Molecular Catalysis
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2024
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IF 3.9
Zhijiao Huang,Yong Liu,Lungang Chen,Xinghua Zhang,Jianguo Liu,Chenguang Wang,Qi Zhang,Longlong Ma
2,5-dimethylfuran (DMF), a promising biomass-derived fuel, is synthesized via the hydrodeoxygenation of 5-hydroxymethylfurfural (HMF). This study focuses on the inherent activity of a 5Pt5Fe/C catalyst for HMF hydrodeoxygenation to DMF. The catalyst exhibited exceptional performance, achieving a remarkable DMF yield of 99.6 %. It displayed specific selectivity for C = O bond hydrogenation and C O bond cleavage in diverse substrates, producing high yield of 2-methylfuran from furfural and furfury alcohol, and high yield of toluene from benzaldehyde, benzyl alcohol. In-depth characterizations unveiled valuable insights into the 5Pt5Fe/C catalyst's properties, emphasizing a harmonious balance between metal and acid sites due to the interactive synergy between Pt and Fe species, enhancing hydrodeoxygenation activity. Additionally, the catalyst demonstrated satisfactory stability, maintaining a commendable DMF yield over five reaction cycles despite observed changes.
研究领域:
化学工程
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催化
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Handan Zhang,Liping Li,Xinhui Liu,Linshuai Duan,Xin Zhang,Lu Dong,Xiqin Liu,Pengcheng Li,Bohan Li,Mengzhu Xue,Guohui Xia
Humin, endowed with abundant redox functional groups, can be reduced anaerobically under dark. When reduced humin encounters O2, the possibility of ·OH formation arises. However, the exploration of ·OH generation mediated by humin has not been comprehensively conducted. The study found that O2 oxidized the reduced humin, generating 8.61 μmol/g of ·OH. After isolating humin using the methyl isobutyl ketone (MIBK) method, the lipid component was identified as the primary contributor to ·OH generation. Subsequent polar separation revealed that the lipid fraction extracted from the ethanol–water mixture with a volume ratio of 7:3 (LFEW7:3) played the most significant role in ·OH production. Further characterization confirmed that the simultaneous presence of aromatic C═C and C═O were the predominant features contributing to the ·OH generation. The ·OH generation experiments with humin-pyridine analogue compound demonstrated that polycyclic pyridine N (≥3 rings) played a significant role in promoting the ·OH generation. Most importantly, the study compared the ·OH production by humin and homologous humic acid, indicating that ·OH generated by humin was higher than that of humic acid. Overall, these affirmative findings manifested the overlooked role of humin in ·OH production and offered valuable insights into the mechanism of ·OH generation by humin in the dark.
研究领域:
环境科学
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生物化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysts
·
2021
·Vol. 11
·期 3
·370
·
IF 4.146
Yue Yang,Xiaochen Liu,Yuanjie Xu,Xing Gao,Yihu Dai,Yu Tang
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-Mo2C catalysts. The TOF of 1%Pd/α-MoC catalyst at 160 °C is 0.115 h−1and 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 H2dissociation 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.Keywords:hydrodeoxygenation;carbide;palladium;anisole;biomass;C–O bond cleavage
研究领域:
催化
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化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Yuqaio Ma,Xinping Ouyang,Lisha Zhao,Lifeng Li,Xueqing Qiu
The lignin-first strategy is a crucial approach for highly efficient depolymerization of lignin to produce aromatic monomers as the condensation of lignin occurred during the separating process which increased the difficulty in depolymerization. In this work, a cobalt atom clusters supported on nitrogen-doped carbon catalysts (Co/NC-15) was prepared by adjusting the dosage of melamine to control the morphology, structure, and pyridinic nitrogen content of the catalysts. DFT calculations based on lignin model showed that the doping of nitrogen increased the adsorption energy of the lignin on the supports and decreased the dissociation energy of C-O bonds. Under lignin first strategy, Co/NC-15 exhibited good ability to break C-O bonds at 220 °C of mild condition, in which 84.32 wt% of lignin in lignocellulosic biomass was converted into 40.62 wt% of aromatic monomers, while 84.02 wt% of cellulose was preserved. The atom clusters Co/NC-15 exhibited good catalytic activity to lignin depolymerization due to efficient cleavage of C-O bonds, and hence showed the promising prospect in potential industrial application.
