Journal of Cleaner Production
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2025
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IF 10
Hongguang Zhang,Zi Yu,Yongxin Liang,Tao Gan,Zuqiang Huang,Huayu Hu,Yanjuan Zhang
The utilization of organic molecules as in-situ hydrogen donors for producing γ-valerolactone (GVL) biofuel from biomass-derived levulinic acid (LA) represents one of the promising sustainable approaches. However, this process still faces challenges, including the difficult activation of the hydrogen source and the transport limitations of active hydrogen species. Herein, a Co-MnO/spontaneously polarized ceramic-carbon (Co-MnO/SPCE-C) composite catalyst, featuring a unique spontaneous polarization effect, was developed for catalytic transfer hydrogenation (CTH) of LA to GVL in the isopropanol/H 2 O (volume ratio = 1/19) cosolvent system. Co-MnO/SPCE-C contributed to an outstanding LA conversion of 99.9% and a favorable GVL yield of 93.5%, surpassing the performance achieved by comparative catalysts. Various characterization techniques demonstrate that SPCE with far-infrared emission and surface electric field increased the oxygen vacancies, thereby promoting hydrogen spillover and enhancing the properties of CoO x –MnO acidic sites. The 17 O NMR spectra reveal that SPCE activated water clusters by weakening the hydrogen bonding network. Moreover, D 2 O experiments show that SPCE facilitated the participation of water in the reaction. This work provides valuable insights into the development of an efficient strategy for producing GVL from LA. Before the catalyst can be considered for commercial applications, the focus in the future should be on a comprehensive computational analysis, long-term evaluation of catalyst stability, and additional industrial-scale testing.
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高影响因子
ACS Sustainable Chemistry & Engineering
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2022
·
IF 9.224
Yun Wang,Haimei Wu,Jiale Wang,Kaiyue Zhang,Yingxin Liu,Zuojun Wei
A highly effective transformation from renewable biomass and its derivatives into high-value-added chemicals and biofuels is important and challenging. Herein, a N-doped mesoporous carbon (NMC)-supported Ru catalyst developed by an incipient wetness impregnation method was reported for the reductive amination of levulinic acid (LA)/esters with amines to N-substituted 5-methyl-2-pyrrolidinones. A complete conversion of LA with a 99.8% yield of N-hexyl-5-methyl-2-pyrrolidinone (HMP) was achieved over 0.05 mol % Ru/NMC under mild conditions of 120 °C and 1.5 MPa H2 for 4 h, giving a high turnover frequency (3667 h–1). Furthermore, Ru/NMC exhibited superior stability and recyclability (reusable 21 cycles without loss of activity). The excellent performance of the Ru/NMC catalyst was mainly attributed to the introduction of N species to the mesoporous carbon, which not only improved the anchoring and the dispersion of Ru nanoparticles on the catalyst surface but also provided moderate basic sites and transferred electrons from NMC to Ru nanoparticles, as revealed by detailed characterizations. Additionally, the developed Ru/NMC catalytic system was applicable to LA/esters and various amines to afford the corresponding N-substituted 5-methyl-2-pyrrolidinones with excellent yields (80–99%).
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APPLIED ORGANOMETALLIC CHEMISTRY
·
2022
·Vol. 36
·期 5
·e6646
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IF 4.072
Yanyun Wang,Yuming Zhou,Jiehua Bao,Jiajia Wang,Yiwei Zhang,Xiaoli Sheng,Yuzhong Huang
Pt nanocatalysts have received enthusiastic attention in the field of clean energy technologies due to their high catalytic activity and selectivity. The growth size and dispersion of Pt particles play significant effects on the reaction activity, especially in high temperature catalytic reactions where catalysts are prone to deactivation due to agglomeration and sintering of Pt particles. Herein, the Pt nanoparticles were effectively stabilized on AIPO-18 molecular sieve by a biomolecule-mediated green synthesis method. Based on the biocompatibility and electrostatic synergy of carboxymethyl chitosan (CMC), a high degree of Pt nanoclusters dispersion in AIPO-18 zeolites was achieved. The hydroconversion of levulinic acid (LA)was carried out at 160°C and 2 MPa hydrogen pressure, and the LA conversion of Pt/AIPO-18 (5CMC) reached 95.2% and the selectivity of γ-valerolactone (GVL) was 97.9% after 2 h. Pt/AIPO-18 (5CMC) exhibited satisfactory results that superior to the initial reactivity of Pt/AIPO-18 (0CMC) after five runs.
