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Optimized the vanadium electrolyte with sulfate-phosphoric mixed acids to enhance the stable operation at high-temperature

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Frontiers of Chemical Science and engineering 2024年第2期18卷 13-26页

作者： Ling Ge Tao Liu Yimin Zhang Hong Liu School of resource and Environmental engineering Wuhan University of Science and TechnologyWuhan 430081China State Environmental Protection Key Laboratory of mineral Metallurgical resources Utilization and Pollution Control Wuhan University of Science and TechnologyWuhan 430081China Hubei Collaborative Innovation Center for High Efficient Utilization of Vanadium resources Wuhan University of Science and TechnologyWuhan 430081China Hubei Provincial engineering technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium resource Wuhan University of Science and TechnologyWuhan 430081China School of resource and Environmental engineering Wuhan University of TechnologyWuhan 430070China

Herein, the influence of the concentration design and comprehensive performance of the sulfate-phosphoric mixed acid system electrolyte is investigated to realize an electrolyte that maintains high energy density and stable operation at high temperatures. Static stability tests have shown that VOPO4 precipitation occurs only with vanadium(V) electrolyte. The concentration of vanadium ion of 2.0–2.2 mol·L^(–1), phosphoric acid of 0.10–0.15 mol·L^(–1), and sulfuric acid of 2.5–3.0 mol·L^(–1) are suitable for a vanadium redox flow battery in the temperature range from –20 to 50 ℃. The equations for predicting the viscosity and conductivity of electrolytes are obtained by the response surface method. The optimized electrolyte overcomes precipitation generation. It has 2.8 times higher energy density than the non-phosphate electrolyte, and a coulomb efficiency of 94.0% at 50 ℃. The sulfate-phosphoric mixed acid system electrolyte promotes the electrode reaction process, increases the current density, and reduces the resistance. This work systematically optimizes the concentrations of composition of positive and negative vanadium electrolytes with mixed sulfate-phosphoric acid. It provides a basis for the different valence states and comprehensive properties of sulfate-phosphoric mixed acid system vanadium electrolytes under extreme environments, guiding engineering applications.

关键词： all vanadium redox flow battery mixed-acid vanadium electrolyte concentration optimization response surface methodology high-temperature stability

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Review of the research on the development and utilization of clay-type lithium resources

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Particuology 2024年第4期87卷 46-53页

作者： Ruiqi Xie Zhihui Zhao Xiong Tong Xian Xie Qiang Song Peiqiang Fan Faculty of Land resource engineering Kunming University of Science and TechnologyKunming650093China Yunnan engineering Research Center for Metal Tailings resource Utilization Kunming650093China

Since the demands for lithium have been in explosive growth recently and several great clay lithium resources were founded in China,the development and utilization of clay-type lithium resources become a hot *** order to provide a guidance for the concentration and extracting lithium of clay-type lithium resources,this review systematically summarized the main types and characteristics of clay-type lithium resources and the research status of lithium extraction from clay lithium ***,the flotation research status of the main mineral of clay lithium ore was also ***,we discussed the difficulties in the development and utilization of clay-type lithium ore and put forward the subsequent research *** paper can provide a guidance for the con-centration and extracting lithium of clay-type lithium resources in the future.

关键词： Clay lithium Clay mineral flotation Lithium extraction Leaching

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Molecular-scale co-assembly membranes derived from keplerate cluster: carbonic anhydrase-mimicking nanocapsules for enhanced CO2/N2 separation

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Science China Chemistry 2024年第10期67卷 3271-3282页

作者： Wan-Lei Zhao Hongqiang Li Ruoxuan Zheng Yixin Yang Wei Chen Yu-Fei Song State Key Laboratory of Chemical resource engineering Beijing University of Chemical Technology Quzhou Institute for Innovation in resource Chemical engineering

