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Green Energy & Environment · 2019 ·Vol. 4 ·期 4 ·424-431 · IF 0

Highly efficient catalytic valorization of biomass-derived hexoses and furfuryl alcohol in the presence of polymer-based catalysts

Yangyang Zhang,Xinli Tong,Linhao Yu,Lingwu Meng,Pengfei Guo,Song Xue

The catalytic transformation of furfuryl alcohol and hexose into value-added chemicals have been investigated with a series of polymer-based catalysts including poly(styrenesulfonic acid) (PSS), graphite oxide-doped poly(styrenesulfonic acid) (PSS-GO), and graphite-doped poly(styrenesulfonic acid) (PSS-C). It is found that the selective conversion of furfuryl alcohol to methyl levulinate (MLE) was successfully performed with PSS as the catalyst, in which a 96.4% yield is attained in methanol solvent. Moreover, the efficient dehydration of d -fructose to produce 5-hydroxymethylfurfural (HMF) has also been achieved using PSS-GO as the catalyst, where a 76.5% yield of HMF was obtained in N -methylpyrrodinone solvent. The effects of reaction temperature, time and solvent were investigated. Furthermore, the used catalysts have been respectively characterized by XRD, TG, FTIR, SEM and TEM techniques to reveal the physical properties and structures of these polymeric catalytic materials.

研究领域: 催化化学 · 生物质能源 · 绿色化学 · 有机转化 · 高分子材料 · 可持续化学 · 生物基化学品
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

Synthesis and performance of piperidinium-based ionic liquids as catalyst for biomass conversion into 3-acetamido-5-acetylfuran

Hongjun Zang,Yimo Feng,Jing Lou,Kai Wang,Changchun Wu,Zhipeng Liu,Xi Zhu

Ionic liquids have shown good catalytic performance and been widely used in the biomass conversion process due to their unique properties, including environmental   friendship, low toxicity, and simple preparation. In this work, a series of novel piperidinium-based ionic liquids were synthesized under mild conditions via a simple protonation reaction or nucleophilic substitution reaction. Among them, 4,4′-(propane-1,3-diyl)bis(1-(carboxymethyl)piperidin-1-ium) chloride ([PDCMPi]Cl) displayed the best catalytic performance. The highest yield (42.81 %) of 3A5AF from NAG was obtained after reacting in N-methyl-pyrrolidone (NMP) in the presence of piperidinium-based ionic liquids at 180 °C for 20 min under normal atmospheric conditions. Additionally, ionic liquid [PDCMPi]Cl showed good catalytic activity in six repeated catalytic runs. Meanwhile, a possible reaction pathway was also proposed on the basis of the results of NMR spectra.

研究领域: 催化化学 · 绿色化学 · 生物质能源 · 有机合成 · 离子液体化学
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COMBUSTION AND FLAME · 2021 · IF 4.185

Pyrolysis of 2-methylfuran/jet fuel surrogate blends: An experimental and kinetic modeling study

