RESEARCH ON CHEMICAL INTERMEDIATES
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2022
·Vol. 48
·期 3
·1181-1198
·
IF 3.134
Zhang Zhongze,Liu Zonghui,Gu Zhiyuan,Wen Zhe,Xue Bing
The catalytic transfer hydrogenation (CTH) reaction of ethyl levulinate (EL) with alcohol to γ-valerolactone (GVL) has been investigated over a series of Zr-based catalysts, including ZrO 2 , ZrP, Zrβ, ZrP/Hβ and ZrO 2 /HZSM-5. It is found that the simplest ZrO 2 was the most efficient for GVL production, giving an EL conversion as high as 97% and GVL selectivity of 91% after 7 h at 170 °C using 2-propanol as the hydrogen donor and solvent. The effects of reaction temperature, time and solvent on catalytic performance were investigated. Moreover, the kinetic behavior of CTH reaction of EL was also studied over ZrO 2 catalyst. The as-prepared ZrO 2 gives an Ea value of 32.9 kJ/mol, which is much lower than other catalysts in the literatures. Furthermore, those catalysts have been, respectively, characterized by XRD, IR, BET and NH 3 -TPD techniques to reveal the physical properties and structures of these materials. Correlating the catalyst performance with its physical and chemical properties uncovers that the higher pore diameter, lower total acidity and higher Lewis acid sites of catalyst surface would be the key to the catalyst performance. Graphical abstract
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高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2021
·
IF 5.455
Haibiao Yu,Xiu Jia,Peng Wang,Ying Xiong,Weijun Shan,Congge Zhang,Zhimeng Song
A series of x wt%Al-SBA-15 catalysts prepared by modified wetness impregnation was investigated for γ-valerolactone (GVL) decarboxylation to butene . It was found that the impregnation of Al species not only remained the ordered mesoporous structure of parent SBA-15, but also created large amounts of Brønsted and Lewis acid sites on the surface of catalyst. The considerable amount of solid acid sites and the suitable Brønsted/Lewis acid ratio endowed 2.23 wt%Al-SBA-15 catalyst an excellent catalytic performance. Under the optimized conditions, the GVL conversion and butene yield can reach 99.8% and 96.6% at 320 °C, respectively. Mechanism studies indicated that the decarboxylation of γ-protonated PEA controlled speed of the whole reaction. Moreover, the catalytic activity of regenerated 2.23 wt%Al-SBA-15 catalyst was satisfactory after eight cycle tests, and the butene yield could still reach 92.2%.
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
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高影响因子
FUEL PROCESSING TECHNOLOGY
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2022
·
IF 8.129
Yiwei Tang,Junyan Fu,Yicong Wang,Haixin Guo,Xinhua Qi
Hydrogenation of levulinic acid to γ-valerolactone is one of the important reactions for conversion of biomass into renewable fuels and chemicals. Ni-Zn non-noble bimetallic catalysts supported on ordered mesoporous carbon (Ni-Zn@OMC) were prepared by one-pot solvent evaporation induced self-assembly (EISA) method and used for hydrogenation of levulinic acid to γ-valerolactone (GVL) in water. A GVL yield of 93% was obtained over bimetallic Ni 1 -Zn 1 @OMC catalyst at 180 °C in 90 min reaction time, with a turnover frequency (TOF) of 686.4 h −1 . Compared with Ni@OMC, the incorporation of Zn metal leads to the formation of Ni-Zn alloy and high dispersion of Ni particle on the catalyst surface . NiO sites on the catalysts lowered competitive adsorption between H 2 and levulinic acid on Ni 0 sites, as well as the Ni-Zn alloy is beneficial to the activation of carbonyl group in levulinic acid, and they synergistically promote the hydrogenation of levulinic acid to 4-hydroxyvaleric acid (4-HVA). Zn content in the catalyst influences both the activity of Lewis acid sites and the ratio of Lewis acid to Brønsted acid sites, and the active sites of Ni δ– Zn δ+ can facilitates the weakening and cleavage of C-O in 4-HVA, both of them are beneficial to the dehydration of 4-HVA to GVL.
