Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature c...Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature catalysts has become a current research focus.In this study,Nb was used to dope and modify the Mn_(7)-Cu_(3)/BCN catalyst to construct the Mn_(7)-Cu_(3)-Nb_(x)/BCN system.The doping amount was optimized through selective catalytic reduction(SCR)activity tests.The reaction mechanism was explored by combining in situ DRIFTS and density functional theory(DFT)simulations.Experimental findings revealed that the catalyst doped with 0.05%Nb achieved the optimal performance,sustaining a NO conversion efficiency of≥94%within the temperature window of 150−275℃while demonstrating improved resistance to alkali metal K poisoning.Mechanistic analyses showed that at low temperatures,the catalyst facilitated the SCR reaction via both the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)pathways,with the synergistic interaction between multiple active sites driving the efficient conversion of NH3 and NO.DFT calculations further confirmed that both pathways had the characteristics of low reaction energy barriers and significant exothermicity,ensuring the high activity and feasibility of the low-temperature reaction.The findings provided foundational theoretical support for the design of Nb-doped Mn-Cu-supported catalysts and the exploration of the underlying working mechanisms.展开更多
The paleo-geothermal gradient is a crucial parameter for converting the thermal history to the exhumation history.However,the precise estimation of this parameter has been a challenge.This paper presents a simple two-...The paleo-geothermal gradient is a crucial parameter for converting the thermal history to the exhumation history.However,the precise estimation of this parameter has been a challenge.This paper presents a simple two-step method to model the paleo-geothermal gradient using low-temperature thermochronology.(1)It uses the Monte Carlo approach to generate thermal histories in a vertical section randomly and calculates the entire thermal history within the goodnessof-fit thresholds based on different paleo-geothermal gradients.(2)It selects the optimum paleogeothermal gradient by comparing the entire thermal history within different goodness-of-fit thresholds.We validated the method with apatite(U-Th)/He and fission track data collected from two drill cores in the Haiyuan-Liupanshan region.The result revealed that the best-fit paleo-geothermal gradient was~42℃/km during the Early Cretaceous–Miocene and has decreased rapidly to 20℃/km since~10 Ma.The crust thickening in the study area may explain the rapid reduction in the paleogeothermal gradient since~10 Ma.Our results are consistent with earlier studies in the region,suggesting that our simple and more intuitive approach provides an alternative method for paleogeothermal gradient modeling.展开更多
A photocatalysis process-enabled thioacylation of amines has been developed with eco-friendly feedstock potassium dithiocarboxylates as green thioacyl sources and water as the reaction solvent.The key to the success o...A photocatalysis process-enabled thioacylation of amines has been developed with eco-friendly feedstock potassium dithiocarboxylates as green thioacyl sources and water as the reaction solvent.The key to the success of this transformation is the light-induced generation of active dithioacyl disulfides as thioacyl donors.This green methodology has been successfully employed for the late-stage thioacylation of various amino compounds including drugs,hormones,amino acids and peptides under mild conditions.展开更多
In igneous-intruded coal seams,coal undergoes significant metamorphism,which critically alters its pore structure and oxygen consumption dynamics,thereby elevating its spontaneous combustion tendency.This study invest...In igneous-intruded coal seams,coal undergoes significant metamorphism,which critically alters its pore structure and oxygen consumption dynamics,thereby elevating its spontaneous combustion tendency.This study investigates the specific surface area,pore volume,structure complexity/connectivity,heterogeneity/local features of pore size distribution,and oxygen consumption dynamics of igneous metamorphic coal through N_(2)/CO_(2) isothermal adsorption tests and low-temperature oxidation experiments,and elucidates the influence mechanisms of pore structure evolution on oxygen consumption dynamics during low-temperature oxidation.With increasing metamorphic degree,igneous metamorphic coal exhibits a more pronounced reduction in specific surface area during oxidation,while the increase in structure complexity due to coal-oxygen reactions is suppressed.Thermally metamorphic coal demonstrates accelerated oxygen consumption,with oxidation amplifying the difference in reaction rates compared to raw coal.Key mechanisms include oxidation-induced reduction in mesopore complexity and micropore volume,decreased dominance of small-pore-volume apertures,and increased heterogeneity,collectively leading to a lower half-oxygen-consuming temperature and steeper oxygen consumption curves.Simultaneously,increased pore volume/complexity and reduced uniformity/connectivity act synergistically to enhance oxygen consumption capacity,highlighting the coupling between pore structure evolution and oxidation behavior in igneous metamorphic coal.This study provides theoretical insights into the pore-oxygen coupling mechanisms governing coal spontaneous combustion in igneous intrusion areas.展开更多
Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
High-entropy materials(HEMs),characterized by their unique compositional diversity and configurational entropy,have emerged as promising candidates in the field of photocatalysis.These materials,typically composed of ...High-entropy materials(HEMs),characterized by their unique compositional diversity and configurational entropy,have emerged as promising candidates in the field of photocatalysis.These materials,typically composed of five or more principal elements,exhibit remarkable structural stability,enhanced electronic properties,and superior resistance to corrosion and oxidation.In the realm of photocatalysis,HEMs offer several advantages,including broad spectral absorption,efficient charge separation,and robust catalytic activity under various environmental conditions.This review summarizes recent advancements in the synthesis,characterization,and application of HEMs for photocatalytic processes,such as H_(2)evolution,CO_(2)conversion,organic pollutant degradation,and organic conversion.By exploring the intrinsic properties of HEMs and their synergistic effects,we aim to highlight their potential to revolutionize the design and development of next-generation photocatalysts.The integration of HEMs into photocatalytic systems not only paves the way for more efficient and sustainable energy conversion technologies but also opens new avenues for environmental remediation.展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent ...Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent is investigated as an aqueous proton battery electrolyte,which not only enhances the cycling performance of MoO_(3) nanorod anode but also improves its low-temperature electrochemical performance.Specifically,the EG tightly adsorbs onto the surface of MoO_(3) nanorods,thereby inhibiting the corrosion from H_(2)O molecules in the electrolyte and suppressing the dissolution of MoO_(3).In addition,EG molecule disturbs the hydrogen-bond network between H_(2)O molecules,which greatly decreases the freezing point of the electrolyte,endowing the MoO_(3) nanorods with excellent low-temperature electrochemical performance.Therefore,the MoO_(3) nanorods exhibit a capacity retention of 96.9%after 2000 cycles at a current density of 10 A g^(-1)in a three-electrode system.After assembling with CuHCF cathode,under-40℃,the full battery displays negligible capacity decay for over 2500 cycles at 1 A g^(-1).These results indicate that the cosolvent strategy has the promising potential in enhancing the performance of aqueous proton batteries.展开更多
Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development...Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development of highly efficient SACs and a comprehensive understanding of their structure-activity relationships remain enormously challenging.Herein,a novel kind of Fe-based SAC featuring an asymmetric FeN_(5)-TeN_(4) coordination structure was precisely designed by introducing Te atom adjacent to the Fe active center to enhance the catalytic activity.Theoretical calculations reveal that the neighboring Te atom modulates the local coordination environment of the central Fe site,elevating the d-band center closer to the Fermi level and strengthening the d-p orbital hybridization between the catalyst and sulfur species,thereby immobilizing polysulfides and improving the bidirectional catalysis of Li-S redox.Consequently,the Fe-Te atom pair catalyst endows Li-S batteries with exceptional rate performance,achieving a high specific capacity of 735 mAh g^(−1) at 5 C,and remarkable cycling stability with a low decay rate of 0.038%per cycle over 1000 cycles at 1 C.This work provides fundamental insights into the electronic structure modulation of SACs and establishes a clear correlation between precisely engineered atomic configurations and their enhanced catalytic performance in Li-S electrochemistry.展开更多
The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexit...The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.展开更多
Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization w...Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar(MHC)for Fenton-like degradation of tetracycline in aqueous solution.Diverse shapes of Fe_(3)O_(4) and nano zero-valent iron(nZVI)were doped with abundant oxygen containing groups and persistent free radicals(PFRs).Multiple catalysis sites including iron species,PFRs,oxygen containing groups,and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect.Notably,MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L,with a total organic carbon(TOC)removal rate of 35%.Furthermore,after four cycles of reuse,the degradation efficiency slightly decreased to 93%.This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.展开更多
The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasoni...The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.展开更多
