Metal–Organic Frameworks as Promising Photosensitizers for Photoelectrochemical Water Splitting

Zhang, Liping; Cui, Ping; Yang, Hongbin; Chen, Jiazang; Xiao, Fang‐Xing; Guo, Yuanyuan; Liu, Ye; Zhang, Weina; Huo, Fengwei; Liu, Bin

doi:10.1002/advs.201500243

Cited by 116 publications

(83 citation statements)

References 37 publications

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“…As shown in Figure a, linear‐sweep‐voltammetry (LSV) with the rate of 50 mV s −1 from 0 to 1.8 V was measured in 0.5 m Na 2 SO 4 (PH = 7) electrolyte. It is not difficult to find that the bare TiO 2 exhibited a low photocurrent density of 0.334 mA cm −2 (at 1.23 V vs reversible hydrogen electrode [RHE]) under 100 mW cm −2 , and the result can be assigned to the bulk recombination of photogenerated charge carriers . FeOOH as co‐catalyst has significantly improved the photocurrent density of FeOOH/TiO 2 .…”

Section: Resultsmentioning

confidence: 99%

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO₂ Photoanode

Cui

Bai

et al. 2019

Energy Tech

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Kinetics play a critical role in the photoelectrochemical (PEC) system, whereas co‐catalysis is mainly responsible for reducing the reaction barrier and facilitates water splitting. Here, the unsaturated Fe sites through the metal‐organic framework (MOFs) structure promote the kinetics of water oxidation over TiO2 are successfully in situ decorated. This heterostructure further helps us to better understand the PEC behaviors of organic–inorganic hybrid systems. MIL‐100(Fe), as the typical MOFs model, is facilely achieved by an FeOOH sacrificial template method, a strategy which could anchor the compact and ultrathin MIL‐100(Fe) films on the surface of TiO2 to obtain abundant unsaturated Fe sites. The photocurrent density of MIL‐100(Fe)/TiO2 reaches about 2.4 times at 1.23 V vs reversible hydrogen electrode (RHE) compared with bare TiO2, and the incident photon to current conversion efficiency value increases up to 47% (at 390 nm). Furthermore, the photocurrent density of MIL‐100(Fe)/TiO2 is maintained at 84% after 3 h, showing that the organic component of MIL‐100(Fe) takes a nature of favorable stability. The configuration of MIL‐100(Fe)/TiO2 will bring a new insight for learning the basic function of unsaturated metal sites in the PEC system.

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Section: Resultsmentioning

confidence: 99%

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO₂ Photoanode

Cui

Bai

et al. 2019

Energy Tech

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“…[1] At present, fossil fuels are the main source to meet the energy demands of humans at an affordable cost. [13] Moreover,M OFs can also be used directly as photo-or photoelectrocatalysts. [3] In this regard, solar energy and water are considered to be the most sustainable and renewable resources.…”

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confidence: 99%

“…MOFs adopt highly ordered structures with significantlyh igh surface areas. [13] Moreover,M OFs can also be used directly as photo-or photoelectrocatalysts. [11] In general, most MOFs are insulators and are used only as ah igh-surface-area support for metal-based semiconducting nanostructured catalytic centers.…”

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confidence: 99%

“…[14,16] However,v ery few works are known for the more challenging and energy-demanding oxygen-evolution half reaction. [13] Nevertheless,t he development of earth-abundant metal-based MOFs is highly important for cost-effective photoelectrochemical water oxidation. The need for strong oxidizing agents, complementarys acrificial agents, and controlo fp Hv alue makes it tedious to use MOFs for these applications.P reviously,n anocompositesw ere developedf or water oxidation by doping Ir-and Mn-based photocatalysts in relativelys table MOFs (UiO-67 and Zr-MOF) for Ce IV -drivenw ater oxidation.…”

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confidence: 99%

“…[12] In recent studies, MOFs have been applied as ac ocatalyst supported on TiO 2 for light harvestinga nd can significantly enhance the visible-light watersplitting activity of TiO 2 photocatalysts. [13] Moreover,M OFs can also be used directly as photo-or photoelectrocatalysts. [12,14] Notably,M OFs act as heterogeneousa nd homogeneous catalysts as well as semiconducting materials based on metals and organic linker moieties.…”

