Perfluoroalkylsufonic (PFS) and alkylsufonic (AS) acid-functionalized magnetic nanoparticles were synthesized and characterized, then evaluated for their ability to hydrolyze hemicelluloses. The magnetic core was made...Perfluoroalkylsufonic (PFS) and alkylsufonic (AS) acid-functionalized magnetic nanoparticles were synthesized and characterized, then evaluated for their ability to hydrolyze hemicelluloses. The magnetic core was made of cobalt spinel ferrite and was coated with silica to protect it from oxidation. The silanol groups allowed surface chemical modification of the nanoparticles with the PFS and AS acid functionalities. Thermogravimetric analysis gave a total organic load of 12.6% and 32.5% (w/w) for AS and PFS nanoparticles, respectively. The surface sulfur content was calculated from XPS analysis as 1.37% and 1.93% for PFS and AS nanoparticles, respectively. Wheat straw samples were treated with the acid-functionalized nanoparticles at two different conditions: 80℃ for 24 h and 160℃ for 2 h. These experiments aimed to hydrolyze wheat straw hemicelluloses to soluble oligosaccharides. PFS nanoparticles solubilized significantly higher amounts of hemicelluloses (24.0% ± 1.1%) than their alkyl-sulfonic counterparts (9.1% ± 1.7%) at 80℃, whereas the hydrothermolysis control solubilized 7.7% ± 0.8% of the original hemicelluloses in the sample. At 160℃, PFS and AS nanoparticles gave significantly higher amounts of oligosaccharides (46.3% ± 0.4% and 45 ± 1.2%, respectively) than the control (35.0% ± 1.8%). The hemicelluloses conversion at 160?C reached 66.3% ± 0.9% using PFS nanoparticles and 61.0% ± 1.2% using AS nanoparticles compared with the control experiment, which solubilized 50.9% ± 1.7% of hemicelluloses in the biomass.展开更多
Carboxylic acid-functionalized nano-sized magnetic composite polymers (COOH-NMPs) were synthesized and used for the preparation of the modified glassy carbon electrode, i.e., COOH-NMPs/GCE and DNA/COOH-NMPs/GCE. The e...Carboxylic acid-functionalized nano-sized magnetic composite polymers (COOH-NMPs) were synthesized and used for the preparation of the modified glassy carbon electrode, i.e., COOH-NMPs/GCE and DNA/COOH-NMPs/GCE. The electrochemical behaviors of melamine (MM) were investigated on COOH-NMPs/GCE by cyclic voltammetry (CV) in both cases of DNA in the solution and immobilized on the electrode surface. The electron transfer coefficient (a) and the rate constant (ks) kept unchanged in the absence and presence of DNA. Based on the electrochemical properties of the interaction of MM on the surface of the DNA/COOH-NMPs/GCE, a direct method for the determination of MM in liquid milk was established. The detection limit of this method was 2.0 ng·L﹣1, with average recoveries at 95.9% - 104.2% and RSD at 4.5% - 8.2%. The proposed method was provided to have a good accuracy, high stability and good reproducibility with a simple and environmental friendly process. 10 kinds of liquid milk samples bought from the market randomly were tested, and only 1 of them was found at relatively low level of MM residue with the amount of 0.12 ug·L﹣1.展开更多
Green and recyclable solid acid catalysts are in urgent demand as a substitute for conventional liquid mineral acids.In this work,a series of novel sulfonic acid-functionalized core-shell Fe_(3)O_(4)@carbon microspher...Green and recyclable solid acid catalysts are in urgent demand as a substitute for conventional liquid mineral acids.In this work,a series of novel sulfonic acid-functionalized core-shell Fe_(3)O_(4)@carbon microspheres(Fe_(3)O_(4)@C-SO_(3)H)have been designed and synthesized as an efficient and recyclable heterogeneous acid catalyst.For the synthesis,core-shell Fe_(3)O_(4)@RF(resorcinol-formaldehyde)microspheres with tunable shell thickness were achieved by interfacial polymerization on magnetic Fe_(3)O_(4)microspheres.After high-temperature carbonization,the microspheres were eventually treated by surface sulfonation,re sulting in Fe_(3)O_(4)@C-x-SO_(3)H(x stands for carbonization temperature)microspheres with abundant surface SO_(3)H groups.The obtained microspheres possess uniform core-shell structure,partially-graphitized carbon skeletons,superparamagnetic property,high magnetization saturation value of 10.6 emu/g,and rich SO_(3)H groups.The surface acid amounts can be adju sted in the range of 0.59-1.04 mmol/g via sulfonation treatment of carbon shells with different graphitization degrees.The magnetic Fe_(3)O_(4)@C-x-SO_(3)H microspheres were utilized as a solid acid catalyst for the acetalization reaction between benzaldehyde and ethylene glycol,demonstrating high selectivity(97%)to benzaldehyde ethylene glycol acetal.More importantly,by applying an external magnetic field,the catalysts can be easily separated from the heterogeneous reaction solutions,which later show well preserved catalytic activity even after 9 cycles,revealing good recyclability and high stability.展开更多
基金This project is supported by the NSF award CNET-1033538 and the NSF EPSCoR Kansas Center for Solar Energy ResearchThis material is also based upon work supported by NSF Grant#0903701:“Integrating the Socioeconomic,Technical,and Agricultural Aspects of Renewable and Sustainable Biorefining Program awarded to Kansas State University.”Contribution number 12-367-J from the Kansas Agricultural Experiment Station.