Zhi-Hao Jin,Jin-Tao Chen,Wang Li,Shu-Bao Song,Jiu-Zhong Yang,Zhen-Yu Tian

Owing to significant advantages over traditional biofuels, 2-methylfuran (MF) has arisen extensive interest as next generation biofuels . Atmospheric pressure pyrolysis of a 1:1 blend of MF with a three-component (3C) surrogate jet fuel was conducted in a flow tube using synchrotronphotoionization and molecular beam mass spectrometry techniques within a temperature range of 898–1223 K. Therein, the 3C surrogate fuel consists of 66.2% n-dodecane (NC 12 H 26 ), 18.0% 1,3,5-trimethylcyclohexane (T135MCH) and 15.8% n-propylbenzene (NPB, A1C 3 H 7 ). The detailed kinetic model including 579 species and 3474 reactions was developed via validating against both measured and literature data with reasonable agreement. MF exhibits no obvious influence on the 3C components pyrolysis . However, 3C mixtures play an important roles in MF decomposition: lower initial temperature and different decomposition pathways. In the meantime, n-propylbenzene (NPB) pyrolysis curve in 3C and 3C+MF significantly transfers to low temperature zone after 1000 K in contrast to pure NPB, while smaller change was found in the decomposition curve of n-dodecane. Compared with 3C pyrolysis, 3C+MF blends have less formation of aromatic species and light hydrocarbons except for vinylacetylene (C 4 H 4 ) and acetylene (C 2 H 2 ). Allyl radical (C 3 H 3 ) has significant roles in benzene ring formation. The combination of allyl radical with propargyl radical producing benzene and H radical (aC 3 H 5  + C 3 H 3  = A1 + 2H) has the highest contribution to the benzene formation in both 3C and 3C+MF. Moreover, most of naphthalene (A2) formation is also related to C 3 H 3 radical via reaction: A1CH 2  + C 3 H 3  = A2 + H, rather than via HACA (hydrogen abstraction carbon addition) reaction. Interaction of fuel blends was mainly presented through the common and important sensitive reactions which are much to do with CH 3 and H radicals. The overview of product distribution was investigated by providing comparisons of carbon conversion rates during the pyrolysis of 3C and 3C+MF. These results will be helpful to better understand the pyrolysis properties of MF/jet fuel surrogate blends and could contribute to developing new generation biofuels for aviation.

研究领域: 燃料化学 · 燃烧动力学 · 生物燃料 · 能源化学 · 反应机理 · 质谱分析
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APPLIED ENERGY · 2024 · IF 10.1

Ultra-rapid formation of mixed H2/DIOX/THF hydrate under low driving force: Important insight for hydrate-based hydrogen storage

Yaning Kong,Honglin Yu,Mengqi Liu,Guodong Zhang,Fei Wang

Hydrate was considered to be the next generation hydrogen storage material , and hydrate-based hydrogen storage (HBHS) would play an important role in future hydrogen economy, but sluggish hydrate formation kinetics presents huge technological challenge for its application. Herein, a nano promoter of -SO 3 − @PSNS was prepared by soap-free emulsion polymerization , and a dual kinetic promoter system (L-methionine/-SO 3 − @PSNS) was applied to enhance the formation kinetics of mixed H 2 /DIOX hydrate. At a moderate condition (12 MPa and 274.15 K), hydration efficiency under a driving force of 2.1 MPa is significantly enhanced by the synergy of the dual kinetic promoters, hydrate induction time reduces from 443.2 ± 209.73 min to 24.7 ± 17.16 min, while hydrate growth rate increases by 43.75%, and hydrogen storage capacity is up to 0.473 ± 0.041 wt% that increases by 62.8%. At a more moderate condition (10 MPa and 274.15 K) with an extremely low driving force of 0.1 MPa, enhanced hydrate formation was obtained in a composite promotion system of the dual kinetic promoters and dual thermodynamic promoters (THF/DIOX), which also performs exceptionally in term of recycling. The presence of a small amount (0.35 mol%) of THF reduces the induction time by 93.5%, and hydrate growth rate increases by 130.18%, while satisfactory hydrogen storage capacity (0.346 ± 0.017 g/g) is still remained in mixed H 2 /DIOX/THF hydrate, the structure of which was confirmed by Raman spectrum . This work presents an effect approach on enhancing the formation kinetics of H 2 -contained hydrate under low driving force, and this finding provides important insight for HBHS.

