Exploring structure and reactivity of Cu sites in functionalized UiO-67 MOFs

Braglia, Luca; Borfecchia, Elisa; Maddalena, Lorenza; Øien, Sigurd; Lomachenko, Kirill A.; Bugaev, Aram L.; Bordiga, Silvia; Soldatov, A. V.; Lillerud, Karl Petter; Lamberti, Carlo

doi:10.1016/j.cattod.2016.02.039

Cited by 58 publications

(49 citation statements)

References 130 publications

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“…In summary, Ce 4+ was incorporated into UiO-67 containing bpydc as a mixed linker, based on the previous research [24,28,[31][32][33]. The obtained UiO-67-Ce displays a much higher photocatalytic HER efficiency than UiO-67.…”

Section: Discussionmentioning

confidence: 98%

“…The resulting UiO-67 materials were found to display efficient photocatalytic CO 2 reduction, water oxidation or other catalytic activities [29,30]. In a similar manner, complexes of Cu, Co or Mn can be incorporated into UiO-67 [31][32][33]. In general, the transition metal complexes incorporated into MOFs act as active sites for photocatalytic activities via the LMCT process.…”

Section: Introductionmentioning

confidence: 99%

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Improving the photocatalytic hydrogen evolution of UiO-67 by incorporating Ce4+-coordinated bipyridinedicarboxylate ligands

Liu

Bian

et al. 2019

Science Bulletin

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Section: Discussionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Improving the photocatalytic hydrogen evolution of UiO-67 by incorporating Ce4+-coordinated bipyridinedicarboxylate ligands

Liu

Bian

et al. 2019

Science Bulletin

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“…This strategy has been widely applied in frameworks comprising pyridine or derivative units, amine groups, thiocatechol groups, or phosphine ligands, which have high affinity for metal ions. With such a postsynthetic strategy, a variety of metal precursors, such as Pt, Pd, Ru, Rh, Ir, Au, Mn, Ni, Co, Cr, Ga, and Cu, based species, have been introduced into MOFs or COFs to create catalytically active sites. For example, our group reported the construction of a bi‐functional MOF (MOF‐253‐Pt) photocatalyst by immobilizing a platinum complex in 2,2′‐bipyridine‐based MOF (MOF‐253) .…”

Section: Rational Design Of the Diverse Catalytic Sites In Crystallinmentioning

confidence: 99%

Rational Design of Catalytic Centers in Crystalline Frameworks

Yin

et al. 2018

Advanced Materials

117

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Crystalline frameworks including primarily metal organic frameworks (MOF) and covalent organic frameworks (COF) have received much attention in the field of heterogeneous catalysts recently. Beyond providing large surface area and spatial confinement, these crystalline frameworks can be designed to either directly act as or influence the catalytic sites at molecular level. This approach offers a unique advantage to gain deeper insights of structure-activity correlations in solid materials, leading to new guiding principles for rational design of advanced solid catalysts for potential important applications related to energy and fine chemical synthesis. In this review, recent key progress achieved in designing MOF- and COF-based molecular solid catalysts and the mechanistic understanding of the catalytic centers and associated reaction pathways are summarized. The state-of-the-art rational design of MOF- and COF-based solid catalysts in this review is grouped into seven different areas: (i) metalated linkers, (ii) metalated moieties anchored on linkers, (iii) organic moieties anchored on linkers, (iv) encapsulated single sites in pores, and (v) metal-mode-based active sites in MOFs. Along with this, some attention is paid to theoretical studies about the reaction mechanisms. Finally, technical challenges and possible solutions in applying these catalysts for practical applications are also presented.

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“…Furthermore, Braglia et al . investigated a Cu‐functionalized UiO‐67‐bpy MOF via XAS and FT‐IR spectroscopy to prove the presence of the well‐defined copper complex in the framework …”

Section: Introductionmentioning

confidence: 99%

“…[8] Furthermore, Braglia et al investigated a Cu-functionalized UiO-67-bpy MOF via XAS and FT-IR spectroscopy to prove the presence of the well-defined copper complex in the framework. [9] Various methods have been reported to introduce catalytically active centers into MOFs. Post-synthetic modification (PSM), [10] i. e. the chemical modification of the material after framework synthesis, has received great interest and plays an important role for the design of well-defined single-site catalysts.…”

Section: Introductionmentioning

confidence: 99%

Post‐synthetic Modification of DUT‐5‐based Metal Organic Frameworks for the Generation of Single‐site Catalysts and their Application in Selective Epoxidation Reactions

et al. 2020

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New single‐site catalysts based on mixed‐linker metal‐organic frameworks with DUT‐5 structure, which contain immobilized Co2+, Mn2+ and Mn3+ complexes, have successfully been synthesized via post‐synthetic modification. 2,2’‐Bipyridine‐5,5’‐dicarboxylate linkers were directly metalated, while 2‐amino‐4,4’‐biphenyldicarboxylate linkers were post‐synthetically modified by their conversion to Schiff‐base ligands and a subsequent immobilization of the metal complexes. The resulting materials were used as catalysts in the selective epoxidation of trans‐stilbene and the activities and selectivities of the different catalysts were compared. The influence of various reaction parameters on conversion, yield and selectivity were investigated. Very low catalyst amounts of 0.02 mol % were sufficient to obtain a high conversion of trans‐stilbene using molecular oxygen from air as the oxidant. For cobalt‐containing MOF catalysts, conversions up to 90 % were observed and, thus, they were more active than their manganese‐containing counterparts. Recycling experiments and hot filtration tests proved that the reactions were mainly catalyzed via heterogeneous pathways.

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Exploring structure and reactivity of Cu sites in functionalized UiO-67 MOFs

Cited by 58 publications

References 130 publications

Improving the photocatalytic hydrogen evolution of UiO-67 by incorporating Ce4+-coordinated bipyridinedicarboxylate ligands

Improving the photocatalytic hydrogen evolution of UiO-67 by incorporating Ce4+-coordinated bipyridinedicarboxylate ligands

Rational Design of Catalytic Centers in Crystalline Frameworks

Post‐synthetic Modification of DUT‐5‐based Metal Organic Frameworks for the Generation of Single‐site Catalysts and their Application in Selective Epoxidation Reactions

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