ACS Omega
·
2023
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IF 4.1
Ning Shi,Tianlang Zhu,Hongyan Zhang,Hongsheng Huang,Liang Zhou,Ying Liu,Riyang Shu
Catalytic conversion of cellulose into the novel platform molecule 2,5-hexanedione (HXD) is regarded as one feasible approach for high-value utilization of biomass resources. Here, we reported one efficient way of one-pot conversion of cellulose into HXD with high yield of 80.3% in H2O and tetrahydrofuran (THF) mixture within Al2(SO4)3 combined with Pd/C as a catalyst. In the catalytic reaction system, Al2(SO4)3 could catalyze the conversion of cellulose into 5-hydroxymethylfurfural (HMF), and Pd/C combined with Al2(SO4)3 could catalyze the hydrogenolysis of HMF into furanic intermediates such as 5-methylfurfuryl alcohol and 2,5-dimethylfuran (DMF) without causing over-hydrogenation of these furanic intermediates. These furanic intermediates were finally transformed into HXD catalyzed by Al2(SO4)3. Besides, the H2O/THF ratio could significantly influence the reactivity of the hydrolytic furanic ring-opening of the furanic intermediates. The catalytic system also showed excellent performance on the conversion of other carbohydrates (glucose and sucrose) into HXD.
研究领域:
生物质化学
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催化反应工程
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产品关联
DOI
PubMed
高影响因子
MOLECULES
·
2020
·Vol. 25
·期 11
·2475
·
IF 3.267
Yanliang Yang,Dexi Yang,Chi Zhang,Min Zheng,Ying Duan
The development of a simple and durable catalytic system for the production of chemicals from a high concentration of a substrate is important for biomass conversion. In this manuscript, 5-hydroxymethylfurfural (HMF) was converted to 1-hydroxy-2,5-hexanedione (HHD) using the combination of commercial Pd/C and acetic acid (AcOH) in water. The influence of temperature, H2pressure, reaction time, catalyst amount and the concentration of AcOH and HMF on this transformation was investigated. A 68% yield of HHD was able to be obtained from HMF at a 13.6 wt% aqueous solution with a 98% conversion of HMF. The resinification of intermediates on the catalyst was characterized to be the main reason for the deactivation of Pd/C. The reusability of the used Pd/C was studied to find that most of the activity could be recovered by being washed in hot tetrahydrofuran.Keywords:HMF;1-hydroxy-2,5-hexanedione;acetic acid;Pd/C;high concentration
研究领域:
化学工程
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生物质转化
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产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2021
·
IF 13.084
Ran Wang,Yanting Liu,Guangyi Li,Aiqin Wang,Xiaodong Wang,Yu Cong,Tao Zhang,Ning Li
Methylcyclopentadiene (MCPD) is a widely utilized intermediate in the synthesis of advanced aviation fuels and valuable chemicals. However, the low yield from fossil energy and the high price of MCPD greatly limit its application on a large scale. To fulfill the increasing market demand of MCPD, it is imperative to explore efficient and integrated technologies for the production of renewable MCPD from low cost and more available biomass. In this work, Zn3Mo2O9 was obtained via a simple precipitation method and demonstrated excellent catalytic performance for the direct synthesis of MCPD with 2,5-hexanedione (HD), a platform compound that can be directly produced by the selective hydrogenolysis of cellulose. Over it, a good molar yield of MCPD (65%) was obtained by the cascade intramolecular aldol condensation/selective hydrodeoxygenation reaction at 400 °C under atmospheric pressure. On the basis of the characterization results, the Zn3Mo2O9 catalyst has a higher specific BET surface area than the rest of the catalysts, which are favorable for the adsorption and mass transfer of the reactant. Meanwhile, the Zn3Mo2O9 catalyst also has relatively higher reducibility that will lead to the emergence of more oxygen vacancies (or Mo5+ species) under the investigated conditions. All of these characteristics lead to higher activity, better selectivity, and good stability of the Zn3Mo2O9 catalyst in the direct conversion of HD to MCPD. Because of its excellent hydrodeoxygenation performance, the Zn3Mo2O9 catalyst can also be used as the catalyst for the direct production of renewable dienes with other biomass-derived α,β-unsaturated ketones.
研究领域:
化学工程
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催化材料
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2016
·Vol. 18
·期 10
·3075-3081
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IF 8.506
Dezhang Ren,Zhiyuan Song,Lu Li,Yunjie Liu,Fangming Jin,Zhibao Huo
A novel approach for the production of 2,5-hexanedione (HDN) and 3-methyl-2-cyclopenten-1-one (3-MCO) from 5-hydroxymethylfurfural (HMF) by water splitting with Zn is reported for the first time. The use of high temperature water (HTW) conditions is the key for the efficient conversion of HMF to HDN and 3-MCO. Parameters regarding the Zn amount, temperature and reaction time are optimized and HDN and 3-MCO are produced in 27.3% and 30.5% yields, respectively. The roles of HTW and ZnO obtained by oxidation of Zn in water for the conversion of HMF, together with intermediate structures, are discussed to understand the mechanism of the reaction.