文摘Perfluoroalkylsufonic (PFS) and alkylsufonic (AS) acid-functionalized magnetic nanoparticles were synthesized and characterized, then evaluated for their ability to hydrolyze hemicelluloses. The magnetic core was made of cobalt spinel ferrite and was coated with silica to protect it from oxidation. The silanol groups allowed surface chemical modification of the nanoparticles with the PFS and AS acid functionalities. Thermogravimetric analysis gave a total organic load of 12.6% and 32.5% (w/w) for AS and PFS nanoparticles, respectively. The surface sulfur content was calculated from XPS analysis as 1.37% and 1.93% for PFS and AS nanoparticles, respectively. Wheat straw samples were treated with the acid-functionalized nanoparticles at two different conditions: 80℃ for 24 h and 160℃ for 2 h. These experiments aimed to hydrolyze wheat straw hemicelluloses to soluble oligosaccharides. PFS nanoparticles solubilized significantly higher amounts of hemicelluloses (24.0% ± 1.1%) than their alkyl-sulfonic counterparts (9.1% ± 1.7%) at 80℃, whereas the hydrothermolysis control solubilized 7.7% ± 0.8% of the original hemicelluloses in the sample. At 160℃, PFS and AS nanoparticles gave significantly higher amounts of oligosaccharides (46.3% ± 0.4% and 45 ± 1.2%, respectively) than the control (35.0% ± 1.8%). The hemicelluloses conversion at 160?C reached 66.3% ± 0.9% using PFS nanoparticles and 61.0% ± 1.2% using AS nanoparticles compared with the control experiment, which solubilized 50.9% ± 1.7% of hemicelluloses in the biomass.
文摘Carboxylic acid-functionalized nano-sized magnetic composite polymers (COOH-NMPs) were synthesized and used for the preparation of the modified glassy carbon electrode, i.e., COOH-NMPs/GCE and DNA/COOH-NMPs/GCE. The electrochemical behaviors of melamine (MM) were investigated on COOH-NMPs/GCE by cyclic voltammetry (CV) in both cases of DNA in the solution and immobilized on the electrode surface. The electron transfer coefficient (a) and the rate constant (ks) kept unchanged in the absence and presence of DNA. Based on the electrochemical properties of the interaction of MM on the surface of the DNA/COOH-NMPs/GCE, a direct method for the determination of MM in liquid milk was established. The detection limit of this method was 2.0 ng·L﹣1, with average recoveries at 95.9% - 104.2% and RSD at 4.5% - 8.2%. The proposed method was provided to have a good accuracy, high stability and good reproducibility with a simple and environmental friendly process. 10 kinds of liquid milk samples bought from the market randomly were tested, and only 1 of them was found at relatively low level of MM residue with the amount of 0.12 ug·L﹣1.
基金financially supported by the National Natural Science Foundation of China(Nos.21875044,52073064,22005058 and 22005057)National Key R&D Program of China(No.2020YFB2008600)+3 种基金Key Basic Research Program of Science and Technology Commission of Shanghai Municipality(No.20JC1415300)Program of Shanghai Academic Research Leader(No.19XD1420300)China Post-doctoral Science Foundation(Nos.2020M670973,BX20200085)the State Key Laboratory of Transducer Technology of China(No.SKT1904)。
文摘Green and recyclable solid acid catalysts are in urgent demand as a substitute for conventional liquid mineral acids.In this work,a series of novel sulfonic acid-functionalized core-shell Fe_(3)O_(4)@carbon microspheres(Fe_(3)O_(4)@C-SO_(3)H)have been designed and synthesized as an efficient and recyclable heterogeneous acid catalyst.For the synthesis,core-shell Fe_(3)O_(4)@RF(resorcinol-formaldehyde)microspheres with tunable shell thickness were achieved by interfacial polymerization on magnetic Fe_(3)O_(4)microspheres.After high-temperature carbonization,the microspheres were eventually treated by surface sulfonation,re sulting in Fe_(3)O_(4)@C-x-SO_(3)H(x stands for carbonization temperature)microspheres with abundant surface SO_(3)H groups.The obtained microspheres possess uniform core-shell structure,partially-graphitized carbon skeletons,superparamagnetic property,high magnetization saturation value of 10.6 emu/g,and rich SO_(3)H groups.The surface acid amounts can be adju sted in the range of 0.59-1.04 mmol/g via sulfonation treatment of carbon shells with different graphitization degrees.The magnetic Fe_(3)O_(4)@C-x-SO_(3)H microspheres were utilized as a solid acid catalyst for the acetalization reaction between benzaldehyde and ethylene glycol,demonstrating high selectivity(97%)to benzaldehyde ethylene glycol acetal.More importantly,by applying an external magnetic field,the catalysts can be easily separated from the heterogeneous reaction solutions,which later show well preserved catalytic activity even after 9 cycles,revealing good recyclability and high stability.