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Biomass Conversion and Biorefinery
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2022
·
IF 4.05
Zhou Shuolin,Long Min,Wu Lu,Lei Min,Bai JunZhuo,Huang Keying,Liu XianXiang,Yin Dulin
Covalently bonded sulfamic acid on the titanate nanotubes (TNTs-N(SO 3 H)-(CH 2 ) 2 -NHSO 3 H) was designed and successfully fabricated by the post-synthesis modification method. The as-prepared catalyst was characterized by a variety of characterization techniques such as FT-IR, TEM, XRD, XPS, and TG-DTG. The catalytic activity of TNTs-N(SO 3 H)-(CH 2 ) 2 -NHSO 3 H was evaluated for the synthesis of n-butyl levulinate (BL) from levulinic acid (LA). It was found that the tube-like structure of the TNTs still maintained during the modification process, and Brønsted and Lewis acid sites can be efficiently immobilized on the TNTs. The effects of reaction factors such as reaction time, reaction temperature, and catalyst dosage on the esterification of LA were systematically studied. Under the optimal reaction conditions, a relatively high yield of BL (95.3%) was achieved for esterification of levulinic acid owing to the strong Brønsted acidic sites. Furthermore, the hybrid catalyst TNTs-N(SO 3 H)-(CH 2 ) 2 -NHSO 3 H was used at least five times without significant decrease in activity, and no leaching of the active species in hot filtration test was observed. Graphical abstract
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Sustainable Energy & Fuels
·
2020
·Vol. 4
·期 4
·2018-2025
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IF 5.503
Songyan Jia,Jiao Ma,Dongping Wang,Kangjun Wang,Qiang Zheng,Chunshan Song,Xinwen Guo
Levulinic acid (LA) is a promising renewable platform compound derived from biomass for the manufacture of various valuable chemicals, among which levulinate esters have been demonstrated to be good fuel additives. Many previous studies have focused on the production of short-chain levulinates for biofuels such as methyl and ethyl levulinates, but these esters suffer from some essential issues including a high oxygen content, low energy density (or heating value) and water solubility. Long-chain levulinate esters have similar structures to biodiesel. The long carbon chain may provide a higher carbon content and strong hydrophobicity, therefore improving the energy density and water insolubility. In this work, the synthesis of a long-chain levulinate ester, n-hexyl levulinate (HL), has been fast and efficiently achieved by the catalytic esterification of LA and 1-hexanol at low temperature. Tungsten hexachloride (WCl6) showed the most superior activity among the tested metal salt catalysts under mild conditions. A HL yield of ∼85% with almost complete LA conversion could be obtained at 50 °C after only 30 min. Other hexanols that have larger steric hindrances, such as 2-ethyl-1-butanol, 2-hexanol, 3-hexanol and cyclohexanol, could also promote efficient esterification with LA over the WCl6 catalyst, resulting in excellent product yields of ∼82–91%. The strategy applies to the efficient synthesis of longer chain levulinate esters such as n-octyl levulinate (OL) as well. The WCl6 catalyst was reusable several times in a consecutive batch reaction mode. The method reported herein offers a strategy for the efficient production of liquid fuels from LA, potentially bridging raw biomass feedstocks and terminal utilization of biobased products.
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Molecular Catalysis
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2020
·
IF 3.687
Yaowei Lu,Yongxing Wang,Yinghao Wang,Qiue Cao,Xiaoguang Xie,Wenhao Fang
A bifunctional Ru/(AlO)(ZrO) n catalyst was reported for efficient hydrogenation of levulinic acid to γ-valerolactone, an important and environmental-benign upgrading process of bio-platform compound. The optimal Ru/(AlO)(ZrO) 0.1 catalyst showed 100% yield to γ-valerolactone in water at 120 °C under 1 MPa H 2 , one of the best performances among Ru catalysts under mild conditions. And this catalyst also presented good stability and reusability. PXRD, TEM, XPS, CO chemisorption, CO adsorption DRIFT-IR, NH 3 -TPD and pyridine adsorption IR gave insights into the acidic property and surface synergy of the catalysts. Highly active electron-rich Ru 0 sites stabilized by strong metal-support interaction (SMSI) can effectively adsorb and activate molecular H 2 and C O bond in levulinic acid. Varying Zr/Al ratio and calcination temperature can rationally control the acid strength and acid sites distribution of support, and (AlO)(ZrO) 0.1 calcined at 400 °C exhibited the maximal proportion of Lewis acid sites. Ru 0 species and Lewis acid sites synergistically enhanced the conversion of levulinic acid and facilitated the intramolecular dehydration of 4-hydroxypentanoic acid as intermediate to γ-valerolactone ( i.e. , the rate-limiting step).
