CN1473763A - Water phase synthetically preparing method of homophase base oriented arranged hydroxy iron oxide nano line - Google Patents
Water phase synthetically preparing method of homophase base oriented arranged hydroxy iron oxide nano line Download PDFInfo
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- CN1473763A CN1473763A CNA031322565A CN03132256A CN1473763A CN 1473763 A CN1473763 A CN 1473763A CN A031322565 A CNA031322565 A CN A031322565A CN 03132256 A CN03132256 A CN 03132256A CN 1473763 A CN1473763 A CN 1473763A
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Abstract
The water phase synthesis process of preparing homophase base oriented hydroxy iron oxide non line includes adding reactant ferrous chloride and o-dinitro phenanthrene in the molar ratio of 1 to 3 and water to reach the concentration of FeCl2 0.05 mol/L; reaction at 50-70 deg.c for over 6 hr and filtering to obtain coarse product; conventional washing and drying of the coarse product to obtain end product. The FeCl2 material in the water solution is reused. The product of the present invention has narrow granularity distribution, average diameter of nano line 40 nm, good charge and discharge performance, easy transplantation and semiconductor performance, and is suitable for being used as the anode material in lithium battery.
Description
The technical field is as follows:
the invention belongs to the technical field of preparation methods based on aqueous phase synthesis, and particularly relates to a preparation method of directionally arranged FeOOH β -nanowire.
Secondly, background art:
β -FeOOH has wide application in lithium battery anode material, semiconductor material, catalysis, dye industry and magnetic material preparation etc. for lithium battery anode material, nano-wire has potential application prospect as minimum unit of electron transmissionThe method for preparing the magnetic material has the problems of simple process, high yield and large-scale production, and the methods for synthesizing β -FeOOH nanowires have been reported in Journal of Physical Chemistry (1757 and 1763 of 1962), Nature (Nature, 1970, vol 226, 1225 and 1228), and the Journal of Material Science in the Netherlands (Journal of Materials Science, 2001, vol 36, 2461 and 2471), and the Journal of Material Science (Journal of Materials Science, 2002, vol 21 1781 and 1783), but the methods for synthesizing the β -FeOOH nanowires have not been reported, but the methods for synthesizing the nanowires have not been reported in oriented arrangement, the Journal of Materials Chemistry (Chemistry of Materials Science, Letters, 2002, vol 13 and 1783, WO 233-1395, and No. 32O3) Or tin dioxide (SnO)2) The adhesion on the substrate is not favorable for being transplanted on the electrode, the procedure for processing the substrate is complicated, and the raw materials can not be recycled.
Thirdly, the invention content:
1. technical problem
The invention aims to provide a water phase synthesis preparation method of directionally arranged iron oxyhydroxide nanowires of an in-phase substrate at low temperature and normal pressure in an aqueous solution system, so as to overcome the defects that the procedure for treating a substrate is complex, the substrate is difficult to transplant to an electrode, raw materials cannot be recycled and the like in the existing method.
2. Technical scheme
The invention relates to a water phase synthesis preparation method of oriented arrangement FeOOH β -FeOOH nano-wire with same-phase substrate, which is characterized in that a reactant ferrous chloride (FeCl) is added into a vessel according to the molar ratio of 1: 32) And phenanthroline (1, 10-phenanthroline), and adding water to make ferrous chloride (FeCl)2) The concentration of (A) reaches 0.05 mol/L; at 50-70 deg.CReacting for more than 6 hours, and filtering to obtain a crude product; and (3) washing and drying the crude product by using water conventionally to obtain a product, wherein the proportion and the concentration error are both 10%. .
On the basis of the scheme, the content of the residual ferrous chloride in the water solution left after filtration is calculated according to the weight of the obtained product, then the ferrous chloride is supplemented in the solution to ensure that the molar ratio of the ferrous chloride to the o-phenanthroline of the reaction raw material is maintained at 1: 3, and the reaction is continued according to the original reaction conditions. Or, detecting the content of the residual ferrous chloride in the water solution left after filtration by using a fluorimeter, then supplementing a certain amount of ferrous chloride in the solution to ensure that the reaction raw materials maintain the ferrous chloride and the phenanthroline in a ratio of 1: 3, and continuing the reaction according to the original reaction conditions.
