Simple preparation of C(CS)/g-C_(3)N_(4)/Co carbon aerogel and its catalytic performance for ammonium perchlorate

Biomass chitosan(CS)was used as a template,graphitic phase carbon nitride(g-C_(3)N_(4))with high nitrogen content and certain catalytic activity was used as a dopant,and nano-transition metal cobalt(Co)was used as a catalytic center point.The carbon aerogel(C(CS)/g-C_(3)N_(4)/Co)with a three-dimensional network-like structure was prepared by assembling the three materials through experimental operations such as freeze-drying and high-temperature carbonization.It was demonstrated by scanning and transmission characterization that the CS in the carbon aerogel could provide more active sites for the cobalt nanoparticles,and the doping of graphite-phase carbon nitride as a template dispersed the cobalt nanoparticles and changed the conductivity of the CS.To investigate the catalytic effect of carbon aerogel on ammonium perchlorate(AP),it was investigated by differential thermal analyzer and TG thermal analysis.This carbon aerogel was very effective in catalyzing AP,and the 10 wt% content of the catalyst reduced the AP pyrolysis peak from 703.9 to 595.5 K.And to further investigate the synergistic effect of the three materials,further carbon aerogels such as C(CS)/Co,g-C_(3)N_(4)/Co were prepared and applied to catalyze AP,and the same ratio reduced the AP pyrolysis peak by 98.1℃ and 97.7℃.This result indicates a synergistic effect of the assembly of the three materials.

Micro-aluminum powder with bi-or tri-component alloy coating as a promising catalyst:Boosting pyrolysis and combustion of ammonium perchlorate

A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.

Synthesis of Co Nanoparticles and Their Catalytic Effect on the Decomposition of Ammonium Perchlorate

The monodispersed Co nanoparticles were successfully prepared by means of hydrogen plasma method in inert atmosphere. The particle size, specific surface area, crystal structure and morphology of the samples were characterized by transmission electron microscopy （TEM）, BET equation, X-ray diffraction （XRD）, and the corresponding selected area electron diffraction （SAED）. The catalytic effect of Co nanoparticles on the decomposition of ammonium perchlorate （AP） was investigated by differential thermal analyzer （DTA）. Compared with the thermal decomposition of pure AP, the addition of Co nanoparticles （2%-10%, by mass） decreases the decomposition temperature of AP by 145.01-155.72℃. Compared with Co3O4 nano-particles and microsized Co particles, the catalytic effect of Co nanoparticles for AP is stronger. Such effect is attributed to the large specific surface area and its interaction of Co with decomposition intermediate gases. The present work provides useful information for the application of Co nanoparficles in the AP-based propellant.

The catalytic activity of transition metal oxide nanoparticles on thermal decomposition of ammonium perchlorate

The catalytic proficiency of three MONs for AP thermal decomposition was studied in this work.A chemical co-precipitation method was used for synthesis of MONs(CuZnO,CoZnO,and NiZnO)and their characterization carried out by utilizing XRD,FTIR,and SEM.The TGA/DSC technique was employed for the investigation of the catalytic proficiency of MONs on the AP.The DSC data were used for measuring activation energy of catalyzed AP by using Ozawa,Kissinger,and Starink method.The MONs were much sensitive for AP decomposition,and the performance of AP decomposition was further improved.Among all the MONs,the CuZnO exhibits higher catalytic action than others and decomposition temperature of AP is descending around 117℃ by CuZnO.The reduction in the activation energy was noticed after the incorporation of MONs in AP.

Thermal decomposition of ammonium perchlorate catalyzed with CuO nanoparticles

Ammonium perchlorate(APC)is the most common oxidizer in use for solid rocket propulsion systems.However its initial thermal decomposition is an endothermic process that requires 102.5 J·g^-1.This manner involves high activation energy and could render high burning rate regime.This study reports on the sustainable fabrication of CuO nanoparticles as a novel catalyzing agent for APC oxidizer.Colloidal CuO nanoparticles with consistent product quality were fabricated by using hydrothermal processing.TEM micrographs demonstrated mono-dispersed particles of 15 nm particle size.XRD diffractogram demonstrated highly crystalline material.The synthesized colloidal CuO particles were effectively coated with APC particles via co-precipitation by using fast-crash solvent-antisolvent technique.The impact of copper oxide particles on APC thermal behavior has been investigated using DSC and TGA techniques.APC demonstrated an initial endothermic decomposition stage at 242℃ with subsequent two exothermic decomposition stages at 297,8℃ and 452.8℃ respectively.At 1 wt%,copper oxide offered decrease in initial endothermic decomposition stage by 30%.The main outcome of this study is that the two main exothermic decomposition peaks were merged into one single peak with an increase in total heat release by 53%.These novel features can inherit copper oxide particles unique catalyzing ability for advanced highly energetic systems.

