In recent years,artificial intelligence(AI)has been widely used in the field of electricity,such as load prediction,fault diagnosis of the power equipment,intelligent scheduling of power grids.However,the application ...In recent years,artificial intelligence(AI)has been widely used in the field of electricity,such as load prediction,fault diagnosis of the power equipment,intelligent scheduling of power grids.However,the application of latest AI technology still has many technical difficulties to be solved.In the process of upgrading from the traditional power system to the new-type power system,AC grids,DC grids and micro grids coexist.In addition,there are huge amount of power equipment and electronic devices,and the coupling relationship is very complicated.Moreover,the high proportion of clean energy and flexible loads connected to the grid leads to the enhancement of the stochastic characteristics of the system.And short-term and ultra-short-term forecasts are much more difficult.Therefore,the editorial office of Global Energy Interconnection has planned the special issue of“Artificial Intelligence Applied in New-Type Power System”.展开更多
Phase change materials(PCMs)offer a promising solution to address the challenges posed by intermittency and fluctuations in solar thermal utilization.However,for organic solid-liquid PCMs,issues such as leakage,low th...Phase change materials(PCMs)offer a promising solution to address the challenges posed by intermittency and fluctuations in solar thermal utilization.However,for organic solid-liquid PCMs,issues such as leakage,low thermal conductivity,lack of efficient solar-thermal media,and flamma-bility have constrained their broad applications.Herein,we present an innova-tive class of versatile composite phase change materials(CPCMs)developed through a facile and environmentally friendly synthesis approach,leveraging the inherent anisotropy and unidirectional porosity of wood aerogel(nanowood)to support polyethylene glycol(PEG).The wood modification process involves the incorporation of phytic acid(PA)and MXene hybrid structure through an evaporation-induced assembly method,which could impart non-leaking PEG filling while concurrently facilitating thermal conduction,light absorption,and flame-retardant.Consequently,the as-prepared wood-based CPCMs showcase enhanced thermal conductivity(0.82 W m^(-1)K^(-1),about 4.6 times than PEG)as well as high latent heat of 135.5 kJ kg^(-1)(91.5%encapsula-tion)with thermal durability and stability throughout at least 200 heating and cooling cycles,featuring dramatic solar-thermal conversion efficiency up to 98.58%.In addition,with the synergistic effect of phytic acid and MXene,the flame-retardant performance of the CPCMs has been significantly enhanced,showing a self-extinguishing behavior.Moreover,the excellent electromagnetic shielding of 44.45 dB was endowed to the CPCMs,relieving contemporary health hazards associated with electromagnetic waves.Overall,we capitalize on the exquisite wood cell structure with unidirectional transport inherent in the development of multifunctional CPCMs,showcasing the operational principle through a proof-of-concept prototype system.展开更多
Atomically dispersed metal sites(ADMSs)play key roles in electrochemical energy conversion.The covalent organic frameworks(COFs)enable the precise control of the chemical compositions and structures at the molecular l...Atomically dispersed metal sites(ADMSs)play key roles in electrochemical energy conversion.The covalent organic frameworks(COFs)enable the precise control of the chemical compositions and structures at the molecular level,making them ideal substrates for supporting ADMSs.In this review,we systematically summarize the recent progress on the design and synthesis of ADMSs in COFs,including embedding molecular catalysts into COFs,immobilizing ADMSs on heteroatom-containing COFs,and preparing COF-derived carbon materials through pyrolysis.The electrocatalytic performance of the resulting catalysts is presented for various electrochemical reactions,involving oxygen reduction reaction(ORR),carbon dioxide reduction reaction(CO_(2)RR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and nitrogen reduction reaction(NRR).The modulation strategies of AMDSs in COFs for enhanced activity,selectivity,and stability are highlighted,together with a perspective of the current challenges and the future opportunities in this field.展开更多
Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,hi...Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.展开更多
Parameterization is a critical step in modelling ecosystem dynamics.However,assigning parameter values can be a technical challenge for structurally complex natural plant communities;uncertainties in model simulations...Parameterization is a critical step in modelling ecosystem dynamics.However,assigning parameter values can be a technical challenge for structurally complex natural plant communities;uncertainties in model simulations often arise from inappropriate model parameterization.Here we compared five methods for defining community-level specific leaf area(SLA)and leaf C:N across nine contrasting forest sites along the North-South Transect of Eastern China,including biomass-weighted average for the entire plant community(AP_BW)and four simplified selective sampling(biomass-weighted average over five dominant tree species[5DT_BW],basal area weighted average over five dominant tree species[5DT_AW],biomass-weighted average over all tree species[AT_BW]and basal area weighted average over all tree species[AT_AW]).We found that the default values for SLA and leaf C:N embedded in the Biome-BGC v4.2 were higher than the five computational methods produced across the nine sites,with deviations ranging from 28.0 to 73.3%.In addition,there were only slight deviations(<10%)between the whole plant community sampling(AP_BW)predicted NPP and the four simplified selective sampling methods,and no significant difference between the predictions of AT_BW and AP_BW except the Shennongjia site.The findings in this study highlights the critical importance of computational strategies for community-level parameterization in ecosystem process modelling,and will support the choice of parameterization methods.展开更多
The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal...The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In 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 performance.The 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 hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The 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.展开更多
The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of ...The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.展开更多
Elucidating the effect of growth periods on the quality of calcium sulfate whiskers(CSWs)prepared from calcium sulfate dihydrate(DH)is imperative.Herein,crystal seeds and whiskers were prepared from DH in a water–gly...Elucidating the effect of growth periods on the quality of calcium sulfate whiskers(CSWs)prepared from calcium sulfate dihydrate(DH)is imperative.Herein,crystal seeds and whiskers were prepared from DH in a water–glycerol system.Longer whiskers were obtained from crystal seeds prepared via hydration of DH for 30 s than via ball milling for 5 min followed by hydration for 20 s.The attachment of cetyltrimethyl ammonium bromide and glycerol additives to the whisker tops promoted whisker growth.The whisker sponges exhibited good thermal barrier properties and compression cycle stability.展开更多
Developing low-cost and green simultaneous desulfurization and denitrification technologies is of great significance for sulfur dioxide(SO_(2))and nitrogen oxide(NO_(x))emission control at low temperatures,especially ...Developing low-cost and green simultaneous desulfurization and denitrification technologies is of great significance for sulfur dioxide(SO_(2))and nitrogen oxide(NO_(x))emission control at low temperatures,especially for small and medium-sized coal-fired boilers and furnaces.Herein,phosphorus sludge,an industrial waste from the production process of yellow phosphorus,has been developed to simultaneously eliminate SO_(2)and NO_(x)from coal-fired flue gas.The key factors affecting the experimental results indicate that desulfurization and denitrification efficiency of over 95%can be achieved at a low temperature of 55℃.Further,the absorption mechanism was investigated by characterizing the solid and liquid phases of the phosphorus sludge during the absorption process.The efficient removal of SO_(2)is attributed to the abundance of iron(Fe^(3+))and manganese(Mn^(2+))in the absorbent.SO_(2)can be rapidly catalyzed and converted to SO_(4)^(2-)by them.The key to NOx removal is the oxidation of NO toward watersoluble high-valent nitrogen oxides by oxidizing reactive substances induced via yellow phosphorus,which are then absorbed by water and converted to NO_(3)^(-).Meanwhile,yellow phosphorus is oxidized to phosphoric acid(H_(3)PO_(4)).The spent absorption slurry can be reused through wet process phosphoric acid production,as it contains sulfuric acid(H_(2)SO_(4)),nitric acid(HNO_(3)),and H_(3)PO_(4).Accordingly,this is a technology with broad application prospects.展开更多
Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges re...Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges remain in their low site density and unsatisfactory mass transfer structure.Herein,we present a structural engineering approach employing a soft-template coating strategy to fabricate a hollow and hierarchically porous N-doped carbon framework anchored with atomically dispersed Fe sites(FeNCh) as an efficient ORR catalyst.The combination of hierarchical porosity and high exterior surface area is proven crucial for exposing more active sites,which gives rise to a remarkable ORR performance with a half-wave potential of 0.902 V in 0.1 m KOH and 0.814 V in 0.1 m HClO_(4),significantly outperforming its counterpart with solid structure and dominance of micropores(FeNC-s).The mass transfer property is revealed by in-situ electrochemical impedance spectroscopy(EIS) measurement.The distribution of relaxation time(DRT) analysis is further introduced to deconvolve the kinetic and mass transport processes,which demonstrates an alleviated mass transport resistance for FeNC-h,validating the effectiveness of structural engineering.This work not only provides an effective structural engineering approach but also contributes to the comprehensive mass transfer evaluation on advanced electrocatalyst for energy conversion applications.展开更多
Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have bee...Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.展开更多
This study developed a numerical model to efficiently treat solid waste magnesium nitrate hydrate through multi-step chemical reactions.The model simulates two-phase flow,heat,and mass transfer processes in a pyrolysi...This study developed a numerical model to efficiently treat solid waste magnesium nitrate hydrate through multi-step chemical reactions.The model simulates two-phase flow,heat,and mass transfer processes in a pyrolysis furnace to improve the decomposition rate of magnesium nitrate.The performance of multi-nozzle and single-nozzle injection methods was evaluated,and the effects of primary and secondary nozzle flow ratios,velocity ratios,and secondary nozzle inclination angles on the decomposition rate were investigated.Results indicate that multi-nozzle injection has a higher conversion efficiency and decomposition rate than single-nozzle injection,with a 10.3%higher conversion rate under the design parameters.The decomposition rate is primarily dependent on the average residence time of particles,which can be increased by decreasing flow rate and velocity ratios and increasing the inclination angle of secondary nozzles.The optimal parameters are injection flow ratio of 40%,injection velocity ratio of 0.6,and secondary nozzle inclination of 30°,corresponding to a maximum decomposition rate of 99.33%.展开更多
Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticle...Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.展开更多
The phase equilibrium and mechanical behaviors of natural gas hydrate-bearing sediment are essential for gas recovery from hydrate reservoirs.In heating closed systems,the temperature-pressure path of hydrate-bearing ...The phase equilibrium and mechanical behaviors of natural gas hydrate-bearing sediment are essential for gas recovery from hydrate reservoirs.In heating closed systems,the temperature-pressure path of hydrate-bearing sediment deviates from that of pure bulk hydrate,reflecting the porous media effect in phase equilibrium.A generalized phase equilibrium equation was established for hydrate-bearing sediments,which indicates that both capillary and osmotic pressures cause the phase equilibrium curve to shift leftward on the temperature-pressure plane.In contrast to bulk hydrate,hydrate-bearing sediment always contains a certain amount of unhydrated water,which keeps phase equilibrium with the hydrate within the hydrate stability field.With changes in temperature and pressure,a portion of pore hydrate and unhydrated water may transform into each other,affecting the shear strength of hydrate-bearing sediment.A shear strength model is proposed to consider not only hydrate saturation but also the change in temperature and pressure of hydrate-bearing sediment.The model is validated by experimental data with various hydrate saturation,temperature and pressure conditions.The deformation induced by partial dissociation was studied through depressurization tests under constant effective stress.The reduction in gas pressure within the hydrate stability field indeed caused sediment deformation.The dissociation-induced deformation can be reasonably estimated as the difference in volume between hydrate-bearing and hydrate-free sediments from the compression curves.展开更多
Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition...Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition,and lattice defects are still the key challenges limiting the quality of FAPbI_(3) films.Previous studies show that the introduction or adding of seeds in the precursor is effective to promote the nucleation and crystallization of perovskite films.Nevertheless,the seed-assisted approach focuses on heterogeneous seeds or hetero-composites,which inevitably induce a lattice-mismatch,the genera-tion of strain or defects,and the phase segregation in the perovskite films.Herein,we first demonstrate that high-quality perovskite films are controllably prepared using α-and δ-phases mixed FAPbI_(3) micro-crystal as the homogeneous seeds with the one-step antisolvent method.The partially dissolved seeds with suitable sizes improve the crystallinity of the perovskite flm with preferable orientation,improved carrier lifetime,and increased carrier mobility.More importantly,the α-phase-containing seeds promote the formation of α-phase FAPbI_(3) films,leading to the reduction of residual lattice strain and the suppres-sion of I-ion migration.Besides,the adding of dimethyl 2,6-pyridine dicarboxylate(DPD)into the pre-cursor further suppresses the generation of defects,contributing to the PCE of devices prepared in air ambient being significantly improved to 23.75%,among the highest PCEs for fully air-processed FAPbI_(3) solar cells.The unpackaged target devices possess a high stability,maintaining 80%of the initial PCE under simulated solar illumination exceeding 800 h.展开更多
