CN115236022B - Method and system for characterizing and predicting flame synthesis characteristics of precursor - Google Patents
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Abstract
本发明提供一种通过FTIR、TGA测量手段表征和预测前驱物火焰合成特性的方法及系统，其中的方法包括：测量常规前驱物固体粉末及化合物为前驱物阳离子和添加剂阴离子的固体物粉末的TGA曲线及DTG曲线；测量前驱物‑溶剂混合溶液的TGA及DTG曲线；测量纯溶剂溶液及前驱物‑溶剂的ATG‑FTIR光谱；测量纯添加剂溶液、溶剂‑添加剂的混合溶液、前驱物‑溶剂‑添加剂的混合溶液的TGA曲线；测量纯添加剂溶液、溶剂‑添加剂的混合溶液、前驱物‑溶剂‑添加剂的混合溶液的ATG‑FTIR光谱。本发明结合衰减全反射傅里叶变换红外光谱和热重分析，测量溶剂与添加剂混合前后的组分变化，能够预测采用不同添加剂‑前驱物溶液配方时溶液内前驱物的转化程度，简便快捷的推测合成产物形貌。
The present invention provides a method and system for characterizing and predicting the flame synthesis characteristics of precursors by FTIR and TGA measurement means, wherein the method includes: measuring the TGA curve and DTG curve of conventional precursor solid powder and solid powder whose compound is precursor cation and additive anion; measuring the TGA and DTG curves of precursor-solvent mixed solution; measuring the ATG-FTIR spectrum of pure solvent solution and precursor-solvent; measuring the TGA curve of pure additive solution, solvent-additive mixed solution, and precursor-solvent-additive mixed solution; measuring the ATG-FTIR spectrum of pure additive solution, solvent-additive mixed solution, and precursor-solvent-additive mixed solution. The present invention combines attenuated total reflection Fourier transform infrared spectroscopy and thermogravimetric analysis to measure the component changes before and after the solvent and additive are mixed, and can predict the degree of conversion of the precursor in the solution when different additive-precursor solution formulas are used, and simply and quickly infer the morphology of the synthetic product.
Description
技术领域Technical Field
本发明涉及纳米材料合成技术领域，尤其涉及通过FTIR、TGA测量手段表征和预测前驱物火焰合成特性的方法。The invention relates to the technical field of nano material synthesis, and in particular to a method for characterizing and predicting precursor flame synthesis characteristics by FTIR and TGA measurement means.
背景技术Background technique
纳米氧化物颗粒材料凭借其出色的物理化学性能，在光学和催化等领域都展现出优异的应用价值，火焰合成作为一种在生成粒径均匀、高纯度、原子尺度均匀掺混的纳米复合颗粒材料上具有天然性能优势的方法，已经在纳米材料领域得到了广泛应用。不同的应用背景和功能需求对纳米颗粒的组成和形貌提出了更加复杂多样的要求，对火焰合成中常常选用价格低廉的无机盐(如金属硝酸盐)来作为前驱物，乙醇作为溶剂的组合，合成颗粒多呈现空心且粒径较大的特点，若采用羧酸作为添加剂，羧酸的存在会使溶液中形成挥发性的金属羧酸盐，从而使得前驱物经由蒸发-成核-碰撞-聚并的气相-颗粒相路径转变形成颗粒。这一结论表明，在采用廉价金属硝酸盐作为前驱物的情况下，可以考虑选择合适的溶剂来实现均相纳米氧化物颗粒的制备，而无需购买价格高昂的有机金属前驱物。但不同添加剂的具体作用机理以及对产物形貌的改善程度仍然未知。Nano oxide particle materials have excellent application value in the fields of optics and catalysis due to their excellent physical and chemical properties. Flame synthesis, as a method with natural performance advantages in generating nano composite particle materials with uniform particle size, high purity and uniform mixing at the atomic scale, has been widely used in the field of nano materials. Different application backgrounds and functional requirements put forward more complex and diverse requirements for the composition and morphology of nano particles. In flame synthesis, low-cost inorganic salts (such as metal nitrates) are often used as precursors. Ethanol is used as a solvent combination. The synthesized particles are mostly hollow and have large particle sizes. If carboxylic acid is used as an additive, the presence of carboxylic acid will form volatile metal carboxylates in the solution, so that the precursors are transformed into particles through the gas phase-particle phase path of evaporation-nucleation-collision-coalescence. This conclusion shows that when using cheap metal nitrates as precursors, it is possible to consider choosing a suitable solvent to achieve the preparation of homogeneous nano oxide particles without purchasing expensive organometallic precursors. However, the specific mechanism of action of different additives and the degree of improvement in product morphology are still unknown.
因此，如何简便快捷的表征和预测前驱物火焰合成纳米颗粒物形貌已成为一个重要的研究问题，并有必要建立一套简便易行且能在室温和高温下分别测量前驱物溶液性质的前驱物-溶剂-添加剂系统的测试方法。Therefore, how to simply and quickly characterize and predict the morphology of precursor flame synthesized nanoparticles has become an important research issue, and it is necessary to establish a simple and easy test method for the precursor-solvent-additive system that can measure the properties of the precursor solution at room temperature and high temperature respectively.
发明内容Summary of the invention
鉴于上述问题，本发明提供一种通过FTIR、TGA测量手段表征和预测前驱物火焰合成特性的方法，通过结合衰减全反射傅里叶变换红外光谱(ATR-FTIR)和热重分析(TGA)方法，测量溶剂与添加剂混合前后的组分变化，能够预测采用不同添加剂-前驱物溶液配方时溶液内前驱物的转化程度，具有简便快捷的推测合成产物形貌的优点。In view of the above problems, the present invention provides a method for characterizing and predicting the flame synthesis characteristics of precursors by means of FTIR and TGA measurement. By combining attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and thermogravimetric analysis (TGA) methods, the component changes before and after the solvent and additives are mixed are measured, and the degree of conversion of the precursor in the solution when different additive-precursor solution formulas are used can be predicted, which has the advantage of simply and quickly inferring the morphology of the synthetic product.
本发明提供的表征和预测前驱物火焰合成特性的方法，通过热重分析仪和红外光谱仪测量火焰合成过程中前驱物的特性，包括如下步骤：The method for characterizing and predicting the flame synthesis characteristics of a precursor provided by the present invention measures the characteristics of the precursor during the flame synthesis process by a thermogravimetric analyzer and an infrared spectrometer, and comprises the following steps:
S110：分别测量常规前驱物粉末和化学式为添加剂阴离子与所述前驱物阳离子结合的固体粉末的第一TGA曲线，并对所述第一TGA曲线进行一阶微分处理，得到第一DTG曲线；其中，所述第一TGA曲线用于表征所述前驱物粉末由固体转变为目标产物的分解过程，所述第一DTG曲线用于表征在所述分解过程中样品质量变化速率随温度的变化过程；S110: measuring first TGA curves of conventional precursor powder and solid powder whose chemical formula is a combination of additive anions and precursor cations, respectively, and performing first-order differential processing on the first TGA curve to obtain a first DTG curve; wherein the first TGA curve is used to characterize the decomposition process of the precursor powder from a solid to a target product, and the first DTG curve is used to characterize the change process of the sample mass change rate with temperature during the decomposition process;
S120：测量所述前驱物粉末的前驱物-溶剂的混合溶液TGA曲线，并对所述混合溶液TGA曲线进行一阶微分处理，得到混合溶液DTG曲线；S120: measuring a TGA curve of a precursor-solvent mixed solution of the precursor powder, and performing first-order differential processing on the TGA curve of the mixed solution to obtain a DTG curve of the mixed solution;
S130：分别测量纯溶剂溶液及所述前驱物-溶剂的混合溶液的第一红外吸收光谱；S130: measuring first infrared absorption spectra of a pure solvent solution and a mixed solution of the precursor and the solvent respectively;
S140：分别测量纯添加剂溶液、溶剂-添加剂的混合溶液、前驱物-溶剂-添加剂的混合溶液的第三TGA曲线，并对所述第三TGA曲线进行一阶微分处理，得到第三DTG曲线；S140: measuring third TGA curves of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution respectively, and performing first-order differential processing on the third TGA curve to obtain a third DTG curve;
S150：分别测量所述纯添加剂溶液、所述溶剂-添加剂的混合溶液、所述前驱物-溶剂-添加剂的混合溶液的第二红外吸收光谱。S150: measuring the second infrared absorption spectra of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution respectively.
