Promoting Electrochemical CO₂ Reduction to Formate via Sulfur‐Assisted Electrolysis

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: May 16, 2024

Abstract Electrochemical CO 2 reduction reaction (CO RR) provides a renewable approach to transform produce chemicals and fuels. Unfortunately, it faces the challenges of sluggish activation slow water dissociation. This study reports modification Bi‐based electrocatalyst by S, which leads remarkable enhancement in activity selectivity during electrochemical formate. Based on comprehensive situ examinations kinetic evaluations, is observed that presence S species over Bi catalyst can significantly enhance its interaction with K + (H O) n , facilitating fast dissociation molecules generate protons. Further attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) Raman measurements reveal able decrease oxidation state active site, effectively facilitate HCOO * intermediate formation while suppressing competing hydrogen evolution reaction. Consequently, S‐modified achieves impressive RR performance, reaching formate Faradaic efficiency (FE ) 91.2% at partial current density ≈135 mA cm −2 potential −0.8 V versus RHE an alkaline electrolyte.

Language: Английский

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Conversion of Propargylic Amines with CO₂ Catalyzed by a Highly Stable Copper(I) Iodide Thorium-Based Heterometal–Organic Framework

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(29), P. 13450 - 13458

Published: July 3, 2024

The conversion of CO2 to generate high-value-added chemicals has become one the hot research topics in green synthesis. Thereinto, cyclization reaction propargylic amines with is highly attractive because resultant oxazolidinones are widely found pharmaceutical chemistry. Cu(I)-based metal-organic frameworks (MOFs) as catalysts exhibit promising application prospects for conversion. However, their practical was greatly limited due Cu(I) being liable disproportionation or oxidization. Herein, solid copper(I) iodide thorium-based porous framework {[Cu5I6Th6(μ3-O)4(μ3-OH)4(H2O)10(L)10]·OH·4DMF·H2O}n (1) (HL = 2-methylpyridine-4-carboxylic acid) constructed by [Th6] clusters and [CuxIy] subunits successfully prepared structurally characterized. To our knowledge, this first iodide-based actinide organic framework. Catalytic investigations indicate that 1 can effectively catalyze under ambient conditions, which be reused at least five times without a remarkable decline catalytic activity. Importantly, exhibits excellent chemical stability oxidation state it remain stable various conditions. This work provide valuable strategy synthesis Cu(I)-MOF materials.

Language: Английский

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NAD(P)H-Inspired CO₂ Reduction Based on Organohydrides

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: unknown

Published: March 29, 2024

The conversion of CO2 into value-added chemicals and fuels using stable, cost-effective, eco-friendly metal-free catalysts is a promising technology to mitigate the global environmental crisis. In Calvin cycle natural photosynthesis, reduction (CO2R) achieved cofactor NADPH as reducing agent through 2e–/1H+ or H– transfer. Consequently, inspired by NAD(P)H, series organohydrides with adjustable reducibility show remarkable potential for efficient CO2R. this review, we first summarize photosensitizers NAD(P)H regeneration list representative photoenzyme CO2R system. Then, introduce NAD(P)H-inspired their applications in redox reactions. Furthermore, discuss recent progress breakthroughs utilizing catalysts. Moreover, delve reaction mechanisms these organohydrides, shedding light on sustainable alternatives metal-based Finally, offer insights prospects directions advancing intriguing avenue organohydride-based

Language: Английский

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Rational Design of Conjugated Polymers for Photocatalytic CO₂ Reduction: Towards Localized CO Production and Macrophage Polarization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(36), P. 24832 - 24841