The large-scale development of wind power is an important means to reduce greenhouse gas emissions, alleviate environmental pollution and improve the utilization rate of renewable energy. At the same time, large-scale...The large-scale development of wind power is an important means to reduce greenhouse gas emissions, alleviate environmental pollution and improve the utilization rate of renewable energy. At the same time, large-scale non grid connected wind power generation theory avoids the technical difficulties of wind power integration [1]. However, due to the randomness and uncontrollability of wind energy, the output power of the wind power generation system will fluctuate accordingly [2]. Therefore, the corresponding energy storage devices are arranged in the non-grid-connected wind power generation system to ensure the power quality, and it has become the key to full utilization of renewable energy. In the case of wind speed fluctuation, the DC bus control strategy of the wind turbine is proposed in this paper. It can reduce the impact on the unit converter and the power load;this ensures safe and stable operation of non-grid connected wind turbines.展开更多
1.Present characteristics of Beijing's energy consumption 1.1 The slowing of the growth in total energy consumption In 2008,Beijing's total energy consumption reached 63.437 million tons of standard coal,an in...1.Present characteristics of Beijing's energy consumption 1.1 The slowing of the growth in total energy consumption In 2008,Beijing's total energy consumption reached 63.437 million tons of standard coal,an increase of 586.6 thousand tons compared with the previous year.The increasing range was 1%,dropping 5.45%compared with the展开更多
Taking I-Magic Cube - the entry of Shandong Jianzhu University for Solar Decathlon 2013 - for example, the paper analyzes the conceptual, technological, functional and aesthetic solutions of zero energy solar house co...Taking I-Magic Cube - the entry of Shandong Jianzhu University for Solar Decathlon 2013 - for example, the paper analyzes the conceptual, technological, functional and aesthetic solutions of zero energy solar house coping with ecological, economic, social and cultural challenges. Passive strategies, the solar thermal and PV system, and the building integrated solar system tactics are elaborated. Finally, industrialization and marketing viability of the solar house prototypes are discussed.展开更多
Cutting fluid is crucial in ensuring surface quality and machining accuracy during machining.However,traditional mineral oil-based cutting fluids no longer meet modern machining’s health and environmental protection ...Cutting fluid is crucial in ensuring surface quality and machining accuracy during machining.However,traditional mineral oil-based cutting fluids no longer meet modern machining’s health and environmental protection require-ments.As a renewable,pollution-free alternative with excellent processing characteristics,vegetable oil has become an inevitable replacement.However,vegetable oil lacks oxidation stability,extreme pressure,and antiwear proper-ties,which are essential for machining requirements.The physicochemical characteristics of vegetable oils and the improved methods’application mechanism are not fully understood.This study aims to investigate the effects of viscosity,surface tension,and molecular structure of vegetable oil on cooling and lubricating properties.The mechanisms of autoxidation and high-temperature oxidation based on the molecular structure of vegetable oil are also discussed.The study further investigates the application mechanism and performance of chemical modification and antioxidant additives.The study shows that the propionic ester of methyl hydroxy-oleate obtained by epoxidation has an initial oxidation temperature of 175℃.The application mechanism and extreme pressure performance of conventional extreme pressure additives and nanoparticle additives were also investigated to solve the problem of insufficient oxidation resistance and extreme pressure performance of nanobiological lubricants.Finally,the study discusses the future prospects of vegetable oil for chemical modification and nanoparticle addition.The study provides theoretical guidance and technical support for the industrial application and scientific research of vegetable oil in the field of lubrication and cooling.It is expected to promote sustainable development in the manufacturing industry.展开更多
Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid...Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.展开更多
文摘In recent years,artificial intelligence(AI)has been widely used in the field of electricity,such as load prediction,fault diagnosis of the power equipment,intelligent scheduling of power grids.However,the application of latest AI technology still has many technical difficulties to be solved.In the process of upgrading from the traditional power system to the new-type power system,AC grids,DC grids and micro grids coexist.In addition,there are huge amount of power equipment and electronic devices,and the coupling relationship is very complicated.Moreover,the high proportion of clean energy and flexible loads connected to the grid leads to the enhancement of the stochastic characteristics of the system.And short-term and ultra-short-term forecasts are much more difficult.Therefore,the editorial office of Global Energy Interconnection has planned the special issue of“Artificial Intelligence Applied in New-Type Power System”.