进一步，可选的方案为，在S110中，进一步包括，通过对比常规前驱物粉末与所述化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的结果，得到所述添加剂与所述前驱物结合后，对所述前驱物分解形成产物路径的改变。Furthermore, an optional solution is that in S110, it further includes comparing the results of conventional precursor powder with the solid powder whose chemical formula is the combination of additive anions and precursor cations, to obtain the change in the decomposition path of the precursor to form products after the additive is combined with the precursor.
进一步，可选的方案为，在S120中，进一步包括，根据所述混合溶液TGA曲线和所述混合溶液DTG曲线，通过分析测量所述混合溶液TGA曲线时的升温过程中吸热及放热的信息，得到反映样品质量变化的各阶段的质量损失，将所述混合溶液TGA曲线与S110中的所述前驱物粉末的第一TGA曲线进行对比，以获得所述前驱物加入所述溶剂后，分解路径的改变。Furthermore, an optional scheme is that in S120, it further includes, according to the TGA curve of the mixed solution and the DTG curve of the mixed solution, by analyzing the information of heat absorption and heat release during the heating process when measuring the TGA curve of the mixed solution, to obtain the mass loss at each stage reflecting the change of the sample mass, and compare the TGA curve of the mixed solution with the first TGA curve of the precursor powder in S110 to obtain the change of the decomposition path of the precursor after the solvent is added.
进一步，可选的方案为，在S130中，进一步包括，通过对比纯溶剂溶液的第一红外吸收光谱和所述混合溶液的第一红外吸收光谱中的特征吸收峰，得到所述前驱物溶于溶剂后，是否发生化学反应产生新的物质。Furthermore, an optional solution is that in S130, it is further included to determine whether a chemical reaction occurs to produce a new substance after the precursor is dissolved in the solvent by comparing the characteristic absorption peaks in the first infrared absorption spectrum of the pure solvent solution and the first infrared absorption spectrum of the mixed solution.
进一步，可选的方案为，在S140中，进一步包括，通过对比所述第三TGA曲线和所述第三DTG曲线与S110中的所述第一TGA曲线和所述第一DTG曲线的特征峰值，确定所述添加剂与所述前驱物是否完全结合；其中，Further, an optional solution is that in S140, further comprising: determining whether the additive is completely combined with the precursor by comparing the characteristic peaks of the third TGA curve and the third DTG curve with the first TGA curve and the first DTG curve in S110; wherein,
若所述前驱物-溶剂-添加剂的混合溶液的第三TGA曲线与所述化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的第一TGA曲线的失重阶梯形状类似，且所述第一DTG曲线与所述第三DTG曲线对应的最大质量损失区间内的峰值点相吻合，认为所述添加剂完全与所述前驱物结合。If the third TGA curve of the mixed solution of the precursor-solvent-additive is similar in weight loss step shape to the first TGA curve of the solid powder whose chemical formula is the combination of the additive anion and the precursor cation, and the peak points in the maximum mass loss interval corresponding to the first DTG curve and the third DTG curve coincide, it is considered that the additive is completely combined with the precursor.
进一步，可选的方案为，所述添加剂完全与所述前驱物结合，说明所有的前驱物阳离子均与添加剂阴离子相结合，产物生成路线将从常规前驱物分解路径转为化学式为添加剂阴离子与前驱物阳离子结合的物质的分解路径。Furthermore, an optional solution is that the additive is completely combined with the precursor, which means that all precursor cations are combined with additive anions, and the product generation route will be converted from the conventional precursor decomposition path to the decomposition path of a substance with a chemical formula of additive anions combined with precursor cations.
进一步，可选的方案为，在S150中，进一步包括，通过对比三种所述第二红外吸收光谱的峰值信息，确定所述添加剂是否与溶剂发生化学反应形成新的物质，以及所述前驱物是否与添加剂发生化学反应形成新的物质。Furthermore, an optional solution is that in S150, it further includes determining whether the additive chemically reacts with the solvent to form a new substance, and whether the precursor chemically reacts with the additive to form a new substance by comparing the peak information of the three second infrared absorption spectra.
本发明还保护一种表征和预测前驱物火焰合成特性的系统，其特征在于，通过热重分析仪和红外光谱仪测量火焰合成过程中前驱物的特性，包括：The present invention also protects a system for characterizing and predicting the flame synthesis characteristics of a precursor, characterized in that the characteristics of the precursor in the flame synthesis process are measured by a thermogravimetric analyzer and an infrared spectrometer, including:
固体粉末热重测量单元，用于分别测量常规前驱物粉末和化学式为添加剂阴离子与所述前驱物阳离子结合的固体粉末的第一TGA曲线，并对所述第一TGA曲线进行一阶微分处理，得到第一DTG曲线；其中，所述第一TGA曲线用于表征所述前驱物粉末由固体转变为目标产物的分解过程，所述第一DTG曲线用于表征在所述分解过程中样品质量变化速率随温度的变化过程；A solid powder thermogravimetric measurement unit, used to measure the first TGA curves of a conventional precursor powder and a solid powder having a chemical formula of an additive anion combined with the precursor cation, respectively, and to perform first-order differential processing on the first TGA curve to obtain a first DTG curve; wherein the first TGA curve is used to characterize the decomposition process of the precursor powder from a solid to a target product, and the first DTG curve is used to characterize the change process of the sample mass change rate with temperature during the decomposition process;
混合溶液热重测量单元，用于测量所述前驱物粉末的前驱物-溶剂的混合溶液TGA曲线，并对所述混合溶液TGA曲线进行一阶微分处理，得到混合溶液DTG曲线；A mixed solution thermogravimetric measurement unit, used to measure a TGA curve of a mixed solution of a precursor and a solvent of the precursor powder, and to perform first-order differential processing on the mixed solution TGA curve to obtain a DTG curve of the mixed solution;
第一红外测量单元，用于分别测量纯溶剂溶液及所述前驱物-溶剂的混合溶液的第一红外吸收光谱；A first infrared measurement unit, used to measure first infrared absorption spectra of a pure solvent solution and a mixed solution of the precursor-solvent, respectively;
添加剂热重测量单元，用于分别测量纯添加剂溶液、溶剂-添加剂的混合溶液、前驱物-溶剂-添加剂的混合溶液的第三TGA曲线，并对所述第三TGA曲线进行一阶微分处理，得到第三DTG曲线；An additive thermogravimetric measurement unit, used to measure the third TGA curves of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution, respectively, and perform first-order differential processing on the third TGA curve to obtain a third DTG curve;
第二红外测量单元，用于分别测量所述纯添加剂溶液、所述溶剂-添加剂的混合溶液、所述前驱物-溶剂-添加剂的混合溶液的第二红外吸收光谱。The second infrared measurement unit is used to measure the second infrared absorption spectra of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution respectively.