A New Nickel(Ⅱ) Coordination Compound Constructed by Pyridyl-triazole and Oxybis(Benzoic Acid): Synthesis,Crystal Structure and the Effect on the Thermal Decomposition of Ammonium Perchlorate

A new energetic complex, Ni（3,4＇-Hbpt）2（Hoba）2（H20）2 （3,4＇-Hbpt = 3-（3-pyridyl）- 5-（4＇-pyridyl）-l-H-l,2,4-triazole and H2oba = 4,4＇-oxybis（benzoic acid））, has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P2j/c with a = 10.2357（9）, b = 24.594（2）, c = 10.4225（9）/k, β = 114.0110（10）°, V = 2396.7（4） A3, Dc = 1.460 g/cm3,μ = 0.482 mm-1, Mr = 1053.63, F（000） = 1088, Z = 2, the final R = 0.0358 and wR = 0.0973 with I 〉 2σ（I）. Both 3,4＇-Hbpt and H2oba ligands adopt monodentate modes linking one Ni（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate （AP） is explored by differential scanning calorimetry （DSC）, which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.

Studies on composite solid propellant with tri-modal ammonium perchlorate containing an ultrafine fraction

Composite solid propellant is prepared using tri-modal Ammonium perchlorate(AP)containing coarse,fine and ultrafine fractions of AP with average particle size(APS)340,40 and 5 mm respectively,in various compositions and their rheological,mechanical and burn rate characteristics are evaluated.The optimum combination of AP coarse to fine to ultrafine weight fraction was obtained by testing of series of propellant samples by varying the AP fractions at fixed solid loading.The concentration of aluminium was maintained constant throughout the experiments for ballistics requirement.The propellant formulation prepared using AP with coarse to fine to ultrafine ratio of 67:24:9 has lowest viscosity for the propellant paste and highest tensile strength due to dense packing as supported by the literature.A minimum modulus value was also observed at 9 wt.%of ultrafine AP concentration indicates the maximum solids packing density at this ratio of AP fractions.The burn rate is evaluated at different pressures to obtain pressure exponent.Incorporation of ultrafine fraction of AP in propellant increased burn rate without adversely affecting the pressure exponent.Higher solid loading propellants are prepared by increased AP concentration from 67 to 71 wt.%using AP with coarse to fine to ultrafine ratio of67:24:9.Higher solid content up to 89 wt.%was achieved and hence increased solid motor performance.The unloading viscosity showed a trend with increased AP content and the propellant couldn't able to cast beyond 71 wt.%of AP.Mechanical properties were also studied and from the experiments noticed that%elongation decreased with increased AP content from 67 to 71 wt.%,whereas tensile strength and modulus increased.Burn rate increased with increased AP content and observed that pressure exponent also increased and it is high for the propellant containing with 71 wt.%of AP due to increased oxidiser to fuel ratio.Catalysed composite solid propellant is prepared by using burn rate modifiers Copper chromite and Iron oxide.Addition of Copper chromite and Iron oxide has enhanced the burn rate of tri-modal AP based composite solid propellant.The catalytic propensity of copper chromite is higher than that of iron oxide.The pressure exponent increased with the catalyst concentration and the values obtained are compatible for solid rocket motor applications.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

Recent progress on transition metal oxides and carbon-supported transition metal oxides as catalysts for thermal decomposition of ammonium perchlorate

As a main oxidizer in solid composite propellants,ammonium perchlorate(AP)plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid composite propellants.To improve the performance of solid composite propellant,it is necessary to take measures to modify the thermal decomposition behavior of AP.In recent years,transition metal oxides and carbon-supported transition metal oxides have drawn considerable attention due to their extraordinary catalytic activity.In this review,we highlight strategies to enhance the thermal decomposition of AP by tuning morphology,varying the types of metal ion,and coupling with carbon analogue.The enhanced catalytic performance can be ascribed to synergistic effect,increased surface area,more exposed active sites,and accelerated electron transportation and so on.The mechanism of AP decomposition mixed with catalyst has also been briefly summarized.Finally,a conclusive outlook and possible research directions are suggested to address challenges such as lacking practical application in actual formulation of solid composite propellant and batch manufacturing.