The reliable operation of lithium-ion batteries(LIBs)in low temperatures has long been hindered by severe side reactions on graphite anodes.To develop a commercially viable low-temperature electrolyte,we design a solv...The reliable operation of lithium-ion batteries(LIBs)in low temperatures has long been hindered by severe side reactions on graphite anodes.To develop a commercially viable low-temperature electrolyte,we design a solvent-resistant Nitrate-coordinated electrolyte.The practical Ah-level graphite LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) pouch cell with the newly developed electrolyte demonstrates a significant breakthrough in cycling stability,exhibiting negligible capacity fade after 250 cycles at-30℃ and 0.1 C.NO_(3)^(-),as the functional additive,compresses the electric field around Li^(+)through electrostatic interactions,mimicking the Debye-screening effect and inducing the coordinative exclusion of free ethyl acetate molecules at low temperatures.The transformation from contact ion pairs(CIPs)formed by Pto solventseparated ion pairs is significantly restrained,which mitigates the continuous reactions between the electrolyte and inevitable lithium deposition at low temperature.Additionally,this customized inert CIPs form a solid electrolyte interphase on graphite that exhibits remarkable ionic conductivity and rigidity,preventing excessive Li dendrite growth.This finding offers new insights into the relationship of microstructure-performance for low-temperature electrolytes,demonstrating that relying solely on inert CIPs can also inhibit the decomposition of the interfacial electrolyte,and inspires a unique design concept for high-performance,commercially viable LIBs that operate reliably in sub-zero environments.展开更多
Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent c...Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.展开更多
Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is g...Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is generally slow at low temperature,resulting in large overpotential and low current efficiency.Thus,the application of external physical fields has emerged as an effective strategy for improving the mass and charge transfer processes during electrochemical reactions.This review highlights the challenges associated with low-temperature electrochemical processes and briefly discusses recent achievements in optimizing electrodeposition processes through the use of external physical fields.The regulating effects on the optimization of the electrodeposition process and the strategies for select-ing various external physical fields,including magnetic,supergravity,and ultrasonic fields are summarized from the perspectives of equipment and mechanisms.Finally,advanced methods for in-situ characterization of external physical field-assisted electrodeposition processes are reviewed to gain a deeper understanding of metallic electrodeposition.An in-depth exploration of the mechanism by which external physical fields affect the electrode process is essential for enhancing the efficiency of metal extraction at low temperatures.展开更多
Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-form...Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.展开更多
To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the character...To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the characteristics of low-tempe rature sulfuric acid deco mposition.When a single monazite was leached using 75 wt% H_(2)SO_(4) solution with phosphoric acid,the size and number of monazite particles in the washing slag gradually decrease with the increase in phosphoric acid content in the leaching solution.The monazite phase can hardly be found in the slag when the phosphoric acid content reaches 70 g/L,which indicates that phosphoric acid is favorable for monazite decomposition.The mixed rare earth concentrate was leached by 75 wt% H_(2)SO_(4) containing 70 g/L phosphoric acid,the mineral compositions of the washing slag are only gypsum and unwashed rare earth sulfuric acid.After cyclic leaching of75 wt% H_(2)SO_(4),the mineral compositions of the primary leaching washing slag are mainly undecomposed monazite,rare earth sulfate and calcium sulfate.However,monazite is not found in the mineral phase of the second and third leaching washing slag.The leaching rates of rare earth and phosphorus gradually increase with the increase in cyclic leaching times.In addition,the phosphoric acid content in the leaching solution increases with the increase in the number of cyclic leaching time.However,the rising trend decreases when the phosphoric acid content reaches 50 g/L by adsorption and crystallization of phosphoric acid.A small amount of water can be used to clean the leaching residue before washing to recover the more soluble phosphorus acid according to the difference of dissolution between phosphoric acid and rare earth sulfuric acid.展开更多