本发明提供的表征和预测前驱物火焰合成特性的方法及系统，具有如下有益效果：The method and system for characterizing and predicting precursor flame synthesis characteristics provided by the present invention have the following beneficial effects:
(1)本发明构建的表征和预测前驱物火焰合成特性的方法及系统，实现了在液相进给火焰合成的前驱物配制阶段对最终火焰合成产物形貌进行预测，避免了开展高温下液相进给火焰合成，收集产物并对其进行表征来得到前驱物配方对产物颗粒形貌的影响这种耗时长且花费较高的方法；(1) The method and system for characterizing and predicting the flame synthesis characteristics of precursors constructed by the present invention realizes the prediction of the morphology of the final flame synthesis product during the precursor preparation stage of liquid-phase fed flame synthesis, avoiding the time-consuming and costly method of conducting liquid-phase fed flame synthesis at high temperature, collecting the products and characterizing them to obtain the influence of the precursor formula on the product particle morphology;
(2)本发明中所采用的热重分析仪以及红外光谱仪对火焰合成中前驱物特性进行测试，通过改变测试样品的温度，可以实现室温和高温下分别测量添加剂对前驱物的转化程度，能在不同温度下表征的测量前驱物-溶剂-添加剂系统的性质，适应性广泛；(2) The thermogravimetric analyzer and infrared spectrometer used in the present invention are used to test the characteristics of the precursor in flame synthesis. By changing the temperature of the test sample, the degree of conversion of the additive to the precursor can be measured at room temperature and high temperature respectively. The properties of the precursor-solvent-additive system can be characterized at different temperatures, and the adaptability is wide;
(3)本发明适用于对多种前驱物-溶剂-添加剂系统，除了本发明实施实例中给出的氧化钇前驱物溶液系统，对其他原理类似的，如二氧化钛，二氧化硅等前驱物溶液系统，也能进行同样的预测。(3) The present invention is applicable to a variety of precursor-solvent-additive systems. In addition to the yttrium oxide precursor solution system given in the embodiment of the present invention, the same prediction can be made for other precursor solution systems with similar principles, such as titanium dioxide, silicon dioxide, etc.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为根据本发明实施例的表征和预测前驱物火焰合成特性的方法的流程框图。FIG. 1 is a flowchart of a method for characterizing and predicting precursor flame synthesis characteristics according to an embodiment of the present invention.
图2为根据本发明实施例的(a,b)硝酸钇和(c,d)2-乙基己酸钇固体粉末的TGA和DTG曲线图；FIG2 is a TGA and DTG graph of (a, b) yttrium nitrate and (c, d) yttrium 2-ethylhexanoate solid powders according to an embodiment of the present invention;
图3为根据本发明实施例的(a)硝酸钇的乙醇溶液的TGA曲线及(b)乙醇、硝酸钇的乙醇溶液的红外吸收光谱；3 is a TGA curve of (a) an ethanol solution of yttrium nitrate and (b) an infrared absorption spectrum of ethanol and an ethanol solution of yttrium nitrate according to an embodiment of the present invention;
图4为根据本发明实施例的EHA、EHA与乙醇混合溶液、硝酸钇溶于EHA与乙醇所得前驱物溶液的(a)TGA和(b)DTG曲线；FIG4 is a graph showing (a) TGA and (b) DTG curves of EHA, a mixed solution of EHA and ethanol, and a precursor solution obtained by dissolving yttrium nitrate in EHA and ethanol according to an embodiment of the present invention;
图5为根据本发明实施例的EHA、EHA与乙醇混合溶液、硝酸钇溶于混合溶液所得前驱物溶液的红外吸收光谱；5 is an infrared absorption spectrum of EHA, a mixed solution of EHA and ethanol, and a precursor solution obtained by dissolving yttrium nitrate in the mixed solution according to an embodiment of the present invention;
图6为根据本发明实施例的异丁酸、异丁酸与乙醇混合溶液、硝酸钇溶于混合溶液所得前驱物溶液的(a,b)TGA和DTG曲线及(c)红外透射光谱；6 is (a, b) TGA and DTG curves and (c) infrared transmission spectrum of isobutyric acid, a mixed solution of isobutyric acid and ethanol, and a precursor solution obtained by dissolving yttrium nitrate in the mixed solution according to an embodiment of the present invention;
图7为根据本发明实施例的前驱物溶液中加入EHA或iBA添加剂最终火焰合成的颗粒形貌图。FIG. 7 is a particle morphology diagram of the final flame synthesis after adding EHA or iBA additives to the precursor solution according to an embodiment of the present invention.
具体实施方式Detailed ways
针对前述现有技术中存在的问题，本发明旨在提供一种通过FTIR、TGA测量手段表征和预测前驱物火焰合成特性的方法及系统，通过结合衰减全反射傅里叶变换红外光谱(ATR-FTIR)和热重分析(TGA)方法，测量溶剂与添加剂混合前后的组分变化，能够预测采用不同添加剂-前驱物溶液配方时溶液内前驱物的转化程度，从而以建立一套简便易行且能在室温和高温下分别测量前驱物溶液性质的前驱物-溶剂-添加剂系统的测试方案。In view of the problems existing in the aforementioned prior art, the present invention aims to provide a method and system for characterizing and predicting the flame synthesis characteristics of precursors by means of FTIR and TGA measurement. By combining attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and thermogravimetric analysis (TGA) methods, the changes in components before and after the mixing of solvents and additives are measured, and the degree of conversion of the precursor in the solution when different additive-precursor solution formulas are used can be predicted, thereby establishing a simple and easy test scheme for the precursor-solvent-additive system that can measure the properties of the precursor solution at room temperature and high temperature respectively.
本发明将结合附图和下述实施例对本发明的技术方案进行更具体的说明。然而，本发明的保护范围并不受限于下列的实施例。The present invention will be described in more detail with reference to the accompanying drawings and the following embodiments. However, the protection scope of the present invention is not limited to the following embodiments.
图1为根据本发明实施例的表征和预测前驱物火焰合成特性的方法的流程框图。如图1所示，本发明提供的表征和预测前驱物火焰合成特性的方法，通过热重分析仪和红外光谱仪测量火焰合成过程中前驱物的特性，包括如下步骤：Fig. 1 is a flowchart of a method for characterizing and predicting flame synthesis characteristics of a precursor according to an embodiment of the present invention. As shown in Fig. 1, the method for characterizing and predicting flame synthesis characteristics of a precursor provided by the present invention measures the characteristics of the precursor during the flame synthesis process by a thermogravimetric analyzer and an infrared spectrometer, and comprises the following steps:
S110：分别测量常规前驱物粉末和化学式为添加剂阴离子与所述前驱物阳离子结合的固体粉末的第一TGA曲线，并对所述第一TGA曲线进行一阶微分处理，得到第一DTG曲线；其中，所述第一TGA曲线用于表征所述前驱物粉末由固体转变为目标产物的分解过程，所述第一DTG(微商热重分析)曲线用于表征在所述分解过程中样品质量变化速率随温度的变化过程；S110: respectively measuring the first TGA curves of a conventional precursor powder and a solid powder having a chemical formula of an additive anion combined with the precursor cation, and performing first-order differential processing on the first TGA curve to obtain a first DTG curve; wherein the first TGA curve is used to characterize the decomposition process of the precursor powder from a solid to a target product, and the first DTG (derivative thermogravimetric analysis) curve is used to characterize the change process of the sample mass change rate with temperature during the decomposition process;
本发明采用的TGA(热重分析)方法，简单来说就是通过一直加热样品，观察样品的质量随温度的变化，根据该变化数据形成TGA曲线，然后对该TGA曲线进行分析的方法。The TGA (thermogravimetric analysis) method used in the present invention is simply a method of continuously heating a sample, observing changes in the mass of the sample with temperature, forming a TGA curve based on the change data, and then analyzing the TGA curve.
