CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Chunrui Rong,Dongxia Yan,Jiabao Li,Jian Feng,Jiayu Xin,Qing Zhou,Yi Li,Junli Xu,Xingmei Lu
The increase in the usage of polyethylene terephthalate (PET) leads to the generation of a large amount of waste, which may cause carbon emissions and waste of petroleum resources. The methanolysis method has attracted global attention, but limited by high reaction temperature and excessive use of methanol. We report here an efficient catalyst, tetramethylguanidine/1,5-diazabicyclo[4.3.0]-5-non-ene (TMG/DBN), converting waste PET into regenerated dimethyl terephthalate (rDMT) under 100 °C with almost equivalent methanol, achieving 100 % PET conversion and 93.1 % yield of rDMT. A series of analytical methods and theoretical calculations were used to reveal the enhanced interaction between the catalyst and reactants, which facilitates the degradation of PET at low methanol dosages. In addition, a kinetic model was also developed with a relatively low activation energy of 84.9 kJ/mol. This work provides an effective strategy for the up-grading recycling of waste PET under mild reaction conditions.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2024
·
IF 4.7
Yingdan Ye,Han Wang,Yibin Zhang,Huaiyuan Zhao,Weichen Du,Ping Chen,Zhaoyin Hou
Chemical upcycling of end-of-life plastics is an economically and environmentally feasible way to tackle plastics crisis. Among them, methanol alcoholysis of polylactic acid (PLA) is a promising approach, which can produce methyl lactate (MLA) that can be further converted to lactide to achieve a sustainable development. In this work, a series of WO x /ZrP catalysts with WO x active sites in low coverage and high surface area were synthesized via anchoring WO x species on the surface of zirconium phosphate (ZrP). Characterizations indicated that the strong interaction between WO x and ZrP promoted the formation of WO x active sites in low coverage. In particular, 10 %WO x /ZrP catalyst was highly active and stable for the alcoholysis of PLA plastics under mild conditions due to the abundant WO x active sites and strong acidity. The yield of MLA over 10 %WO x /ZrP catalyst reached 94.5 % within 4 h at 160 °C, which was superior to the performance of traditional solid acids ( α -ZrP, HZSM-5, H β and Amberlyst-45). In addition, 10 %WO x /ZrP was versatile for the alcoholysis of discarded PLA-based products and could be recycled at least five times. The prominent performance of 10 %WO x /ZrP catalyst and the possible reaction mechanism were discussed.
研究领域:
化学工程
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 23
·期 4
·1871-1882
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IF 10.182
Xiaoling Qu,Guangyuan Zhou,Rui Wang,Bolei Yuan,Min Jiang,Jun Tang
Alcoholysis is a potential method for the degradation of polyesters to their precursor building blocks, which can then be polymerized again to form new qualified polyester materials. This method therefore makes recycling possible in a permanent polymer–monomer–polymer loop. In this study, a series of metal-free tetrabutylphosphonium-based ionic liquids (ILs) were prepared as catalysts for the methanolysis of poly(ethylene 2,5-furandicarboxylate) (PEF), which is well known as an ideal alternative to the petroleum-based plastic poly(ethylene terephthalate) (PET). It was found that anions with stronger electronegativity were more efficient for the methanolysis of PEF. By adjusting the structures of the anions and cations of ILs, 1-butyl-3-methylimidazole acetate ([BMIm][OAc]) exhibited excellent catalytic activity in the methanolysis of PEF. The optimization of reaction parameters enabled the [BMIm][OAc]-catalyzed methanolysis of PEF with nearly 100% PEF degradation and a 77.6% dimethyl furan-2,5-dicarboxylate (DMFD) yield at 130 °C for 30 min. Furthermore, [BMIm][OAc] could keep high-activity after using for six times under the optimum conditions. Assisting with 1H NMR, FT-IR and density functional theory (DFT) calculations, an in-depth study was performed on the feasible synergetic catalytic mechanism of [BMIm][OAc] for the methanolysis of PEF, induced by hydrogen bonds formed between reactants and [BMIm][OAc]. Finally, on the basis of experimental results and scanning electron microscopy (SEM), it was confirmed that PEF with the spiral motif could be degraded under milder conditions than PET. Therefore, this strategy of using adjustable cation and anion structures in ILs provides an opportunity to develop other more efficient ILs for the alcoholysis of furan-based polymers via a green and mild pathway.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
POLYMER
·
2025
·
IF 4.5