Photothermal catalysis is a synergetic process where photocatalysis and thermal catalysis work together to promote catalytic reactions,which compensates for the critical shortcomings of photocatalysis and thermal cata...Photothermal catalysis is a synergetic process where photocatalysis and thermal catalysis work together to promote catalytic reactions,which compensates for the critical shortcomings of photocatalysis and thermal catalysis,achieving an effect of 1+1>2.Previous reviews have summarized the mechanism of photothermal catalysis and its specific application in certain fields,but few have systematically analyzed the essential factors affecting the activity of photothermal catalysis,or provided a comprehensive summary of its application fields.In this review,the superiority of photothermal catalysis over individual photocatalysis and thermal catalysis will be comprehensively discussed with the aim to emphasize the importance of developing photothermal catalysis.After elucidating the basic mechanism of photothermal catalysis,an ample discussion on the factors influencing the catalytic activity of photothermal materials is provided from the following three perspectives:morphology,localized surface plasmon resonance,and defective structure of photothermal materials.Subsequently,this review summarizes the broad applications of photothermal catalysis in environmental management and energy conversion.Finally,this review discusses the challenges encountered in photothermal catalysis technology and proposes directions for future development.It provides new perspectives and a profound understanding of photothermal materials in photothermal environmental governance and energy conversion.展开更多
Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modificat...Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.展开更多
基金Supported by National Key Research and Development Program of China(2020YFD1100302)。
文摘Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature catalysts has become a current research focus.In this study,Nb was used to dope and modify the Mn_(7)-Cu_(3)/BCN catalyst to construct the Mn_(7)-Cu_(3)-Nb_(x)/BCN system.The doping amount was optimized through selective catalytic reduction(SCR)activity tests.The reaction mechanism was explored by combining in situ DRIFTS and density functional theory(DFT)simulations.Experimental findings revealed that the catalyst doped with 0.05%Nb achieved the optimal performance,sustaining a NO conversion efficiency of≥94%within the temperature window of 150−275℃while demonstrating improved resistance to alkali metal K poisoning.Mechanistic analyses showed that at low temperatures,the catalyst facilitated the SCR reaction via both the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)pathways,with the synergistic interaction between multiple active sites driving the efficient conversion of NH3 and NO.DFT calculations further confirmed that both pathways had the characteristics of low reaction energy barriers and significant exothermicity,ensuring the high activity and feasibility of the low-temperature reaction.The findings provided foundational theoretical support for the design of Nb-doped Mn-Cu-supported catalysts and the exploration of the underlying working mechanisms.
基金supported by the National Natural Science Foundation of China(Nos.42072229,42030301,41102131,41972049,41972302 and 41977231)the Guangdong Basic and Applied Basic Research Foundation(No.2025A1515010724)+3 种基金the Guangdong Natural Science Foundation(No.2021A1515011658)the Science and Technology Program of Guangzhou(No.202002030184)the Special Fund for Basic Scientific Research of Central Colleges,Chang'an University(No.300102260502)the Deep Earth Probe and Mineral Resources Exploration-National Science and Technology Major Project(No.2024ZD1001003)。
文摘The paleo-geothermal gradient is a crucial parameter for converting the thermal history to the exhumation history.However,the precise estimation of this parameter has been a challenge.This paper presents a simple two-step method to model the paleo-geothermal gradient using low-temperature thermochronology.(1)It uses the Monte Carlo approach to generate thermal histories in a vertical section randomly and calculates the entire thermal history within the goodnessof-fit thresholds based on different paleo-geothermal gradients.(2)It selects the optimum paleogeothermal gradient by comparing the entire thermal history within different goodness-of-fit thresholds.We validated the method with apatite(U-Th)/He and fission track data collected from two drill cores in the Haiyuan-Liupanshan region.The result revealed that the best-fit paleo-geothermal gradient was~42℃/km during the Early Cretaceous–Miocene and has decreased rapidly to 20℃/km since~10 Ma.The crust thickening in the study area may explain the rapid reduction in the paleogeothermal gradient since~10 Ma.Our results are consistent with earlier studies in the region,suggesting that our simple and more intuitive approach provides an alternative method for paleogeothermal gradient modeling.
基金supported by the National Natural Science Foundation of China(No.21901179)the Natural Science Foundation of Shanxi Province(No.202103021224067)the Scientific Activities of Selected Returned Overseas Professionals of Shanxi Province(No.20200002).
文摘A photocatalysis process-enabled thioacylation of amines has been developed with eco-friendly feedstock potassium dithiocarboxylates as green thioacyl sources and water as the reaction solvent.The key to the success of this transformation is the light-induced generation of active dithioacyl disulfides as thioacyl donors.This green methodology has been successfully employed for the late-stage thioacylation of various amino compounds including drugs,hormones,amino acids and peptides under mild conditions.
