Antenna Effect in Noble Metal‐Free Dye‐Sensitized Photocatalytic Systems Enhances CO₂‐to‐CO Conversion

Abstract

Dye‐sensitized photocatalytic systems (DSPs) have been extensively investigated for solar‐driven hydrogen (H2) evolution. However, their application in carbon dioxide (CO2) reduction remains limited. Furthermore, current solar‐driven CO2‐to‐CO DSPs typically employ rhenium complexes as catalysts. In this study, we have developed DSPs that incorporate noble metal‐free components, specifically a zinc‐porphyrin as photosensitizer (PS) and a cobalt‐quaterpyridine as catalyst (CAT). Taking a significant stride forward, we have achieved an antenna effect for the first time in CO2‐to‐CO DSPs by introducing a Bodipy as an additional chromophore to enhance light harvesting efficiency. The energy transfer from Bodipy to zinc porphyrin resulted in remarkable stability (turn over number (TON) = 759 vs. CAT), and high CO evolution activity (42 mmol g‐1 h‐1vs. CAT).

Recycling Organic Dyes within the Metal–Organic Framework for Photothermal Conversion

“…Solution UV−vis absorption measurements were recorded with an Agilent Technologies Cary 100 spectrometer, while solid UV−vis absorption measurements were carried out by using a PE Lambda 950 spectrometer. 1 H nuclear magnetic resonance ( 1 H NMR) spectra were recorded on a Bruker AV-400 NMR spectrometer. The photoluminescence spectrum was recorded by using an FLS980 fluorescence spectrometer at room temperature.…”

“…Yield: 72%. 1 H NMR (CF 3 COOD, 400 MHz,): δ 8.69 ppm (d, J = 5.9 Hz, 2H), δ 8.27 ppm (d, J = 5.9 Hz, 2H), δ 8.16 ppm (d, J = 8.0 Hz, 2H), δ 7.88 ppm (dd, J = 22.7, 7.9 Hz, 4H), δ 7.73 ppm (dd, J = 8.0 Hz, 2H) (Figure S34).…”

“…Organic dyes are considered important industrial materials particularly in textile manufacturing, due to the inherent inclusion of a chromophore within their molecular structure. − Such a characteristic endows them with the remarkable ability to capture photons across a broad spectrum of light. − The multifaceted energy release mechanisms, which contain radiative and nonradiative transition in the excited state, pave the way to find diverse solar energy utilizations such as photodynamics therapy, photocatalysis, solar cells technology, and more. − However, the inefficiency of dyeing processes leads to the release of 15–50% of these dyes into the environment without adequate treatment, thus presenting a grave threat to both human health and ecological systems due to their xenobiotic nature and sluggish degradation rate. − In this regard, there is a compelling drive to innovate effective dye recycling methods from effluents and refabricate them into valuable materials with solar energy utilization, which holds significant importance in championing the sustainable evolution of our ecological landscape.…”

“…More structural details, IR spectrum, PXRD pattern, TGA curve, fluorescence, XPS result, and1 H NMR spectrum (PDF) CCDC 2345241 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.…”

Noble Metal Plasmon–Molecular Catalyst Hybrids for Renewable Energy Relevant Small Molecule Activation

“…These photocatalytic models provide the template for designing photoreactors utilizing finely tuned catalysts with the desired product selectivity and reactivity. Organic dyes and molecular metal coordination complexes have been extensively investigated as efficient photosensitizers due to their strong visible-light absorption and tunable photophysical activities. ,, Nevertheless, the instability caused by their photobleaching during prolonged irradiation and the absorption of only a limited portion of the solar spectrum raise serious concerns regarding their practical applications. Later, the strategy to anchor molecular complexes covalently or noncovalently on wide and narrow band gap semiconductor surfaces has been explored in both homogeneous and heterogeneous media .…”