研究领域: 物理化学 · 能源材料 · 气体储存 · 化学工程 · 纳米材料科学 · 分子模拟 · 可持续能源
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Configurational Entropy Regulation in Polyolefin Elastomer/Paraffin Wax Vitrimers by Thermally Responsive Liquid–Solid Transition for Force Storage

Zhao Xu,Yong-Bo Liu,Dun-Wen Wei,Rui-Ying Bao,Yu Wang,Kai Ke,Wei Yang

The work output of shape memory polymers during shape shifting is desired for practical application as actuators. Herein, a polyolefin elastomer (POE) and paraffin wax (PW) are co-cross-linked by dynamic boronic ester bonds to enhance the network elasticity and the stress transfer between the two phases, endowing high force storage capacity to the prepared vitrimers. Depending on the phase of PW, one-way force storage is realized by programming at a low temperature (25 °C), owing to which solid PW can promote the locking of POE chains in a low-entropy state, while reversible force storage can be realized by programming at a high temperature (75 °C), owing to which the relaxation of chains facilitated by liquid PW can promote the construction of a stable structure. Based on one-way force storage, a weight-lifting machine with a weight of 20 mg prestrained at 25 °C can lift a 100 g weight, showing a lifting ratio of no less than 5000, with a high work output of 0.98 J/g. A high-temperature alarm can be triggered at varied temperatures (43–56 °C) through controlled force release by adjusting the PW content and programmed prestrains. Based on the reversible force storage, crawling robots and artificial muscles with a work output of 0.025 J/g are demonstrated. The dynamic cross-linking network also confers mold-free self-healing capability to POE/PW vitrimers, and the repair efficiency is enhanced compared with the POE vitrimer due to the improved POE chain motion by liquid PW. The realized one-way and reversible force storage and self-healing by POE/PW vitrimers pave the way for the application of SMPs in the fields of soft robotic actuators.

CAS / MDL: 110-00-9
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CHEMOSPHERE · 2023 · IF 8.8

Efficiency and mechanism of the degradation of ciprofloxacin by the oxidation of peroxymonosulfate under the catalysis of a Fe3O4/N co-doped sludge biochar

Dayang Zheng,Jiali Zou,Hao Xu,Min Wu,Yayi Wang,Cang Feng,Eryang Zheng,Teng Wang,Yuxiang Shi,Yongjian Chen,Binyang Li

A novel and recyclable composite material, Fe 3 O 4 /N co-doped sludge biochar (FNBC), was developed from original sludge biochar (BC) and found to have excellent stability and superior catalytic capacity during the ciprofloxacin (CIP) degradation under the action of peroxymonosulfate (PMS). In the FNBC/PMS system, an approximately complete removal of CIP was achieved within 60 min under the condition of 1.0 g/L FNBC, 3.0 mM PMS, and 20 mg/L CIP, which was about 2.08 times of that in BC/PMS system (48.01%). Besides, FNBC/PMS system could effectively remove CIP under the influence of wide pH (2.0–10.0) or inorganic ions compared with BC/PMS system. Moreover, it was found that there were radical produced under the effect of Fe element, defects, functional groups, pyridinic N and pyrrolic N and non-radical caused by graphitic N, carbon atoms next to the iron atoms and better adsorption capacity in the FNBC/PMS system. It was observed that the contribution of hydroxyl radical (•OH), sulfate radical (SO 4 •− ) and singlet oxygen ( 1 O 2 ), which were the main reactive oxygen species , during the CIP degradation, were 75.80%, 11.49% and 10.26%, respectively. Furthermore, total organic carbon (TOC) variation was analyzed and the degradation pathway of CIP was speculated. The application of this material could combine the recycling of sludge with the effective degradation of refractory organic pollutant, providing an environmentally friendly and economic method.

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JOURNAL OF POLYMER RESEARCH · 2023 ·Vol. 30 ·期 3 ·1-9 · IF 2.8

Synthesis of poly(maleimide)s with promising performance via Diels–Alder reaction and ring-opening metathesis polymerization

Li Wanrong,Zhan Qingyan,Yang Po

This work aims to generate maleimides to polymers via Diels–Alder reaction and ring-opening metathesis polymerization (ROMP). Maleimides were converted to adducts through Diels–Alder reactions by reacting with cyclopentadiene or furan, then these adducts were generated to the corresponding polymers via ring-opening metathesis polymerization. The chemical structures of adducts were confirmed by 1 H NMR, FTIR and elemental analysis. After investigating the polymerization behaviors and properties, we found that the adducts could be converted into polymers via ROMP and affording polymers exhibited excellent performance. For example, the glass transition temperature of PBMC is 252 °C, 5% and 10% weight loss temperatures are successively 381 °C and 475 °C, and the relative dielectric constant ( D k ) and dissipation (D f ) at 1 Hz and 1 MHz are respectively 3.41 and 0.006, 3.35 and 0.020. Moreover, the adducts can be used to enhance other ROMP-derived polymers as the comonomers. We believe these may help researchers design and explore novel maleimides polymers and copolymers with promising properties.

