Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole
Hydrodeoxygenation (HDO) is one of the promising catalytic routes for converting biomass derived molecules to high value products. A key step of HDO is the cleavage of an aromatic C–O bond to accomplish the deoxygenation step, however, which is energetically unfavorable. Herein, we report a series o...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-03-01
|
| Series: | Catalysts |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4344/11/3/370 |
| _version_ | 1797541609166864384 |
|---|---|
| author | Yue Yang Xiaochen Liu Yuanjie Xu Xing Gao Yihu Dai Yu Tang |
| author_facet | Yue Yang Xiaochen Liu Yuanjie Xu Xing Gao Yihu Dai Yu Tang |
| author_sort | Yue Yang |
| collection | DOAJ |
| description | Hydrodeoxygenation (HDO) is one of the promising catalytic routes for converting biomass derived molecules to high value products. A key step of HDO is the cleavage of an aromatic C–O bond to accomplish the deoxygenation step, however, which is energetically unfavorable. Herein, we report a series of palladium (Pd)-incorporated α-phase of molybdenum carbide (α-MoC) mesoporous composites for enhanced HDO activity of a biomass model molecule, anisole. The catalysts, x%Pd/α-MoC (x% is the molar ratio of Pd/Mo), were investigated by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption (TPD), Brunauer–Emmett–Teller (BET), Raman, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques. Pd is highly dispersed on α-MoC when x% ≤ 1%, but aggregate to form nanoparticles when x% = 5%. The x%Pd/α-MoC catalysts (x% ≤ 1%) show enhanced HDO activity in terms of turnover frequency (TOF) and apparent activation energy barrier (Ea) compared with α-MoC and β-Mo<sub>2</sub>C catalysts. The TOF of 1%Pd/α-MoC catalyst at 160 °C is 0.115 h<sup>−1</sup> and the Ea is 48.2 kJ/mol. Moreover, the direct cleavage of aromatic C–O bond is preferred on 1%Pd/α-MoC catalyst. The enhanced HDO activity is attributed to superior H<sub>2</sub> dissociation ability by the highly dispersed Pd sites on carbide. This work brings new insights for rational design of the catalyst for selective C–O bond activation. |
| first_indexed | 2024-03-10T13:19:18Z |
| format | Article |
| id | doaj.art-6cf46ccbff1a4a959ee578014b61f22f |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-10T13:19:18Z |
| publishDate | 2021-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-6cf46ccbff1a4a959ee578014b61f22f2023-11-21T10:11:05ZengMDPI AGCatalysts2073-43442021-03-0111337010.3390/catal11030370Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of AnisoleYue Yang0Xiaochen Liu1Yuanjie Xu2Xing Gao3Yihu Dai4Yu Tang5Institute of Molecule Catalysis and In-Situ/Operando Studies, College of Chemistry, Fuzhou University, Fuzhou 350108, ChinaInstitute of Molecule Catalysis and In-Situ/Operando Studies, College of Chemistry, Fuzhou University, Fuzhou 350108, ChinaInstitute of Molecule Catalysis and In-Situ/Operando Studies, College of Chemistry, Fuzhou University, Fuzhou 350108, ChinaInstitute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaInstitute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, ChinaInstitute of Molecule Catalysis and In-Situ/Operando Studies, College of Chemistry, Fuzhou University, Fuzhou 350108, ChinaHydrodeoxygenation (HDO) is one of the promising catalytic routes for converting biomass derived molecules to high value products. A key step of HDO is the cleavage of an aromatic C–O bond to accomplish the deoxygenation step, however, which is energetically unfavorable. Herein, we report a series of palladium (Pd)-incorporated α-phase of molybdenum carbide (α-MoC) mesoporous composites for enhanced HDO activity of a biomass model molecule, anisole. The catalysts, x%Pd/α-MoC (x% is the molar ratio of Pd/Mo), were investigated by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption (TPD), Brunauer–Emmett–Teller (BET), Raman, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques. Pd is highly dispersed on α-MoC when x% ≤ 1%, but aggregate to form nanoparticles when x% = 5%. The x%Pd/α-MoC catalysts (x% ≤ 1%) show enhanced HDO activity in terms of turnover frequency (TOF) and apparent activation energy barrier (Ea) compared with α-MoC and β-Mo<sub>2</sub>C catalysts. The TOF of 1%Pd/α-MoC catalyst at 160 °C is 0.115 h<sup>−1</sup> and the Ea is 48.2 kJ/mol. Moreover, the direct cleavage of aromatic C–O bond is preferred on 1%Pd/α-MoC catalyst. The enhanced HDO activity is attributed to superior H<sub>2</sub> dissociation ability by the highly dispersed Pd sites on carbide. This work brings new insights for rational design of the catalyst for selective C–O bond activation.https://www.mdpi.com/2073-4344/11/3/370hydrodeoxygenationcarbidepalladiumanisolebiomassC–O bond cleavage |
| spellingShingle | Yue Yang Xiaochen Liu Yuanjie Xu Xing Gao Yihu Dai Yu Tang Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole Catalysts hydrodeoxygenation carbide palladium anisole biomass C–O bond cleavage |
| title | Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole |
| title_full | Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole |
| title_fullStr | Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole |
| title_full_unstemmed | Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole |
| title_short | Palladium-Incorporated α-MoC Mesoporous Composites for Enhanced Direct Hydrodeoxygenation of Anisole |
| title_sort | palladium incorporated α moc mesoporous composites for enhanced direct hydrodeoxygenation of anisole |
| topic | hydrodeoxygenation carbide palladium anisole biomass C–O bond cleavage |
| url | https://www.mdpi.com/2073-4344/11/3/370 |
| work_keys_str_mv | AT yueyang palladiumincorporatedamocmesoporouscompositesforenhanceddirecthydrodeoxygenationofanisole AT xiaochenliu palladiumincorporatedamocmesoporouscompositesforenhanceddirecthydrodeoxygenationofanisole AT yuanjiexu palladiumincorporatedamocmesoporouscompositesforenhanceddirecthydrodeoxygenationofanisole AT xinggao palladiumincorporatedamocmesoporouscompositesforenhanceddirecthydrodeoxygenationofanisole AT yihudai palladiumincorporatedamocmesoporouscompositesforenhanceddirecthydrodeoxygenationofanisole AT yutang palladiumincorporatedamocmesoporouscompositesforenhanceddirecthydrodeoxygenationofanisole |