Multivariate Functionalization of UiO‐66 for Photocatalytic Water Remediation

Valverde, Ainara; Payno, David; Lezama, Luís; Laza, José Manuel; Wuttke, Stefan; Luis, Roberto Fernández de

doi:10.1002/adsu.202200024

Cited by 17 publications

(13 citation statements)

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“…Overall, Cr(VI), stabilized as CrO 4 2− chromate anions, gains three electrons and incorporates two hydroxyl or water molecules within its coordination environment during its reduction to Cr(III). During this process, the highly reactive and transient intermediate Cr(V) species are formed as well, as A. Valverde et al [ 136 ] proved through EPR. The authors stated that the first step of the immobilization and transformation of Cr(VI) to Cr(III) into the UiO-66 frameworks is the adsorption of chromate anions ( Figure 16 a,b).…”

Section: Multivariate Metal-organic Framework For Chromium Photoreduc...mentioning

confidence: 83%

“…Recently, Valverde et al [ 136 ] designed a multivariate UiO-66 to develop dual sorbent photocatalysis for the removal of Cr(VI) in wastewater. Many studies have explored how replacing the original terephthalate (TPA) linker of the UiO-66 framework for some of its derivatives can endow the material with chemical (i.e., dihydroxyterephtalate (TPA-(OH) 2 )) and photocatalytic (i.e., aminoterephtalate (TPA-NH 2 )) capacity to reduce Cr(VI) to Cr(III), as with the chemical affinity to adsorb both Cr(VI) (i.e., TPA-NH 2 ) and Cr(III) (i.e., TPA-(OH) 2 ).…”

Section: Multivariate Metal-organic Framework For Chromium Photoreduc...mentioning

confidence: 99%

“…Again, during the last few years, it has been duly proved that the chemical variance introduced by the multivariate encoding of the organic linkers within the ordered MOF structure can lead to cooperative or coupled functionalities ( Figure 3 ). For instance, multivariate reticular chemistry offers interesting advantages to combine electron donors or withdrawing functions able to expand the band gap to the visible range, and enhance the photoconduction of the MOFs’ three-dimensional scaffolds [ 136 ]. Although this strategy has been rarely studied for Cr(VI) photoreduction, the initial results seed the light to a promising perspective to further implement the MOF potentials in this research area.…”

Section: Introductionmentioning

confidence: 99%

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A State-of-the-Art of Metal-Organic Frameworks for Chromium Photoreduction vs. Photocatalytic Water Remediation

et al. 2022

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Hexavalent chromium (Cr(VI)) is a highly mobile cancerogenic and teratogenic heavy metal ion. Among the varied technologies applied today to address chromium water pollution, photocatalysis offers a rapid reduction of Cr(VI) to the less toxic Cr(III). In contrast to classic photocatalysts, Metal-Organic frameworks (MOFs) are porous semiconductors that can couple the Cr(VI) to Cr(III) photoreduction to the chromium species immobilization. In this minireview, we wish to discuss and analyze the state-of-the-art of MOFs for Cr(VI) detoxification and contextualizing it to the most recent advances and strategies of MOFs for photocatalysis purposes. The minireview has been structured in three sections: (i) a detailed discussion of the specific experimental techniques employed to characterize MOF photocatalysts, (ii) a description and identification of the key characteristics of MOFs for Cr(VI) photoreduction, and (iii) an outlook and perspective section in order to identify future trends.

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Section: Multivariate Metal-organic Framework For Chromium Photoreduc...mentioning

confidence: 83%

Section: Multivariate Metal-organic Framework For Chromium Photoreduc...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A State-of-the-Art of Metal-Organic Frameworks for Chromium Photoreduction vs. Photocatalytic Water Remediation

et al. 2022

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“…For example, Luis' and Kumar's team designed a hybrid ligand UiO-66 with binary and ternary ligands, including UiO-66-NH 2 -NO 2 , UiO-66-NH 2 -(OH) 2 , UiO-66-(OH) 2 -NO 2 , and UiO-66-NH 2 -(OH) 2 -NO 2 , respectively, for photocatalytic water remediation (Figure 11e). [164,166] In the former work, excellent adsorption performance depends on the electrostatic interaction between the functional groups on the ligand side chains and the chromate anion, particularly -(OH) 2 and -NH 2 . While the latter attributes the enhanced photoactivity to the different electronic properties of the substituents, this is because the photoactive performance of UiO-66-X maintains a good correlation with the Hammett constant.…”