Leqing He,Shuangbai Li,Chongpin Huang
In the context of composite materials that elude classification via conventional pretreatment methodologies such as crushing, granulating, and flotation—specifically within the domains of food packaging, construction materials, and engineering plastics—this research employed a one-step methanolysis-separation technique for the graded recycling of polypropylene (PP), polyethylene (PE), and polyethylene terephthalate (PET) in mixed plastics. Employing methanol as the reaction solvent, the benign and eco-friendly ionic liquid BMIMOH as the catalyst for the degradation of PET. PET was methanolized to produce dimethyl terephthalate (DMT), while PP and PE remained highly stable, were separated after the reaction, and subjected to subsequent recycling. The stability of PP and PE under methanolysis conditions was revealed through structural and thermodynamic analyses. Single-factor analysis and response surface methodology were employed to determine the optimal conditions for the methanolysis reaction. Additionally, the impact of different contents of PP and PE on the recovery of PET from the mixed plastics during the swelling-condensation process at high temperatures was explored. Under the optimal conditions, the yield of DMT was 94 % for the degradation of single PET, and when the ratio of PET in the mixed plastics was 50 %, the yield of DMT could still reach 90 %.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
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2015
·Vol. 5
·期 48
·38783-38791
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IF 3.84
Junfeng Feng,Jianchun Jiang,Junming Xu,Zhongzhi Yang
One-pot acid-catalyzed methanolysis was applied to the liquefaction of biomass to obtain a high molar yield of methyl-D-glucoside at moderate temperature in a short time. A high bamboo conversion ratio (85 wt%) of bamboo and high molar yield of methyl-D-glucoside (40.6 mol%) were achieved. The conditions for high yield were methanol/bamboo mass ratio of 7 (350 mL methanol and 40 g bamboo), 2.0 wt% of catalyst, reaction temperature of 200 °C and reaction time of 10 min. Both hemicelluloses and cellulose (holocellulose) in the lignocellulosic biomass can convert into methyl-D-glucoside, a key and stable product. Methanolysis of biomass proved more efficient than its hydrolysis with an acid catalyst under similar reaction conditions, in water glucose yields were reduced to only 2–8 mol%.
研究领域:
生物化学
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可再生资源工程
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2017
·Vol. 10
·期 4
·710-715
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IF 4.803
Liang Cui,Xueying Cao,Xuping Sun,Wenrong Yang,Jingquan Liu
Graphical Pick of the bunch : A bunch-like CuO nanowire array on copper foam (b-CuO NA/CF) is obtained by a facile and economical method. This nanowire array behaves as an efficient and durable catalyst for hydrogen generation from the controlled methanolysis of ammonia borane (AB). The dehydrogenation of ammonia borane (AB) is an effective method to produce and store hydrogen, but efficient, durable, and low-costing dehydrogenation catalysts are lacking. In this work, we successfully prepared a self-supported bunch-like copper oxide nanowire array on copper foam (b-CuO NA/CF) through a facile in situ wet oxidation and annealing method. b-CuO NA/CF shows high catalytic activity for the methanolysis of AB with an initial turnover frequency of 13.3 mol mol CuO −1 min −1 and an activation energy of 34.7 kJ mol −1 . Moreover, this self-supported bunch-like nanoarray catalyst could be easily separated from fuel solutions with excellent stability and maintained its activity even after prolonged use. It is thus an efficient, economical, and durable catalyst for hydrogen fuel cells.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
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2024
·
IF 6.9
Zhongqing Shen,Zixian Jia,Kunpeng Yu,Jing Xie,Lijiao Qin,Lin Gao,Baozhong Li,Xuehai Wang,Jianzhong Yin
Depolymerization shows promise as a strategy for converting waste plastic into monomers that can be used for repolymerization. However, catalytic approaches would be more complex and expensive due to catalyst separation, recovery, and recycling. Here, we present a CO 2 -enhanced subcritical methanolysis method without catalyst that can generate monomer from poly(ethylene terephthalate)(PET). The synergistic effect of CO 2 on the subcritical methanolysis process for PET depolymerization was investigated including the CO 2 initial pressure, reaction temperature and reaction time. Under subcritical conditions, the optimal reaction parameters with PET conversion ratio of 100% and DMT yield of 79.1% are as follows: temperature of 220℃, methanol to PET mass ratio of 6:1 and reaction time of 50 min. Moreover, through the analysis of experimental data, it was concluded that the depolymerization reaction follows a first-order kinetics, with the reaction rate being 2–3 times faster than the traditional process. However, the apparent activation energy for both reactions is found to be similar, with values of 135.1 kJ·mol −1 and 146.2 kJ·mol −1 , respectively.