基金funding from the National Natural Science Foundation of China(No.22268025)China Postdoctoral Science Foundation(NO.2022MD713757)+2 种基金Yunnan Provincial Postdoctoral Science Foundation(NO.34Y2022)Yunnan Province Joint Special Project for Enterprise Fundamental Research and Applied Basic Research(No.202101BC070001-016)Guangdong Basic and Applied Basic Research Foundation(No.2023A1515011985).
文摘Phase change materials(PCMs)offer a promising solution to address the challenges posed by intermittency and fluctuations in solar thermal utilization.However,for organic solid-liquid PCMs,issues such as leakage,low thermal conductivity,lack of efficient solar-thermal media,and flamma-bility have constrained their broad applications.Herein,we present an innova-tive class of versatile composite phase change materials(CPCMs)developed through a facile and environmentally friendly synthesis approach,leveraging the inherent anisotropy and unidirectional porosity of wood aerogel(nanowood)to support polyethylene glycol(PEG).The wood modification process involves the incorporation of phytic acid(PA)and MXene hybrid structure through an evaporation-induced assembly method,which could impart non-leaking PEG filling while concurrently facilitating thermal conduction,light absorption,and flame-retardant.Consequently,the as-prepared wood-based CPCMs showcase enhanced thermal conductivity(0.82 W m^(-1)K^(-1),about 4.6 times than PEG)as well as high latent heat of 135.5 kJ kg^(-1)(91.5%encapsula-tion)with thermal durability and stability throughout at least 200 heating and cooling cycles,featuring dramatic solar-thermal conversion efficiency up to 98.58%.In addition,with the synergistic effect of phytic acid and MXene,the flame-retardant performance of the CPCMs has been significantly enhanced,showing a self-extinguishing behavior.Moreover,the excellent electromagnetic shielding of 44.45 dB was endowed to the CPCMs,relieving contemporary health hazards associated with electromagnetic waves.Overall,we capitalize on the exquisite wood cell structure with unidirectional transport inherent in the development of multifunctional CPCMs,showcasing the operational principle through a proof-of-concept prototype system.
基金supported by the National Natural Science Funds(No.21878226)Innovative Research Group Project of the National Natural Science Foundation of China(No.22121004)。
文摘Atomically dispersed metal sites(ADMSs)play key roles in electrochemical energy conversion.The covalent organic frameworks(COFs)enable the precise control of the chemical compositions and structures at the molecular level,making them ideal substrates for supporting ADMSs.In this review,we systematically summarize the recent progress on the design and synthesis of ADMSs in COFs,including embedding molecular catalysts into COFs,immobilizing ADMSs on heteroatom-containing COFs,and preparing COF-derived carbon materials through pyrolysis.The electrocatalytic performance of the resulting catalysts is presented for various electrochemical reactions,involving oxygen reduction reaction(ORR),carbon dioxide reduction reaction(CO_(2)RR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and nitrogen reduction reaction(NRR).The modulation strategies of AMDSs in COFs for enhanced activity,selectivity,and stability are highlighted,together with a perspective of the current challenges and the future opportunities in this field.
基金the financial support from the Australian Research Council,Centre for Materials Science,Queensland University of Technologythe Supported by the Fundamental Research Funds for the Central Universities。
文摘Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.
基金This research was funded by the National Natural Science Foundation of China(Grant Nos.31870426).