Change of Iodine Load and Thyroid Homeostasis Induced by Ammonium Perchlorate in Rats

Ammonium perchlorate （AP）, mainly used as solid propellants, was reported to interfere with homeostasis via competitive inhibition of iodide uptake. However, detailed mechanisms remain to be elucidated. In this study, AP was administered at 0, 130, 260 and 520 mg/kg every day to 24 male SD rats for 13 weeks. The concentrations of iodine in urine, serum thyroid hormones levels, to- tal iodine, relative iodine and total protein, and malondialdehyde （MDA）, superoxide dismutase （SOD） and catalase （CAT） activity in thyroid tissues were measured, respectively. Our results showed that high-dose perchlorate induced a significant increase in urinary iodine and serum thyroid stimu- lating hormone （TSH）, with a decrease of total iodine and relative iodine content. Meanwhile, free thyroxine （FT4） was decreased and CAT activity was remarkably increased. Particularly, the CAT activity was increased in a dose-dependent manner. These results suggested that CAT might be en- hanced to promote the synthesis of iodine, resulting in elevated urinary iodine level. Furthermore, these findings suggested that iodine in the urine and CAT activity in the thyroid might be used as biomarkers for exposure to AP, associated with thyroid hormone indicators such as TSH. FT4.

Hydrothermal Synthesis of V-Cr-Al-O Nanospheres and Their Effect on Decomposition of Ammonium Perchlorate

V-Cr-Al-O nanospheres were successfully synthesized using V2O5, Al(OH)3, CrO3, and H2C2O4·H2O as the starting materials by a facile one-pot hydrothermal approach. Several techniques containing X-ray powder diffraction, hydrogen temperature programmed reduction, scanning electron microscopy were used to characterize the composition, morphology and redox property of V-Cr-Al-O nanospheres. The catalytic behavior of prepared nanospheres on the thermal decomposition of AP was investigated by the thermogravimetric analysis and differential thermal analysis(TG/DTA). The experimental results show that the thermal decomposition temperature of AP in the presence of V-Cr-Al-O nanospheres is to 395 ℃(decreased by 35 ℃), which proves better catalyst for the thermal decomposition of AP.

The Thermal Decomposition of Ammonium Perchlorate-Aluminum Propellants in Presence of Metallic Zinc Particles

The thermal decomposition of ammonium perchlorate (AP) with Al and Zn metallic particles was studied at different heating rates in dry air atmosphere and the combustion behavior of AP/Al/Zn propellant was evaluated. The exothermic reaction kinetics was studied by differential thermal analysis (DTA) in non-isothermal conditions and compare with the thermal decomposition of pure AP and AP/aluminum particles analyzed in the same experimental conditions. The Arrhenius parameters were estimated according to the Ozawa and Kissinger methods. The calculated activation energies for the low and high temperature exothermic reactions were 91 and 229 kJ/mol for pure AP, 90 and 112 kJ/mol for 80 wt% AP/20 wt% Al particles. When zinc was incorporated, activation energy of 56 kJ/mol was determined for the only exothermic peak observed for 90 wt% AP/10 wt% Zn and 44 kJ/mol for 78.4 wt% AP/19.6 wt% Al/2 wt% Zn propellant composition.

Salt-Assisted Combustion Synthesis of NdCoO_3 Nanoparticles and Their Catalytic Properties in Thermal Decomposition of Ammonium Perchlorate

Highly dispersed perovskite NdCoO3 nanoparticles were prepared by a novel salt-assisted combustion process. The effects of NaCl content and calcination temperature on the characteristics of the products were characterized by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and BET surface area measurement. The facile introduction of NaCl in the conventional combustion synthesis process was found to result in the formation of well-dispersed perovskite nanoparticles and increase specific surface areas of the resultants from 1.7 to 43.2 m2·g-1. The catalytic properties of the typical NdCoO3 samples for thermal decomposition of ammonia perchlorate (AP) and their correlation with the NdCoO3 microstructure were investigated by Differential Scanning Calorimetry (DSC). The DSC results indicate that the addition of the amorphous NdCoO3 nanoparticles to AP incorporates two small exothermic peaks of AP into a strong exothermic peak, decreases the temperature of the AP exothermic peak to 314.0 ℃ by reduction of 138.3 ℃ and increases the apparent decomposition heat from 515 J·g-1 to over 1441 J·g-1, showing the intense catalytic activity for thermal decomposition of AP. It is also clear that the catalytic activity of the resultant NdCoO3 is related to their microstructure. According to Kissinger′s method, the kinetics parameters of the thermal decomposition of AP catalyzed by the as-prepared NdCoO3 samples were calculated to account for the order of their catalytic activity.