CAS / MDL: 110-00-9
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Patternable thermal conductive interface materials enabled by vitrimeric phase change materials

Li-Mei Peng,Zhao Xu,Jie Yang,Lu Bai,Rui-Ying Bao,Ming-Bo Yang,Wei Yang

Thermal interface materials (TIMs) with mechanical integrity and interfacial adaptability over rough surfaces without applying high pressure to the sandwiched thermal interfaces are challenging. Herein, patternable thermal conductive interface materials enabled by vitrimeric phase change materials (PCMs) for reconfigurable package procedures and reduction in thermal contact resistance are proposed. The incorporated dynamic crosslinked network in paraffin wax/polyolefin elastomer (PW/POE) PCMs forms a robust 3D supporting skeleton, giving rise to the PCMs with mechanical integrity even when POE is melted. Lowered modulus by solid–liquid phase change of PW and activated exchange of dynamic covalent bonds when POE is melted allow for reconfigurable package procedures by plastic deformation with small stress. Hybrid fillers with different sizes and dimensions form effective heat conduction pathways in the vitrimeric PW/POE PCMs. Notably, the resulting composites can still conformally adapt to the rough surfaces of the heat sink and heat source at 80 °C and 13 KPa, resulting in an interlocked structure, which can essentially reduce the thermal contact resistance and promote thermal transport. The prepared composites as TIM demonstrate better heat dissipation performance than the commercial thermal pad. The strategy of vitrimeric PCMs combines mechanical integrity and thermally triggered interfacial adaptability through reconfigurable package procedures, providing inspiration for the bulk compliance of TIMs that can adapt to rough surfaces.

CAS / MDL: 110-00-9
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2023 · IF 6.1

Cysteine-Induced pH-Dependent Formation of Thiols and Sulfides or 2-Acetylthiazole and Pyrazines during Thermal Treatment of N-(1-Deoxy-d-xylulos-1-yl)-alanine

Tong Zhou,Xue Xia,Heping Cui,Yun Zhai,Foxin Zhang,Khizar Hayat,Xiaoming Zhang,Chi-Tang Ho

The influence of pH was studied on volatile flavor formation during thermal treatment of an Amadori rearrangement product (ARP) with or without the addition of cysteine (Cys). The formation of thiols and sulfides or 2-acetylthiazole and pyrazines induced by Cys during thermal degradation of ARP was pH-dependent. At low pH levels, the hydrolysis of Cys to hydrogen sulfide (H2S) was promoted, giving rise to the increase of thiols and sulfides with an obvious meaty aroma. However, alkaline conditions were beneficial for enhancing the cyclization or transformation of imine to the enol structure, which strengthened the formation of 2-acetylthiazole and pyrazines with a roasted and nutty aroma. The imine was derived from the nucleophilic addition of Cys and methylglyoxal (MGO) and subsequent decarboxylation. At pH 8, Cys-induced variation of the flavor profile was weakened during thermal degradation of ARP. Accordingly, the combinational effect of pH and added Cys could be beneficial for achieving the desirable flavors during thermal processing of ARP.