Section: Ligands Substitutionmentioning

confidence: 99%

“…e) Key functions needed in MOF for the Cr VI to Cr III capture and transformation (I) and multivariate encoding strategy of the UiO-66 framework developed (II). Adapted with permission [166]. Copyright 2022, Elsevier B.V. f) Modification of UiO-MOF via a click reaction was used to form new catalysts UiO-MOF-Fe 2 S 2 incorporating [Fe 2 S 2 ] catalytic sites.…”

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confidence: 99%

Trace to the Source: Self‐Tuning of MOF Photocatalysts

Zhou

Zhang

Xiao

et al. 2023

Advanced Energy Materials

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Benefitting from ultra‐high porosity, large specific surface area (SSA), and rich active sites, metal–organic frameworks (MOFs) have emerged as a star material in energy and environment related applications, especially in photocatalysis. In comparison with conventional photocatalysts, MOFs can be customized in terms of electronic structure, photo‐responsiveness, and morphological dimensions by rational design, which means that MOFs eliminate the need for other species to achieve enhanced photocatalytic performance, such as metals, compounds, and polymers, which may introduce extra costs, be time‐consuming, be multi‐phase, or have an unclear mechanism. Most previous review works related to MOF photocatalysis have mixed self‐tuning and assisted‐tuning, which often gives an incomplete understanding. In this work, the self‐tunning of MOFs by analyzing component (as clusters, ligands, and inclusions), defect (defect engineering, as linkers, clusters, and oxygen vacancies (OVs), and crystal (as facets, dimensions, and amorphization) is summarized. Then, outstanding examples of these strategies applied to water redox, CO2/N2 reduction, organic conversion, and environmental treatment are discussed. Finally, the opportunities and challenges faced in the self‐tuning of MOFs are analyzed from different perspectives. This paper is a comprehensive and systematic review on the self‐tuning of MOFs to enhance photocatalytic activity.

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Direct Visualization of Chemically Resolved Multilayered Domains in Mixed‐Linker Metal–Organic Frameworks

Centrone

Lerma‐Berlanga

Biacchi

et al. 2023

Adv Funct Materials

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The modular synthesis approach for assembling inorganic nodes and organic multidentate linkers into reticular solids enables rational engineering in porous materials known as metal–organic frameworks (MOFs). Incorporation of two or more linker types in MOF crystals holds great potential for engineering complex pore functionalities, by virtue of chemically heterogeneous domains. However, deciphering linkers distributions in MOFs crystals is challenging because of the insufficient spatial resolution of conventional, chemically sensitive techniques hinders the verification of rational design. Herein, the high spatial resolution and chemical specificity of infrared nanoscopy is leveraged in combination with high‐throughput diffraction‐limited hyperspectral photoluminescence imaging to determine the composition of individual multivariate UiO‐68 MOF crystals (UiO, Universitetet‐i‐Oslo), after linker‐exchange with optically active tetrazine units. The results reveal that the crystals display a three‐layer onion‐like structure composed of a core‐rich in the parent linker, an intermediate multivariate layer with a gradient in linker composition and a proto‐MOF external shell. In this outer layer, a fraction of the linkers’ binding groups is hydrogen bonded rather than coordinated with metal nodes, suggestive of superficial reconstruction during the linker‐exchange. This study advances the analytical capabilities for studying and engineering heterogeneous domains in mixed‐linker MOF crystals down to the nanoscale.

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Multivariate Functionalization of UiO‐66 for Photocatalytic Water Remediation

Cited by 17 publications

References 79 publications

A State-of-the-Art of Metal-Organic Frameworks for Chromium Photoreduction vs. Photocatalytic Water Remediation

A State-of-the-Art of Metal-Organic Frameworks for Chromium Photoreduction vs. Photocatalytic Water Remediation

Trace to the Source: Self‐Tuning of MOF Photocatalysts

Direct Visualization of Chemically Resolved Multilayered Domains in Mixed‐Linker Metal–Organic Frameworks

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