Metal-Oxo Electronic Tuning via In Situ CO Decoration for Promoting Methane Conversion to Oxygenates over Single-Atom Catalysts
© 2024 Wiley‐VCH GmbH..
Direct methane conversion (DMC) to oxygenates at low temperature is of great value but remains challenging due to the high energy barrier for C-H bond activation. Here, we report that in situ decoration of Pd1-ZSM-5 single atom catalyst (SAC) by CO molecules significantly promoted the DMC reaction, giving the highest turnover frequency of 207 h-1 ever reported at room temperature and ~100 % oxygenates selectivity with H2O2 as oxidant. Combined characterizations and DFT calculations illustrate that the C-atom of CO prefers to coordinate with Pd1, which donates electrons to the Pd1-O active center (L-Pd1-O, L=CO) generated by H2O2 oxidation. The correspondingly improved electron density over Pd-O pair renders a favorable heterolytic dissociation of C-H bond with low energy barrier of 0.48 eV. Applying CO decoration strategy to M1-ZSM-5 (M=Pd, Rh, Ru, Fe) enables improvement of oxygenates productivity by 3.2-11.3 times, highlighting the generalizability of this method in tuning metal-oxo electronic structure of SACs for efficient DMC process.
| Medienart: |
E-Artikel |
|---|
| Erscheinungsjahr: |
2024 |
|---|---|
| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:63 |
|---|---|
| Enthalten in: |
Angewandte Chemie (International ed. in English) - 63(2024), 16 vom: 15. Apr., Seite e202315343 |
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
Xu, Weibin [VerfasserIn] |
|---|
| Links: |
|---|
| Themen: |
C−H bond activation |
|---|
| Anmerkungen: |
Date Revised 09.04.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
|---|
| doi: |
10.1002/anie.202315343 |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
NLM369150252 |
|---|
| LEADER | 01000caa a22002652 4500 | ||
|---|---|---|---|
| 001 | NLM369150252 | ||
| 003 | DE-627 | ||
| 005 | 20240409232525.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 240301s2024 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1002/anie.202315343 |2 doi | |
| 028 | 5 | 2 | |a pubmed24n1370.xml |
| 035 | |a (DE-627)NLM369150252 | ||
| 035 | |a (NLM)38425130 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a Xu, Weibin |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Metal-Oxo Electronic Tuning via In Situ CO Decoration for Promoting Methane Conversion to Oxygenates over Single-Atom Catalysts |
| 264 | 1 | |c 2024 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ƒaComputermedien |b c |2 rdamedia | ||
| 338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Date Revised 09.04.2024 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2024 Wiley‐VCH GmbH. | ||
| 520 | |a Direct methane conversion (DMC) to oxygenates at low temperature is of great value but remains challenging due to the high energy barrier for C-H bond activation. Here, we report that in situ decoration of Pd1-ZSM-5 single atom catalyst (SAC) by CO molecules significantly promoted the DMC reaction, giving the highest turnover frequency of 207 h-1 ever reported at room temperature and ~100 % oxygenates selectivity with H2O2 as oxidant. Combined characterizations and DFT calculations illustrate that the C-atom of CO prefers to coordinate with Pd1, which donates electrons to the Pd1-O active center (L-Pd1-O, L=CO) generated by H2O2 oxidation. The correspondingly improved electron density over Pd-O pair renders a favorable heterolytic dissociation of C-H bond with low energy barrier of 0.48 eV. Applying CO decoration strategy to M1-ZSM-5 (M=Pd, Rh, Ru, Fe) enables improvement of oxygenates productivity by 3.2-11.3 times, highlighting the generalizability of this method in tuning metal-oxo electronic structure of SACs for efficient DMC process | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a C−H bond activation | |
| 650 | 4 | |a direct methane conversion | |
| 650 | 4 | |a heterolytic dissociation of C−H bond | |
| 650 | 4 | |a molecular decoration | |
| 650 | 4 | |a single-atom catalysts | |
| 700 | 1 | |a Liu, Han-Xuan |e verfasserin |4 aut | |
| 700 | 1 | |a Hu, Yue |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Zhen |e verfasserin |4 aut | |
| 700 | 1 | |a Huang, Zheng-Qing |e verfasserin |4 aut | |
| 700 | 1 | |a Huang, Chuande |e verfasserin |4 aut | |
| 700 | 1 | |a Lin, Jian |e verfasserin |4 aut | |
| 700 | 1 | |a Chang, Chun-Ran |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Aiqin |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Xiaodong |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Tao |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Angewandte Chemie (International ed. in English) |d 1964 |g 63(2024), 16 vom: 15. Apr., Seite e202315343 |w (DE-627)NLM000105422 |x 1521-3773 |7 nnns |
| 773 | 1 | 8 | |g volume:63 |g year:2024 |g number:16 |g day:15 |g month:04 |g pages:e202315343 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1002/anie.202315343 |3 Volltext |
| 912 | |a GBV_USEFLAG_A | ||
| 912 | |a GBV_NLM | ||
| 951 | |a AR | ||
| 952 | |d 63 |j 2024 |e 16 |b 15 |c 04 |h e202315343 | ||