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Sustainable Energy & Fuels
·
2023
·Vol. 7
·期 11
·2645-2652
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IF 5.6
Rulu Huang,Yuan Cheng,Huai Liu,Lincai Peng,Junhua Zhang
It is incredibly challenging to design a catalyst with high activity for catalytic transfer hydrogenation (CTH) of levulinic acid (LvA) into gamma-valerolactone (GVL). In our previous work, we have designed a mesoporous acid-base bifunctional hybrid (Zr-FDCA) with high contents of Lewis acid (LA) and Lewis base (LB) sites from zirconium and 2,5-furandicarboxylic acid (FDCA) by using acetic acid as the modulator, which exhibited an outstanding performance in CTH of furfural into furfuryl alcohol. However, the catalytic performance was not satisfactory in CTH of LvA into GVL. Herein, we modified a Zr-FDCA hybrid with the introduction of phosphotungstic acid (HPWO). Comprehensive characterization revealed that HPWO could significantly affect the acidity, which afforded acid catalytic activity and introduced a Brønsted acid (BA) site. The synergistic effect between LA and BA sites resulted in the outstanding catalytic activity in CTH of LvA into GVL; a GVL yield of 95.4% with a high formation rate of GVL (12.72 mmol g−1 h−1) was obtained over Zr-FDCA-HPWO. Simultaneously, it also showed an ideal cycle stability and could be used for at least five consecutive runs with no significant loss in the catalytic activity.
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NANOTECHNOLOGY
·
2018
·Vol. 29
·期 7
·075708
·
IF 3.404
Hengcong Tao,Jingjing Ding,Chao Xie,Yunnan Gao,Jinliang Song,Zhenyu Sun
We demonstrate a facile and versatile method to grow Ru particles uniformly on pristine few-layer graphene (FLG) in supercritical diethylamine. In particular, a large number of Ru subnanometer clusters less than 1.0 nm were observed. The particle size can be tuned by manipulating the loading content of Ru and controlling the reaction temperature. The resulting Ru/FLG showed remarkably high activity, selectivity, and reusability towards the hydrogenation of levulinic acid to γ-valerolactone. This method is flexible, and can be extended to the synthesis of a variety of other ultrafine metal particles supported on FLG.
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PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Fengyi Zhou,Yurun Tian,Hongyuan Zhang,Yijun Yin,Zeyu Wang,Rui Qin,Yu Chen,Zhiyong Li,Tiancheng Mu
The rapid growth of spent lithium-ion batteries (LIBs) raises concerns over the supply chain of critical metals and environmental impacts, emphasizing the urgent need for efficient recycling technologies. Due to their potential to reduce the consumption of energy and avoid the use of corrosive acid, deep eutectic solvents (DESs) have been widely studied to selectively leach and recover valuable metals from spent LIBs. There is general agreement that DESs with high acidity, coordination, reducibility, and low viscosity could efficiently dissolve cathode materials. However, it is hard to design binary DES compositions to fulfill all of these requirements simultaneously. Herein, this study focuses on the design of ternary DESs, leveraging the synergistic effects of their components to achieve strong coordination and low viscosity, enhanced acidity, and reducibility to efficiently extract valuable metals. Specifically, ChCl/CuCl:4Levulinic acid demonstrated exceptional leaching capabilities, recovering over 90% of LiCoO2 within 10 min. Furthermore, to ensure the purity of recovered metal products, ChCl/LiCl:8Levulinic acid was investigated to realize the efficient leaching, recovery, and DES regeneration process. It was verified that ChCl/LiCl/8Levulinic acid has high leaching efficiency and good cycling stability and facilitates a convenient recycling process. Overall, this work demonstrates the potential of tailored ternary DESs for the efficient leaching of cathode materials and proposes a sustainable process to realize metal recovery from spent LIB cathode and DES regeneration.
