Titanium Hydroxide Secondary Building Units in Metal–Organic Frameworks Catalyze Hydrogen Evolution under Visible Light

Song, Yang; Li, Zhe; Zhu, Yuan‐Yuan; Feng, Xuanyu; Chen, Justin S.; Kaufmann, Michael; Wang, Cheng; Lin, Wenbin

doi:10.1021/jacs.9b05964

Cited by 96 publications

(82 citation statements)

References 36 publications

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“…Fortunately, there is a wealth of experimental and theoretical literature that demonstrate the emergence of conduction band states centered on titanium in these scenarios. The resultant LMCT is predicted by DOS plots and electronic band diagrams from DFT performed by other groups and evidenced experimentally by a range of spectroscopic methods . Thus, transmetallation of MOFs with an organic VBM presents an opportunity to instill the beneficial photocatalytic property of long‐lived, spatially separated excitons, formed with a tunable wavelength, in virtually any scaffold.…”

mentioning

confidence: 88%

Titanium(IV) Inclusion as a Versatile Route to Photoactivity in Metal–Organic Frameworks

Mancuso

Hendon

2019

Advcd Theory and Sims

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Titanium-containing metal-organic frameworks (MOFs) are known to perform light-promoted chemical transformations. Formation of these frameworks, accessed either natively or via transmetallation, can instill beneficial photocatalytic properties in previously photo-inert scaffolds. Band edge diagrams coupled with their density of states illustrate the persistent nature of the accessible titanium d-states at the conduction band edge, independent of linker identity. In essentially all of these Ti-containing frameworks, the valence band edge localizes on the organic component, permitting facile modulation of the band gap. In sum, the spatial separation of photogenerated excitons will be observed in both the native and titanium(IV)-substituted MOFs, and this exciton pair is useful in photocatalysis.

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confidence: 88%

Titanium(IV) Inclusion as a Versatile Route to Photoactivity in Metal–Organic Frameworks

Mancuso

Hendon

2019

Advcd Theory and Sims

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“…The hydrogen production rate of Ti 3 -BPDC-Ir is 925 μmol g −1 h −1 under visible light thanks to the hierarchical assembly of photosensitizing Ir(ppy) 2 (dcbpy)] Cl linkers and Ti 3 clusters which facilitates multielectron transfer (Figure 10). [143] Gao and co-workers introduced triphenylamino-based ligands into Ti-O-chain-based MOFs, which can also absorb visible light. [146] Therefore, ZSTU-1 and ZSTU-3 show excellent photocatalytic performance with hydrogen production rate of 1060 and 1350 μmol g −1 h −1 , respectively.…”

Section: Photocatalysismentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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“…[ 5,6 ] The metallic blocks mainly correspond to di/trivalent cations of 3d transition metals (e.g., Fe, Zn, Ni) and 3p metals, [ 5–9 ] among which Ti is an attractive candidate because of its relatively low cost, redox activity, and photocatalytic properties. [ 10–16 ] Incorporating Ti‐oxo clusters delivers the semiconductor behavior of the MOFs with decent solar energy conversion efficiency, due to the facilitated electron transfer from the photoexcited organic linkers to the Ti‐oxo clusters (i.e., linker‐to‐cluster charge transfer, termed as LCCT). [ 13–18 ] Particularly, bandgaps in the MOFs can be adjusted via modifying the organic linkers (e.g., introducing new functional groups), which can open up new possibilities to control the electronic structures/states of photocatalysts at the molecular level.…”

Section: Figurementioning

confidence: 99%

Highly Stable Phosphonate‐Based MOFs with Engineered Bandgaps for Efficient Photocatalytic Hydrogen Production

et al. 2020

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Sunlight-driven water splitting to produce H 2 is an active field of energy research due to its promising potential to obtain renewable energy sources in a sustainable way. [1] One of the key requirements for achieving water photolysis with high "solar-tohydrogen" efficiencies is developing efficient photocatalysts. [2,3] Photoactive metal-organic frameworks (MOFs) represent one of the most promising materials for photocatalytic hydrogen production, but phosphonate-based MOFs have remained largely underdeveloped compared to other conventional MOFs. Herein, a photocatalyst of 1D titanium phosphonate MOF is designed through an easy and scalable stirring hydrothermal method. Homogeneous incorporation of organophosphonic linkers can narrow the bandgap, which is due to the strong electron-donating ability of the OH functional group that can efficiently shift the top of the valence band, moving the light absorption to the visible portion of the spectrum. In addition, the unique 1D nanowire topology enhances the photoinduced charge carrier transport and separation. Accordingly, the titanium phosphonate nanowires deliver remarkably enhanced photocatalytic hydrogen evolution activity under irradiation of both visible light and a full-spectrum simulator. Such concepts of engineering both nanostructures and electronic states herald a new paradigm for designing MOF-based photocatalysts.

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Titanium Hydroxide Secondary Building Units in Metal–Organic Frameworks Catalyze Hydrogen Evolution under Visible Light

Cited by 96 publications

References 36 publications

Titanium(IV) Inclusion as a Versatile Route to Photoactivity in Metal–Organic Frameworks

Titanium(IV) Inclusion as a Versatile Route to Photoactivity in Metal–Organic Frameworks

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Highly Stable Phosphonate‐Based MOFs with Engineered Bandgaps for Efficient Photocatalytic Hydrogen Production

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