Published: Aug. 15, 2024

Light presents substantial potential in disease treatment, where the development of efficient photocatalysts could enhance utilization photocatalytic systems biomedicine. Here, we devised a novel approach to designing and synthesizing conjugated polymers for CO2 reduction, relying on multiple linear regression model built with theoretically calculated descriptors. We established logarithmic relationship between molecular structure CO yield identified poly(fluorene-co-thiophene) deviant (PFT) as optimal one. PFT excited regeneration ratio 231 nmol h–1 acetonitrile 46 an aqueous solution reaction selectivity 88%. Further advancements were made through liposomes encapsulating targeted macrophage delivery. By distributing liposome membranes, our constructed system efficiently generated situ from surrounding CO2. This localized production served endogenous signaling molecule, promoting desirable polarization macrophages M1 M2 phenotype. Consequently, cells reduced secretion pro-inflammatory cytokines (TNF-α, IL-6, IL-1β). also demonstrated efficacy treating lipopolysaccharide-induced inflammation cardiomyocytes under white light irradiation. Moreover, research provides comprehensive understanding intricate processes involved reduction by combination theoretical calculations experimental techniques including transient absorption, femtosecond ultrafast spectroscopy, infrared spectroscopy. These findings pave way further biomedical investigation.

Language: Английский

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Multiscale structural regulation of Two-Dimensional materials for photocatalytic reduction of CO2

Progress in Materials Science, Journal Year: 2024, Volume and Issue: unknown, P. 101386 - 101386

Published: Oct. 1, 2024

Language: Английский

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Photocatalytic Reduction of CO₂ to HCOOH and CO by a Phosphine‐Bipyridine‐Phosphine Ir(III) Catalyst: Photophysics, Nonadiabatic Effects, Mechanism, and Selectivity

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 13, 2023

Photocatalytic CO

Language: Английский

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Fluorinated chlorin chromophores for red-light-driven CO2 reduction

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 8, 2024

Abstract The utilization of low-energy photons in light-driven reactions is an effective strategy for improving the efficiency solar energy conversion. In nature, photosynthetic organisms use chlorophylls to harvest red portion sunlight, which ultimately drives reduction CO 2 . However, a molecular system that mimics such function extremely rare non-noble-metal catalysis. Here we report series synthetic fluorinated chlorins as biomimetic chromophores reduction, catalytically produces under both 630 nm and 730 light irradiation, with turnover numbers 1790 510, respectively. Under appropriate conditions, lasts over 240 h stays active 1% concentration Mechanistic studies reveal chlorin chlorinphlorin are two key intermediates red-light-driven while corresponding porphyrin bacteriochlorin much less forms chromophores.

Language: Английский

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Sustained, Selective, and Efficient Photochemical CO₂ Reduction to Formate by Electron-Deficient Ruthenium Polypyridyl Complexes

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

Published: Feb. 2, 2025

Metal hydrides play a significant role in variety of reactions, including chemical, electrochemical, and photochemical CO2 reduction. Molecular metal have the distinct advantage allowing tunability their hydricities by rational ligand modifications, with more electron-rich being general hydridic. We report here new approach to generate highly hydridic type [Ru(tpy)(LL)(H)]n+ introducing electron-withdrawing substituents into backbone bidentate LL ligand. This strategy enables generation hydride [Ru(tpy)(LL)(H)]+ at mild negative potentials further one-electron reduction [Ru(tpy)(LL)(H)]0 potential window that is redox silent for analogue [Ru(tpy)(bpy)(H)]+. In addition, formate release takes place from transfer adducts [Ru---HCOO)(tpy)(LL)]0 rather than corresponding formato complexes [Ru(tpy)(LL)(OCHO)]0, which would require [Ru(tpy)(LL)(OCHO)]− as demonstrated IR spectroelectrochemistry. The parent [Ru(tpy)(LL)(CH3CN)]n+ solvento were then tested catalysts four-component homogeneous driven Ru(II) sensitizer. results showed selective (>88%) production record turnover number ∼50,000 frequency 4.4 s–1 when compared other molecular catalysts.

Language: Английский

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Oxygen-tolerant photocatalytic conversion of simulated flue gas to ethylene

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102391 - 102391

Published: March 1, 2025

Language: Английский

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Cooperative chemoenzymatic approaches to transforming CO2 into high-value products

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 101016 - 101016

Published: March 1, 2025

Language: Английский

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