研究领域:
催化
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可再生能源
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化学工程
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材料科学
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高影响因子
AICHE JOURNAL
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2022
·Vol. 69
·期 2
·e17973
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IF 4.167
Hong Xu,Di Hu,Lu Lin,Man Zhang,Xin Li,Yongjian Zeng,Mahmoud Amer,Wenhao Luo,Kai Yan
The selective hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) is one of pivotal reactions in many of the biorefinery schemes for the production of value-added chemicals and biofuels. Herein, we have fabricated carbon-supported bimetallic NiCo catalysts based on the metal–organic framework (MOF) material via a pyrolysis method. The as-obtained Ni 1 Co 1 bimetallic catalyst outperforms monometallic counterparts in the catalytic performance of LA-to-GVL, with a nearly full conversion of LA and a GVL yield of 95.2%, in particular with an excellent catalyst stability up to seven consecutive runs at 160°C and 4 MPa H 2 . Based on a combined characterization study by employing advanced techniques, for example, extended x-ray absorption fine structure (EXAFS), high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), and electron paramagnetic resonance (EPR), we reveal that the enhanced catalytic performance, in particular the excellent stability, could be attributed to the formation of the bimetallic alloys, which efficiently alleviates the metal leaching and sintering during catalysis.
研究领域:
催化
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材料科学
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化学工程
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生物化学
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DOI
高影响因子
FUEL
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2023
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IF 7.4
Biao Yang,Ke Fan,Shanshan Yu,Rongguang Yang,Linfeng Zhang,Fuqing Zhang,Weijie Chi,Huadong Wu,Jia Guo
Deep eutectic solvents (DESs) are widely used in oxidative desulfurization (ODS) to produce clean fuel. However, some DESs with good ODS efficiencies are generally consisted of harmful components, and the ODS efficiencies of most DESs with green components need to be further improved. Herein, a DES with two natural compounds of γ-valerolactone (γ-Val) and formic acid (FA) was prepared and used in ODS. The hydrogen bond interaction of DES was characterized by FT-IR, 1 H NMR, DSC, and calculated by density functional theory (DFT) computation. The radical quenching experiments, EPR, and kinetic study were carried out to investigate the active radical and apparent activation energy of ODS process. The desulfurization efficiencies of γ-Val and FA (molar ratio 1: 4) DES was capable of reaching 100% of dibenzothiophene (DBT) removal within 100 min at an energy saving way of room temperature (25 °C) with a low O/S molar ratio of 2. When the temperature was raised to 70 °C and the O/S molar ratio was raised to 5, 100% sulfur removal of dibenzothiophene, 4,6-dimethyldibenzothiophene (4,6-DMDBT), and benzothiophene (BT) could be achieved in 4 min, 6 min, and 10 min respectively. DFT calculations revealed that the introduction of γ-Val could reduce the transition state energy barrier of ODS compared with a single FA ODS process. This work provides a novel high ODS efficiency DES with natural compounds, indicating the potential application of green DESs in ODS catalysts.
研究领域:
化学工程
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环境科学
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催化
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高影响因子
GREEN CHEMISTRY
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2017
·Vol. 19
·期 16
·3869-3879
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IF 9.125
Shurong Wang,Yuan Zhao,Haizhou Lin,Jingping Chen,Lingjun Zhu,Zhongyang Luo
For the purpose of building a green reaction system to produce furfural (FF), the conversion of two important pentoses from hemicellulose, namely xylose and arabinose, was investigated in an aqueous reaction system including a Lewis acidic ionic liquid as a catalyst and renewable γ-valerolactone (GVL) as a co-solvent. The results showed that the introduction of GVL greatly improved the reactivity of pentose and inhibited the secondary decomposition reaction of FF compared to a pure-water reaction system. NMR analysis suggested that the composition of pentose conformers was greatly altered towards a reactive distribution. The highest FF yields were 79.76% (from xylose) and 58.70% (from arabinose), which were obtained at 140 °C. The influence of reaction parameters on pentose conversion was also studied. A comparison between different reaction conditions suggested that arabinose had less reactivity than xylose, leading to its lower conversion rate and FF yield. Furthermore, xylan and real biomass materials were tested in the proposed reaction system, and decent FF yields of up to 69.66% (from xylan) and 47.96% (from corn stalk) were obtained.