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confidence: 99%

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Synthesis, Characterization, and Photoelectrochemical Catalytic Studies of a Water‐Stable Zinc‐Based Metal–Organic Framework

et al. 2018

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Metal-organic frameworks (MOFs) are class of porous materials that can be assembled in a modular manner by using different metal ions and organic linkers. Owing to their tunable structural properties, these materials are found to be useful for gas storage and separation technologies, as well as for catalytic applications. A cost-effective zinc-based MOF ([Zn(bpcda)(bdc)] ) is prepared by using N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine [N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine] and benzenedicarboxylic acid (bdc) linkers. This new material exhibits remarkable photoelectrochemical (PEC) catalytic activity in water splitting for the evolution of oxygen. Notably, this non-noble metal-based MOF, without requiring immobilization on other supports or containing metal particles, produced a highest photocurrent density of 31 μA cm at 0.9 V, with appreciable stability and negligible photocorrosion. Advantageously for the oxygen evolution process, no external reagents or sacrificial agents are required in the aqueous electrolyte solution.

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Plasmon‐Dictated Photo‐Electrochemical Water Splitting for Solar‐to‐Chemical Energy Conversion: Current Status and Future Perspectives

Xiao

Liu

2018

Adv Materials Inter

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attention has been devoted to the conversion of solar light into chemical energy for satisfying increasing demands of energy consumption, such as photocatalysis, photovoltaics, and photoelectrocatalysis. [3,4] In particular, photo-electrochemical (PEC) water splitting with assistance of solar light for hydrogen production has been deemed as a rather promising route to ameliorate the increasing energy crisis since the pioneer work launched in 1972 by Honda and Fujishima, who judiciously harnessed TiO 2 powder electrode to achieve water splitting under UV light irradiation. [5][6][7] Thereafter, various semiconductors especially transition metal oxides have been extensively explored for PEC water splitting. Notwithstanding the advancements achieved in the past few decades, there still remain two issues that need to be circumvented with a view to fully utilizing the semiconducting materials for water splitting, including poor light-harvesting efficiency of wideband-gap semiconductors (e.g., TiO 2 , ZnO, SrTiO 3 , etc.), which only absorb UV light that accounts for merely 5% of the solar spectrum, and high recombination rate of photogenerated electron-hole charge carriers. To solve these problems, diverse strategies have been developed including (1) structure and/or morphology engineering for improving light trapping and shortening the travel distance of charge carriers to their surfaces, [8] (2) elemental doping to induce the formation of intraband gap state, [9,10] (3) sensitizing the semiconductor with organic dyes or narrow-band-gap quantum dots to improve the visible light absorption, [11][12][13][14][15][16][17][18] (4) construction of heterostructures or heterojunctions, [19,20] and (5) optimization of the crystal structure. [21] Nonetheless, it is worth noting that possible formation of undesirable defects at the interface and unfavorable stability of photosensitizers may occur in the above-mentioned strategies, which eventually retard the fabrication of highly efficient semiconductor-based photoelectrodes. Therefore, it is highly desirable to seek a more efficacious tactic to boost the photoresponse of wide band gap semiconductors.Decoration of semiconductors with metal nanostructures has been regarded as an alternative and powerful approach to improve the solar-to-hydrogen conversion efficiency of wideband-gap semiconductors by virtue of the intrinsically unique surface plasmon resonance (SPR) effect and electron capturing

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Metal–Organic Frameworks as Promising Photosensitizers for Photoelectrochemical Water Splitting

Cited by 116 publications

References 37 publications

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO₂ Photoanode

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO₂ Photoanode

Synthesis, Characterization, and Photoelectrochemical Catalytic Studies of a Water‐Stable Zinc‐Based Metal–Organic Framework

Plasmon‐Dictated Photo‐Electrochemical Water Splitting for Solar‐to‐Chemical Energy Conversion: Current Status and Future Perspectives

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Metal–Organic Frameworks as Promising Photosensitizers for Photoelectrochemical Water Splitting

Cited by 116 publications

References 37 publications

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO2 Photoanode

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO2 Photoanode

Synthesis, Characterization, and Photoelectrochemical Catalytic Studies of a Water‐Stable Zinc‐Based Metal–Organic Framework

Plasmon‐Dictated Photo‐Electrochemical Water Splitting for Solar‐to‐Chemical Energy Conversion: Current Status and Future Perspectives

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In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO₂ Photoanode

In Situ Decorating Coordinatively Unsaturated Fe Sites for Boosting Water Oxidation Performance of TiO₂ Photoanode