Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity a...Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance,highly efficient catalytic reduction systems containing sodium borohydride(NaBH_(4))and rare-earth chloride(RECl_(3))were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer,aiming to facilitate the conversion of chainend carboxyl groups into hydroxyl groups and improvement in end-group reactivity.To achieve this,lanthanum chloride(LaCl_(3)),cerium chloride(CeCl_(3)),and neodymium chloride(NdCl_(3))were used separately to form catalytic reduction systems with NaBH_(4).The effects of solvent dosage,reaction temperature,reaction time length,and reductant dosage on carboxylic conversion were investigated,and the molecular chain structure,molecular weight,and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy(FTIR),proton nuclear magnetic resonance(^(1)H-NMR),fluorine-19 nuclear magnetic resonance(^(19)F-NMR),gel permeation chromatography(GPC),and chemical titration.Moreover,the catalytic activity and selectivity of the rare-earth chlorides,as well as the corresponding underlying interactions were discussed.Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups,with a highest conversion up to 87.0%and differing catalytic reduction activities ranked as NaBH_(4)/CeCl_(3)>NaBH_(4)/LaCl_(3)>NaBH_(4)/NdCl_(3).Compared with the conventional lithium aluminum hydride(LiAIH_(4))reduction system,the NaBH_(4)/RECl_(3)systems provide multiple advantages such as mild reaction conditions,high conversion ratio with good selectivity,and environmental innocuity,and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.展开更多
The development of efficient and robust oxygen non-precious catalysts for the oxygen evolution reaction(OER)remains a critical scientific hurdle in realizing cost-effective renewable energy conversion systems.Herein,w...The development of efficient and robust oxygen non-precious catalysts for the oxygen evolution reaction(OER)remains a critical scientific hurdle in realizing cost-effective renewable energy conversion systems.Herein,we present a rapid laser irradiation synthesis strategy for the successful fabrication of sub-10 nm FeCoNiMnCr high-entropy alloy nanoparticles(HEA-NPs)on multi-wall carbon nanotube(MWCNT)paper,serving as highly efficient OER electrocatalysts.The synthesis of high-entropy alloy nanoparticles with pre-cise control was accomplished through systematic optimization of laser processing parameters.Structural characterization via X-ray diffraction,high-resolution transmission electron microscopy,and high-angle annular dark-field scanning transmission electron microscopy collectively verified the formation of a phase-pure face-centered cubic crystal structure with homogeneous elemental mixing at the atomic scale.Furthermore,COMSOL Multiphysics simulations confirm that this rapid and discontinuous laser irradiation approach enables the precursor material to undergo ultrafast heating and quenching processes,effectively suppressing Ostwald ripening phenomena,which is conducive to the formation of ultrafine(sub-10 nm)high-entropy alloy nanoparticles.The synthesized HEA-NPs catalyst demonstrates exceptional oxygen evolution activity in alkaline electrolyte(1 M KOH),achieving a current density of 10 mA·cm^(−2) at a low overpoten-tial of 255 mV while maintaining remarkable stability with negligible activity decay during prolonged operation(>100 h),representing state-of-the-art performance among non-precious metal catalysts.This study provides perspectives on the rapid preparation and performance regulation of HEA-NPs catalysts.展开更多
The volume FeO and TiO_2 abundances(FTAs) of lunar regolith can be more important for understanding the geological evolution of the Moon compared to the optical and gamma-ray results. In this paper, the volume FTAs ar...The volume FeO and TiO_2 abundances(FTAs) of lunar regolith can be more important for understanding the geological evolution of the Moon compared to the optical and gamma-ray results. In this paper, the volume FTAs are retrieved with microwave sounder(CELMS) data from the Chang'E-2 satellite using the back propagation neural network(BPNN) method. Firstly, a three-layered BPNN network with five-dimensional input is constructed by taking nonlinearity into account. Then, the brightness temperature(TB) and surface slope are set as the inputs and the volume FTAs are set as the outputs of the BPNN network.Thereafter, the BPNN network is trained with the corresponding parameters collected from Apollo, Luna,and Surveyor missions. Finally, the volume FTAs are retrieved with the trained BPNN network using the four-channel TBderived from the CELMS data and the surface slope estimated from Lunar Orbiter Laser Altimeter(LOLA) data. The rationality of the retrieved FTAs is verified by comparing with the Clementine UV-VIS results and Lunar Prospector(LP) GRS results. The retrieved volume FTAs enable us to re-evaluate the geological features of the lunar surface. Several important results are as follows. Firstly, very-low-Ti(<1.5 wt.%) basalts are the most spatially abundant, and the surfaces with TiO_2> 5 wt.% constitute less than 10% of the maria. Also, two linear relationships occur between the FeO abundance(FA) and the TiO_2 abundance before and after the threshold, 16 wt.% for FA. Secondly, a new perspective on mare volcanism is derived with the volume FTAs in several important mare basins, although this conclusion should be verified with more sources of data. Thirdly, FTAs in the lunar regolith change with depth to the uppermost surface,and the change is complex over the lunar surface. Finally, the distribution of volume FTAs hints that the highlands crust is probably homogeneous, at least in terms of the microwave thermophysical parameters.展开更多
文摘Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance,highly efficient catalytic reduction systems containing sodium borohydride(NaBH_(4))and rare-earth chloride(RECl_(3))were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer,aiming to facilitate the conversion of chainend carboxyl groups into hydroxyl groups and improvement in end-group reactivity.To achieve this,lanthanum chloride(LaCl_(3)),cerium chloride(CeCl_(3)),and neodymium chloride(NdCl_(3))were used separately to form catalytic reduction systems with NaBH_(4).The effects of solvent dosage,reaction temperature,reaction time length,and reductant dosage on carboxylic conversion were investigated,and the molecular chain structure,molecular weight,and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy(FTIR),proton nuclear magnetic resonance(^(1)H-NMR),fluorine-19 nuclear magnetic resonance(^(19)F-NMR),gel permeation chromatography(GPC),and chemical titration.Moreover,the catalytic activity and selectivity of the rare-earth chlorides,as well as the corresponding underlying interactions were discussed.Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups,with a highest conversion up to 87.0%and differing catalytic reduction activities ranked as NaBH_(4)/CeCl_(3)>NaBH_(4)/LaCl_(3)>NaBH_(4)/NdCl_(3).Compared with the conventional lithium aluminum hydride(LiAIH_(4))reduction system,the NaBH_(4)/RECl_(3)systems provide multiple advantages such as mild reaction conditions,high conversion ratio with good selectivity,and environmental innocuity,and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.