S120：测量所述前驱物粉末的前驱物-溶剂的混合溶液TGA曲线，并对所述混合溶液TGA曲线进行一阶微分处理，得到混合溶液DTG曲线；S120: measuring a TGA curve of a precursor-solvent mixed solution of the precursor powder, and performing first-order differential processing on the TGA curve of the mixed solution to obtain a DTG curve of the mixed solution;
S130：分别测量纯溶剂溶液及所述前驱物-溶剂的混合溶液的第一红外吸收光谱；S130: measuring first infrared absorption spectra of a pure solvent solution and a mixed solution of the precursor and the solvent respectively;
S140：分别测量纯添加剂溶液、溶剂-添加剂的混合溶液、前驱物-溶剂-添加剂的混合溶液的第三TGA曲线，并对所述第三TGA曲线进行一阶微分处理，得到第三DTG曲线；S140: measuring third TGA curves of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution respectively, and performing first-order differential processing on the third TGA curve to obtain a third DTG curve;
S150：分别测量所述纯添加剂溶液、所述溶剂-添加剂的混合溶液、所述前驱物-溶剂-添加剂的混合溶液的第二红外吸收光谱。S150: measuring the second infrared absorption spectra of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution respectively.
具体的，在步骤S110中，采用热重分析仪，分别测量常规前驱物粉末和化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的热重(TGA)曲线(此处称为第一TGA曲线)，并对该TGA曲线进行一阶微分处理，得到微商热重分析曲线(此处称为第一DTG曲线)。Specifically, in step S110, a thermogravimetric analyzer is used to measure the thermogravimetric (TGA) curves of a conventional precursor powder and a solid powder having a chemical formula of an additive anion combined with a precursor cation (referred to herein as a first TGA curve), respectively, and the TGA curve is subjected to first-order differential processing to obtain a derivative thermogravimetric analysis curve (referred to herein as a first DTG curve).
显然，该第一TGA曲线包括两种，分别是常规前驱物粉末的第一TGA曲线和化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的第一TGA曲线，对应的一阶微分处理后的第一DTG曲线也有两种。Obviously, the first TGA curve includes two types, namely the first TGA curve of conventional precursor powder and the first TGA curve of solid powder whose chemical formula is the combination of additive anions and precursor cations. There are also two corresponding first DTG curves after first-order differential processing.
上述两种第一TGA曲线能够反映由固体前驱物粉末转变为目标产物的分解过程，两种第一DTG曲线能够表征了样品质量变化速率随温度的变化过程。The two first TGA curves can reflect the decomposition process of the solid precursor powder into the target product, and the two first DTG curves can characterize the change process of the sample mass change rate with temperature.
其中，通过对比该常规前驱物粉末与化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的结果，即将两种第一TGA曲线进行对比和将两种第一DTG曲线进行对比，可以反映出添加剂与前驱物结合后，对前驱物分解形成产物路径的改变。Among them, by comparing the results of the conventional precursor powder with the solid powder whose chemical formula is the combination of the additive anion and the precursor cation, that is, comparing the two first TGA curves and comparing the two first DTG curves, it can be reflected that after the additive combines with the precursor, the change in the path of the precursor decomposition to form products can be reflected.
在步骤S120中，采用热重分析仪，测量前述前驱物粉末的前驱物-溶剂的混合溶液TGA曲线作为第二TGA曲线，并对该混合溶液TGA曲线进行一阶微分处理，得到该前驱物-溶剂的混合溶液DTG曲线作为第二DTG曲线。In step S120, a thermogravimetric analyzer is used to measure a TGA curve of a precursor-solvent mixed solution of the precursor powder as a second TGA curve, and the mixed solution TGA curve is subjected to first-order differential processing to obtain a DTG curve of the precursor-solvent mixed solution as a second DTG curve.
然后，可以根据该混合溶液TGA曲线和混合溶液DTG曲线，分析测量该混合溶液TGA曲线时的升温过程中吸热及放热的信息，得到反映样品质量变化的各阶段的质量损失，与步骤S110中的纯前驱物固体粉末TGA测试结果(即第一TGA曲线)进行对比，从而获得前驱物加入溶剂后，分解路径的改变。Then, based on the TGA curve of the mixed solution and the DTG curve of the mixed solution, the information on heat absorption and heat release during the heating process when measuring the TGA curve of the mixed solution can be analyzed to obtain the mass loss at each stage reflecting the change in sample mass, and compared with the TGA test result of the pure precursor solid powder in step S110 (i.e., the first TGA curve), so as to obtain the change in the decomposition path of the precursor after the solvent is added.
在步骤S130中，采用红外光谱仪，分别测量纯溶剂溶液与前述前驱物-溶剂的混合溶液的红外吸收光谱，作为第一红外吸收光谱。In step S130, an infrared spectrometer is used to measure the infrared absorption spectra of the pure solvent solution and the precursor-solvent mixed solution as first infrared absorption spectra.
然后，可以通过对比两次测试结果的吸收光谱中的特征吸收峰，即通过对比纯溶剂溶液的第一红外吸收光谱和所述混合溶液的第一红外吸收光谱中的特征吸收峰，得到前驱物溶于溶剂后，是否发生化学反应产生新的物质。Then, by comparing the characteristic absorption peaks in the absorption spectra of the two test results, that is, by comparing the characteristic absorption peaks in the first infrared absorption spectrum of the pure solvent solution and the first infrared absorption spectrum of the mixed solution, it can be determined whether a chemical reaction occurs to produce new substances after the precursor is dissolved in the solvent.
在步骤S140中，采用热重分析仪，分别测量纯添加剂溶液、溶剂-添加剂的混合溶液、前驱物-溶剂-添加剂的混合溶液的第三TGA(热重分析)曲线，并对该第三热重分析曲线进行一阶微分处理，得到第三DTG曲线。In step S140, a thermogravimetric analyzer is used to measure the third TGA (thermogravimetric analysis) curves of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution, respectively, and the third thermogravimetric analysis curve is subjected to first-order differential processing to obtain a third DTG curve.
显然，该第三TGA曲线包括三种，即纯添加剂溶液的第三TGA曲线、溶剂-添加剂的混合溶液的第三TGA曲线和前驱物-溶剂-添加剂的混合溶液的第三TGA曲线，对应的一阶微分处理后的第三DTG曲线也有三种。Obviously, the third TGA curve includes three types, namely, the third TGA curve of the pure additive solution, the third TGA curve of the solvent-additive mixed solution and the third TGA curve of the precursor-solvent-additive mixed solution. There are also three corresponding third DTG curves after first-order differential processing.