研究领域:
生物化学
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绿色化学
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高影响因子
Molecular Catalysis
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2020
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IF 3.687
Na Ji,Zhenyu Liu,Xinyong Diao,Jinrong Bao,Zhihao Yu,Chunfeng Song,Qingling Liu,Degang Ma,Xuebin Lu
GVL (γ-valerolactone) is identified as an important biomass platform molecule due to its wide application. In this work, a series of novel supported Ni catalysts with different supports and Ni loading were synthesized via metal-organic chemical vapor deposition (MOCVD) method for the hydrogenation of EL (ethyl levulinate) to GVL. Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), nitrogen adsorption/desorption, inductively coupled plasma optical emission spectroscopy (ICP-OES) and transmission electron microscopy (TEM) were used to characterize the as-synthesized catalysts. The results showed that the 2 wt.% Ni/AC(MOCVD) presented superior catalytic activity when compared with the catalyst prepared by impregnation method. This behavior is explained in terms of the smaller Ni nanoparticles (4.28 nm) and higher dispersion on 2 wt.% Ni/AC(MOCVD). Among the catalysts, the 2 wt.% Ni/AC catalyst exhibited the best catalytic performance with 99.7 % EL conversion and 79.8 % GVL yield under 1 MPa initial H 2 pressure (measured at room temperature) at 250 °C for 2 h. In addition, the reaction conditions were optimized and the stability of the catalyst were also investigated. The insights gained from this study in the design of high dispersed Ni particles with smaller particle size via MOCVD method will facilitate the metal-catalyzed hydrogenation of EL to GVL.
研究领域:
化学工程
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生物质能源
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催化科学
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高影响因子
ACS Catalysis
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2016
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IF 9.307
Shanhui Zhu,Yanfeng Xue,Jing Guo,Youliang Cen,Jianguo Wang,Weibin Fan
The high-yield synthesis of the biofuel γ-valerolactone (GVL) is a challenging task, which currently stems from the depolymerization of cellulose to levulinic acid, followed by its hydrogenation. We have developed a novel integrated process for the production of GVL from hemicellulose without using liquid acids and external hydrogen. The hemicellulose feed underwent hydrolysis and consecutive dehydration to produce furfural over ZSM-5 catalyst. Subsequently, the formed furfural with 2-propanol performed tandem conversion to GVL over Au/ZrO2 catalyst combined with ZSM-5. This process gave a high yield of GVL under mild conditions: up to 61.5% based on hemicellulose. The outstanding performance was mainly ascribed to the strong interface interaction of Au with ZrO2 species, large amounts of medium-strength acid sites over ZSM-5, and efficient synergy between active metal and acid sites.
研究领域:
生物化学
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催化化学
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高影响因子
ACS Nano
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2025
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IF 16
Jingjing Cao,Wenji Zhan,Meng Ren,Yao Wang,Haifei Wang,Ni Zhang,Yuetian Chen,Tianfu Wang,Yanfeng Miao,Yixin Zhao
The application of promising perovskite light-emitting diodes (PeLEDs) faces a significant challenge known as efficiency roll-off, which refers to the decline in external quantum efficiency (EQE) at high current densities. This issue arises mainly from high trap densities in perovskite films and imbalanced carrier injection, which limit improvements in brightness and stability of PeLEDs. Here, we develop a green solvent strategy using γ-valerolactone (GVL) to suppress efficiency roll-off in PeLEDs. This strategy effectively slows down the crystallization kinetics, yielding cubic-phase formamidinium lead triiodide (α-FAPbI3) films with reduced trap states, enhanced charge carrier injection, and suppressed Auger recombination. As a result, we achieve a record radiance of 1411 W sr–1 m–2 for GVL-based PeLEDs. These PeLEDs exhibit a substantially reduced efficiency roll-off, maintaining an EQE above 20% even at a high current density of 900 mA cm–2. Our findings highlight the potential of the green solvent approach for developing high-brightness, high-efficiency PeLEDs for practical applications.