The mechanism of the invention is as follows: ferrous chloride (FeCl)2) And the ligand phenanthroline (1, 10-phenanthroline) in solution to form a simple complex [ Fe (phen)3]2+According to our research, the complex is converted to β -FeOOH under the action of warm aqueous solution,and in the conversion process, a series of steps of hydration, oxidation and hydrolysis are carried out to form [ Fe (H)2O)2(phen)2]2+、[Fe(H2O)2(phen)2]3+、[Fe(H2O)4phen]2+、[Fe(H2O)4phen]3+And [ Fe (H)2O)6]2+. Wherein [ Fe (H)2O)2(phen)2]2+And [ Fe (H)2O)2(phen)2]3+Are respectively beneficial to [001]Formation of oriented β -FeOOH nano wire and (001) oriented β -FeOOH substrate due to the matching of the two orientations, it is able to form β -FeOOH nano wire oriented arrangement structure of the same phase substrate.
The method for preparing β -FeOOH nanowires in oriented arrangement with the same phase substrate is one of the keys of success in the addition of ligand phenanthroline (1, 10-phenanthroline). if no phenanthroline is added, β -FeOOH cannot have two oriented growth modes, so that oriented arrangement of the nanowires cannot be formed2) And ligandsSimple complex generated by o-diazepine (1, 10-phenanthroline) [ Fe (phen)]3]2+The fluorescent agent is a common fluorescent agent, so that the content of ferrous chloride in a solution can be conveniently detected by fluorescence, and the ligand phenanthroline is not consumed in the reaction process, so that convenience is provided for recycling of raw materials.
When the reaction is carried out for a certain time (more than 6 hours), the obtained β -FeOOH product can be filtered out, the content of the residual ferrous chloride in the water solution left after the filtration is detected by fluorescence, then a certain amount of ferrous chloride is supplied, the molar ratio of the reaction raw materials is kept at 1: 3, a new reaction is continuously carried out to produce the β -FeOOH product, the utilization rate of the raw materials is made to reach 100%, or the content of the residual ferrous chloride in the water solution left after the filtration is calculated according to the weight of the obtained product, and then the ferrous chloride is supplied in the solution, so that the reaction raw materials are kept at 1: 3 of FeCl2And o-phenanthroline 1, 10-phenanthroline in a molar ratio, and continuously reacting according to the original reaction conditions.
The longer the reaction time, the more product is formed, but the morphology of the product is not affected. When the reaction time reaches 6 hours, the utilization rate of the raw materials reaches about 22.4 percent, and when the reaction time reaches 48 hours, the utilization rate of the raw materials reaches about 89.9 percent; after which the reaction speed will be significantly slowed down.
The reaction temperature also has a great influence on the final product of the reaction. Reaction at room temperature, [ Fe (H)]2O)2(phen)2]3+It is difficult to obtain disordered β -FeOOH nano wire, and can only obtain submicro β -FeOOH polyhedral crystal by high-temp reaction (greater than 90 deg.C), oxidation and hydrolysis, and can only obtain β -FeOOH nano wire with same-phase substrate and directional arrangement at proper temp (50-70 deg.C), and its reaction speed is basically identical in 50-70 deg.C.
The vessel used for the reaction can be made of glass or other materials which do not react with ferrous chloride.
3. Advantageous effects
The β -FeOOH nanowire which is directionally arranged and has the same phase as the substrate and is prepared by the method has the following advantages:
compared with the methods of the United states'Materials Chemistry' (Chemistry of Materials, 13 th volume 233-3]2+The method is a common fluorescent agent, so that the method can conveniently detect the content of ferrous chloride in a solution by using fluorescence, thereby providing convenience for recycling of raw materials, can filter out β -FeOOH products after reacting for a certain time, then detect the content of the residual ferrous chloride in the remaining aqueous solution after filtering by using the fluorescence, then appropriately supply the raw materials, and continue to start a new reaction to produce β -FeOOH products, so that the utilization rate of the raw materials is 100 percent, the raw materials are cheap and easy to obtain, the operation is simple and convenient, the process is simple, the system is clean, the amplification is easy to carry out and the batch production is carried out, the cost is lower, and by adopting the method, the product has narrow particle size distribution range and the average diameter of 40nm, the charge and discharge performance is good, the transplantation is easy, the method is suitable for being used as an anode material of a lithium battery, has the semiconductor performance, the yield is higher, the raw materials can be.