通过对比前驱物-溶剂-添加剂的混合溶液的第三TGA曲线与步骤S110中两种固体粉末的TGA曲线和DTG曲线(即第一TGA曲线和第一DTG曲线)的特征峰值，可以确定所述添加剂与所述前驱物是否完全结合。By comparing the characteristic peaks of the third TGA curve of the precursor-solvent-additive mixed solution with the TGA curve and DTG curve (ie, the first TGA curve and the first DTG curve) of the two solid powders in step S110, it can be determined whether the additive is completely combined with the precursor.
其中，若前驱物-溶剂-添加剂的混合溶液的第三TGA曲线与化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的第一TGA曲线的失重阶梯形状类似，且第一DTG曲线与所述第三DTG曲线对应的最大质量损失区间内的峰值点相吻合，则认为添加剂完全与前驱物结合，即所有的前驱物阳离子均与添加剂阴离子相结合，产物生成路线将从常规前驱物分解路径转为化学式为添加剂阴离子与前驱物阳离子结合的物质的分解路径。Among them, if the third TGA curve of the mixed solution of precursor-solvent-additive is similar to the weight loss step shape of the first TGA curve of the solid powder whose chemical formula is the combination of additive anions and precursor cations, and the peak points in the maximum mass loss interval corresponding to the first DTG curve and the third DTG curve coincide with each other, then it is considered that the additive is completely combined with the precursor, that is, all the precursor cations are combined with the additive anions, and the product generation route will be converted from the conventional precursor decomposition path to the decomposition path of the substance whose chemical formula is the combination of additive anions and precursor cations.
在步骤S150中，采用红外光谱仪，分别测量纯添加剂溶液、溶剂-添加剂的混合溶液、前驱物-溶剂-添加剂的混合溶液的红外吸收光谱作为第二红外吸收光谱。In step S150, an infrared spectrometer is used to measure infrared absorption spectra of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution as second infrared absorption spectra.
同样，该第二红外吸收光谱包括纯添加剂溶液的第二红外吸收光谱、溶剂-添加剂的混合溶液的第二红外吸收光谱以及的前驱物-溶剂-添加剂的混合溶液的第二红外吸收光谱。Likewise, the second infrared absorption spectrum includes the second infrared absorption spectrum of a pure additive solution, the second infrared absorption spectrum of a solvent-additive mixed solution, and the second infrared absorption spectrum of a precursor-solvent-additive mixed solution.
通过对比上述三种第二红外吸收光谱的峰值信息，可以得知添加剂是否与溶剂发生化学反应新城新的物质，以及前驱物是否与添加剂发生化学反应形成新的物质。By comparing the peak information of the above three second infrared absorption spectra, it can be known whether the additive chemically reacts with the solvent to form a new substance, and whether the precursor chemically reacts with the additive to form a new substance.
将以上结果与TGA的结果相互验证，通过补充提供溶液中生成的其他组分的信息，就能够揭示添加剂在溶液中的反应机制。The above results are verified with the results of TGA, and by providing supplementary information on other components generated in the solution, the reaction mechanism of the additive in the solution can be revealed.
具体的，在对比三种第二红外吸收光谱的峰值信息之后，可以进一步利用对比三种第二红外吸收光谱的峰值信息的结果与第三TGA曲线的分析结果进行相互验证；其中，如果第三TGA曲线表明所述添加剂完全与所述前驱物结合，而第二红外吸收光谱的峰值也表明了前驱物与添加物发生化学反应形成了新的物质，则两种诊断方法实现了相互验证；通过补充提供所述溶液中生成的其他组分的信息，如前驱物阳离子发生水解，产生的H+与前驱物阴离子形成新的酸(如HNO3)组分，确定所述添加剂在所述溶液中是否与前驱物阳离子结合，从而判断添加剂是否能提高前驱物的挥发性，是否对火焰合成更有利。Specifically, after comparing the peak information of the three second infrared absorption spectra, the results of comparing the peak information of the three second infrared absorption spectra can be further used to verify each other with the analysis results of the third TGA curve; wherein, if the third TGA curve shows that the additive is completely combined with the precursor, and the peak of the second infrared absorption spectrum also shows that the precursor and the additive undergo a chemical reaction to form a new substance, then the two diagnostic methods achieve mutual verification; by providing additional information on other components generated in the solution, such as the hydrolysis of the precursor cation, the generated H + and the precursor anion forming a new acid (such as HNO 3 ) component, it is determined whether the additive is combined with the precursor cation in the solution, thereby judging whether the additive can increase the volatility of the precursor and whether it is more beneficial to flame synthesis.
下面将结合更为具体的实施例详细介绍采用ATR-FTIR与热重分析相结合的手段进行表征和预测前驱物火焰合成特性的方法。The following will introduce in detail the method of characterizing and predicting the flame synthesis characteristics of precursors by combining ATR-FTIR with thermogravimetric analysis in conjunction with more specific embodiments.
实施例一Embodiment 1
预测添加剂为2-乙基己酸(EHA)和异丁酸(iBA)的火焰合成氧化钇(Y2O3)产物形貌的过程，具体火焰合成的选用参数如下：The process of predicting the morphology of the product of flame synthesis of yttrium oxide (Y2O3) with additives of 2-ethylhexanoic acid (EHA) and isobutyric acid (iBA) is as follows:
火焰合成氧化钇时，选用的常规前驱物为硝酸钇，溶剂为乙醇(EtOH)；When yttrium oxide is synthesized by flame, the conventional precursor used is yttrium nitrate and the solvent is ethanol (EtOH);
热重分析测试条件统一选择为升温范围为35-900℃，升温速率优选为10K/min，热重分析仪的载气为氮气，载气流速100ml/min，样品质量为10mg；The test conditions for thermogravimetric analysis were uniformly selected as a temperature rise range of 35-900°C, a temperature rise rate of preferably 10K/min, a carrier gas of the thermogravimetric analyzer of nitrogen, a carrier gas flow rate of 100ml/min, and a sample mass of 10mg;
在所有含有前驱物的溶液中，Y3+的摩尔浓度均为0.3mol/L；In all solutions containing precursors, the molar concentration of Y3+ was 0.3 mol/L;
在所有有添加剂和溶剂存在的溶液中，液体添加剂与溶剂的比例均为1:1；In all solutions where additives and solvents are present, the ratio of liquid additive to solvent is 1:1;
在确定了上述参数之后，进行具体火焰合成特征的表征和预测的流程如下：After determining the above parameters, the process of characterizing and predicting specific flame synthesis characteristics is as follows:
首先，测量硝酸钇和2-乙基己酸钇的固体粉末的TGA曲线，并对其做一阶微分，得到DTG曲线。First, the TGA curves of the solid powders of yttrium nitrate and yttrium 2-ethylhexanoate are measured, and the first-order differential is performed to obtain the DTG curve.