基金supported by the National Natural Science Foundation of China(No.52374247)the Joint Funds of the National Natural Science Foundation of China(No.U24B2042).
文摘In igneous-intruded coal seams,coal undergoes significant metamorphism,which critically alters its pore structure and oxygen consumption dynamics,thereby elevating its spontaneous combustion tendency.This study investigates the specific surface area,pore volume,structure complexity/connectivity,heterogeneity/local features of pore size distribution,and oxygen consumption dynamics of igneous metamorphic coal through N_(2)/CO_(2) isothermal adsorption tests and low-temperature oxidation experiments,and elucidates the influence mechanisms of pore structure evolution on oxygen consumption dynamics during low-temperature oxidation.With increasing metamorphic degree,igneous metamorphic coal exhibits a more pronounced reduction in specific surface area during oxidation,while the increase in structure complexity due to coal-oxygen reactions is suppressed.Thermally metamorphic coal demonstrates accelerated oxygen consumption,with oxidation amplifying the difference in reaction rates compared to raw coal.Key mechanisms include oxidation-induced reduction in mesopore complexity and micropore volume,decreased dominance of small-pore-volume apertures,and increased heterogeneity,collectively leading to a lower half-oxygen-consuming temperature and steeper oxygen consumption curves.Simultaneously,increased pore volume/complexity and reduced uniformity/connectivity act synergistically to enhance oxygen consumption capacity,highlighting the coupling between pore structure evolution and oxidation behavior in igneous metamorphic coal.This study provides theoretical insights into the pore-oxygen coupling mechanisms governing coal spontaneous combustion in igneous intrusion areas.
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金financially supported by the Eastern Institute of Technology,Ningbo。
文摘High-entropy materials(HEMs),characterized by their unique compositional diversity and configurational entropy,have emerged as promising candidates in the field of photocatalysis.These materials,typically composed of five or more principal elements,exhibit remarkable structural stability,enhanced electronic properties,and superior resistance to corrosion and oxidation.In the realm of photocatalysis,HEMs offer several advantages,including broad spectral absorption,efficient charge separation,and robust catalytic activity under various environmental conditions.This review summarizes recent advancements in the synthesis,characterization,and application of HEMs for photocatalytic processes,such as H_(2)evolution,CO_(2)conversion,organic pollutant degradation,and organic conversion.By exploring the intrinsic properties of HEMs and their synergistic effects,we aim to highlight their potential to revolutionize the design and development of next-generation photocatalysts.The integration of HEMs into photocatalytic systems not only paves the way for more efficient and sustainable energy conversion technologies but also opens new avenues for environmental remediation.
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金supported by the National Natural Science Foundation of China(22409071)Natural Foundation of Shandong Province(ZR2024QB120)+2 种基金Youth Innovation Group Plan of Shandong Province(2024KJG046)Higher-Level Talent Initial Scientific Research and Discipline Construction Fund(511/1009530)Joint Funds of the National Natural Science Foundation of China(No.U22A20140)。
文摘Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent is investigated as an aqueous proton battery electrolyte,which not only enhances the cycling performance of MoO_(3) nanorod anode but also improves its low-temperature electrochemical performance.Specifically,the EG tightly adsorbs onto the surface of MoO_(3) nanorods,thereby inhibiting the corrosion from H_(2)O molecules in the electrolyte and suppressing the dissolution of MoO_(3).In addition,EG molecule disturbs the hydrogen-bond network between H_(2)O molecules,which greatly decreases the freezing point of the electrolyte,endowing the MoO_(3) nanorods with excellent low-temperature electrochemical performance.Therefore,the MoO_(3) nanorods exhibit a capacity retention of 96.9%after 2000 cycles at a current density of 10 A g^(-1)in a three-electrode system.After assembling with CuHCF cathode,under-40℃,the full battery displays negligible capacity decay for over 2500 cycles at 1 A g^(-1).These results indicate that the cosolvent strategy has the promising potential in enhancing the performance of aqueous proton batteries.
基金supported by the National Natural Science Foundation(52302284,22002086,22204096)Shanghai Sailing Program(23YF1412200)the Fundamental Research Funds for the Central Universities(22120240314).