Fourthly, explanation of the attached drawings:
FIG. 1 is a pattern obtained by a targeted X-ray powder diffraction (XRD) analysis of a product prepared in accordance with the present invention;
FIG. 2 is a field emission scanning electron microscope (FE-SEM) photograph of a product prepared according to the present invention;
FIG. 3A is a High Resolution Transmission Electron Microscope (HRTEM) photograph and Electron Diffraction (ED) pattern of product nanowires prepared according to the present invention; b is HRTEM picture and ED pattern of the product substrate prepared by the invention;
FIG. 4 is a charge and discharge curve of a product prepared according to the present invention;
FIG. 5A is a 2p peak of elemental Fe in an X-ray photoelectron spectroscopy (XPS) spectrum of a product made in accordance with the present invention prior to discharge; b is the peak of 2p of element Fe in an XPS spectrogram of a product prepared by the method after discharge; c is the 1S peak of the element Li in the XPS spectrogram of the product prepared by the invention after discharge;
FIG. 6 is a UV-VIS absorption spectrum of a product prepared according to the present invention.
The fifth embodiment is as follows:
example 1:
2.5mmol of ferrous chloride (FeCl) was added to the glass jar2) And 7.5mmol of phenanthroline (1, 10-phenanthroline) as ligand, adding 50ml of water, and keeping the temperature at 60 ℃ for 6 hours; the product obtained by filtering is washed by water for 2 times and is dried in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain 0.05g of product powder. The remaining aqueous solution after filtration was calculated to have a residual ferrous chloride content of 1.94mmol, based on 0.05g (0.56mmol) of the obtained product; or detecting the content of the residual ferrous chloride in the solution to be 1.94mmol by using a fluorimeter, then supplying 0.56mmol of ferrous chloride in the water solution left after filtering, and continuing the reaction to ensure that the utilization rate of the raw material reaches 100%.
Example 2:
2.5mmol of ferrous chloride (FeCl) was added to the glass jar2) And 7.5mmol of phenanthroline (1, 10-phenanthroline) as ligand, adding 50ml of water, and keeping the temperature at 50 ℃ for 6 hours; the product obtained by filtering is washed by water for 2 times and is dried in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain 0.05g of product powder. The remaining aqueous solution after filtration was calculated to have a residual ferrous chloride content of 1.94mmol, based on 0.05g (0.56mmol) of the obtained product; or detecting the content of the residual ferrous chloride in the solution to be 1.94mmol by using a fluorimeter, then supplying 0.56mmol of ferrous chloride in the water solution left after filtering, and continuing the reaction to ensure that the utilization rate of the raw material reaches 100%.
Example 3:
2.5mmol of ferrous chloride (FeCl) was added to the glass jar2) And 7.5mmol of phenanthroline (1, 10-phenanthroline) as ligand, adding 50ml of water, and keeping the temperature at 70 ℃ for 6 hours; the product obtained by filtering is washed by water for 2 times and is dried in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain 0.05g of product powder. The remaining aqueous solution after filtration was calculated to have a residual ferrous chloride content of 1.94mmol, based on 0.05g (0.56mmol) of the obtained product; or detecting the content of the residual ferrous chloride in the solution to be 1.94mmol by using a fluorimeter,then 0.56mmol of ferrous chloride is supplemented in the water solution left after filtration, and the reaction is continued, so that the utilization rate of the raw material reaches 100 percent.
Example 4:
2.5mmol of ferrous chloride (FeCl) was added to the glass jar2) And 7.5mmol of phenanthroline (1, 10-phenanthroline) as ligand, adding 50ml of water, and keeping the temperature at 60 ℃ for 12 hours; the product obtained by filtering iswashed by water for 2 times and is dried in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain 0.10g of product powder. The remaining aqueous solution after filtration was calculated to have a residual ferrous chloride content of 1.38mmol, based on 0.10g (1.12mmol) of the weight of the product obtained; or detecting the content of the residual ferrous chloride in the solution to be 1.38mmol by using a fluorimeter, then supplementing 1.12mmol of ferrous chloride in the water solution left after filtering, and continuing the reaction to ensure that the utilization rate of the raw material reaches 100%.
Example 5:
2.5mmol of ferrous chloride (FeCl) was added to the glass jar2) And 7.5mmol of phenanthroline (1, 10-phenanthroline) as ligand, adding 50ml of water, and keeping the temperature at 60 ℃ for 24 hours; the product obtained by filtering is washed by water for 2 times and is dried in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain 0.15g of product powder. The remaining aqueous solution after filtration was calculated to have a residual ferrous chloride content of 0.82mmol, based on 0.15g (1.68mmol) of the weight of the product obtained; or detecting the content of the residual ferrous chloride in the solution to be 0.82mmol by using a fluorimeter, then supplementing 1.68mmol of ferrous chloride in the water solution left after filtering, and continuing the reaction to ensure that the utilization rate of the raw material reaches 100%.