图2为本发明实施例的(a,b)硝酸钇和(c,d)2-乙基己酸钇固体粉末的TGA和DTG曲线图。如图2的(a)和(b)所示，固体硝酸钇粉末热重分析曲线呈阶梯式下降，DTG曲线反映最大的样品质量损失速率约在375℃。如图2的(c)和(d)所示，2-乙基己酸钇固体样品的TGA曲线，与硝酸钇的分解曲线差别明显，其仅包含一个主要的失重区间，DTG曲线反映最大的样品质量损失速率约在469.2℃。Figure 2 is a TGA and DTG curve diagram of (a, b) yttrium nitrate and (c, d) yttrium 2-ethylhexanoate solid powders of the embodiments of the present invention. As shown in (a) and (b) of Figure 2, the thermogravimetric analysis curve of the solid yttrium nitrate powder decreases in a step-like manner, and the DTG curve reflects that the maximum sample mass loss rate is about 375°C. As shown in (c) and (d) of Figure 2, the TGA curve of the solid sample of yttrium 2-ethylhexanoate is significantly different from the decomposition curve of yttrium nitrate, which only contains one major weight loss interval, and the DTG curve reflects that the maximum sample mass loss rate is about 469.2°C.
其次，测量硝酸钇的乙醇溶液的TGA曲线，并对其做一阶微分，得到DTG曲线。图3为本发明实施例的硝酸钇的乙醇溶液的TGA曲线及乙醇、硝酸钇的乙醇溶液的红外吸收光谱示意图。Secondly, the TGA curve of the ethanol solution of yttrium nitrate is measured and first-order differential is performed to obtain the DTG curve. Figure 3 is a schematic diagram of the TGA curve of the ethanol solution of yttrium nitrate and the infrared absorption spectrum of ethanol and the ethanol solution of yttrium nitrate according to an embodiment of the present invention.
其中，图3中的(a)为硝酸钇的乙醇溶液的TGA曲线示意图，图3中的(b)为硝酸钇的乙醇溶液的红外吸收光谱示意图。如图3的(a)所示，硝酸钇的乙醇溶液的TGA曲线与固态硝酸钇粉末的TGA曲线存在明显差异。DTG曲线中，两个失重区间内最大失重速率对应温度分别为323.7℃和394.7℃。Among them, (a) in Figure 3 is a schematic diagram of the TGA curve of the ethanol solution of yttrium nitrate, and (b) in Figure 3 is a schematic diagram of the infrared absorption spectrum of the ethanol solution of yttrium nitrate. As shown in Figure 3 (a), there is a significant difference between the TGA curve of the ethanol solution of yttrium nitrate and the TGA curve of the solid yttrium nitrate powder. In the DTG curve, the temperatures corresponding to the maximum weight loss rates in the two weight loss intervals are 323.7°C and 394.7°C, respectively.
而后，测量纯乙醇溶液和加入硝酸钇的乙醇溶液的红外吸收光谱，如图3的(b)所示，加入硝酸钇后乙醇溶液的红外吸收峰均可在纯乙醇溶液和固体硝酸钇粉末的红外吸收光谱中找到，说明乙醇和硝酸钇之间没有发生化学反应生成新的物质。Then, the infrared absorption spectra of the pure ethanol solution and the ethanol solution with yttrium nitrate added were measured. As shown in FIG3( b ), the infrared absorption peaks of the ethanol solution after the addition of yttrium nitrate can be found in the infrared absorption spectra of the pure ethanol solution and the solid yttrium nitrate powder, indicating that no chemical reaction occurred between ethanol and yttrium nitrate to generate new substances.
进一步，测量2-乙基己酸、2-乙基己酸与乙醇等比例的混合溶液、硝酸钇溶解于2-乙基己酸与乙醇的前驱物溶液的TGA曲线，并对其做一阶微分，得到DTG曲线，结果如图4所示。Furthermore, the TGA curves of 2-ethylhexanoic acid, a mixed solution of 2-ethylhexanoic acid and ethanol in equal proportions, and a precursor solution of yttrium nitrate dissolved in 2-ethylhexanoic acid and ethanol were measured, and the first-order differentiation was performed to obtain the DTG curve, and the result is shown in FIG4 .
图4为本发明实施例的EHA、EHA与乙醇混合溶液、硝酸钇溶于EHA与乙醇所得前驱物溶液的(a)TGA和(b)DTG曲线。如图4所示，对硝酸钇溶解于2-乙基己酸与乙醇的前驱物溶液的TGA曲线形态，不再有图3的(a)的乙醇和硝酸钇溶液的多个失重阶梯，其DTG曲线反映的最大质量损失区间内的峰值点为464.8℃，与2-乙基己酸钇固体样品的失重区间及最大质量损失速率所处温度469.2℃吻合。这一结果充分表明加入2-乙基己酸将溶液中的硝酸钇全部转化为2-乙基己酸钇。Figure 4 is the (a) TGA and (b) DTG curves of EHA, a mixed solution of EHA and ethanol, and a precursor solution obtained by dissolving yttrium nitrate in EHA and ethanol according to an embodiment of the present invention. As shown in Figure 4, the TGA curve of the precursor solution of yttrium nitrate dissolved in 2-ethylhexanoic acid and ethanol no longer has the multiple weight loss steps of the ethanol and yttrium nitrate solutions in Figure 3 (a), and the peak point in the maximum mass loss range reflected by its DTG curve is 464.8°C, which is consistent with the weight loss range of the solid sample of yttrium 2-ethylhexanoate and the temperature of 469.2°C at which the maximum mass loss rate is located. This result fully shows that the addition of 2-ethylhexanoic acid converts all the yttrium nitrate in the solution into yttrium 2-ethylhexanoate.
最后，测量2-乙基己酸、2-乙基己酸与乙醇等比例的混合溶液、硝酸钇溶解于2-乙基己酸与乙醇的前驱物溶液的红外吸收光谱，结果如图5所示。Finally, the infrared absorption spectra of 2-ethylhexanoic acid, a mixed solution of 2-ethylhexanoic acid and ethanol in equal proportions, and a precursor solution of yttrium nitrate dissolved in 2-ethylhexanoic acid and ethanol were measured, and the results are shown in FIG5 .
图5为本发明实施例的EHA、EHA与乙醇混合溶液、硝酸钇溶于混合溶液所得前驱物溶液的红外吸收光谱。如图5所示，2-乙基己酸与乙醇混合溶液的红外吸收图谱中包含来自2-乙基己酸和乙醇各自的特征吸收峰，表明添加剂与溶剂未发生反应。对于硝酸钇溶解于乙醇和2-乙基己酸的前驱物溶液，与无硝酸钇的混合溶液对比，大多数吸收峰的位置保持不变。在1520cm-1出现的峰对应2-乙基己酸钇的R-COO-基团，表明硝酸钇转化为2-乙基己酸钇，以上结果与TGA的结果相互验证，通过补充提供溶液中生成的其他组分的信息，揭示了2-乙基己酸在溶液中的反应机制。Fig. 5 is the infrared absorption spectra of the precursor solution obtained by dissolving EHA, EHA and ethanol mixed solution, and yttrium nitrate in the mixed solution of the embodiment of the present invention. As shown in Fig. 5, the infrared absorption spectrum of the mixed solution of 2-ethylhexanoic acid and ethanol contains characteristic absorption peaks from 2-ethylhexanoic acid and ethanol respectively, indicating that the additive and the solvent do not react. For the precursor solution of yttrium nitrate dissolved in ethanol and 2-ethylhexanoic acid, compared with the mixed solution without yttrium nitrate, the positions of most absorption peaks remain unchanged. The peak appearing at 1520cm-1 corresponds to the R-COO- group of yttrium 2-ethylhexanoate, indicating that yttrium nitrate is converted into yttrium 2-ethylhexanoate. The above results are mutually verified with the results of TGA, and the reaction mechanism of 2-ethylhexanoic acid in solution is revealed by supplementing the information of other components generated in the solution.