文摘Parameterization is a critical step in modelling ecosystem dynamics.However,assigning parameter values can be a technical challenge for structurally complex natural plant communities;uncertainties in model simulations often arise from inappropriate model parameterization.Here we compared five methods for defining community-level specific leaf area(SLA)and leaf C:N across nine contrasting forest sites along the North-South Transect of Eastern China,including biomass-weighted average for the entire plant community(AP_BW)and four simplified selective sampling(biomass-weighted average over five dominant tree species[5DT_BW],basal area weighted average over five dominant tree species[5DT_AW],biomass-weighted average over all tree species[AT_BW]and basal area weighted average over all tree species[AT_AW]).We found that the default values for SLA and leaf C:N embedded in the Biome-BGC v4.2 were higher than the five computational methods produced across the nine sites,with deviations ranging from 28.0 to 73.3%.In addition,there were only slight deviations(<10%)between the whole plant community sampling(AP_BW)predicted NPP and the four simplified selective sampling methods,and no significant difference between the predictions of AT_BW and AP_BW except the Shennongjia site.The findings in this study highlights the critical importance of computational strategies for community-level parameterization in ecosystem process modelling,and will support the choice of parameterization methods.
基金supported by National Natural Science Foundation of China(21978066)Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project(18964308D)the Key Program of Natural Science Foundation of Hebei Province(B2020202048).
文摘The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In 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 performance.The 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 hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The 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.
基金Funded by the National Natural Science Foundation of China(No.51864012)the Key Projects Supported by Science and Technology in Guizhou Province(No.[2002]KEY020)+2 种基金the Major Special Projects in Guizhou Province(No.[2022]003)the Guizhou Provincial Science Cooperation Program(Nos.[2016]5302,[2017]5788,[2018]5781,[2019]1411,and[2019]2841)the Major Special Projects in Tongren City,Guizhou Province(No.[2021]13)。
文摘The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.
基金supported by the Degradable Plastics Engineering Research Center of Yunnan Provincial Education Department(KKPU202205001).
文摘Elucidating the effect of growth periods on the quality of calcium sulfate whiskers(CSWs)prepared from calcium sulfate dihydrate(DH)is imperative.Herein,crystal seeds and whiskers were prepared from DH in a water–glycerol system.Longer whiskers were obtained from crystal seeds prepared via hydration of DH for 30 s than via ball milling for 5 min followed by hydration for 20 s.The attachment of cetyltrimethyl ammonium bromide and glycerol additives to the whisker tops promoted whisker growth.The whisker sponges exhibited good thermal barrier properties and compression cycle stability.
基金The National Natural Science Foundation of China (22068019)Yunnan Major Scientific and Technological Projects (202202AG050001)
文摘Developing low-cost and green simultaneous desulfurization and denitrification technologies is of great significance for sulfur dioxide(SO_(2))and nitrogen oxide(NO_(x))emission control at low temperatures,especially for small and medium-sized coal-fired boilers and furnaces.Herein,phosphorus sludge,an industrial waste from the production process of yellow phosphorus,has been developed to simultaneously eliminate SO_(2)and NO_(x)from coal-fired flue gas.The key factors affecting the experimental results indicate that desulfurization and denitrification efficiency of over 95%can be achieved at a low temperature of 55℃.Further,the absorption mechanism was investigated by characterizing the solid and liquid phases of the phosphorus sludge during the absorption process.The efficient removal of SO_(2)is attributed to the abundance of iron(Fe^(3+))and manganese(Mn^(2+))in the absorbent.SO_(2)can be rapidly catalyzed and converted to SO_(4)^(2-)by them.The key to NOx removal is the oxidation of NO toward watersoluble high-valent nitrogen oxides by oxidizing reactive substances induced via yellow phosphorus,which are then absorbed by water and converted to NO_(3)^(-).Meanwhile,yellow phosphorus is oxidized to phosphoric acid(H_(3)PO_(4)).The spent absorption slurry can be reused through wet process phosphoric acid production,as it contains sulfuric acid(H_(2)SO_(4)),nitric acid(HNO_(3)),and H_(3)PO_(4).Accordingly,this is a technology with broad application prospects.