文摘Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development of highly efficient SACs and a comprehensive understanding of their structure-activity relationships remain enormously challenging.Herein,a novel kind of Fe-based SAC featuring an asymmetric FeN_(5)-TeN_(4) coordination structure was precisely designed by introducing Te atom adjacent to the Fe active center to enhance the catalytic activity.Theoretical calculations reveal that the neighboring Te atom modulates the local coordination environment of the central Fe site,elevating the d-band center closer to the Fermi level and strengthening the d-p orbital hybridization between the catalyst and sulfur species,thereby immobilizing polysulfides and improving the bidirectional catalysis of Li-S redox.Consequently,the Fe-Te atom pair catalyst endows Li-S batteries with exceptional rate performance,achieving a high specific capacity of 735 mAh g^(−1) at 5 C,and remarkable cycling stability with a low decay rate of 0.038%per cycle over 1000 cycles at 1 C.This work provides fundamental insights into the electronic structure modulation of SACs and establishes a clear correlation between precisely engineered atomic configurations and their enhanced catalytic performance in Li-S electrochemistry.
基金supported financially by the Key Project of the National Ministry of Science and Technology (No.2022YFC3705005)the Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering,MOE (KLIEEE-22-05)
文摘The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.
基金supported byHainan Provincial Natural Science Foundation of China(Nos.422RC600,519QN175)National Natural Science Foundation ofChina(Nos.52160018,21801053,52400206,52500209)High-Level Talent Program of Hainan Province(Nos.XJ2400008202,XJ2400011473).
文摘Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar(MHC)for Fenton-like degradation of tetracycline in aqueous solution.Diverse shapes of Fe_(3)O_(4) and nano zero-valent iron(nZVI)were doped with abundant oxygen containing groups and persistent free radicals(PFRs).Multiple catalysis sites including iron species,PFRs,oxygen containing groups,and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect.Notably,MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L,with a total organic carbon(TOC)removal rate of 35%.Furthermore,after four cycles of reuse,the degradation efficiency slightly decreased to 93%.This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.
基金supported by Yunnan Major Scientific and Technological Projects (Grant No. 202402AB080004)Yunnan Provincial Education Department Universities Serve Key Industry Science and Technology Projects (Grant No: FWCY-BSPY2024043)+1 种基金Top Innovative Talents for Graduate Students of KUST (Grant No: CA24163M116A)Analysis and Testing Fund of KUST (Grant No: 2024P20233102006)
文摘The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.
基金support from the Heilongjiang Touyan Innovation Team Program(HITTY-20190033)National Natural Science Foundation of China(22278096)Innovation Special Project on Science and Technology for Carbon Peaking and Carbon Neutrality in Jiangsu Province(WSSJH20230015)。
文摘The reliable operation of lithium-ion batteries(LIBs)in low temperatures has long been hindered by severe side reactions on graphite anodes.To develop a commercially viable low-temperature electrolyte,we design a solvent-resistant Nitrate-coordinated electrolyte.The practical Ah-level graphite LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) pouch cell with the newly developed electrolyte demonstrates a significant breakthrough in cycling stability,exhibiting negligible capacity fade after 250 cycles at-30℃ and 0.1 C.NO_(3)^(-),as the functional additive,compresses the electric field around Li^(+)through electrostatic interactions,mimicking the Debye-screening effect and inducing the coordinative exclusion of free ethyl acetate molecules at low temperatures.The transformation from contact ion pairs(CIPs)formed by Pto solventseparated ion pairs is significantly restrained,which mitigates the continuous reactions between the electrolyte and inevitable lithium deposition at low temperature.Additionally,this customized inert CIPs form a solid electrolyte interphase on graphite that exhibits remarkable ionic conductivity and rigidity,preventing excessive Li dendrite growth.This finding offers new insights into the relationship of microstructure-performance for low-temperature electrolytes,demonstrating that relying solely on inert CIPs can also inhibit the decomposition of the interfacial electrolyte,and inspires a unique design concept for high-performance,commercially viable LIBs that operate reliably in sub-zero environments.
文摘Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.
基金supported by Southern Marine Science and Engineering Guangdong Laboratory(Zhuhai)(No.SML2023SP243)the National Key Research and Development Program of China(No.2022YFC2906100)the National Natural Science Foundation of China(No.92475202)are acknowledged.