Effect of the microporous structure of ammonium perchlorate on thermal behaviour and combustion characteristics

Ammonium perchlorate(AP)is the component with the highest content in composite propellants,and it plays a crucial role in propellant performance.In view of the effects of low-temperature AP thermal decomposition on thermal safety and combustion characteristics,porous ammonium perchlorate(PAP)samples with different mass losses were first prepared by thermal convection heating,and the structures were characterized and analysed.Second,the effects of decomposition degree on the thermal decomposition characteristics of PAP were studied by DSC-TG.Finally,the combustion characteristics of AP/Al binary mixtures were tested with high-speed photography and in a sealed bomb.The results showed that low-temperature decomposition of AP resulted in formation of porous structures for AP particles.The pores first appeared near the surfaces of the particles and began from multiple points at the same time.The pores increased in size to approximately 5 mm and then expanded,and finally,the AP particles were full of pores.After partial decomposition,the crystal structure of AP remained unchanged,but the low and high decomposition temperatures decreased obviously.The decomposition rate accelerated.Due to the porous structure of PAP,the combustion rate of the AP/Al system increased obviously with increasing decomposition of AP.The relationship between the combustion rate and the mass loss was approximately linear under open conditions,and it was exponential for a high-pressure environment.A computational model of the combustion process for the AP/Al binary system was established to explain the effects of pore structure and pressure on the combustion process.

A Polymerase Chain Reaction Based DNA Fingerprinting Technique: Amplified Fragment Length Polymorphism for Molecular Typing of Perchlorate Reducing Bacteria

Genetic profiling of environmentally important organisms is very essential for easy identification of biodegrading bacteria. In the previous study, we have reported the perchlorate biodegrading bacteria and characterized them by biochemical analysis and 16 S sequencing. We have observed a very similar isolates of Arthrobacter (Actinobacteria) degrading 4.1 mM and 4.7 mM of ammonium perchlorate [1] 08D0C9EA79F9BACE118C8200AA004BA90B02000000080000000E0000005F005200650066003300390038003100390037003300340037000000 . In this study, we report PCR based DNA fingerprinting technique to generate the genomic signature of these closely related group of Arthrobacter species. This study also effectively generates unique genomic signature for each of these isolates that has potential for use in molecular monitoring as well as for tracking genomic variation and rearrangements.

基于疏水仿生学提升超细高氯酸铵热分解、安全及防吸湿性能的研究

为了研制出兼具高燃速和高安全性能的固体推进剂,以改善高氯酸铵的性能为目标,采用液相沉积法制备了具有核壳结构的超细高氯酸铵@硬脂酸锌(UF-AP@ZnSA)复合物;使用扫描电镜(SEM)、热重-差示扫描量热法(TG-DSC)、傅里叶变换红外光谱(FT-IR)等对样品的形貌、结构和热分解性能进行了表征;并测量了样品的撞击感度、摩擦感度、吸湿率和接触角等参数;采用热分析-红外联用技术分析并解释了硬脂酸锌(ZnSA)催化UF-AP的热分解机理。结果表明,UF-AP表面生成了ZnSA壳层;不同壳层含量的复合物中UF-AP高温分解峰从424.3℃降至370~385℃,相较于原料UF-AP,放热区间更加集中,放热量更大;UF-AP@ZnSA复合物特性落高(H_(50))相较于原料增加了27.6 cm,摩擦感度的爆炸概率减小了76%,安全性能大幅度提升;壳层质量分数为5%的UF-AP@ZnSA复合物72 h的吸湿率为0.05%,较原料UF-AP的吸湿率降低约90%,防吸湿性能得到明显提升。