基金National Natural Science Foundation of China (Nos. 22078242 and U20A20153)Applied Basic Research Program of Yunnan Province (Nos. 202101BE070001-032 and 202101BH070002)。
文摘Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges remain in their low site density and unsatisfactory mass transfer structure.Herein,we present a structural engineering approach employing a soft-template coating strategy to fabricate a hollow and hierarchically porous N-doped carbon framework anchored with atomically dispersed Fe sites(FeNCh) as an efficient ORR catalyst.The combination of hierarchical porosity and high exterior surface area is proven crucial for exposing more active sites,which gives rise to a remarkable ORR performance with a half-wave potential of 0.902 V in 0.1 m KOH and 0.814 V in 0.1 m HClO_(4),significantly outperforming its counterpart with solid structure and dominance of micropores(FeNC-s).The mass transfer property is revealed by in-situ electrochemical impedance spectroscopy(EIS) measurement.The distribution of relaxation time(DRT) analysis is further introduced to deconvolve the kinetic and mass transport processes,which demonstrates an alleviated mass transport resistance for FeNC-h,validating the effectiveness of structural engineering.This work not only provides an effective structural engineering approach but also contributes to the comprehensive mass transfer evaluation on advanced electrocatalyst for energy conversion applications.
文摘Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.
基金the financial support for this work provided by the National Key R&D Program of China‘Technologies and Integrated Application of Magnesite Waste Utilization for High-Valued Chemicals and Materials’(2020YFC1909303)。
文摘This study developed a numerical model to efficiently treat solid waste magnesium nitrate hydrate through multi-step chemical reactions.The model simulates two-phase flow,heat,and mass transfer processes in a pyrolysis furnace to improve the decomposition rate of magnesium nitrate.The performance of multi-nozzle and single-nozzle injection methods was evaluated,and the effects of primary and secondary nozzle flow ratios,velocity ratios,and secondary nozzle inclination angles on the decomposition rate were investigated.Results indicate that multi-nozzle injection has a higher conversion efficiency and decomposition rate than single-nozzle injection,with a 10.3%higher conversion rate under the design parameters.The decomposition rate is primarily dependent on the average residence time of particles,which can be increased by decreasing flow rate and velocity ratios and increasing the inclination angle of secondary nozzles.The optimal parameters are injection flow ratio of 40%,injection velocity ratio of 0.6,and secondary nozzle inclination of 30°,corresponding to a maximum decomposition rate of 99.33%.
基金support by the National Natural Science Foundation of China(U21A20306,U20A20152)Natural Science Foundation of Hebei Province(B2022202077).
文摘Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.42171135 and 12262009)the“CUG Scholar”Scientific Research Funds at China University of Geosciences(Wuhan)(Project No.2022098).
文摘The phase equilibrium and mechanical behaviors of natural gas hydrate-bearing sediment are essential for gas recovery from hydrate reservoirs.In heating closed systems,the temperature-pressure path of hydrate-bearing sediment deviates from that of pure bulk hydrate,reflecting the porous media effect in phase equilibrium.A generalized phase equilibrium equation was established for hydrate-bearing sediments,which indicates that both capillary and osmotic pressures cause the phase equilibrium curve to shift leftward on the temperature-pressure plane.In contrast to bulk hydrate,hydrate-bearing sediment always contains a certain amount of unhydrated water,which keeps phase equilibrium with the hydrate within the hydrate stability field.With changes in temperature and pressure,a portion of pore hydrate and unhydrated water may transform into each other,affecting the shear strength of hydrate-bearing sediment.A shear strength model is proposed to consider not only hydrate saturation but also the change in temperature and pressure of hydrate-bearing sediment.The model is validated by experimental data with various hydrate saturation,temperature and pressure conditions.The deformation induced by partial dissociation was studied through depressurization tests under constant effective stress.The reduction in gas pressure within the hydrate stability field indeed caused sediment deformation.The dissociation-induced deformation can be reasonably estimated as the difference in volume between hydrate-bearing and hydrate-free sediments from the compression curves.
