From molecular metal complex to metal-organic framework: The CO2 reduction photocatalysts with clear and tunable structure

Luo, Yu‐Hui; Dong, Long‐Zhang; Liu, Jiang; Li, Shun-Li; Lan, Ya‐Qian

doi:10.1016/j.ccr.2019.03.019

Cited by 245 publications

(102 citation statements)

References 323 publications

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“…Homogeneous AP systems usually offer distinct advantages with respect to structural optimization and product selectivity 9 . For example, the reduction potentials of all components can be finely tuned through functional group manipulation to facilitate efficient light-driven electron transfer 10 . In a typical homogeneous AP system, a photosensitizer (PS) is a key component responsible for light-harvesting and photochemical reactions 10 , 11 .…”

Section: Introductionmentioning

confidence: 99%

“…For example, the reduction potentials of all components can be finely tuned through functional group manipulation to facilitate efficient light-driven electron transfer 10 . In a typical homogeneous AP system, a photosensitizer (PS) is a key component responsible for light-harvesting and photochemical reactions 10 , 11 . 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.…”

Section: Introductionmentioning

confidence: 99%

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Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

et al. 2021

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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.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

et al. 2021

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“…Thevisible light-driven photochemical reduction of carbon dioxide catalyzed by molecularly defined species shows high activity at short reaction times. [1][2][3] So far, improvements of photocatalytic systems have been focused almost exclusively on the catalyst side.Enhancement of lifetime and efficiency of molecular catalysts has been achieved by their single-site heterogenization within molecularly defined porous solids. [2,4,5] In most of those photosystems,I r-and Ru-based organometallic photosensitizers were used, although they suffer from photodegradation under continuous illumination.…”

Section: Introductionmentioning

confidence: 99%

Molecular Porous Photosystems Tailored for Long‐Term Photocatalytic CO₂ Reduction

et al. 2020

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The molecular‐level structuration of two full photosystems into conjugated porous organic polymers is reported. The strategy of heterogenization gives rise to photosystems which are still fully active after 4 days of continuous illumination. Those materials catalyze the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst. The covalent tethering of the two active sites into a single framework is shown to play a key role in the visible light activation of the catalyst. The unprecedented long‐term efficiency arises from an optimal photoinduced electron transfer from the light harvesting moiety to the catalytic site as anticipated by quantum mechanical calculations and evidenced by in situ ultrafast time‐resolved spectroscopy.

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“…As such, a variety of tethered photocatalyst-metal complexes have been developed and used in applications that require singlet oxygen generation, such as photocatalysis [24][25][26][27][28] and photodynamic therapy. [26,[29][30] Despite the increasing use of tethered catalysts that feature both a photocatalyst and a transition metal catalyst, [23,25,28,[31][32][33][34] there have been limited mechanistic investigations into the origins of the synergistic effects between the catalytic centres. For example, our group recently developed a series of complexes that feature an organic photocatalyst (1,3,5,7tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene, BDP 1) tethered to an Ir complex ligated with a bis(pyrazolemethane) (bpm) ligand, Ir(I) 2 ( Figure 2).…”

Section: Introductionmentioning

confidence: 99%

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

et al. 2020

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Dual catalysis, where two different catalysts work cooperatively to promote a chemical reaction, is an important synthetic approach as it can allow a wide range of unique reactivity to be accessed. Whilst most dual catalysis strategies utilise separate catalysts in the reaction mixture, there is a growing interest in using tethered dual catalysts to increase cooperativity between the catalytic centres. In this current work we sought to determine the origin of the catalytic synergy observed for a series of Ir(I) based complexes tethered to a BODIPY type photocatalyst through different tethering modes. Kinetic analyses revealed that the tethered dual catalysts were more effective at promoting heat activated intermolecular hydro-amination than the un-tethered analogues. The tethering mode had a significant influence on the magnitude of this synergistic enhancement observed for the hydroamination reaction, likely due to a combination of steric and electronic ligand effects. Investigations into the effect of the tethered dual catalysts on the light activated oxidation of thioanisole demonstrated that chemical tethering leads to substantial increases in photocatalytic activity, which was once again impacted by the tethering mode. The origin of the observed enhancement was found to be due to both increased singlet oxygen generation through the heavy atom effect, as well as direct involvement of the Ir centre in the oxidation reaction pathway.

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From molecular metal complex to metal-organic framework: The CO2 reduction photocatalysts with clear and tunable structure

Cited by 245 publications

References 323 publications

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Molecular Porous Photosystems Tailored for Long‐Term Photocatalytic CO₂ Reduction

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

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From molecular metal complex to metal-organic framework: The CO2 reduction photocatalysts with clear and tunable structure

Cited by 245 publications

References 323 publications

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore

Molecular Porous Photosystems Tailored for Long‐Term Photocatalytic CO2 Reduction

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

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Molecular Porous Photosystems Tailored for Long‐Term Photocatalytic CO₂ Reduction