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APPLIED CATALYSIS A-GENERAL
·
2025
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IF 4.8
Weimeng Cai,Haojie Du,Erju Wang,Yuting Qiang,Kunhong Hu,Jianhua Guo
The synthesis of value-added chemicals from renewable biomass is becoming increasingly important in the transition to a sustainable and low-carbon energy system. Herein, we demonstrate a solvent-polarity modulation strategy to engineer biomass-derived Cu-MOF using 2,5-furandicarboxylic acid (FDCA) as a renewable ligand, where tailored β/α ratios via Kamlet-Taft parameters balance nucleation-growth kinetics to optimize textural properties. Pyrolyzed Cu-MOF at 500 °C under a nitrogen atmosphere yield the Cu/C catalysts, which were subsequently employed in the selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). Among the various solvents used, the Cu-MOF precursor synthesized in a mixed solvent of methanol and N, N-dimethylformamide (DMF) demonstrated the highest catalytic performance, outperforming those synthesized in other solvents. This highlights the significant impact of solvent selection on the structure of Cu-MOF, which in turn affects their hydrogenation activity. Advanced characterization confirming that the uniform Cu dispersion (confirmed by HRTEM mapping) and Cu⁰/Cu⁺ electronic synergy (via Cu Auger analysis) enhanced hydrogenation performance. Additionally, the biomass-derived catalysts exhibited excellent durability. Overall, this research provides a promising approach to develop highly efficient catalysts using renewable ligands and demonstrates the potential of regulating catalyst properties through the strategic selection of solvents, as informed by Kamlet-Taft parameters.
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Journal of Materials Chemistry A
·
2025
·
IF 9.5
Xiaohao Liu,Dali Han,Jinming Xia,Dongxu Yan,Rui Diao,Fenglei Qi,Zhenyu Wang,Lei Yang,Xiang Wu,Peiyong Ma,Ying Zhang
Nanopore-confining strategy is an effective way to inhibit catalyst sintering and improve catalytic performance. However, the expensive material precursors and complex preparation process greatly limit the scale utilization of this particularly structured catalyst. Herein, nanopore-confined catalysts (Ni@PAC) with adjustable active species were successfully prepared by a very simple method exploiting the characteristics of phosphoric acid-activated biochar (PAC). The abundant phosphorous functional groups in PAC confined Ni well in pores and significantly inhibited sintering through the spatial-confined effect of nanopore. Moreover, the evolution and migration of P functional groups can be regulated by changing the reduction temperature, and the modulation of active species of Ni metal or nickel phosphide can be achieved. Using biomass-based levulinic acid hydrogenation as the probe reaction, it was found that the catalytic activity of 20Ni@PAC-600 was one order of magnitude higher than that of the non-phosphated 20Ni/ZAC-600 catalyst, and γ-valerolactone could be selectively prepared at near atmospheric pressure (1 bar). The formation of Ni2P and the spatial-confined effect of nanopore could be the main reasons for the high catalytic activity.
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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2020
·Vol. 95
·期 9
·2537-2548
·
IF 2.75
Liquan Zhang,Can Wang,Hairong Zhang,Haijun Guo,Lian Xiong,Hailong Li,Xuefang Chen,Xinde Chen
BACKGROUND Levulinic acid (LA) and furfural are important biomass-based platform compounds. During the preparation of LA and furfural from lignocellulosic biomass, other organic chemicals including sugars, formic acid, acetic acid, and acid-soluble lignin (ASL) will be produced simultaneously. Thus, the purification of LA and furfural is an important process. In this work, a series of glycidyl methacrylate (GMA) modified hyper-cross-linked resins were synthesized and the mechanism of pore formation of the resins was studied. Furthermore, the effect of their textural properties on adsorption performance towards LA and furfural was investigated. RESULTS The hyper-cross-linked resin modified with 50 wt% GMA (PC-4) achieved the best adsorption performance. The adsorption capacities of LA and furfural onto PC-4 were 100.81 and 40.22 mg g −1 , respectively, which were 2423.76% and 249.24% higher than the un-modified resin HQ-8, and 31.0% and 22.7% higher than its precursor PR-4. During desorption process, the average desorption ratio of LA and furfural were 94.96% and 97.86%, respectively. Moreover, PC-4 also showed a good adsorption performance towards formic acid, acetic acid, and ASL, while sugar loss rate was about 5%. CONCLUSION This study not only reported a potential adsorbent, PC-4, for the comprehensive utilization of sugarcane bagasse hydrolysate, but it also studied the relationship between synthesis conditions, resin structures, and its adsorption performance of GMA modified hyper-cross-linked resins, which provides a guidance for new adsorbent design. © 2020 Society of Chemical Industry
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