The development of CO2separation membranes with high permeability and high selectivity,as well as ultra-thin selective layers,has always been ***,a molecular-scaled co-assembly strategy is employed to fabricate the Pebax-Mo132(Pebax=polyether-block-amide copolymer;Mo132=（NH4）42[Mo72ⅥMoⅤ60O372（CH3COO）30（H2O）72]) *** optimal selfstanding membrane,Pebax-Mo132-5%,shows a CO2permeability of～384 Barrer and an ultra-high ideal CO2/N2selectivity of～244,outperforming most membranes reported in the *** CO2permeability and ideal CO2/N2selectivity are increased by 70%and 367%,respectively,compared with the pristine Pebax membrane.A thin-film composite membrane prepared by spin-coating technique on a support membrane with gutter layers also exhibits a CO2permeance of 838 GPU and a CO2/N2selectivity of *** excellent performance can be attributed to the following reasons:（1） strong hydrogen bonding interactions between{Mo132}clusters and Pebax confer excellent interfacial compatibility to the mixed matrix membranes;（2）incorporation of hollow{Mo132}clusters into the Pebax molecular chain decreases the crystallinity of Pebax,and thereby accelerates the chain dynamics and increases the free volume of the membrane;（3） in situ diffuse reflectance infrared Fouriertransform spectroscopy demonstrates that the{Mo132}clusters can effectively catalyze the hydration reaction of CO2and promote the transport of CO2;（4） furthermore,the 0.35 nm pores of the crown ether-type{Mo9O9}allow the accurate size sieving of CO2（0.33 nm） and N2（0.36 nm） molecules.

关键词： polyoxometalates molecular-scale assembly CO2 capture mixed matrix membranes

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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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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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Advances in depressants for flotation separation of Cu–Fe sulfide minerals at low alkalinity:A critical review

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International Journal of minerals,Metallurgy and Materials 2024年第1期31卷 1-17页

作者： Qicheng Feng Wenhang Yang Maohan Chang Shuming Wen Dianwen Liu Guang Han State Key Laboratory of Complex Nonferrous Metal resources Clean Utilization Faculty of Land Resource EngineeringKunming University of Science and TechnologyKunming 650093China Yunnan Key Laboratory of Green Separation and Enrichment of Strategic mineral resources Kunming University of Science and TechnologyKunming 650093China

The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective *** the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the *** review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low *** advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and *** potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is *** advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively ***,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are ***,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.

关键词： Cu–Fe sulfide minerals flotation separation selective depressants depression mechanism

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Evaluation of the Relative Tectonic Activity from the Faults in the Gengma-Lancang-Menghai Seismic Belt(Southwestern China)

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Journal of Earth Science 2024年第1期35卷 131-143页

作者： Dan Wang Youpu Dong Zhipeng Xi Dongyue Zhang Jiaxin Duan Huayu Yu Liang Yu Faculty of Land resource engineering Kunming University of Science and TechnologyKunming 650093China

The Gengma-Lancang-Menghai seismic belt,the southernmost part of the North-South seismic belt,is controlled by four active faults:the Nantinghe fault(NTHF),the Sanjianshan fault(SJSF),the Hanmuba-Lancang fault(HMB-LCF),and the Heihe fault(HHF),from northwest to ***,the tectonic activity of the faults in the Gengma-Lancang-Menghai seismic belt has not been fully studied *** the present work,we conducted tectonic geomorphic indices to analyze the relative tectonic activity along the faults in the seismic belt based on the digital elevation *** interpreted asymmetric factor,index of drainage basin shape,hypsometric integral,normalized streamlength gradient,valley floor-to-width to height ratio,and longitudinal profiles to show that the relative tectonic activity is higher in the north and lower in the south,and is strong in the region from Shanjia to Huimin in the center of the seismic belt.

关键词： Gengma-Lancang-Menghai seismic belt southeastern Tibetan Plateau geomorphic indices longitudinal profile

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Layered double hydroxides functionalization toward rechargeable batteries Author links open overlay panel

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Particuology 2024年第8期91卷 138-154页

作者： Jianxiong Gao Bowen Jin Mingfei Shao State Key Laboratory of Chemical resource engineering Beijing University of Chemical TechnologyBeijing100029China Renewable Energy Research Institute Quzhou Institute for Innovation in Resource Chemical EngineeringQuzhou324000China