研究领域:
材料科学
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光电技术
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2025
·
IF 4.3
Chanjuan Yang,Shoukang Xiao,Liyu Chen,Yingwei Li,Kui Shen
γ-Valerolactone (GVL) as an important high-value chemical can be readily produced through the catalytic hydrogenation of renewable levulinic acid (LA). However, high reaction temperatures (70–240 ℃) and H 2 pressures (0.5–6 MPa) are usually required to achieve full LA conversion and desired GVL yield in previous studies. Herein, we report, for the first time, the ambient-condition upgrading of LA to GVL by rationally constructing a series of metallic–acidic Ru x Pt y /MIL-101 catalysts comprising RuPt-alloyed nanoparticles (NPs) and Lewis-acid sites within a chromium-based MOF (namely MIL-101). Benefiting from the favorable synergy between Ru and Pt in their alloyed NPs and abundant Lewis-acid sites in MIL-101, the best Ru 4 Pt 1 /MIL-101 featuring an optimized Ru/Pt molar ratio of 4:1 shows a complete LA conversion with > 99.9 % yield of GVL under unprecedented ambient temperature and pressure, affording a high turnover frequency (TOF) of 1480.5h −1 , which is 15.1 and 10.1 times that of its monometallic Pt/MIL-101 (98.3 h −1 ) and Ru/MIL-101 (146.7 h −1 ) counterparts, respectively. Detailed experiments and density functional theory (DFT) calculations suggest the RuPt-alloyed effect and Lewis-acid sites in Ru 4 Pt 1 /MIL-101 can optimize the adsorption energy of 4-hydroxyvaleric acid (HPA) to remarkably boosting its catalytic performance for this reaction.
研究领域:
催化
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绿色化学
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可再生能源
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材料科学
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化学工程
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高影响因子
BIOMASS & BIOENERGY
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2025
·
IF 5.8
Zonghui Liu,Xueting Zhu,Chao Cai,Jiayi Zheng,Bing Yan,Liangmin Ning,Dan Yang,Bing Xue
Developing conversion routes from lignocellulosic platform compounds to high-value chemicals is fundamental to advancing sustainable resource utilization in the bioeconomy. In this study, we designed a series of SBA-15-supported bifunctional catalysts with precisely tunable Lewis acid sites (LAS), Brønsted acid sites (BAS), and basic sites through strategic incorporation of hafnium species and heteropolyacids (HPAs), demonstrating their exceptional performance in the multi-step tandem conversion of furfural (FUR) to γ-valerolactone (GVL). HfO 2 was used LAS and basic sites to catalyze the transfer hydrogenation reaction of FUR and levulinate ester using 2-propanol as the H-donor. Complementary to this, HPA could catalyze the hydrolytic ring-opening of furans. The amount of LAS, BAS, and basic sites was adjusted by changing the ratio of HPA to HfO 2 and the types of HPA (phosphotungstic acid (HPW), phosphomolybdic acid (HPMo), silicotungstic acid (HSiW) and silicomolybdic acid (HSiMo)). The ratio of HPA to HfO 2 and types of HPA have a great influence on the catalytic performance, among which HPW/Hf-SBA-15_0.37 (W/Hf = 0.37) was identified as the best catalyst and presented the highest GVL selectivity (73.5 %) under optimized reaction conditions. The poison experiment (addition of benzoic acid, pyridine, or 2,6-lutidine to the reaction) indicated that both acidic and basic sites play important role in the FUR to GVL reaction. Moreover, by correlating the catalyst performance with the BAS/LAS ratio of catalysts, it can be found that the balance between the BAS and LAS is also the key to higher GVL selectivity.
研究领域:
催化
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绿色化学
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生物经济
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材料科学
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化学工程
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高影响因子
APPLIED CATALYSIS A-GENERAL
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2025
·
IF 4.8
Tinghao Han,Zhongdi Liu,Lincai Peng,Weipeng Song,Huai Liu,Wenlong Jia,Rui Zhang
The efficient production of γ-valerolactone (GVL) with high yield directly from xylose is of particular interest but remains a great challenge due to the long reaction path. We herein developed a facile catalytic system to directly convert xylose to GVL with a record-high yield of 54.3 %, employing β-zeolite supported Zr-based catalyst in 1,4-dioxane/isopropanol co-solvent. Using Zr(NO 3 ) 4 ·5 H 2 O as the Zr sources resulting in well-retained β-zeolite structure, larger surface area and pore volume and better dispersion of Zr species, as well as balanced acidic sites where higher amount of Brønsted acid sites promoted the ring-opening of furfural alcohol for this cascade reaction. Notably, the introduction of 1,4-dioxane facilitated the in situ formation of furfural (i.e. yield-determining step) by diluting the competitive adsorption behavior between isopropanol and xylose, allowing more xylose molecules to access the active center, thus promoting the sequential production of GVL with unexpectedly high yield. The present work provides a efficient and straightforward preparation of GVL from xylose, paving the pathway towards higher atom economy.
研究领域:
催化
·
绿色化学
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生物质转化
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化学工程
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高影响因子
危险品化学品经营许可证（带存储）