An integrated Re(<scp>i</scp>) photocatalyst/sensitizer that activates the formation of formic acid from reduction of CO<sub>2</sub>

Hameed, Yasmeen; Berro, Patrick; Gabidullin, Bulat; Richeson, Darrin S.

doi:10.1039/c9cc03943k

Cited by 29 publications

(16 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To achieve a high activity in photocatalytic CO 2 conversion, it is essential to develop satisfactory photosensitizers that have large absorption cross sections in the visible region and are capable of promoting efficient multiple electron transfer processes. Recent studies on precious metal-based PS (such as Ru, Ir, and Re) have shown good activity for CO 2 reduction [12][13][14][15][16][17][18][19][20][21][22][23][24][25] . However, molecular chromophores comprising earth-abundant elements usually give relatively low turnover numbers (TONs), which is a significant limitation in developing inexpensive AP systems [26][27][28][29] .…”

mentioning

confidence: 99%

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

et al. 2021

View full text Add to dashboard Cite

CO2 reduction through artificial photosynthesis represents a prominent strategy toward the conversion of solar energy into fuels or useful chemical feedstocks. In such configuration, designing highly efficient chromophores comprising earth-abundant elements is essential for both light harvesting and electron transfer. Herein, we report that a copper purpurin complex bearing an additional redox-active center in natural organic chromophores is capable to shift the reduction potential 540 mV more negative than its organic dye component. When this copper photosensitizer is employed with an iron porphyrin as the catalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as the sacrificial reductant, the system achieves over 16100 turnover number of CO from CO2 with a 95% selectivity (CO vs H2) under visible-light irradiation, which is among the highest reported for a homogeneous noble metal-free system. This work may open up an effective approach for the rational design of highly efficient chromophores in artificial photosynthesis.

show abstract

mentioning

confidence: 99%

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Several examples of single-active-site photocatalysts that function as both the photosensitizer and catalyst for CO 2 reduction based on Re, Os, Ir, Ru, and other metals have been reported. The development of self-photosensitized metal complexes is advantageous in terms of lowering the activation energy of the catalytic reaction and controlling its selectivity; thus, extensive efforts have been devoted to designing new molecular photocatalysts by changing the metal center and/or ligands.…”

mentioning

confidence: 99%

Photocatalytic CO₂ Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

et al. 2020

View full text Add to dashboard Cite

A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO 2 H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO 2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO 2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO 2 -saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO 2 H and CO. Electron paramagnetic resonance and UV−vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO 2 H.

show abstract

“…As expected, the reactivity of the photocatalytic system increased (TON FA of 2750), where at the same time the selectivity slightly dropped (88%). 71 In conclusion, switching from Earth abundant metal catalysts to Ir-and Re-based photocatalysts ensured higher TONs (TON FA > 2000). Compared to the Rh-based catalysts, the activity was lower, but the selectivity increased to almost 90%.…”

Section: Manganese Complexesmentioning

confidence: 83%

Photochemical reduction of carbon dioxide to formic acid

Cauwenbergh

Das

2021

Green Chem.

View full text Add to dashboard Cite

show abstract

An integrated Re(i) photocatalyst/sensitizer that activates the formation of formic acid from reduction of CO₂

Abstract: cis-[Re(bpy)2(CO)2]+OTf− is a new integrated photosensitizer/catalyst for the selective visible light promoted photocatalytic reduction of CO2 to yield formic acid.

Cited by 29 publications

References 42 publications

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Photocatalytic CO₂ Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

Photochemical reduction of carbon dioxide to formic acid

Contact Info

Product

Resources

About

An integrated Re(i) photocatalyst/sensitizer that activates the formation of formic acid from reduction of CO2

Abstract: cis-[Re(bpy)2(CO)2]+OTf− is a new integrated photosensitizer/catalyst for the selective visible light promoted photocatalytic reduction of CO2 to yield formic acid.

Cited by 29 publications

References 42 publications

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Photocatalytic CO2 Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

Photochemical reduction of carbon dioxide to formic acid

Contact Info

Product

Resources

About

An integrated Re(i) photocatalyst/sensitizer that activates the formation of formic acid from reduction of CO₂

Photocatalytic CO₂ Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid