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Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

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Chinese Journal of chemical Engineering 2024年第3期67卷 9-15页

作者： Shutong Pang Hualiang An Xinqiang Zhao Yanji Wang Hebei Provincial key laboratory of Green chemical Technology and Efficient Energy Saving Tianjin Key Laboratory of Chemical Process SafetySchool of Chemical Engineering and TechnologyHebei University of TechnologyTianjin 300130China

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil *** order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic *** results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of ***[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of *** fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of *** hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic *** suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

关键词： Ionic liquid Hydroxyapatite Itaconic acid Methacrylic Decarboxylation reaction

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Insights into the role of oxygen-containing functional groups on carbon surface in water–electricity generation

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Nano Research 2024年第7期17卷 6645-6653页

作者： Wan Xue Zongbin Zhao Honghui Bi Bolun Zhang Xuzhen Wang Jieshan Qiu state key laboratory of Fine chemicals Liaoning Key Laboratory for Energy Materials and Chemical EngineeringSchool of Chemical EngineeringDalian University of TechnologyDalian 116024China state key laboratory of Fine chemicals Liaoning Key Laboratory for Energy Materials and Chemical EngineeringSchool of ChemistryDalian University of TechnologyDalian 116024China state key laboratory of chemical Resource Engineering College of Chemical EngineeringBeijing University of Chemical TechnologyBeijing 100029China

A deep understanding of the electricity generation mechanism from the interaction between water molecules and carbon material surfaces is attractive for next-generation water-based energy conversion and storage ***,an asymmetric generator was assembled based on functionalized carbon nanotubes films to investigate the relative contribution from various oxygen functional groups on carbon surface to the water-electrical *** and calculations demonstrate that the electricity mainly originates from the water molecule adsorption by carboxyl groups and dissociation of functional groups on carbon surface,which leads to the formation of electrical double layers at *** device allows the electricity generation with a variety of water sources,such as deionized water,tap water,as well as *** particular,the generator based on carboxyl carbon nanotubes can induce a voltage of over 200 mV spontaneously in natural seawater with the power density of about 0.11 mW·g^(−1).High voltages can be achieved easily through the series-connection strategy to power electronic products such as a liquid crystal *** work reveals the dominant role of carboxyl groups in carbon-based water–electricity conversion and is expected to offer inspiration for the preparation of carbon materials with high electrical performance.

关键词： electricity generation water adsorption dissociation carboxyl groups carbon nanotubes

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Cross-linkedα-amylase aggregates on Fe3O4 magnetic nanoparticles modified with polydopamine/polyethyleneimine for efficient hydrolysis of starch

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Particuology 2024年第7期90卷 98-105页

作者： Jiandong Cui Xiuming Tang Qingqing Ma Yuyan Chang Qunli Zhang Shiru Jia state key laboratory of Food Nutrition and safety Laboratory of Industrial Fermentation MicrobiologyMinistry of EducationTianjin University of Science and TechnologyTianjin 300457China key laboratory of Biomass chemical Engineering of Ministry of Education Zhejiang UniversityHangzhou 310027China

In this workα-amylase was immobilized on magnetic Fe3O4 nanoparticles with polyethylenimine(PEI)/polydopamine(PDA)coating or 3-aminopropyl triethoxysilane(APTES)for the first time via adsorption–precipitation–*** with the freeα-amylase,the resultant magnetic cross-linkedα-amylase aggregates(PEI/PDA-M-CLEAs and N-M-CLEAs)exhibited excellent thermal and storage stability as well as pH *** storage at 25°C for 60 days,freeα-amylase only retained 60%of its initial activity,while PEI/PDA-M-CLEAs and N-M-CLEAs retained 80%and 78%of their initial activities,***,N-M-CLEAs and PEI/PDA-M-CLEAs showed good *** 6 repeated uses,PEI/PDA-M-CLEAs and N-M-CLEAs still maintained 65%and 62%of their initial activities,***,PEI/PDA-M-CLEAs and N-M-CLEAs exhibited higher starch hydrolysis efficiency than freeα-*** maximum dextrose equivalent(DE)values of starch hydrolysis by PEI/PDA-M-CLEAs and N-M-CLEAs reached 29.24%and 28.79%within 90 min,***,the maximum DE values of starch hydrolysis by the freeα-amylase was only 27.89%even in 150 *** magnetic cross-linkedα-amylase aggregates could be introduced as effective biocatalyst for industrial applications in production of maltose syrups.

关键词： α-amylase Magnetic nanoparticles Functional modification Magnetic cross-linked enzyme aggregates Hydrolysis of starch

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Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

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Chinese Journal of Polymer Science 2024年第1期42卷 32-41,I0006页

作者： Yi-Cong Wang Hui Zhat Pei-Yi Cheng Shu Zhang Xiang-Wei Liu Yi-Xian Wu state key laboratory of chemical Resource Engineering Beijing University of Chemical TechnologyBejing 100029China

The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl_(3).The total isolated yield of VOCl_(3)[1,3-(2,4,6-Me_(3)C_(6)H_(2))_(2)(NCH=)_(2)C:](V4') reached 86% by transmetallation reaction,which is much higher than that(48%) by direct coordination *** methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl_(3)[PhCH_(2)NCH=CHNR)C:](V5',R=2,4,6-Me_(3)C_(6)H_(2);V6',R=2,4-Me_(2)-6-Ph-C_(6)H_(2);V7',R=2,6-^(i)Pr_(2)-C_(6)H_(3)) with high yield,which could not be obtained by direct coordination *** catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky *** vanadium complex V5' containing unsymmetrical NHC ligand exhibits higher catalytic activity(3.7×10^(5)g_(copolymer)·mol^(-1) of V·h^(-1)) than that of V4' containing symmetrical NHC ***,the higher propylene incorporation ratio(45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using V5' than that(39.9%) by using V4'.The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands,affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.

关键词： Vanadium complex N-heterocyclic carbene ligand Transmetallation reaction Copolymerization of ethylene with propylene

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Microfluidic-oriented synthesis of enriched iridium nanodots/carbon architecture for robust electrocatalytic nitrogen fixation

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Green Energy & Environment 2024年第3期9卷 544-555页

作者： Hengyuan Liu Xingjiang Wu Yuhao Geng Xin Li Jianhong Xu The state key laboratory of chemical Engineering Department of Chemical EngineeringTsinghua UniversityBeijing100084China

Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless ***,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic ***,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon *** to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption *** a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH ***,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) *** microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.

关键词： Iridium nanodots Carbon Microfluidic technology Efficient synthesis Electrocatalytic nitrogen fixation

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Empirical model of concrete block fragment behavior under explosion loads

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Science China Technological Sciences 2024年第8期67卷 2515-2529页

作者： YANG Shuai NING JianGuo REN HuiLan XU XiangZhao state key laboratory of Explosion Science and safety Protection Beijing Institute of Technology

Concrete structures undergo integral fragmentation under explosion loads. The fragmentation degree and particle-size distribution of concrete blocks under explosion loads must be considered during mining to ensure safety. In this study, the impulse is calculated based on the relationship between overpressure and time, and the impact energy of the explosion wave is obtained based on blast theory. Subsequently, the Mohr-Coulomb shear strength fracture criterion is introduced to determine the ultimate shear stress of the concrete materials, and an empirical model that can effectively calculate the energy consumption of concrete blocks under explosion loads is established. Furthermore, concrete fragments with different particle sizes under explosion scenarios are quantitatively predicted with the principle of energy conservation. Finally, explosion tests with different top standoff distances are conducted, and the concrete fragments after the explosion tests are recovered, sieved, weighed, and counted to obtain experimental data. The effectiveness of the fragment empirical model is verified by comparing the model calculation results with the experimental data. The proposed model can be used as a reference for civil blasting, protective engineering design, and explosion-damage assessment.

关键词： concrete structures explosion loads fragment behavior empirical model

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Formation of mesophase microbeads from bulk mesophase pitch induced by fullerene

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新型炭材料（中英文） 2024年第4期39卷 645-654页

作者： CHEN Wen-sheng LIU Lan-tao WANG Zheng DUAN Chun-feng ZHANG Xing-wei MA Zhao-kun CHEN Xiao-hong SONG Huai-he state key laboratory of chemical Resource Engineering Beijing Key Laboratory of Electrochemical Process and Technology for MaterialsBeijing Uni-versity of Chemical TechnologyBeijing 100029China

A transformation of naphthalene-based coalescenced mesophase pitch(NMP)to mesophase microbeads was achieved by heating a mixture of NMP and fullerene(C_(60)).This is different from the conventional process of the liquid-phase carbonization of isotropic pitch to the emergence of carbon microbeads in the matrix and finally their growth to form a 100%anisotropic bulk meso-phase,but rather a reverse *** effects of C_(60) loading and reaction temperature on the morphological transformation of mesophase were investigated by polarizing optical and scanning electron *** physical changes in the NMP induced by C_(60) were characterized by thermogravimetric analysis,Fourier transform infrared spectroscopy,X-ray diffractometry and Raman *** results show that the coalesced NMP can be converted to a spherical type at 300-320℃ with the addition of 5%C_(60),and the size of the mesophase microbeads increases with increasing ***,a model is established to ex-plain the unique induction effect of C_(60) in the transformation *** work makes the morphological transformation of MP con-trollable,and provides a new idea for the understanding and research of mesophase pitch.

关键词： Reversible transformation Fullerene induction mechanism Mesophase texture π-electron-induced effect Mesophase microbeads

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Process intensification for the synthesis and purification of battery-grade Li_(2)CO_(3)with microfluidics

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Particuology 2024年第7期90卷 106-117页

作者： Haodu Li Jie Zhang Lin Dai Le Du Jiqin Zhu The state key laboratory of chemical Resource Engineering College of Chemical EngineeringBeijing University of Chemical TechnologyBeijing 100029China

Battery-grade lithium carbonate(Li_(2)CO_(3))with a purity of higher than 99.5 wt%is of great importance as a high value-added lithium ***,influences of different reaction systems and process control on product purity remain ***,a membrane dispersion microreactor was used to enhance the mass transfer of preparation and purification processes in homogeneous and heterogeneous *** systems of Na_(2)CO_(3)–LiCl,NH_(4)HCO_(3)–LiCl,and NH_(3)·H_(2)O−CO_(2)−LiCl,CO_(2)purification based on carbonation and decomposition were *** Li_(2)CO_(3)purity was increased by the improvement of mixing *** carbonation time was reduced by 62.5%and 58.3%for the NH_(3)·H_(2)O−CO_(2)and CO_(2)purification systems,*** the two ammonia-based systems,Li_(2)CO_(3)particles with a purity of 99.7–99.8 wt%were one-step prepared with a size of 3–5μm,which also met the requirement of the battery-grade *** purity was further increased to 99.9 wt%by CO_(2)purification and LiHCO_(3)*** investigation could provide a feasible alternative for the controllable preparation of battery-grade Li_(2)CO_(3)in one or multiple steps.

关键词： Microfluidics Battery grade Li_(2)CO_(3) Process intensification High purity

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Breakthrough in Li-mediated continuous electrosynthesis of ammonia

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Science China Chemistry 2024年第10期67卷 3191-3192页

作者： Fei Zhan Chang Yu state key laboratory of chemical Resource Engineering College of Chemical EngineeringBeijing University of Chemical Technology state key laboratory of Fine chemicals Liaoning Key Lab for Energy Materials and Chemical EngineeringSchool of Chemical EngineeringDalian University of Technology

Ammonia（NH3） ranks among the manufactured chemicals,with an annual production surpassing 182 million tons [1],which is an indispensable raw material for fertilizer industry and has been recognized as a promising car...

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Effects of orientation on the fatigue crack growth behaviors of the ZK60 magnesium alloy in air and PBS

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Journal of Magnesium and Alloys 2024年第1期12卷 281-294页

作者： Jiaqi Hu Zheng Liu Zuoliang Ning Hong Gao School of chemical Engineering and Technology Tianjin UniversityTianjin 300072China Tianjin key laboratory of chemical Process safety and Equipment Technology Tianjin 300072China

Strong anisotropic corrosion and mechanical properties caused by specimen orientations greatly limit the applications of wrought magnesium *** investigate the influences of specimen orientation,the corrosion tests and(corrosion)fatigue crack growth tests were *** rolled and transverse surfaces of the materials show distinct corrosion rate differences in the stable corrosion stage,but the truth is the opposite for the initial stage of *** air,specimen orientations have a significant influence on the plastic deformation mechanisms near the crack tip,which results in different fatigue fracture surfaces and cracking *** with R-T specimens,N-T specimens show a slower fatigue crack growth(FCG)rate in air,which can be attributed to crack closure effects and deformation twinning near the crack *** corrosion environment will not significantly change the main plastic deformation mechanisms for the same type of ***,the FCG rate in phosphate buffer saline(PBS)is one order of magnitude higher than that in air,which is caused by the combined effects of hydrogen-induced cracking and anodic *** to the similar corrosion rates at crack tips,the specimens with different orientations display close FCG rates in PBS.

关键词： Magnesium alloy Orientation Corrosion Fatigue crack growth

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