Hybrid artificial photosynthetic systems constructed using quantum dots and molecular catalysts for solar fuel production: development and advances

Liu, Jing; Ren, Ying-Yi; Wu, Jin; Wu, Xia; Deng, Bo-Yi; Wang, Feng

doi:10.1039/d1ta02673a

Cited by 23 publications

(21 citation statements)

References 127 publications

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“…From the above discussion, various sacrificial electron donors for supramolecular photocatalysts for CO 2 reduction have been employed, viz. BIH, BNAH, ascorbic acid, TEOA, isopropanol, Na 2 S, and Na 2 SO 3 . The following classes of sacrificial reductants are being extensively used for photocatalytic CO 2 reduction using semiconductor–supramolecule hybrid systems.…”

Section: Resultsmentioning

confidence: 99%

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Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

et al. 2021

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Photocatalytic CO2 reduction into C1 products is one of the most trending research subjects of current times as sustainable energy generation is the utmost need of the hour. In this review, we have tried to comprehensively summarize the potential of supramolecule-based photocatalysts for CO2 reduction into C1 compounds. At the outset, we have thrown light on the inert nature of gaseous CO2 and the various challenges researchers are facing in its reduction. The evolution of photocatalysts used for CO2 reduction, from heterogeneous catalysis to supramolecule-based molecular catalysis, and subsequent semiconductor–supramolecule hybrid catalysis has been thoroughly discussed. Since CO2 is thermodynamically a very stable molecule, a huge reduction potential is required to undergo its one- or multielectron reduction. For this reason, various supramolecule photocatalysts were designed involving a photosensitizer unit and a catalyst unit connected by a linker. Later on, solid semiconductor support was also introduced in this supramolecule system to achieve enhanced durability, structural compactness, enhanced charge mobility, and extra overpotential for CO2 reduction. Reticular chemistry is seen to play a pivotal role as it allows bringing all of the positive features together from various components of this hybrid semiconductor–supramolecule photocatalyst system. Thus, here in this review, we have discussed the selection and role of various components, viz. the photosensitizer component, the catalyst component, the linker, the semiconductor support, the anchoring ligands, and the peripheral ligands for the design of highly performing CO2 reduction photocatalysts. The selection and role of various sacrificial electron donors have also been highlighted. This review is aimed to help researchers reach an understanding that may translate into the development of excellent CO2 reduction photocatalysts that are operational under visible light and possess superior activity, efficiency, and selectivity.

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Section: Resultsmentioning

confidence: 99%

“…BIH, BNAH, ascorbic acid, TEOA, isopropanol, Na 2 S, and Na 2 SO 3 . 248 The following classes of sacrificial reductants are being extensively used for photocatalytic CO 2 reduction using semiconductor−supramolecule hybrid systems.…”

Section: Table 1 Continuedmentioning

confidence: 99%

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

et al. 2021

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“…The photocatalytic conversion of carbon dioxide (CO 2 ) to fuels or chemicals is a blooming research interest. − This photoreaction represents a green and sustainable way for resource utilization of CO 2 . Semiconductor quantum dots (QDs) with an outstanding visible light harvesting property have been widely used as light absorbers in combination with various molecular cocatalysts for photocatalytic CO 2 reduction. − However, examples recorded in documents showed that QDs themselves exhibit poor activity and selectivity for CO 2 photoreduction in the absence of a cocatalyst. − …”

Section: Introductionmentioning

confidence: 99%

Assembling CdSe Quantum Dots into Polymeric Micelles Formed by a Polyethylenimine-Based Amphiphilic Polymer to Enhance Efficiency and Selectivity of CO₂-to-CO Photoreduction in Water