基金supported by the National Natural Science Foundation of China (61604131,62025403)the Natural Science Foundation of Zhejiang Province (LY19F040009)+1 种基金the Fundamental Research Funds of Zhejiang SciTech University (23062120-Y)the Open Project of Key Laboratory of Solar Energy Utilization and Energy Saving Technology of Zhejiang Province (ZJS-OP-2020-07)
文摘Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition,and lattice defects are still the key challenges limiting the quality of FAPbI_(3) films.Previous studies show that the introduction or adding of seeds in the precursor is effective to promote the nucleation and crystallization of perovskite films.Nevertheless,the seed-assisted approach focuses on heterogeneous seeds or hetero-composites,which inevitably induce a lattice-mismatch,the genera-tion of strain or defects,and the phase segregation in the perovskite films.Herein,we first demonstrate that high-quality perovskite films are controllably prepared using α-and δ-phases mixed FAPbI_(3) micro-crystal as the homogeneous seeds with the one-step antisolvent method.The partially dissolved seeds with suitable sizes improve the crystallinity of the perovskite flm with preferable orientation,improved carrier lifetime,and increased carrier mobility.More importantly,the α-phase-containing seeds promote the formation of α-phase FAPbI_(3) films,leading to the reduction of residual lattice strain and the suppres-sion of I-ion migration.Besides,the adding of dimethyl 2,6-pyridine dicarboxylate(DPD)into the pre-cursor further suppresses the generation of defects,contributing to the PCE of devices prepared in air ambient being significantly improved to 23.75%,among the highest PCEs for fully air-processed FAPbI_(3) solar cells.The unpackaged target devices possess a high stability,maintaining 80%of the initial PCE under simulated solar illumination exceeding 800 h.
文摘The large-scale development of wind power is an important means to reduce greenhouse gas emissions, alleviate environmental pollution and improve the utilization rate of renewable energy. At the same time, large-scale non grid connected wind power generation theory avoids the technical difficulties of wind power integration [1]. However, due to the randomness and uncontrollability of wind energy, the output power of the wind power generation system will fluctuate accordingly [2]. Therefore, the corresponding energy storage devices are arranged in the non-grid-connected wind power generation system to ensure the power quality, and it has become the key to full utilization of renewable energy. In the case of wind speed fluctuation, the DC bus control strategy of the wind turbine is proposed in this paper. It can reduce the impact on the unit converter and the power load;this ensures safe and stable operation of non-grid connected wind turbines.
文摘1.Present characteristics of Beijing's energy consumption 1.1 The slowing of the growth in total energy consumption In 2008,Beijing's total energy consumption reached 63.437 million tons of standard coal,an increase of 586.6 thousand tons compared with the previous year.The increasing range was 1%,dropping 5.45%compared with the
文摘Taking I-Magic Cube - the entry of Shandong Jianzhu University for Solar Decathlon 2013 - for example, the paper analyzes the conceptual, technological, functional and aesthetic solutions of zero energy solar house coping with ecological, economic, social and cultural challenges. Passive strategies, the solar thermal and PV system, and the building integrated solar system tactics are elaborated. Finally, industrialization and marketing viability of the solar house prototypes are discussed.
基金Supported by National Key Research and Development Program of China(Grant No.2020YFB2010500)National Natural Science Foundation of China(Grant Nos.51975305,52105457)Shandong Provincial Natural Science Foundation of China(Grant No.ZR2020KE027).
文摘Cutting fluid is crucial in ensuring surface quality and machining accuracy during machining.However,traditional mineral oil-based cutting fluids no longer meet modern machining’s health and environmental protection require-ments.As a renewable,pollution-free alternative with excellent processing characteristics,vegetable oil has become an inevitable replacement.However,vegetable oil lacks oxidation stability,extreme pressure,and antiwear proper-ties,which are essential for machining requirements.The physicochemical characteristics of vegetable oils and the improved methods’application mechanism are not fully understood.This study aims to investigate the effects of viscosity,surface tension,and molecular structure of vegetable oil on cooling and lubricating properties.The mechanisms of autoxidation and high-temperature oxidation based on the molecular structure of vegetable oil are also discussed.The study further investigates the application mechanism and performance of chemical modification and antioxidant additives.The study shows that the propionic ester of methyl hydroxy-oleate obtained by epoxidation has an initial oxidation temperature of 175℃.The application mechanism and extreme pressure performance of conventional extreme pressure additives and nanoparticle additives were also investigated to solve the problem of insufficient oxidation resistance and extreme pressure performance of nanobiological lubricants.Finally,the study discusses the future prospects of vegetable oil for chemical modification and nanoparticle addition.The study provides theoretical guidance and technical support for the industrial application and scientific research of vegetable oil in the field of lubrication and cooling.It is expected to promote sustainable development in the manufacturing industry.
基金supported by the National Natural Science Foundation of China(Grant No.21978066)Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project(Grant No.18964308D)the Key Program of Natural Science Foundation of Hebei Province(Grant No.B2020202048).
文摘Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.