铝锂合金的氧化及燃烧反应特性

为了更好地研究铝锂合金(Al-Li)的反应性能,采用TG-DSC对铝锂合金氧化反应特性及动力学参数进行了分析;使用自制的燃烧实验装置、SEM、XRD等对铝锂合金燃烧过程、燃烧产物组成等进行了分析,并对比不同氧化剂对合金反应特性的影响;分别采用Kissinger法、Ozawa法和Friedman法计算得到合金在空气和氧气环境下反应时的表观活化能。结果表明,铝锂合金氧化分为3个阶段:第一个阶段从开始到800 K左右;第二阶段在800~1100 K左右;第三阶段在温度高于1100 K之后。相比于高氯酸铵(AP),聚四氟乙烯(PTFE)能更好地促进铝锂合金的反应:当Al-Li/PTFE在空气中加热时,剧烈的氧化过程在铝的熔化之后被立即观察到;当Al-Li/PTFE在空气中燃烧时,其具有比Al-Li/AP更大的气相火焰以及更剧烈的燃烧过程,合金中铝的燃烧效率更高,反应更加完全。Kissinger法计算得到合金表观活化能分别是335.9 kJ/mol(空气)和351.3 kJ/mol(氧气);Ozawa法计算得到表观活化能分别是339.9 kJ/mol(空气)和354.6 kJ/mol(氧气);Friedman法计算得到的表观活化能分别为343.1 kJ/mol(空气)和355.4 kJ/mol(氧气)。

铝合金对高氯酸铵反应特性的影响

为了研究推进剂中金属燃料对氧化剂高氯酸铵(AP)反应特性的影响,选取两种铝基金属燃料-铝锂合金和铝镁合金,借助TG-DSC、SEM、XRD以及自制燃烧实验装置等设备,对样品释能过程及反应特性进行了分析,并采用Kissinger法计算了样品的表观活化能。结果表明,铝锂合金对AP低温分解阶段和高温分解阶段皆存在抑制效果,使得其两个阶段的分解放热峰峰温升高;铝镁合金对AP低温分解阶段有较强的促进作用,使得AP低温分解峰峰温降至287.3℃。当加入铝锂合金后,AP低温分解表观活化能为129.7 kJ/mol,高温分解表观活化能约为247.0 kJ/mol;而加入铝镁合金后,AP低温分解表观活化能降为负数(-207.2 kJ/mol);AP/铝镁合金中AP的分解剧烈,样品燃烧时观察到了较大的气相火焰,其燃烧过程中铝、镁基本能完全反应,而AP/铝锂合金的燃烧产物检测到了铝单质。

金属氧化物催化剂表界面效应对AP热分解性能影响进展

高氯酸铵(AP)作为固体推进剂中重要的氧化剂,其热分解性能直接影响固体推进剂的燃烧特性。使用燃烧催化剂能够降低AP的分解温度并提高其分解速率。研究总结了应用于AP热分解的纳米燃烧催化剂微观结构调控的不同手段,分析了晶面、缺陷和复合界面等微结构调控方式对其在AP热分解反应中催化活性和催化机理的影响,并探究能获得最佳催化性能的催化剂特征。结果表明,通过调整暴露晶面、元素掺杂和构建复合界面结构可以提高纳米金属氧化物燃烧催化剂的催化活性;过渡金属氧化物纳米催化剂能通过暴露指定晶面实现催化活性的提升,元素掺杂能通过产生缺陷从而提升催化效果,构建复合界面结构能够利用界面效应调控催化位点的活性,从而有效提升催化性能。过渡金属氧化物纳米催化剂在提升AP热分解性能方面表现出了良好的催化活性。

基于微流控技术制备窄粒径分布的微米级高氯酸铵

为了制备形貌规则、窄粒径分布的微米级高氯酸铵(AP),基于微流控技术设计了一种微通道反应器,通过计算流体动力学(CFD)模拟了不同长度微通道的混合效果,确定了微通道反应器的最佳结构,并通过实验研究了溶剂种类、溶剂和非溶剂流速比对AP晶体形貌和粒径的影响。结果表明:溶剂的混合效率与微通道的长度成正相关;细化后AP的晶体结构不会发生变化;溶剂的改变对AP晶体形貌的影响较大;减小溶剂-非溶剂流速比可以有效减小AP晶体的横向粒径;细化后AP的热分解温度有所提前。该研究为制备微米级AP提供了一种安全、快速的途径。