Photo‐Induced Construction and Recovery of Cu + Sites in Metal–Organic Frameworks
The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu + can interact with molecules possessing unsaturated bonds like CO via π ‐complexation, while Cu 2+ doesn't have such ability. Mea...
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| Published in | Small (Weinheim an der Bergstrasse, Germany) Vol. 19; no. 40; p. e2302885 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
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01.10.2023
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| Abstract | The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu
+
can interact with molecules possessing unsaturated bonds like CO via
π
‐complexation, while Cu
2+
doesn't have such ability. Meanwhile, Cu
+
sites are easily oxidized to Cu
2+
, leading to the loss of activity. Despite great efforts, the development of a facile method to construct and recover Cu
+
sites remains a pronounced challenge. Here, for the first time a facile photo‐induced strategy is reported to fabricate Cu
+
sites in metal–organic frameworks (MOFs) and recover Cu
+
after oxidation. The Cu
2+
precursor was loaded on NH
2
‐MIL‐125, a typical visible‐light responsive Ti‐based MOF. Visible light irradiation triggers the formation of Ti
3+
from Ti
4+
in framework, which reduces the supported Cu
2+
in the absence of any additional reducing agent, thus simplifying the process for Cu
+
generation significantly. Due to
π
‐complexation interaction, the presence of Cu
+
results in remarkably enhanced CO capture capacity (1.16 mmol g
−1
) compared to NH
2
‐MIL‐125 (0.49 mmol g
−1
). More importantly, Cu
+
can be recovered conveniently via re‐irradiation when it is oxidized to Cu
2+
, and the oxidation‐recovery process is reversible. |
|---|---|
| AbstractList | The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu
can interact with molecules possessing unsaturated bonds like CO via π-complexation, while Cu
doesn't have such ability. Meanwhile, Cu
sites are easily oxidized to Cu
, leading to the loss of activity. Despite great efforts, the development of a facile method to construct and recover Cu
sites remains a pronounced challenge. Here, for the first time a facile photo-induced strategy is reported to fabricate Cu
sites in metal-organic frameworks (MOFs) and recover Cu
after oxidation. The Cu
precursor was loaded on NH
-MIL-125, a typical visible-light responsive Ti-based MOF. Visible light irradiation triggers the formation of Ti
from Ti
in framework, which reduces the supported Cu
in the absence of any additional reducing agent, thus simplifying the process for Cu
generation significantly. Due to π-complexation interaction, the presence of Cu
results in remarkably enhanced CO capture capacity (1.16 mmol g
) compared to NH
-MIL-125 (0.49 mmol g
). More importantly, Cu
can be recovered conveniently via re-irradiation when it is oxidized to Cu
, and the oxidation-recovery process is reversible. The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu+ can interact with molecules possessing unsaturated bonds like CO via π‐complexation, while Cu2+ doesn't have such ability. Meanwhile, Cu+ sites are easily oxidized to Cu2+, leading to the loss of activity. Despite great efforts, the development of a facile method to construct and recover Cu+ sites remains a pronounced challenge. Here, for the first time a facile photo‐induced strategy is reported to fabricate Cu+ sites in metal–organic frameworks (MOFs) and recover Cu+ after oxidation. The Cu2+ precursor was loaded on NH2‐MIL‐125, a typical visible‐light responsive Ti‐based MOF. Visible light irradiation triggers the formation of Ti3+ from Ti4+ in framework, which reduces the supported Cu2+ in the absence of any additional reducing agent, thus simplifying the process for Cu+ generation significantly. Due to π‐complexation interaction, the presence of Cu+ results in remarkably enhanced CO capture capacity (1.16 mmol g−1) compared to NH2‐MIL‐125 (0.49 mmol g−1). More importantly, Cu+ can be recovered conveniently via re‐irradiation when it is oxidized to Cu2+, and the oxidation‐recovery process is reversible. The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu + can interact with molecules possessing unsaturated bonds like CO via π ‐complexation, while Cu 2+ doesn't have such ability. Meanwhile, Cu + sites are easily oxidized to Cu 2+ , leading to the loss of activity. Despite great efforts, the development of a facile method to construct and recover Cu + sites remains a pronounced challenge. Here, for the first time a facile photo‐induced strategy is reported to fabricate Cu + sites in metal–organic frameworks (MOFs) and recover Cu + after oxidation. The Cu 2+ precursor was loaded on NH 2 ‐MIL‐125, a typical visible‐light responsive Ti‐based MOF. Visible light irradiation triggers the formation of Ti 3+ from Ti 4+ in framework, which reduces the supported Cu 2+ in the absence of any additional reducing agent, thus simplifying the process for Cu + generation significantly. Due to π ‐complexation interaction, the presence of Cu + results in remarkably enhanced CO capture capacity (1.16 mmol g −1 ) compared to NH 2 ‐MIL‐125 (0.49 mmol g −1 ). More importantly, Cu + can be recovered conveniently via re‐irradiation when it is oxidized to Cu 2+ , and the oxidation‐recovery process is reversible. The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu+ can interact with molecules possessing unsaturated bonds like CO via π-complexation, while Cu2+ doesn't have such ability. Meanwhile, Cu+ sites are easily oxidized to Cu2+ , leading to the loss of activity. Despite great efforts, the development of a facile method to construct and recover Cu+ sites remains a pronounced challenge. Here, for the first time a facile photo-induced strategy is reported to fabricate Cu+ sites in metal-organic frameworks (MOFs) and recover Cu+ after oxidation. The Cu2+ precursor was loaded on NH2 -MIL-125, a typical visible-light responsive Ti-based MOF. Visible light irradiation triggers the formation of Ti3+ from Ti4+ in framework, which reduces the supported Cu2+ in the absence of any additional reducing agent, thus simplifying the process for Cu+ generation significantly. Due to π-complexation interaction, the presence of Cu+ results in remarkably enhanced CO capture capacity (1.16 mmol g-1 ) compared to NH2 -MIL-125 (0.49 mmol g-1 ). More importantly, Cu+ can be recovered conveniently via re-irradiation when it is oxidized to Cu2+ , and the oxidation-recovery process is reversible.The adjustment of the valence state of metal ions is crucial for various applications because peculiar activity originates from metal ions with specific valence. Cu+ can interact with molecules possessing unsaturated bonds like CO via π-complexation, while Cu2+ doesn't have such ability. Meanwhile, Cu+ sites are easily oxidized to Cu2+ , leading to the loss of activity. Despite great efforts, the development of a facile method to construct and recover Cu+ sites remains a pronounced challenge. Here, for the first time a facile photo-induced strategy is reported to fabricate Cu+ sites in metal-organic frameworks (MOFs) and recover Cu+ after oxidation. The Cu2+ precursor was loaded on NH2 -MIL-125, a typical visible-light responsive Ti-based MOF. Visible light irradiation triggers the formation of Ti3+ from Ti4+ in framework, which reduces the supported Cu2+ in the absence of any additional reducing agent, thus simplifying the process for Cu+ generation significantly. Due to π-complexation interaction, the presence of Cu+ results in remarkably enhanced CO capture capacity (1.16 mmol g-1 ) compared to NH2 -MIL-125 (0.49 mmol g-1 ). More importantly, Cu+ can be recovered conveniently via re-irradiation when it is oxidized to Cu2+ , and the oxidation-recovery process is reversible. |
| Author | Li, Ke‐Di Li, Yu‐Xia Liu, Xiao‐Qin Sun, Lin‐Bing Qian, Xin‐Yu |
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| Keywords | cuprous species CO adsorption photoreduction valence adjustment recovery |
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| SubjectTerms | Chemical bonds Complexation Copper Light irradiation Metal-organic frameworks Nanotechnology Oxidation Reagents Recovery Reducing agents Valence |
| Title | Photo‐Induced Construction and Recovery of Cu + Sites in Metal–Organic Frameworks |
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