Deng

Liu

et al. 2022

ACS Appl. Mater. Interfaces

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Colloidal quantum dots (QDs) as photocatalysts enable catalysis of CO2-to-CO conversion in the presence of electron donors. The surface and/or interfacial chemical environment of the QDs is essential for the activity and selectivity of the CO2 photoreduction. Various strategies, including exposing active metal sites or anchoring functional organic ligands, have been applied to tune the QDs’ surface chemical environment and thus to improve both activity and selectivity of CO2 photoreduction, which occurs at surface of the QDs. However, the efficient and selective photocatalytic CO2 reduction with QD photocatalysts in water is still a challenging task due to low CO2 solubility and robust competing reaction of proton reduction in water. Different from state-of-the-art QDs’ surface manipulation, we proposed to ameliorate the interfacial chemical environment of CdSe QDs via assembling the QDs into functional polymeric micelles in water. Herein, CdSe@PEI-LA assemblies were constructed by loading CdSe QDs into polymeric micelles formed by PEI-LA, a polyethylenimine (PEI)-based functional amphiphilic polymer. Due to self-assembly and high CO2 adsorption capacity of PEI-LA in water, the photocatalytic CO2-to-CO conversion efficiency and selectivity of the CdSe@PEI-LA assemblies in water were dramatically improved to 28.0 mmol g–1 and 87.5%, respectively. These two values increased 57 times and 1.5 times, respectively, compared with those of the pristine CdSe QDs. Mechanism studies revealed that CdSe QDs locate in polymeric micelles of high CO2 local concentration and the photoinduced electron transfer from the conduction band of CdSe QDs to Cd–CO2* species is thermodynamically and kinetically improved in the presence of PEI-LA. The CdSe@PEI-LA system represents a successful example of using a functionalized amphiphilic polymer to ameliorate interfacial microenvironments of nanocrystal photocatalysts and realizing efficient and selective CO2 photoreduction in water.

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“…CdSe QDs functionalized with hydrogenase mimics have already shown their high catalytic proficiency with turn-over numbers (TONs) in the order of up to 10⁴ to 10⁵ in the presence of sacrificial electron donors. 1,13,14,15 In a QD-hydrogenase mimic complex, photoexcitation of the QD generates an exciton, i.e., a localized electron-hole pair followed by electron transfer to the mimic, which reduces the [Fe I Fe I ] center to an intermediate [Fe I Fe 0 ] species. As described by Wu and co-workers, 16 this is followed by the addition of a proton, which yields [Fe I Fe II H], and the subsequent uptake of an additional electron and proton.…”

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confidence: 99%

Covalent functionalization of CdSe quantum dot films with molecular [FeFe] hydrogenase mimics for light-driven hydrogen evolution

Benndorf

Schleusener

Müller

et al. 2022

Preprint

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CdSe quantum dots combined with [FeFe] hydrogenase mimics as molecular catalytic reaction centers based on earth abundant elements have demonstrated promising activity for photocatalytic hydrogen generation. Direct linking of the [FeFe] hydrogenase mimics to the quantum dots surface is expected to enhance the activity of the system by establishing close contact between the [FeFe] hydrogenase mimics and the light harvesting quantum dots supporting the transfer and accumulation of several electrons which are needed to drive hydrogen evolution. To circumvent the problem of limited colloidal stability upon covalent functionalization of the quantum dots under optimal pH conditions for hydrogen evolution, in this work, we report on the functionalization of quantum dots immobilized in a thin film architecture on a substrate with [FeFe] hydrogenase mimics by covalent linking via carboxylate groups as anchoring functionality to bind to the QD surface. The functionalization was monitored via UV/Vis absorption, photoluminescence, infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) and quantified via micro X-ray fluorescence spectrometry (μXRF). The activity of the molecularly functionalized thin film was demonstrated and in dependence on the linker length TONs in the range of 360-580 (short linker) and 130-160 (long linker) were achieved. This work presents a proof of concept study showing the potential of thin film architectures of immobilized quantum dots as platform for light-driven hydrogen evolution and beyond.

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Hybrid artificial photosynthetic systems constructed using quantum dots and molecular catalysts for solar fuel production: development and advances

Abstract: The construction of artificial photosynthetic (AP) systems for hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CRR) is one of the hottest topics in the field of energy and...

Cited by 23 publications

References 127 publications

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

Assembling CdSe Quantum Dots into Polymeric Micelles Formed by a Polyethylenimine-Based Amphiphilic Polymer to Enhance Efficiency and Selectivity of CO₂-to-CO Photoreduction in Water

Covalent functionalization of CdSe quantum dot films with molecular [FeFe] hydrogenase mimics for light-driven hydrogen evolution

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Hybrid artificial photosynthetic systems constructed using quantum dots and molecular catalysts for solar fuel production: development and advances

Abstract: The construction of artificial photosynthetic (AP) systems for hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CRR) is one of the hottest topics in the field of energy and...

Cited by 23 publications

References 127 publications

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO2 Reduction

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO2 Reduction

Assembling CdSe Quantum Dots into Polymeric Micelles Formed by a Polyethylenimine-Based Amphiphilic Polymer to Enhance Efficiency and Selectivity of CO2-to-CO Photoreduction in Water

Covalent functionalization of CdSe quantum dot films with molecular [FeFe] hydrogenase mimics for light-driven hydrogen evolution

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Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO₂ Reduction

Assembling CdSe Quantum Dots into Polymeric Micelles Formed by a Polyethylenimine-Based Amphiphilic Polymer to Enhance Efficiency and Selectivity of CO₂-to-CO Photoreduction in Water