研究领域:
化学工程
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有机化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
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IF 7.3
Mengdi Li,Anyan He,Liheng Deng,Qingmao Yang,Haodong Chu,Chun Shen,Tianwei Tan
Catalytic conversion of cellulose in biomass into 2,5-hexanedione is a significant step for the production of biobased p-xylene (PX), and a precise understanding about the effect of the coexisting hemicellulose and lignin components is extremely essential and desirable, but still severely deficient. Herein, we investigate the above issue by catalytic tests, structural characterizations, and composition analysis. Catalytic tests confirm that the coexisting hemicellulose does not affect cellulose conversion and could be converted into 5-chloro-2-pentanone, while the lignin component plays a detrimental role. Lignin and the oligomers from lignin hydrogenolysis can block the catalytic active sites via deposition due to the strong interaction between lignin and Pd/C catalyst. Meanwhile, there is noncovalent interaction between lignin and cellulose, reducing the accessibility of cellulose to the catalytic active sites including the Pd/C and acidic sites. Basic treatment by NaOH aqueous solution could result in simultaneous removal of lignin and fracture of the biomass structure and hence higher accessibility for the Pd/C catalyst. When the biomass is treated by NaOH with the concentration of 1.0 wt %, the amount of lignin (8.3 wt %) is low enough and the structure is fractured enough to achieve the yield of HDO and DMF comparable to that using sole cellulose as the reactant.
研究领域:
生物质化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2025
·
IF 6.2
Fukun Li,Lin Shuai,Yuan Tian,Zheng Tian,QingYa Cao,Jinhang Dai,Song Wang,Haifeng Gong,Junjun Shi
Biomass refinery is considered as an attractive alternative to achieve global sustainability. Among its derivatives, 2,5-dimethyltetrahydrofuran (DMTHF) is a key biochemical that serves as an eco-friendly solvent, a fuel additive and an intermediate for organic synthesis. In this study, various metal triflates were employed as catalysts in the microwave-assisted upgrading of 2,5-hexanedione (2,5-HD) to DMTHF, utilizing alcohol as the hydrogen donor under H 2 -free conditions. Experimental results demonstrate that the product distribution of this cascade process is strongly influenced by both the catalyst and the alcohol. The complex (OTf) 3 Sc-OR···H, formed between Sc(OTf) 3 and isopropanol, features appropriate Lewis and Brønsted acidic strengths. This complex showed the best catalytic activity, giving 100 % 2,5-HD conversion and 92.5 % DMTHF yield at 180 °C after 80 min. The main reaction pathway refers to the sequential reduction of the two carbonyl groups of 2,5-HD to produce 5-hydroxy-2-hexanone and 2,5-hexanediol via transfer hydrogenation. This process is facilitated by Lewis acidic sites based on the classic MPV reduction mechanism. Subsequently, DMTHF is obtained by intramolecular dehydration of the two hydroxyl groups of 2,5-hexanediol catalyzed by Brønsted acidic sites. Notably, the Sc(OTf) 3 catalyst can be effectively recovered through vacuum distillation and reused for five cycles without significant loss of activity. Overall, this work presents an attractive route for producing DMTHF from 2,5-HD upgrading under H 2 -free conditions.
研究领域:
生物化学工程
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催化化学
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产品关联
DOI
高影响因子
Frontiers in Chemistry
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2022
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IF 5.545
Duan Ying,Wang Rui,Liu Qihang,Qin Xuya,Li Zuhuan
The conversion of 5-hydroxymethylfurfural (HMF) to 1-hydroxy-2,5-hexanedione (HHD) represented a typical route for high-value utilization of biomass. However, this reaction was often catalyzed by the noble metal catalyst. In this manuscript, W promoted Ni/Al2O3 was prepared as a noble-metal-free catalyst for this transformation. The catalysts were characterized by XRD, XPS, NH3-TPD, TEM, and EDS-mapping to study the influence of the introduction of W. There was an interaction between Ni and W, and strong acid sites were introduced by the addition of W. The W promoted Ni/Al2O3 showed good selectivity to HHD when used as a catalyst for the hydrogenation of HMF in water. The influences of the content of W, temperature, H2 pressure, reaction time, and acetic acid (AcOH) were studied. NiWOx/Al2O3-0.5 (mole ratio of W:Ni = 0.5) was found to be the most suitable catalyst. The high selectivity to HHD was ascribed to the acid sites introduced by W. This was proved by the fact that the selectivity to HHD was increased a lot when AcOH was added just using Ni/Al2O3 as catalysts. 59% yield of HHD was achieved on NiWOx/Al2O3-0.5 at 393 K, 4 MPa H2 reacting for 6 h, which was comparable to the noble metal catalyst, showing the potential application in the production of HHD from HMF.