基金supported by the National Key Research and Development Program of China(No.2024YFB3411500)the Shihezi Municipal Science and Technology Project(No.2024ZD02)support from the Center for Hydrogen Innovations of National University of Singapore(NUS CHI)research grant(CHI-P2024-06-S1).
文摘The development of efficient and robust oxygen non-precious catalysts for the oxygen evolution reaction(OER)remains a critical scientific hurdle in realizing cost-effective renewable energy conversion systems.Herein,we present a rapid laser irradiation synthesis strategy for the successful fabrication of sub-10 nm FeCoNiMnCr high-entropy alloy nanoparticles(HEA-NPs)on multi-wall carbon nanotube(MWCNT)paper,serving as highly efficient OER electrocatalysts.The synthesis of high-entropy alloy nanoparticles with pre-cise control was accomplished through systematic optimization of laser processing parameters.Structural characterization via X-ray diffraction,high-resolution transmission electron microscopy,and high-angle annular dark-field scanning transmission electron microscopy collectively verified the formation of a phase-pure face-centered cubic crystal structure with homogeneous elemental mixing at the atomic scale.Furthermore,COMSOL Multiphysics simulations confirm that this rapid and discontinuous laser irradiation approach enables the precursor material to undergo ultrafast heating and quenching processes,effectively suppressing Ostwald ripening phenomena,which is conducive to the formation of ultrafine(sub-10 nm)high-entropy alloy nanoparticles.The synthesized HEA-NPs catalyst demonstrates exceptional oxygen evolution activity in alkaline electrolyte(1 M KOH),achieving a current density of 10 mA·cm^(−2) at a low overpoten-tial of 255 mV while maintaining remarkable stability with negligible activity decay during prolonged operation(>100 h),representing state-of-the-art performance among non-precious metal catalysts.This study provides perspectives on the rapid preparation and performance regulation of HEA-NPs catalysts.
基金supported in part by the Key Research Program of the Chinese Academy of Sciences under Grant (XDPB11)in part by opening fund of State Key Laboratory of Lunar and Planetary Sciences (Macao University of Science and Technology) (Macao FDCT Grant No. 119/2017/A3)+1 种基金in part by the National Natural Science Foundation of China (Grant Nos. 41490633, 41371332 and 41802246)in part by the Science and Technology Development Fund of Macao (Grant 0012/2018/A1)
文摘The volume FeO and TiO_2 abundances(FTAs) of lunar regolith can be more important for understanding the geological evolution of the Moon compared to the optical and gamma-ray results. In this paper, the volume FTAs are retrieved with microwave sounder(CELMS) data from the Chang'E-2 satellite using the back propagation neural network(BPNN) method. Firstly, a three-layered BPNN network with five-dimensional input is constructed by taking nonlinearity into account. Then, the brightness temperature(TB) and surface slope are set as the inputs and the volume FTAs are set as the outputs of the BPNN network.Thereafter, the BPNN network is trained with the corresponding parameters collected from Apollo, Luna,and Surveyor missions. Finally, the volume FTAs are retrieved with the trained BPNN network using the four-channel TBderived from the CELMS data and the surface slope estimated from Lunar Orbiter Laser Altimeter(LOLA) data. The rationality of the retrieved FTAs is verified by comparing with the Clementine UV-VIS results and Lunar Prospector(LP) GRS results. The retrieved volume FTAs enable us to re-evaluate the geological features of the lunar surface. Several important results are as follows. Firstly, very-low-Ti(<1.5 wt.%) basalts are the most spatially abundant, and the surfaces with TiO_2> 5 wt.% constitute less than 10% of the maria. Also, two linear relationships occur between the FeO abundance(FA) and the TiO_2 abundance before and after the threshold, 16 wt.% for FA. Secondly, a new perspective on mare volcanism is derived with the volume FTAs in several important mare basins, although this conclusion should be verified with more sources of data. Thirdly, FTAs in the lunar regolith change with depth to the uppermost surface,and the change is complex over the lunar surface. Finally, the distribution of volume FTAs hints that the highlands crust is probably homogeneous, at least in terms of the microwave thermophysical parameters.