实施例二Embodiment 2
对于异丁酸添加剂，与考察2-乙基己酸添加剂流程相同。主要结果如图6所示。图6为本发明实施例的异丁酸、异丁酸与乙醇混合溶液、硝酸钇溶于混合溶液所得前驱物溶液的(a,b)TGA和DTG曲线及(c)红外透射光谱。由图6的(a)和(b)所示，异丁酸钇的分解温度区间为260℃至360℃，对于硝酸钇溶解于乙醇和异丁酸的前驱物溶液，失重区间与异丁酸钇的失重区间部分重合，表明存在部分硝酸钇转化为异丁酸钇。由图6的(c)红外光谱图所示，对于硝酸钇溶解于异丁酸和乙醇的前驱物溶液，与异丁酸和乙醇的混合溶液对比，大多数吸收峰的位置保持不变，在1520cm-1出现的峰对应异丁酸钇的R-COO-基团，与热重测量结果相吻合。；For the isobutyric acid additive, the process is the same as that for investigating the 2-ethylhexanoic acid additive. The main results are shown in Figure 6. Figure 6 shows the (a, b) TGA and DTG curves and (c) infrared transmission spectrum of the precursor solution obtained by dissolving yttrium nitrate in the mixed solution of isobutyric acid, isobutyric acid and ethanol in the embodiment of the present invention. As shown in (a) and (b) of Figure 6, the decomposition temperature range of yttrium isobutyrate is 260°C to 360°C. For the precursor solution of yttrium nitrate dissolved in ethanol and isobutyric acid, the weight loss range partially overlaps with the weight loss range of yttrium isobutyrate, indicating that part of the yttrium nitrate is converted into yttrium isobutyrate. As shown in the infrared spectrum of Figure 6 (c), for the precursor solution of yttrium nitrate dissolved in isobutyric acid and ethanol, compared with the mixed solution of isobutyric acid and ethanol, the positions of most absorption peaks remain unchanged, and the peak appearing at 1520cm-1 corresponds to the R-COO- group of yttrium isobutyrate, which is consistent with the thermogravimetric measurement results. ;
通过结合衰减全反射傅里叶变换红外光谱(ATR-FTIR)和热重分析(TGA)方法，发现2-乙基己酸作为添加剂时，硝酸钇全部转换为2-乙基己酸钇，而异丁酸作为添加剂时，硝酸钇部分转换为异丁酸钇，根据火焰合成原理，可以预测2-乙基己酸作为添加剂时，有助于前驱物通过典型的气相-颗粒相转变路径形成纳米颗粒，而异丁酸作为添加剂时，首先发生溶剂蒸发及燃烧，前驱物在液滴表面沉淀析出，形成外壳包裹残余溶剂，最终经由相对复杂的液相-颗粒相路径形成空心，壳状等非均相颗粒；By combining the attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and thermogravimetric analysis (TGA) methods, it was found that when 2-ethylhexanoic acid was used as an additive, all yttrium nitrate was converted into yttrium 2-ethylhexanoate, while when isobutyric acid was used as an additive, part of yttrium nitrate was converted into yttrium isobutyric acid. According to the principle of flame synthesis, it can be predicted that when 2-ethylhexanoic acid was used as an additive, it would help the precursor to form nanoparticles through a typical gas phase-particle phase transition path, while when isobutyric acid was used as an additive, solvent evaporation and combustion occurred first, and the precursor precipitated on the surface of the droplet to form a shell to wrap the residual solvent, and finally formed hollow, shell-shaped and other heterogeneous particles through a relatively complex liquid phase-particle phase path;
图7为本发明实施例的前驱物溶液中加入EHA或iBA添加剂最终火焰合成的颗粒形貌图。如图7所示，采用2-乙基己酸和异丁酸分别作为添加剂配制得到相应的前驱物溶液，在高温1500K火焰场中开展合成实验，所得产物的TEM图像中，添加异丁酸时产物中不规则的大颗粒与粒径均匀的小颗粒共存。添加2-乙基己酸时颗粒粒径小而均匀，没有观察到大颗粒的存在。这一合成结果与前驱物溶液中硝酸盐向羧酸盐的转化程度基本相符。Figure 7 is a particle morphology diagram of the final flame synthesis of the precursor solution of the embodiment of the present invention after adding EHA or iBA additives. As shown in Figure 7, 2-ethylhexanoic acid and isobutyric acid were used as additives to prepare the corresponding precursor solutions, and the synthesis experiment was carried out in a high-temperature 1500K flame field. In the TEM image of the obtained product, when isobutyric acid was added, irregular large particles coexisted with small particles with uniform particle size in the product. When 2-ethylhexanoic acid was added, the particle size was small and uniform, and no large particles were observed. This synthesis result is basically consistent with the degree of conversion of nitrate to carboxylate in the precursor solution.
与上述表征和预测前驱物火焰合成特性的方法相对应，本发明还提供一种表征和预测前驱物火焰合成特性的系统，用于通过热重分析仪和红外光谱仪测量火焰合成过程中前驱物的特性，该系统包括：Corresponding to the above-mentioned method for characterizing and predicting the flame synthesis characteristics of a precursor, the present invention also provides a system for characterizing and predicting the flame synthesis characteristics of a precursor, which is used to measure the characteristics of the precursor in the flame synthesis process by a thermogravimetric analyzer and an infrared spectrometer, and the system comprises:
固体粉末热重测量单元，用于分别测量常规前驱物粉末和化学式为添加剂阴离子与所述前驱物阳离子结合的固体粉末的第一TGA曲线，并对所述第一TGA曲线进行一阶微分处理，得到第一DTG曲线；其中，所述第一TGA曲线用于表征所述前驱物粉末由固体转变为目标产物的分解过程，所述第一DTG曲线用于表征在所述分解过程中样品质量变化速率随温度的变化过程；A solid powder thermogravimetric measurement unit, used to measure the first TGA curves of a conventional precursor powder and a solid powder having a chemical formula of an additive anion combined with the precursor cation, respectively, and to perform first-order differential processing on the first TGA curve to obtain a first DTG curve; wherein the first TGA curve is used to characterize the decomposition process of the precursor powder from a solid to a target product, and the first DTG curve is used to characterize the change process of the sample mass change rate with temperature during the decomposition process;
混合溶液热重测量单元，用于测量所述前驱物粉末的前驱物-溶剂的混合溶液TGA曲线，并对所述混合溶液TGA曲线进行一阶微分处理，得到混合溶液DTG曲线；A mixed solution thermogravimetric measurement unit, used to measure a TGA curve of a mixed solution of a precursor and a solvent of the precursor powder, and to perform first-order differential processing on the mixed solution TGA curve to obtain a DTG curve of the mixed solution;
第一红外测量单元，用于分别测量纯溶剂溶液及所述前驱物-溶剂的混合溶液的第一红外吸收光谱；A first infrared measurement unit, used to measure first infrared absorption spectra of a pure solvent solution and a mixed solution of the precursor-solvent, respectively;
添加剂热重测量单元，用于分别测量纯添加剂溶液、溶剂-添加剂的混合溶液、前驱物-溶剂-添加剂的混合溶液的第三TGA曲线，并对所述第三TGA曲线进行一阶微分处理，得到第三DTG曲线；An additive thermogravimetric measurement unit, used to measure the third TGA curves of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution, respectively, and perform first-order differential processing on the third TGA curve to obtain a third DTG curve;
第二红外测量单元，用于分别测量所述纯添加剂溶液、所述溶剂-添加剂的混合溶液、所述前驱物-溶剂-添加剂的混合溶液的第二红外吸收光谱。The second infrared measurement unit is used to measure the second infrared absorption spectra of the pure additive solution, the solvent-additive mixed solution, and the precursor-solvent-additive mixed solution respectively.