研究领域:
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
NANOTECHNOLOGY
·
2014
·Vol. 26
·期 2
·025401
·
IF 3.672
Pengyao Li,Zhengli Xiao,Zhaoyan Liu,Jiale Huang,Qingbiao Li,Daohua Sun
A low-cost and facile route has been developed for the synthesis of monodisperse CuPd nanoparticles with tunable composition. (Scanning transmission electron microscopy-energy-dispersive x-ray spectroscopy) STEM-EDX results verified the structure of the alloy for the obtained nanoparticles. These CuPd nanoparticles supported on carbon were active catalysts for hydrogen generation from the methanolysis of ammonia borane (AB) at room temperature, and their activities were closely related with the compositions. Cu48Pd52 NPs exhibited the highest activity among the tested catalysts. Moreover, their activity can be further improved by thermal annealing at 300 °C under nitrogen flow, with a very high total turnover frequency value of 53.2 min−1. The reusability test indicated that the Cu48Pd52/C catalyst retains 86% of its initial activity and 100% conversion after 8 cycles. The catalyst, which features lost cost and high efficiency, may help move forward the practical application of AB as a sustainable hydrogen storage material.
研究领域:
材料科学
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化学工程
·
能源技术
✓ 已验证
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Yufa Feng,Xuefeng Zhang,Youxiang Shao,Xiaodong Chen,Huize Wang,Junhao Li,Ming Wu,Huafeng Dong,Quanbing Liu,Hao Li
Rational construction of inexpensive, highly efficient, and stable catalysts for ammonia borane (AB) methanolysis is in high demand but still remains a great challenge. In this work, we have successfully fabricated uniform Mox–Ni0.8Cu0.2O nanowires using a simple hydrothermal method followed by a post-calcination treatment and flexibly modulated the acidity of their surface by changing the amount of Mo introduced into Ni0.8Cu0.2O. The Mo0.1–Ni0.8Cu0.2O catalyst displayed strong catalytic activity toward AB methanolysis with an ultrahigh turnover frequency of 46.9 molH2 molcat.–1 min–1, which is even higher than some noble metal catalysts. In this work, an equation regarding the relationship between the quantity of moderated acid sites of catalysts and its corresponding activity toward AB methanolysis was first determined. A plausible mechanism for AB methanolysis catalyzed by Mox–Ni0.8Cu0.2O was proposed, and the benefits of the introduction of MoO3 to Ni0.8Cu0.2O for enhancing the catalytic performance were also discussed. These findings can form a basis for the rational construction of inexpensive catalysts with robust performance toward AB methanolysis for hydrogen production.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Chun Chang,Shijie Wang,Pengkun Guo,Guizhuan Xu,Xiaoyang Zheng,Chaojun Du,Youzhou Jiao
Increasing efforts have been devoted to the production of bio-based chemicals from high solid content of renewable biomass to pursue optimal process efficiency and economics. In this study, the preparation of methyl levulinate (ML) by metal sulfate-catalyzed methanolysis from high solid content of cellulose was investigated. When the cellulose loading was 15%, 38.67% of ML yield can be obtained under the optimum reaction conditions. Al 2 (SO 4 ) 3 can be reused more than five times while maintaining high activity in the process. The characterization of cellulose particles confirmed that cellulose particles shrunk over the reaction time. The heterogeneous degradation kinetics of high solid content of cellulose in methanol could be explained by a shrinking core model. High solid loadings led to a decrease of the reaction rate constants of methanolysis. Using cellulose with a small particle size can improve the methanolysis reaction rate. The study also proposed comprehensive reaction pathways for ML production from high solid content of cellulose. To elucidate the methanolysis mechanism, an assessment of density functional theories for the calculation of glucose methanolysis at the molecular level is presented. All these results can inspire the development of ML synthesis technology through methanolysis from renewable biomass with high solid loadings.