文摘Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is generally slow at low temperature,resulting in large overpotential and low current efficiency.Thus,the application of external physical fields has emerged as an effective strategy for improving the mass and charge transfer processes during electrochemical reactions.This review highlights the challenges associated with low-temperature electrochemical processes and briefly discusses recent achievements in optimizing electrodeposition processes through the use of external physical fields.The regulating effects on the optimization of the electrodeposition process and the strategies for select-ing various external physical fields,including magnetic,supergravity,and ultrasonic fields are summarized from the perspectives of equipment and mechanisms.Finally,advanced methods for in-situ characterization of external physical field-assisted electrodeposition processes are reviewed to gain a deeper understanding of metallic electrodeposition.An in-depth exploration of the mechanism by which external physical fields affect the electrode process is essential for enhancing the efficiency of metal extraction at low temperatures.
基金financial support from the Department of Science and Technology of Jilin Province(20240304104SF,20240304103SF)the Research and Innovation Fund of the Beihua University for the Graduate Student(Major Project 2023012)。
文摘Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.
基金support by the National Natural Science Foundation of Inner Mongolia (2022SHZR1885)Natural Science Foundation of Hebei province (E2022402101,E2022402105)。
文摘To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the characteristics of low-tempe rature sulfuric acid deco mposition.When a single monazite was leached using 75 wt% H_(2)SO_(4) solution with phosphoric acid,the size and number of monazite particles in the washing slag gradually decrease with the increase in phosphoric acid content in the leaching solution.The monazite phase can hardly be found in the slag when the phosphoric acid content reaches 70 g/L,which indicates that phosphoric acid is favorable for monazite decomposition.The mixed rare earth concentrate was leached by 75 wt% H_(2)SO_(4) containing 70 g/L phosphoric acid,the mineral compositions of the washing slag are only gypsum and unwashed rare earth sulfuric acid.After cyclic leaching of75 wt% H_(2)SO_(4),the mineral compositions of the primary leaching washing slag are mainly undecomposed monazite,rare earth sulfate and calcium sulfate.However,monazite is not found in the mineral phase of the second and third leaching washing slag.The leaching rates of rare earth and phosphorus gradually increase with the increase in cyclic leaching times.In addition,the phosphoric acid content in the leaching solution increases with the increase in the number of cyclic leaching time.However,the rising trend decreases when the phosphoric acid content reaches 50 g/L by adsorption and crystallization of phosphoric acid.A small amount of water can be used to clean the leaching residue before washing to recover the more soluble phosphorus acid according to the difference of dissolution between phosphoric acid and rare earth sulfuric acid.
基金supported by the National Natural Science Foundation of China(52161145409,21976116)State Administration of Foreign Experts Affairs(SAFEA)of China(“Belt and Road”Innovative Talent Exchange Foreign Expert Project,2023041004L+1 种基金Highend Foreign Expert Project,G2023041021L)Alexander-vonHumboldt Foundation of Germany(Group-Linkage Program)。
文摘Photothermal catalysis is a synergetic process where photocatalysis and thermal catalysis work together to promote catalytic reactions,which compensates for the critical shortcomings of photocatalysis and thermal catalysis,achieving an effect of 1+1>2.Previous reviews have summarized the mechanism of photothermal catalysis and its specific application in certain fields,but few have systematically analyzed the essential factors affecting the activity of photothermal catalysis,or provided a comprehensive summary of its application fields.In this review,the superiority of photothermal catalysis over individual photocatalysis and thermal catalysis will be comprehensively discussed with the aim to emphasize the importance of developing photothermal catalysis.After elucidating the basic mechanism of photothermal catalysis,an ample discussion on the factors influencing the catalytic activity of photothermal materials is provided from the following three perspectives:morphology,localized surface plasmon resonance,and defective structure of photothermal materials.Subsequently,this review summarizes the broad applications of photothermal catalysis in environmental management and energy conversion.Finally,this review discusses the challenges encountered in photothermal catalysis technology and proposes directions for future development.It provides new perspectives and a profound understanding of photothermal materials in photothermal environmental governance and energy conversion.
基金supported by The National Key R&D Program of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04)。
文摘Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.
