|
|
|
|
| LEADER |
01000caa a22002652 4500 |
| 001 |
NLM38042522X |
| 003 |
DE-627 |
| 005 |
20241204234927.0 |
| 007 |
cr uuu---uuuuu |
| 008 |
241118s2024 xx |||||o 00| ||eng c |
| 024 |
7 |
|
|a 10.1021/acs.langmuir.4c03636
|2 doi
|
| 028 |
5 |
2 |
|a pubmed24n1620.xml
|
| 035 |
|
|
|a (DE-627)NLM38042522X
|
| 035 |
|
|
|a (NLM)39556098
|
| 040 |
|
|
|a DE-627
|b ger
|c DE-627
|e rakwb
|
| 041 |
|
|
|a eng
|
| 100 |
1 |
|
|a Liu, Ting-Hao
|e verfasserin
|4 aut
|
| 245 |
1 |
0 |
|a Theoretical Insight into the Mechanism for the Cellobiose-to-Sorbitol Hydrogenation Over Diatomic Ru2/NC Catalyst
|
| 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 03.12.2024
|
| 500 |
|
|
|a published: Print-Electronic
|
| 500 |
|
|
|a Citation Status PubMed-not-MEDLINE
|
| 520 |
|
|
|a Ru/NC shows a good catalytic performance in cellobiose-to-sorbitol hydrogenation. However, the molecular origins of the selective orientation of the reaction pathway remain unclear. Here, we rationally designed the Ru2/NC catalyst, for which Ru2N8 V4 is preferred as the model. The hydrogenation mechanisms for the hydrogenation of β-cellobiose to sorbitol employing H2 as the H-source in aqueous solution have been investigated over Ru2@N8 V4 at the GGA-PBE/DNP level. For the hydrogenation of β-cellobiose to sorbitol, the optimal reaction pathway involves the ring-opening of cellobiose with H2O as a promoter and then the hydroreduction of aldehyde group, followed by the β-1,4-glycosidic bond hydrolysis. The selective orientation of the optimal reaction pathway originates from the dissociation of H2O on Ru-sites of Ru2@N8 V4 to form Brønsted acid (Ru-H+) and Brønsted base (Ru-OH-), which collaboratively promote the ring-opening. The rate-determining steps are relative to the β-1,4-glycosidic bond cleavage, where an applicable π-π interaction between reactant molecule and Ru2@N8 V4 is of critical importance. Kinetically, the β-1,4-glycosidic bond cleavage from cellubitol is more favorable than that from β-cellobiose. For the hydrogenation of β-cellobiose to cellubitol, the first ring-opening with H2O as promoter and then hydrogenation are kinetically superior to the direct hydrogenation and ring opening. This derives from its dissociation over Ru-sites to Ru-H and Ru-OH groups. Predictably, protic solvents (HOR) are readily dissociated into Ru-H and Ru-OR at Ru-sites, which can promote the ring-opening of pyran-ring. The present research outcomes should contribute to the theoretical understanding necessary for the development of novel supported noble metal N-doped carbon catalysts for the hydrogenation of cellulose
|
| 650 |
|
4 |
|a Journal Article
|
| 700 |
1 |
|
|a Gou, Jin-Tao
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Min, Han-Yun
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Zhang, Ming-Hui
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Hu, Chang-Wei
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Yang, Hua-Qing
|e verfasserin
|4 aut
|
| 773 |
0 |
8 |
|i Enthalten in
|t Langmuir : the ACS journal of surfaces and colloids
|d 1999
|g 40(2024), 48 vom: 03. Dez., Seite 25670-25678
|w (DE-627)NLM098181009
|x 1520-5827
|7 nnns
|
| 773 |
1 |
8 |
|g volume:40
|g year:2024
|g number:48
|g day:03
|g month:12
|g pages:25670-25678
|
| 856 |
4 |
0 |
|u http://dx.doi.org/10.1021/acs.langmuir.4c03636
|3 Volltext
|
| 912 |
|
|
|a GBV_USEFLAG_A
|
| 912 |
|
|
|a SYSFLAG_A
|
| 912 |
|
|
|a GBV_NLM
|
| 912 |
|
|
|a GBV_ILN_22
|
| 912 |
|
|
|a GBV_ILN_350
|
| 912 |
|
|
|a GBV_ILN_721
|
| 951 |
|
|
|a AR
|
| 952 |
|
|
|d 40
|j 2024
|e 48
|b 03
|c 12
|h 25670-25678
|