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Nanoscale · 2023 ·Vol. 15 ·期 11 ·5458-5468 · IF 6.7

Hierarchical network relaxation of a dynamic cross-linked polyolefin elastomer for advanced reversible shape memory effect

Zhao Xu,Sen Meng,Dun-Wen Wei,Rui-Ying Bao,Yu Wang,Kai Ke,Wei Yang

Reversible shape-memory polymers (RSMPs) are highly desired for soft actuators due to the repeatability of deformation. Herein, a polyolefin elastomer vitrimer (POEV) was prepared by constructing a dynamic cross-linked network based on boronic ester bonds. POEV showed varied network relaxation in a wide temperature range due to hierarchical network relaxation, and then the entropy decreased and the relaxation of POEV chains was facilely controlled by temperature. The controllable relaxation of POEV by programming the temperature enabled the actuation domain with a reduction in entropy and the skeleton domain with a relatively high entropy can be built in POEV, greatly affecting the reversible shape memory effects (RSMEs). The topological rearrangement resulted from the activated exchange of dynamic covalent bonds, which enables POEV with good shape reconfigurability, and allows for complicated 3D shapes and shape-shifting on demand. More interestingly, combining the decreasing entropy of POEV chains and fully topological rearrangement tailored by temperature, hybrid aligned carbon nanotubes (CNTs) can be constructed in POEV via a two-stage training. Then, the aligned CNTs can enhance the elasticity and act as a hybrid skeleton for RSMEs, avoiding the negative impact of CNTs on the reversible actuation strain. The hierarchical network relaxation facilitates combining all these unusual properties in one shape memory network synergistically, paving new avenues for realizing smart materials with advanced RSME.

CAS / MDL: 110-00-9
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International Journal of Electrochemical Science · 2023 · IF 1.5

Effects of Pyridine and Furan Pretreatment on the Corrosion Resistance of Rust Coating on Mild Steel

Yinze Zuo,Liang Chen,Yu Wang,Yunxia Guo,Xingling Shi,Yanmin Gao

Pre-processing of a metal surface before coating is a key factor that affects the coating performance. This phenomenon has been puzzling people for a long time. In this paper, a new type of preprocessing using heterocyclic compounds, pyridine and furan, were applied to address this problem. The tests show that the rust layers of mild steel treated by pyridine and furan are more compact than the untreated layers. The corrosion rate of the mild steel with a rust layer treated by pyridine is lower than that of the samples with furan treatment and without treatment, while the impedance is also the largest. The adhesion of an epoxy-polyvinylbutyral (EP-PVB) coating, which is painted on rust layers with pyridine and furan pretreatment, is much stronger. Moreover, the corrosion resistance of EP-PVB coatings that are painted onto the rust layers with pretreatment is much better than that of the coatings that are directly painted onto the rust layer without pretreatment. The impedance of EP-PVB coatings that are painted onto the rust layers with pretreatment is much higher than that of the EP-PVB coating that is directly painted onto the rust layer without pretreatment.

CAS / MDL: 110-00-9 110-86-1
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

Highly selective adsorption of dyes by functional hypercrosslinked-polymers prepared in a facile and chemically stable manner

Jiang Wei,Jia Jia,Tong Liao

One of the challenges in water pollution control is the design of adsorbents aimed at achieving low cost, ultrafast, and selective adsorption of pollutants. Hypercrosslinked-polymers (HCPs) possess abundant microporous structures and advantages such as the ability to manipulate the framework structure, making them highly valuable in the field of adsorption. Three HCPs namely polythiophene (Th-1), polypyrrole (Py-1), and polyfuran (Fu-1) were synthesized through a Friedel's alkylation reaction utilizing different functional monomers (thiophene, pyrrole , and furan) employing a knitting strategy. The HCPs exhibit a heterocyclic structure (C-S-C, C-N-C, C-O-C) with remarkable charge selectivity as well as strong resistance to acids and alkalis. The HCPs, with varying functional monomers, demonstrate selective adsorption of dyes based on their charges and release of dyes dependent on solvent and pH conditions. The ease of synthesis, cost-effectiveness, and high reusability render these HCPs suitable for further design optimization through the utilization of diverse functional monomers to achieve efficient adsorption and removal of environmental pollutants from water.

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