Layered double hydroxides(LDHs),known as typical two-dimensional materials with unique physicochemical properties,are regarded as promising candidates in energy storage ***,some inherent defects,such as poor conductivity and limited active sites,hinder the further development of ***,various functionalization strategies(e.g.,intercalation of guest molecules;metal ions doping and defect introduction of host layer;exfoliation to monolayer;hybridization with functional materials;construction of hierarchical structure;interface engineering and phase transformation)have been used to modify the characteristics of LDHs,which provides guidance for designing novel *** this review,we discuss how these strategies improve the properties of LDH-based materials,which are expected to possess high electronic and ionic conductivity,high specific surface area and high mechanical and chemical stability ***,the application of LDH-based materials in advanced energy conversion and storage techniques,including metal-ions batteries,lithium-sulfur batteries and metal-air batteries,have been comprehensively summarized.

关键词： Layered double hydroxide Functionalization strategy Rechargeable battery

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Extract lithium from clay-type lithium ore by mixed acid and its mechanism Author links open overlay panel

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Particuology 2024年第8期91卷 323-332页

作者： Wuchang Zhou Ruiqi Xie Xiong Tong Xian Xie Yang Liu Zhihui Zhao Faculty of Land resource engineering Kunming University of Science and TechnologyKunming650093China technology Innovation Center for Comprehensive Utilization of Strategic mineral resources Ministry of Natural ResourcesChengdu610041China National&Regional engineering Research Center for Green comprehensive Utilization of Tailing resources from Metal minerals Kunming650093China

A roasting-leaching test was carried out for the efficient utilization of clay-type lithium ore in the central region of Yunnan *** test used the mixed acid of sulfuric acid and phosphoric acid as the leaching *** the conditions of roasting temperature of 600℃,roasting time of 1 h,liquid-solid ratio of 5:1,volume ratio of H_(2)SO_(4)solution to H_(3)PO_(4)solution of 45:5,leaching time of 2 h and leaching temperature of 80℃,the leaching rate of lithium was as high as 97.83%.The leaching mechanism was studied by SEM,pore property analysis,XRD and *** was found that the morphology of the ore changed obviously after roasting and leaching,and a certain degree of collapse and fragmentation occurred,which provided favorable spatial conditions for the leaching of *** porosity,total intrusion volume and total pore area also increased after roasting and leaching,thus promoting the leaching of Li^(+).The results showed that chemical reaction taken placed during the roasting and *** phase of the sample changed from chlorite,kaolinite and diaspore(boehmite)mainly to corundum,hematite,periclase and quartz after ***,after leaching,no new phase was produced in the ore sample,and no S and P elements were found on the surface of the ore sample,indicating that the leaching mechanism of lithium might be the ion exchange between H^(+)and Li^(+).

关键词： Clay-type lithium ore Lithium extraction Roasting Leaching

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Electroactivity of the magnetotactic bacteria Magnetospirillum magneticum AMB-1 and Magnetospirillum gryphiswaldense MSR-1

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Frontiers of Environmental Science & engineering 2024年第4期18卷 103-110页

作者： Mathias Fessler Qingxian Su Marlene Mark Jensen Yifeng Zhang department of Environmental and resource engineering Technical University of DenmarkCopenhagenDK-2800Denmark

Magnetotactic bacteria reside in sediments and stratified water *** are named after their ability to synthesize internal magnetic particles that allow them to align and swim along the Earth’s magnetic field ***,we show that two magnetotactic species,Magnetospirillum magneticum strain AMB-1 and Magnetospirillum gryphiswaldense strain MSR-1,are *** *** and *** were able to generate current in microbial fuel cells with maximum power densities of 27 and 11μW/m^(2),*** the presence of the electron shuttle resazurin both species were able to reduce the crystalline iron oxide hematite(Fe_(2)O_(3)).In addition,*** could reduce poorly crystalline iron oxide(FeOOH).Our study adds *** and *** to the growing list of known electroactive bacteria,and implies that electroactivity might be common for bacteria within the Magnetospirillum genus.

关键词： Magnetotactic bacteria Magnetospirillum magneticum Magnetospirillum gryphiswaldense Extracellular electron transfer Microbial fuel cells

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