研究领域:
生物化学
·
可再生资源工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Yuanzhong Li,Liling Li,Yufa Feng,Huize Wang,Jinyun Liao,Jianwei Ren,Weiyou Zhou,Mingyang He,Hao Li
Engineering and fabricating cost-effective and high-performing bifunctional catalysts for ammonia borane (AB) hydrolysis and methanolysis is paramount for their commercial availability. A series of rattle-structured CuO/Co 3 O 4 @C microsphere bifunctional catalysts for AB hydrolysis and methanolysis were produced using a simple hard template etching approach. The CuO/Co 3 O 4 @C-4 (4 refers to designed the mole ratio of Cu/Co) exhibits the best activity with TOF of 18.8 and 26.8 mol H2 ·mol cat -1 ·min −1 for AB hydrolysis and methanolysis, respectively. It is discovered that the excellent performance is mainly attributed to its unique rattle structure and the synergetic effect between Co 3 O 4 and CuO . Kinetic isotope effect (KIE) experiments and infrared spectroscopy were applied to investigate AB hydrolysis and methanolysis reaction mechanisms. A suggested mechanism for AB methanolysis on rattle-structured CuO/Co 3 O 4 @C-4 is proposed based on the experiment results. This work could provide useful guidance for the construction of high-performance bifunctional catalysts for AB hydrolysis and methanolysis for hydrogen production.
研究领域:
材料科学
·
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Jinyun Liao,Yuanzhong Li,Jingjing Tian,Yufa Feng,Quanbing Liu,Hao Li
Catalytic methanolysis of ammonia borane is an integrated hydrogen production/storage technology with bright prospects, while its wide application is impeded by the high-cost of catalysts. In this work, hollow core@shell structured (HCSS) Co 3 O 4 @CuO-NiO with a size of 300–500 nm and a shell thickness of ca. 100 nm has been designed for ammonia borane (NH 3 BH 3 ) methanolysis for rapid hydrogen release. The possible formation mechanism of HCSS-Co 3 O 4 @CuO-NiO is proposed based on a series of characterization results, which is crucial for the design and preparation of nanocatalysts with similar architectures. Benefiting from the optimized compositions and electronic structures, the best HCSS-Co 3 O 4 @CuO-NiO sample exhibits high catalytic activity in NH 3 BH 3 methanolysis with a turnover frequency of 67.1 min −1 , surpassing that of all the noble-metal-free catalysts in previous reports. A possible reaction mechanism of NH 3 BH 3 methanolysis is put forward based on the in-situ Fourier transform infrared spectrometer (FTIR) characterization and kinetic isotope effect (KIE) experimental results. This work supplies a novel avenue for developing cheap and robust catalysts towards NH 3 BH 3 methanolysis by tailoring the catalysts’ morphology to hollow core@shell structures.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）