此外，该表征和预测前驱物火焰合成特性的系统还可以包括数据分析单元，用于分析上述固体粉末热重测量单元、混合溶液热重测量单元、第一红外测量单元、添加剂热重测量单元以及添加剂热重测量单元的测量结果。In addition, the system for characterizing and predicting precursor flame synthesis characteristics may also include a data analysis unit for analyzing the measurement results of the above-mentioned solid powder thermogravimetric measurement unit, mixed solution thermogravimetric measurement unit, first infrared measurement unit, additive thermogravimetric measurement unit and additive thermogravimetric measurement unit.
具体的，作为示例，数据分析单元分析固体粉末热重测量单元的测量结果，通过对比所述常规前驱物粉末与所述化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的结果，得到所述添加剂与所述前驱物结合后，对所述前驱物分解形成产物路径的改变。Specifically, as an example, the data analysis unit analyzes the measurement results of the solid powder thermogravimetric measurement unit, and by comparing the results of the conventional precursor powder with the solid powder having the chemical formula of the additive anion combined with the precursor cation, the change in the decomposition path of the precursor to form products after the additive combines with the precursor is obtained.
数据分析单元分析混合溶液热重测量单元的测量结果，根据所述混合溶液TGA曲线和所述混合溶液DTG曲线，通过分析测量所述混合溶液TGA曲线时的升温过程中吸热及放热的信息，得到反映样品质量变化的各阶段的质量损失，将所述混合溶液TGA曲线与S110中的所述前驱物粉末的第一TGA曲线进行对比，以获得所述前驱物加入所述溶剂后，分解路径的改变。The data analysis unit analyzes the measurement result of the mixed solution thermogravimetric measurement unit, and obtains the mass loss at each stage reflecting the mass change of the sample by analyzing the information of heat absorption and heat release during the heating process when measuring the TGA curve of the mixed solution according to the mixed solution TGA curve and the mixed solution DTG curve, and compares the TGA curve of the mixed solution with the first TGA curve of the precursor powder in S110 to obtain the change in the decomposition path of the precursor after the solvent is added.
数据分析单元分析第一红外测量单元的测量结果，通过对比纯溶剂溶液的第一红外吸收光谱和所述混合溶液的第一红外吸收光谱中的特征吸收峰，得到所述前驱物溶于溶剂后，是否发生化学反应产生新的物质。The data analysis unit analyzes the measurement result of the first infrared measurement unit, and determines whether a chemical reaction occurs to produce a new substance after the precursor is dissolved in the solvent by comparing the characteristic absorption peaks in the first infrared absorption spectrum of the pure solvent solution and the first infrared absorption spectrum of the mixed solution.
数据分析单元分析添加剂热重测量单元的测量结果，通过对比所述第三TGA曲线和所述第三DTG曲线与S110中的所述第一TGA曲线和所述第一DTG曲线的特征峰值，确定所述添加剂与所述前驱物是否完全结合；其中，若所述前驱物-溶剂-添加剂的混合溶液的第三TGA曲线与所述化学式为添加剂阴离子与前驱物阳离子结合的固体粉末的第一TGA曲线的失重阶梯形状类似，且所述第一DTG曲线与所述第三DTG曲线对应的最大质量损失区间内的峰值点相吻合，认为所述添加剂完全与所述前驱物结合。The data analysis unit analyzes the measurement result of the additive thermogravimetric measurement unit, and determines whether the additive is completely combined with the precursor by comparing the characteristic peaks of the third TGA curve and the third DTG curve with the first TGA curve and the first DTG curve in S110; wherein, if the third TGA curve of the mixed solution of the precursor-solvent-additive is similar to the weight loss step shape of the first TGA curve of the solid powder whose chemical formula is the combination of the additive anion and the precursor cation, and the peak points within the maximum mass loss interval corresponding to the first DTG curve and the third DTG curve are consistent, it is considered that the additive is completely combined with the precursor.
数据分析单元分析第二红外测量单元的测量结果，通过对比三种所述第二红外吸收光谱的峰值信息，确定所述添加剂是否与溶剂发生化学反应形成新的物质，以及所述前驱物是否与添加剂发生化学反应形成新的物质。The data analysis unit analyzes the measurement result of the second infrared measurement unit, and determines whether the additive chemically reacts with the solvent to form a new substance, and whether the precursor chemically reacts with the additive to form a new substance by comparing the peak information of the three second infrared absorption spectra.
另外，数据分析单元在对比三种所述第二红外吸收光谱的峰值信息之后，还通过对比三种所述第二红外吸收光谱的峰值信息的结果与所述第三TGA曲线的分析结果进行相互验证。其中，如果第三TGA曲线表明所述添加剂完全与所述前驱物结合，而第二红外吸收光谱的峰值也表明了前驱物与添加物发生化学反应形成了新的物质，则两种诊断方法实现了相互验证；通过补充提供所述溶液中生成的其他组分的信息，如前驱物阳离子发生水解，产生的H+与前驱物阴离子形成新的酸(如HNO3)组分，确定所述添加剂在所述溶液中是否与前驱物阳离子结合，从而判断添加剂是否能提高前驱物的挥发性，是否对火焰合成更有利。In addition, after comparing the peak information of the three second infrared absorption spectra, the data analysis unit also verifies each other by comparing the peak information of the three second infrared absorption spectra with the analysis result of the third TGA curve. If the third TGA curve shows that the additive is completely combined with the precursor, and the peak of the second infrared absorption spectrum also shows that the precursor and the additive undergo a chemical reaction to form a new substance, the two diagnostic methods achieve mutual verification; by providing additional information on other components generated in the solution, such as the hydrolysis of the precursor cation, the generated H + and the precursor anion to form a new acid (such as HNO 3 ) component, it is determined whether the additive is combined with the precursor cation in the solution, thereby judging whether the additive can increase the volatility of the precursor and whether it is more beneficial to flame synthesis.
上述表征和预测前驱物火焰合成特性的系统的具体实现方式可以参照前述对表征和预测前驱物火焰合成特性的方法的描述，在此不再一一列举。The specific implementation of the above-mentioned system for characterizing and predicting the synthesis characteristics of a precursor flame can refer to the above-mentioned description of the method for characterizing and predicting the synthesis characteristics of a precursor flame, and will not be listed one by one here.
本发明在实施过程中所涉及的各种实验用品(包括但不限于：化学试剂、仪器等)之中，未经特别说明的，均为常规实验用品，可以通过各种方式(例如购买、自行制备等)很方便地获得。Among the various experimental supplies (including but not limited to chemical reagents, instruments, etc.) involved in the implementation of the present invention, unless otherwise specified, they are all conventional experimental supplies and can be easily obtained in various ways (such as purchase, self-preparation, etc.).
虽然，上文中已经用一般性说明、具体实施方式以及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。因此，在不偏离本发明精神的基础上所做的这些修改和改进，均属于本发明要求保护的范围。Although the present invention has been described in detail above by general description, specific embodiments and tests, it is obvious to those skilled in the art that some modifications or improvements can be made thereto on the basis of the present invention. The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. Therefore, these modifications and improvements made on the basis of not departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.
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