produced reaction, on wavelength irradiated light its photoreactivity. That is, Dim-Mn selectively splitting Mn–Mn bond produce [Mn0(bpy)(CO)3] (Mn•) and, contrary this, Mn(0)–CO bonds further decomposition processes are induced by

Language: Английский

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Regulating the Ligand N‐Heterocyclic Coordination in Bismuth‐Based MOFs for Efficient CO₂ Photoreduction

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract The increasing global concern over environmental degradation and resource depletion has driven the search for sustainable technologies to mitigate CO 2 emissions. Recently, bismuth‐based metal organic frameworks (Bi‐MOFs) have garnered significant attention due their high stability, adjustable porosity, excellent light absorption properties. However, weak visible charge recombination are still obstacles wide application. In this study, a new class of Bi‐MOFs based on tribenzoic acid with different ligand N‐atom number was synthesized by solvothermal method. Experimental computational results indicated that introduction one N‐heterocyclic pyridine group within led an enhanced localized internal electric field (LIEF), which could promote efficient separation enhance interaction molecules, thus improving photocatalytic activity. This study highlights potential pyridine‐functionalized ligands design high‐performance MOFs reduction, providing valuable insights development advanced materials in sustainability efforts.

Language: Английский

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N‐Confused Porphyrin as a Highly Active Ligand Scaffold for Molecular Catalysts of CO₂ Reduction

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: May 16, 2025

Abstract Key to CO 2 reduction transformation is the development of catalysts that efficiently activate inert molecules, enabling rapid reaction kinetics with minimal energy inputs. In this study, we introduce N‐confused porphyrin (NCP) as a highly active ligand scaffold for transition metal‐based in reactions. By breaking D 4h symmetry inherent conventional structures, NCP promotes enhanced electron delocalization around corresponding metal complex, improving catalytic efficiency. A comprehensive study demonstrates NCP‐based complexes (Fe, Co, and Ni) significantly outperform their parent metal‐porphyrin counterparts. These results provide new insights into design more effective reduction.

Language: Английский

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Electrostatic Confinement‐Induced Excited Charge Transfer in Ionic Covalent Organic Framework Promoting CO2 Reduction

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 4, 2024

Abstract We demonstrate an electrostatic confinement‐induced charge transfer pathway in a supramolecular photocatalyst comprising of ionic covalent organic framework (COF) and cationic metal complexes. The dynamic interactions not only attract cations around the COF to accept photogenerated electrons, but also allow for retention homogeneous catalytic characters complexes, making subtle balance. Accordingly, confinement effect facilitates forward electron from photoexcited Co complex, realizing remarkable photocatalytic CO 2 reduction performance. Its efficiency is far superior counterparts with Van‐der‐Waals or hydrogen bonding interactions. This work presents insight enhancing systems, provides effective approach construction highly efficient photocatalysts.

Language: Английский

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Synthesis and Reactivity of Rhodium Complex Bearing a PNiP Pincer Ligand

Published: May 7, 2024

Rhodium complexes bearing a pincer-type ligand containing nickel were successfully synthesized. Through single-crystal X-ray diffraction analyses and theoretical calculations, the electronic structures of bimetallic elucidated. Notably, this represents inaugural synthesis complex featuring distinct nickel–rhodium bond. The reactivity these synthesized was probed through catalytic arene C–H borylation reactions.

Language: Английский

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Molecular Copper–Anthraquinone Photocatalysts for Robust Hydrogen Production

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31901 - 31910

Published: Nov. 7, 2024

The development of robust and inexpensive photocatalysts for H2 production under visible light irradiation remains a significant challenge. This study presents series square planar copper anthraquinone complexes (R4N)CuL2 (R = ethyl, L alizarin dianion (CuAA); R n-butyl, purpurin (CuPP), (2-hydroxyanthraquinone)formamide (CuAHA)) as molecular to achieve high long-term stability in visible-light-driven production. These are self-sensitized by the ligands serve proton reduction without additional photosensitizers or catalysts. Under blue light, complex CuAA produces mixture H2O/DMF with undiminished activity over 42 days, giving turnover number exceeding 6800. Electrochemical UV–vis studies consistent an EECC mechanism (E: electron transfer C: protonation) catalytic cycle. initial photochemical steps involve conversion both hydroquinones. Further light-driven reductions hydroquinones followed two protonation results formation H2. Dependence rate on concentration H2O suggests that either generation CuII–H intermediate heterocoupling between H+ produce is turnover-limiting step catalysis.

Language: Английский

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