Titanium‐Carboxylate Metal‐Organic Framework Based on an Unprecedented Ti‐Oxo Chain Cluster
Titanium(IV)‐based metal‐organic frameworks (Ti‐MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single‐crystalline Ti‐carboxylate MOF (DGIST‐1) composed of an unprecedented Ti‐oxo chain cluster and the porphyrinic lig...
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| Published in | Angewandte Chemie International Edition Vol. 57; no. 45; pp. 14852 - 14856 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
| Published |
Germany
Wiley Subscription Services, Inc
05.11.2018
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| Edition | International ed. in English |
| Subjects | |
| Online Access | Get full text |
| ISSN | 1433-7851 1521-3773 1521-3773 |
| DOI | 10.1002/anie.201809762 |
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| Abstract | Titanium(IV)‐based metal‐organic frameworks (Ti‐MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single‐crystalline Ti‐carboxylate MOF (DGIST‐1) composed of an unprecedented Ti‐oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4‐carboxyphenyl)porphyrin). Preformed Ti‐oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti‐alkoxide precursors, thus, enabling the formation of the highly crystalline Ti‐MOF. The successfully activated DGIST‐1 exhibited a higher surface area (i.e., 1957.3 m2 g−1) than previously reported Ti‐MOFs due to its high crystallinity. Furthermore, the visible‐light‐responsive photocatalytic activity of DGIST‐1 was confirmed by the simultaneous generation of singlet oxygen (1O2) and superoxide (.O2−) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.
A single‐crystalline Ti‐porphyrinic MOF with an unprecedented Ti‐oxo chain cluster was newly synthesized. The visible‐light‐induced photocatalytic activity of this MOF was demonstrated by its application to the generation of reactive oxygen species and the selective benzyl alcohol oxidation to give benzaldehyde. |
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| AbstractList | Titanium(IV)‐based metal‐organic frameworks (Ti‐MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single‐crystalline Ti‐carboxylate MOF (DGIST‐1) composed of an unprecedented Ti‐oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4‐carboxyphenyl)porphyrin). Preformed Ti‐oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti‐alkoxide precursors, thus, enabling the formation of the highly crystalline Ti‐MOF. The successfully activated DGIST‐1 exhibited a higher surface area (i.e., 1957.3 m2 g−1) than previously reported Ti‐MOFs due to its high crystallinity. Furthermore, the visible‐light‐responsive photocatalytic activity of DGIST‐1 was confirmed by the simultaneous generation of singlet oxygen (1O2) and superoxide (.O2−) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.
A single‐crystalline Ti‐porphyrinic MOF with an unprecedented Ti‐oxo chain cluster was newly synthesized. The visible‐light‐induced photocatalytic activity of this MOF was demonstrated by its application to the generation of reactive oxygen species and the selective benzyl alcohol oxidation to give benzaldehyde. Titanium(IV)‐based metal‐organic frameworks (Ti‐MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single‐crystalline Ti‐carboxylate MOF (DGIST‐1) composed of an unprecedented Ti‐oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4‐carboxyphenyl)porphyrin). Preformed Ti‐oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti‐alkoxide precursors, thus, enabling the formation of the highly crystalline Ti‐MOF. The successfully activated DGIST‐1 exhibited a higher surface area (i.e., 1957.3 m2 g−1) than previously reported Ti‐MOFs due to its high crystallinity. Furthermore, the visible‐light‐responsive photocatalytic activity of DGIST‐1 was confirmed by the simultaneous generation of singlet oxygen (1O2) and superoxide (.O2−) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde. Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single-crystalline Ti-carboxylate MOF (DGIST-1) composed of an unprecedented Ti-oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4-carboxyphenyl)porphyrin). Preformed Ti-oxo clusters were used as Ti sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti-alkoxide precursors, thus, enabling the formation of the highly crystalline Ti-MOF. The successfully activated DGIST-1 exhibited a higher surface area (i.e., 1957.3 m g ) than previously reported Ti-MOFs due to its high crystallinity. Furthermore, the visible-light-responsive photocatalytic activity of DGIST-1 was confirmed by the simultaneous generation of singlet oxygen ( O ) and superoxide ( O ) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde. Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single-crystalline Ti-carboxylate MOF (DGIST-1) composed of an unprecedented Ti-oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4-carboxyphenyl)porphyrin). Preformed Ti-oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti-alkoxide precursors, thus, enabling the formation of the highly crystalline Ti-MOF. The successfully activated DGIST-1 exhibited a higher surface area (i.e., 1957.3 m2 g-1 ) than previously reported Ti-MOFs due to its high crystallinity. Furthermore, the visible-light-responsive photocatalytic activity of DGIST-1 was confirmed by the simultaneous generation of singlet oxygen (1 O2 ) and superoxide (. O2 - ) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single-crystalline Ti-carboxylate MOF (DGIST-1) composed of an unprecedented Ti-oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4-carboxyphenyl)porphyrin). Preformed Ti-oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti-alkoxide precursors, thus, enabling the formation of the highly crystalline Ti-MOF. The successfully activated DGIST-1 exhibited a higher surface area (i.e., 1957.3 m2 g-1 ) than previously reported Ti-MOFs due to its high crystallinity. Furthermore, the visible-light-responsive photocatalytic activity of DGIST-1 was confirmed by the simultaneous generation of singlet oxygen (1 O2 ) and superoxide (. O2 - ) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde. Titanium(IV)‐based metal‐organic frameworks (Ti‐MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single‐crystalline Ti‐carboxylate MOF (DGIST‐1) composed of an unprecedented Ti‐oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4‐carboxyphenyl)porphyrin). Preformed Ti‐oxo clusters were used as Ti 4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti‐alkoxide precursors, thus, enabling the formation of the highly crystalline Ti‐MOF. The successfully activated DGIST‐1 exhibited a higher surface area (i.e., 1957.3 m 2 g −1 ) than previously reported Ti‐MOFs due to its high crystallinity. Furthermore, the visible‐light‐responsive photocatalytic activity of DGIST‐1 was confirmed by the simultaneous generation of singlet oxygen ( 1 O 2 ) and superoxide ( . O 2 − ) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde. |
| Author | Park, Jinhee Park, Seonghun Chen, Ying‐Pin Keum, Yesub |
| Author_xml | – sequence: 1 givenname: Yesub surname: Keum fullname: Keum, Yesub organization: Daegu-Gyeongbuk Institute of Science & Technology (DGIST) – sequence: 2 givenname: Seonghun surname: Park fullname: Park, Seonghun organization: Daegu-Gyeongbuk Institute of Science & Technology (DGIST) – sequence: 3 givenname: Ying‐Pin surname: Chen fullname: Chen, Ying‐Pin organization: BioNova Scientific Inc – sequence: 4 givenname: Jinhee orcidid: 0000-0001-7755-5889 surname: Park fullname: Park, Jinhee email: jinhee@dgist.ac.kr organization: Daegu-Gyeongbuk Institute of Science & Technology (DGIST) |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/30203511$$D View this record in MEDLINE/PubMed |
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| Keywords | cluster compounds Ti-oxo chain cluster selective alcohol oxidation reactive oxygen species metal-organic frameworks |
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| Snippet | Titanium(IV)‐based metal‐organic frameworks (Ti‐MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We... Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We... |
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| SubjectTerms | Alcohols Benzaldehyde Benzyl alcohol Catalytic activity Chains Chemical industry cluster compounds Clusters Crystal structure Crystallinity Metal-organic frameworks Oxidation Photocatalysis reactive oxygen species selective alcohol oxidation Singlet oxygen Superoxide Ti-oxo chain cluster Titanium |
| Title | Titanium‐Carboxylate Metal‐Organic Framework Based on an Unprecedented Ti‐Oxo Chain Cluster |
| URI | https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fanie.201809762 https://www.ncbi.nlm.nih.gov/pubmed/30203511 https://www.proquest.com/docview/2126475372 https://www.proquest.com/docview/2102320966 |
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