Comparison of homogeneous and heterogeneous catalysts in dye-sensitised photoelectrochemical cells for alcohol oxidation coupled to dihydrogen formation

Bruggeman, Didjay F.; Mathew, Simon; Detz, Remko J.; Reek, Joost N. H.

doi:10.1039/d1se01275d

Cited by 13 publications

(13 citation statements)

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“…Interestingly, similar photoelectrochemical performances were also obtained by adding the TEMPO catalyst in a homogenous solution, avoiding the synthetic effort to bind it to the porphyrin chromophore. The aspect of heterogenizing the TEMPO catalyst for alcohol oxidation was also discussed by Reek et al ( Bruggeman et al, 2021a ; Bruggeman et al, 2021b ), in the development of photoanodes sensitized with thienopyrroledione-based organic dye (AP11, Figure 2B ). The AP11 dye can be efficiently chemisorbed onto TiO 2, and electron injection from the excited state is energetically favorable by 0.3 eV.…”

Section: Systems Based On Noble-metal–free and Organic Sensitizersmentioning

confidence: 77%

“…Under optimized conditions, the photoelectrochemical systems are active toward the oxidation of benzyl alcohol to benzaldehyde with an almost quantitative Faradaic efficiency, characterized by J up to 400 μA/cm 2 at 0 V versus Ag/AgCl, stable for up to 32 h at 50 mW/cm 2 irradiation, although high concentrations of TEMPO and lithium bis(trifluoromethanesulfonyl)imide as a base were required (1.0 and 1.2 M, respectively, in acetonitrile) ( Bruggeman et al, 2021a ). To overcome this drawback, the authors proposed to anchor the TEMPO catalyst onto the TiO 2 layer by exploiting a silatrane linker ( Bruggeman et al, 2021b ). However, the system performed worse (i.e., an order of magnitude lower J and a decreased stability) with respect to the one keeping TEMPO in the solution.…”

Section: Systems Based On Noble-metal–free and Organic Sensitizersmentioning

confidence: 99%

Section: Systems Based On Noble-metal–free and Organic Sensitizersmentioning

confidence: 99%

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Beyond Water Oxidation: Hybrid, Molecular-Based Photoanodes for the Production of Value-Added Organics

2022

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The political and environmental problems related to the massive use of fossil fuels prompted researchers to develop alternative strategies to obtain green and renewable fuels such as hydrogen. The light-driven water splitting process (i.e., the photochemical decomposition of water into hydrogen and oxygen) is one of the most investigated strategies to achieve this goal. However, the water oxidation reaction still constitutes a formidable challenge because of its kinetic and thermodynamic requirements. Recent research efforts have been focused on the exploration of alternative and more favorable oxidation processes, such as the oxidation of organic substrates, to obtain value-added products in addition to solar fuels. In this mini-review, some of the most intriguing and recent results are presented. In particular, attention is directed on hybrid photoanodes comprising molecular light-absorbing moieties (sensitizers) and catalysts grafted onto either mesoporous semiconductors or conductors. Such systems have been exploited so far for the photoelectrochemical oxidation of alcohols to aldehydes in the presence of suitable co-catalysts. Challenges and future perspectives are also briefly discussed, with special focus on the application of such hybrid molecular-based systems to more challenging reactions, such as the activation of C–H bonds.

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Section: Systems Based On Noble-metal–free and Organic Sensitizersmentioning

confidence: 77%

Section: Systems Based On Noble-metal–free and Organic Sensitizersmentioning

confidence: 99%

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Beyond Water Oxidation: Hybrid, Molecular-Based Photoanodes for the Production of Value-Added Organics

2022

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“…Although the TEMPO concentration is lower in the fully aqueous DSPEC, our previous studies have shown that DSPECs with TEMPO concentrations as low as 0.01 M in acetonitrile still work well and outperform the DSPEC based on the aqueous anolyte. [30] Furthermore, it is known that wettability issues for TEMPO-based aqueous electrolytes leading to poor pore infiltration are not an issue. [36] While both DSPECs-the TEMPO redox-gel and the completely aqueous redox system-demonstrate a Faradaic efficiency for glyceraldehyde production of � 100 %, the photocurrent produced by the TEMPO redoxgel based DSPEC is � 10-fold higher than that of the aqueous system.…”