研究领域:
生物化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL RESEARCH
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2021
·
IF 0.782
Chun-Jing Li
We report a direct cross-coupling reaction between (het)aryl pivalates/tosylates and di(het)arylzinc species in 2-methyltetrahydrofuran/N-methyl pyrrolidone (1:1), which occurs via C–O bond cleavage under microwave irradiation. The reaction takes place smoothly in short reaction times without the addition of any catalyst or ligand. The reaction is suitable for a broad scope of substrates and exhibits good functional group compatibility, utilizes a simple work-up procedure, and gives the desired products in high purity.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
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2018
·
IF 0
Jiang Li,Hui Sun,Jia-xing Liu,Jun-jie Zhang,Zhen-xing Li,Yao Fu
Lignin has recently attracted much attention as a promising resource to produce fuels and aromatic chemicals. The selective cleavage of C O bond while preserving the aromatic nature has become one of the major challenges in the catalytic valorization of lignin to aromatic chemicals. In this work, we report that the selective reductive cleavage of C O bond in lignin model compounds can be successfully achieved through heterogeneous iron catalysis. The hydrogenolysis of α-O-4 model linkage shows that the iron catalyst prepared by the simultaneous pyrolysis of iron acetate and 1,10-phenanthroline on activated carbon at 800 °C is the most active iron catalyst, affording phenol and toluene with yields of 95% and 90%, respectively. This aromatics selectivity is found to be much higher than that obtained over noble metal catalysts. The presence of N⋯Fe species as the active center of heterogeneous iron catalyst was confirmed by various technologies especially XPS and H 2 -TPR. For the β-O-4 model linkage, the vicinal OH group was essential for the iron-catalyzed hydrogenolysis of ether linkage. The oxidation of the α-carbon in the β-O-4 model compounds can significantly decrease the bond dissociation energy of ether linkage, giving depolymerization products in moderate to excellent yields.
研究领域:
催化化学
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可再生资源化学
✓ 已验证
产品关联
DOI
ACS Catalysis
·
2016
·
IF 9.307
Nengchao Luo,Min Wang,Hongji Li,Jian Zhang,Huifang Liu,Feng Wang
One of the challenges of depolymerizing lignin to valuable aromatics lies in the selective cleavage of the abundant C–O bonds of β-O-4 linkages. Herein we report a photocatalytic oxidation–hydrogenolysis tandem method for cleaving C–O bonds of β-O-4 alcohols. The Pd/ZnIn2S4 catalyst is used in the aerobic oxidation of α-C–OH of β-O-4 alcohols to α-C═O with 455 nm light, and then a TiO2–NaOAc system is employed for cleaving C–O bonds neighboring the α-C═O bonds through a hydrogenolysis reaction by switching to 365 nm light. Interestingly, the oxidation–hydrogenolysis tandem reaction can be conducted in one pot to offer ketones and phenols (up to 90% selectivity) via a dual light wavelength switching (DLWS) strategy. EPR and metal loading experiments elucidate that Ti3+ in TiO2 is formed in situ and is responsible for the photocatalytic hydrogenolysis through electron transfer from Ti3+ to the β-O-4 ketones.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Han-Bing Gao,Le-Le Qiu,Fa-Peng Wu,Jian Xiao,Yun-Peng Zhao,Jing Liang,Yong-Hui Bai,Fang-Jing Liu,Jing-Pei Cao
Catalytic hydrogenolysis of C O bonds in lignin provides a promising route to produce high value-added biofuels and chemicals. However, designing highly active and stable catalysts for this process is still a challenge. Herein, a series of Ni/Al 2 O 3 catalysts were synthesized by calcination and reduction of layered double hydroxide precursors, and their activities were evaluated in the catalytic conversion of lignin-derived compounds. Diphenyl ether was completely converted with a 100% monomeric selectivity (cyclohexane and cyclohexanol) over the optimized Ni/Al 2 O 3 -500 under the optimal conditions of 200 ℃, 0.5 MPa H 2 and 1.5 h, indicating the excellent catalytic activity in the cleavage of C O bonds of the catalyst. The excellent catalytic performances of Ni/Al 2 O 3 -500 were originated from its relatively large specific surface area, well-developed porosity, small crystallite size, high Ni 0 concentration and strong interaction between the active metal and support. The reusability experiments show that Ni/Al 2 O 3 -500 possesses a relatively high stability for six reuses. Moreover, various lignin model compounds can be completely converted to corresponding monomeric products over Ni/Al 2 O 3 -500, indicating the applicability of this ingenious catalyst. The application of the hydrotalcite-derived Ni-based catalysts with high activity and stability provides a promising approach for the efficient hydrogenolysis of lignin derivatives.
研究领域:
催化化学
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生物质转化
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL PHYSICS LETTERS
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2022
·
IF 2.719
Jie Xu,Feng Lin,Jingyu Wang,Yujie Wang
Photocatalytic cleavage of lignin C O bonds is a promising way to depolymerize lignin into aromatic value-added chemicals. However, the dispersibility of lignin in solvents and photocatalytic efficiency still face great challenges. Here, a micelle aqueous medium (CTAB-15) composed of hexadecyl trimethyl ammonium bromide and water was successfully prepared. 2-phenoxy-1-phenylethanol (lignin model compounds, PPol) and dioxanesolv poplar lignin have a good dispersion in CTAB-15. Compared to the previous reports, the highest photocatalytic efficiency can be obtained under optimal conditions by using the photocatalyst CdS. The main products formed by photocatalytic cleavage of lignin C O bonds are phenols and ketones. Mechanism studies show that CTAB-15 can provide sufficient hydrogen by photo-driven dissociation of water for photocatalytic cleavage of lignin C O bonds, which is critical to rapidly improving photocatalytic efficiency. The hydrogen, which is used to form acetophenone, comes from H 2 O and PPol. However, the hydrogen needed to form phenol comes only from PPol itself. In addition, the photocatalytic reaction follows a photogenerated electron-hole coupled redox process. This work develops a new direction for promoting the high-value utilization of lignin.