研究领域:
催化化学
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可再生资源利用
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材料科学
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产品关联
DOI
PubMed
高影响因子
Reaction Chemistry & Engineering
·
2022
·Vol. 8
·期 1
·64-76
·
IF 5.2
Haosheng Xin,Haiyong Wang,Xiaohong Hu,Xiuzheng Zhuang,Long Yan,Chenguang Wang,Longlong Ma,Qiying Liu
Cellulose hydrolysis and further conversion to diketones and alcohols was performed with graphene layer encapsulated cobalt catalysts (Co@C) in phosphoric acid aqueous solution. A total of 60.5% yield of the products mainly including ethanol, 2,5-hexanedione (2,5-HD) and diols could be achieved in 0.06 M H3PO4 solution. A series of characterization methods such as XRD, XPS, TEM, TG-MS, BET, ICP, H2-TPD, NH3-TPD, and Raman were carried out to explore the catalyst formation mechanism and reaction activity. The results of the analysis indicated that the calcination temperature had a deep influence on the structure formation of the Co@C catalysts, thus leading to differences in the reaction activity. While the calcination temperature was determined at 700 °C, the Co@C catalyst meets with the requirements of optimal reaction activity, appropriate particle size, suitable surface area, and pore size. Besides, it was found that H3PO4 is not only favorable in cellulose hydrolysis but also cooperates with the Co@C catalyst in the hydrogenolysis of C–O bond and C–C bonds for the formation of products. This work provides a possible way for renewable cellulose conversion to diketone and alcohols over encapsulated non-noble metal catalyst combined with phosphoric acid aqueous solution.
研究领域:
化学工程
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催化
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可再生能源
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2022
·
IF 8.047
Yamei Lin,Fei Wang,Enxiang Ren,Fuying Zhu,Qiang Zhang,Guo-Ping Lu
The development of novel iron heterogeneous catalysts for organic synthesis is attractive and significant for both academic and industrial applications. A carbon-based iron heterogeneous catalyst (Fe@NSiC) comprising of different iron species including iron atomic single sites (FeN x Si y ), iron silicate and iron nanoparticles (NPs) has been developed. This catalyst exhibits high performance on the solvent-free synthesis of pyrroles from nitroarenes and 2,5-hexanedione via cascade reaction using HCOOH/DBU as the reductant. Si doping can increase Lewis acid sites of the catalyst and the electron density of iron sites, thus promoting the reaction. Furthermore, a set of pyrroles reflecting potential interest from the pharmaceutical perspective are obtained with moderate to excellent yields in this chemistry.
研究领域:
催化
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有机化学
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药物化学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Haodong Chu,Xinqiang Feng,Xue Wu,Jianting Song,Chun Shen,Tianwei Tan
Green and efficient upgrading of cellulose into p-xylene (PX) is critical to utilizing zymotic biomass wastes and complies with the “recycling economy”. Despite the tremendous efforts devoted by researchers, a bio-based PX production route that is compact with both technical and economic feasibility is extremely desirable but still remains a significant challenge. Here, we put forward a brand new two-step PX production route via 2,5-hexanedione (HDO), efficiently simplifying the whole process and cutting down the cost. We thoroughly investigated the effect of reaction conditions and took insight into the corresponding reaction mechanism in each step. The highest yields of 64 and 85% were achieved for HDO/2,5-dimethylfuran (DMF) and PX during the first and second steps, respectively. Furan ring hydrogenation and condensation into an oligomer comprise the main side reactions during the first step. In comparison with the most promising production route for bio-based PX at present (cellulose → glucose → fructose → 5-hydroxymethyl furfural (HMF) → DMF → PX), the as-proposed two-step route may exhibit tremendous advantages: streamlining with much less operating units and laying solid foundation for industrialized production by dexterously avoiding production and separation of HMF.
研究领域:
化学工程
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生化工程
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可再生能源
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可持续化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2017
·
IF 4.339
Yong-Jian Xu,Jing Shi,Wei-Peng Wu,Rui Zhu,Xing-Long Li,Jin Deng,Yao Fu
In this paper, Cp*Ir (III) Complex and acid co-catalyst system was developed. By using Cp*Ir and γ-Al 2 O 3 (Lewis acid), 5-hydroxymethylfurfural (5-HMF) can be converted efficiently to 3-hydroxymethyl cyclopentanone (HCPN). Meanwhile, Cp*Ir and Brønsted acid can promote conversion of 5-HMF to 1-Hydroxy-2,5-hexanedione (HHD). The effect of Lewis acid and Brønsted acid on the hydrogenation of furan derivatives was studied. Mechanism of conversion of 5-HMF to HCPN was discussed in detail and mechanism proposed by our predecessors was revised. Instead of being an intermediate for the formation of HCPN, it is believed that, HHD is a product of another reaction pathway. HHD condensed via Aldol reaction to produce 3-methylcyclopenten-2-ol-1-one (MCP) instead of HCPN. Under the promotion of Lewis acid, 5-HMF firstly convert to the precursor of HHD. After that, the reaction is through 4 π-electrocyclic ring closure process and HCPN was formed ultimately. Furthermore, we found that our Cp*Ir and acid co-catalyst system is suitable for a variety of furfural compounds. By using Cp*Ir, Brønsted acid can promote conversion of furfural compounds to straight chain ketones and Lewis acid can promote the rearrangement of furfural compounds to cyclopentanone derivatives.
研究领域:
催化
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有机化学
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化学工程
✓ 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）