Section: Methodsmentioning

confidence: 99%

“…As shown by our previous work, it is crucial that in situ photogenerated TEMPO + must migrate away from the semiconductor surface to prevent recombination. [30] Thus, our envisioned biphasic DSPEC design will only function if the TEMPO redox-mediating catalyst resides in the organic-gel layer. The photogenerated TEMPO + should diffuse sufficiently fast to the interface to perform the chemical oxidation reaction.…”

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confidence: 99%

Aqueous Biphasic Dye‐Sensitized Photosynthesis Cells for TEMPO‐Based Oxidation of Glycerol

et al. 2022

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This work reports an aqueous dye‐sensitized photoelectrochemical cell (DSPEC) capable of oxidizing glycerol (an archetypical biobased compound) coupled with H2 production. We employed a mesoporous TiO2 photoanode sensitized with the high potential thienopyrroledione‐based dye AP11, encased in an acetonitrile‐based redox‐gel that protects the photoanode from degradation by aqueous electrolytes. The use of the gel creates a biphasic system with an interface at the organic (gel) electrode and aqueous anolyte. Embedded in the acetonitrile gel is 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO), acting as both a redox‐mediator and a catalyst for oxidative transformations. Upon oxidation of TEMPO by the photoexcited dye, the in situ generated TEMPO+ shuttles through the gel to the acetonitrile–aqueous interface, where it acts as an oxidant for the selective conversion of glycerol to glyceraldehyde. The introduction of the redox‐gel layer affords a 10‐fold increase in the conversion of glycerol compared to the purely aqueous system. Our redox‐gel protected photoanode yielded a stable photocurrent over 48 hours of continuous operation, demonstrating that this DSPEC is compatible with alkaline aqueous reactions.

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Frontiers in Photoelectrochemical Catalysis: A Focus on Valuable Product Synthesis

Sendeku,

Shifa,

Dajan

et al. 2024

Advanced Materials

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Photoelectrochemical (PEC) catalysis provides the most promising avenue for producing value‐added chemicals and consumables from renewable precursors. Over the last decades, PEC catalysis, including reduction of renewable feedstock, oxidation of organics, and activation and functionalization of C‐C and C‐H bonds, are extensively investigated, opening new opportunities for employing the technology in upgrading readily available resources. However, several challenges still remain unsolved, hindering the commercialization of the process. This review offers an overview of PEC catalysis targeted at the synthesis of high‐value chemicals from sustainable precursors. First, we recall the fundamentals of evaluating PEC reactions in the context of value‐added product synthesis at both anode and cathode. Then, we highlight the common photoelectrode fabrication methods that have been employed to produce thin‐film photoelectrodes. Next, we systematically review and discuss the advancements in the PEC conversion of various feedstocks to produce highly valued chemicals. Finally, we present the challenges and prospects in the field. This review aims at facilitating further development of PEC technology for upgrading several renewable precursors to value‐added products and other pharmaceuticals.This article is protected by copyright. All rights reserved

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Comparison of homogeneous and heterogeneous catalysts in dye-sensitised photoelectrochemical cells for alcohol oxidation coupled to dihydrogen formation

Abstract: In this study we examine two different strategies—a homo- and heterogeneous approach—of the light-driven oxidation of benzyl alcohol in dye-sensitized photoelectrochemical cells (DSPECs). The DSPEC consists of a mesoporous anatase...

Cited by 13 publications

References 58 publications

Beyond Water Oxidation: Hybrid, Molecular-Based Photoanodes for the Production of Value-Added Organics

Beyond Water Oxidation: Hybrid, Molecular-Based Photoanodes for the Production of Value-Added Organics

Aqueous Biphasic Dye‐Sensitized Photosynthesis Cells for TEMPO‐Based Oxidation of Glycerol

Frontiers in Photoelectrochemical Catalysis: A Focus on Valuable Product Synthesis

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