研究领域:
化学工程
·
可再生资源利用
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2024
·
IF 5.1
Zhenzhen Yang,Jiahui Cai,Zitong Shen,Jiaqi Bian,Jiashang Chen,Yao Xu,Zecheng Fang,Congkun Du,Xing Xiang,Juan Wang,Peng Yu,Ruiyao Cui,Siwen Bi
Carbonyl-containing polymers have been considered promising candidates as hosts in solid polymer electrolytes (SPEs) due to the reasonable chelating coordination with Li+, better antioxidation for high-voltage cathodes, and higher ion transference number compared with polyether SPEs. In this work, four polyesters of poly(octamethylene succinate), poly(hexmethylene succinate) (PHS), poly(butylene succinate), and polycaprolactone were investigated. In these SPEs with different −C═O/–CH2– ratios, PHS had the highest conductivity (σ) of 1.24 × 10–4 S/cm because of the excellent ability to deionize bis(trifluoromethane)sulfonimide (LiTFSI) up to 88.3 ± 3.2% at 70 °C and the lowest activation energy of Li+ ionic conduction. The effect of Li+/–C═O ratios (r) on the ionic conductivity can be clarified into low-, middle-, and high-concentrated regions. The decrease of PHS crystallinity due to LiTFSI solvation provided ion transport paths and mainly contributed to the improvement of ionic conductivity in the middle-concentrated region, while the solvation degree dominantly facilitated ionic conduction in the high-concentrated region and at higher temperatures. By combining the DFT simulation and polymer thermal analysis, we found the transition of Li+ coordination from multichain to single-chain bindings provided more flexible segment movement. It also proved that the sequence design of active groups in a polymer chain would be a promising strategy for stable and high-performance SPEs.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Jinghu Chen,Mingming Wang,Shude Zhang,Yaju Wang,Jingfeng Hua,Xiangtong Meng,Qineng Xia,Jieshan Qiu,Shaomin Liu
Glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO) is of significance in promoting the biomass valorization. To achieve the efficient conversion, the selective activation of the secondary C–O bonds in the glycerol is vital. In this work, we comparatively investigated the catalytic performances of Pt/Nb 2 W 3 O 14 catalyst for glycerol hydrogenolysis controlled at the reacting conditions of 140 °C and 40 bar. Compared to Pt/WO 3 and Pt/NbO x , the space–time yield (STY) of 1,3-PDO over Pt/Nb 2 W 3 O 14 catalyst can be improved by a factor of 13, reaching 596.4 mg g cat −1 h −1 . The cation ordering of Nb and W on atomic-scale were fully synergized their unique advantages, showing preferential adsorption of the secondary C–O bond under in-situ DRIFTS tracking. The prepared Nb 2 W 3 O 14 is a tetragonal tungsten bronze (TTB) type complex oxides which can effectively promote the dispersion and reduction of Pt nanoparticles. Such strong interaction between Nb 2 W 3 O 14 and Pt can coordinate the precise adsorption and activation of the secondary C–O bond, simultaneously triggering subsequent hydrogenation. Pt/Nb 2 W 3 O 14 affords an ultrahigh activity in glycerol hydrogenolysis to produce 1,3-PDO, tripling the record productivity that was previously reported of these Pt-W based catalysts. This study reported the development of highly synergistic catalyst based on efficient and selective activation of the secondary C–O bond, which can be extended to catalyst design for other biomass valorization.
研究领域:
催化化学
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生物质转化
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS COMMUNICATIONS
·
2013
·
IF 2.915
Shuai Leng,Xinde Wang,Xiaobo He,Lin Liu,Yue'e Liu,Xing Zhong,Guilin Zhuang,Jian-guo Wang
NiFe bimetallic catalyst shows an excellent activity and selectivity for the hydrodeoxygenation (HDO) of three typical model compounds of bio-oil. The conversion of furfuryl alcohol, benzene alcohol and ethyl oenanthate is 100, 95.48 and 97.89% at 400 °C and the yield to 2-methylfuran, toluene and heptane is 98.85, 93.49 and 96.11% at 0.1 ml/min flow speed and atmospheric pressure. It indicates that the major reaction pathway is the cleavage of C–O rather than C–C. After the catalytic HDO of bio-oil over NiFe/Al 2 O 3 catalyst, the heating value changes from 37.8 to 43.9 MJ/kg, the pH changes from 6.65 to 7.50.
研究领域:
能源化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）