Example 6:
2.5mmol of ferrous chloride (FeCl) was added to the glass jar2) And 7.5mmol of phenanthroline (1, 10-phenanthroline) as ligand, adding 50ml of water, and keeping the temperature at 60 ℃ for 48 hours; the product obtained by filtering is washed by water for 2 times and is dried in a vacuum drying oven for 3 hours at the temperature of 60 ℃ to obtain 0.20g of product powder. The residual ferrous chloride content in the aqueous solution after filtration was 0.26mmol calculated from 0.20g (2.24mmol) of the weight of the product obtained; or detecting the content of the residual ferrous chloride in the solution to be 0.26mmol by using a fluorimeter, then supplementing 2.24mmol of ferrous chloride in the water solution left after filtering, and continuing the reaction to ensure that the utilization rate of the raw material reaches 100%.
Target-rotating X-ray powder diffraction (XRD), field emission scanning electron microscope (FE-SEM), X-ray energy spectroscopy (EDXA), High Resolution Transmission Electron Microscope (HRTEM), Electron Diffraction (ED), Electrochemical performance (Electrochemical performance), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible absorption spectroscopy (UV-vis).
The XRD pattern of the product powder shown in FIG. 1 shows that the product is β -FeOOH in tetragonal phase, and the (001) diffraction peak is obviously enhanced, indicating that the nanowire grows along the (001) orientation.
FE-SEM photograph FIG. 2 shows that the obtained product is directionally arranged nanowire (content is more than 98%), diameter is 40nm, length is 6 μm, EDXA analysis shows that the substrate is also β -FeOOH, namely the same phase substrate;
HRTEM and ED pattern fig. 3(a nanowire, B substrate) illustrate the resulting nanowire growth direction as [001], the substrate oriented along (001), the two perpendicular;
the electrochemical test chart 4 shows that the charge-discharge voltage of the material is 2V, the capacity is 278 mA.h/g, the performance is still good after 15 charge-discharge cycles, and the material is a good 2V lithium battery anode material;
XPS spectrum 5 (trivalent Fe (III) before discharging A, divalent Fe(II) after discharging B, and monovalent Li (I) after discharging C) shows that the charging and discharging processes comprise ionization of lithium and reduction of trivalent iron ions;
UV-vis test figure 6 shows that the material has a bandwidth of 2.35eV, has good semiconductor performance and is an excellent inorganic semiconductor material.
The results of the above analysis and characterization prove that the product obtained in this example is β -FeOOH nanowires aligned in the same phase as the substrate, and is a good anode material and inorganic semiconductor material for 2V lithium batteries.
Claims (3)
1. A water phase synthesis preparation method of directionally arranged iron oxyhydroxide nanowires with a same-phase substrate is characterized by comprising the following steps: adding reactants ferrous chloride and phenanthroline into a vessel according to a molar ratio of 1: 3, and adding water to enable the concentration of the ferrous chloride to reach 0.05 mol/L; reacting at 50-70 deg.C for more than 6 hr, and filtering to obtain crude product; and (3) washing and drying the crude product by using water conventionally to obtain a product, wherein the proportion and the concentration error are both 10%.
2. The method for preparing the aligned iron oxyhydroxide nanowires of the in-phase substrate according to claim 1, wherein the method comprises the following steps: calculating the content of the residual ferrous chloride in the water solution after filtration according to the weight of the obtained product, then supplementing the ferrous chloride in the solution to ensure that the reaction raw materials maintain the ferrous chloride and the phenanthroline in a molar ratio of 1: 3, and continuing the reaction according to the original reaction conditions.
3. The method for preparing the aligned iron oxyhydroxide nanowires of the in-phase substrate according to claim 1, wherein the method comprises the following steps: detecting the content of the residual ferrous chloride in the water solution left after filtration by using a fluorimeter, then supplementing a certain amount of ferrous chloride in the solution to ensure that the reaction raw materials maintain the ferrous chloride and the phenanthroline in a molar ratio of 1: 3, and continuing the reaction according to the original reaction conditions.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319646C (en) * | 2004-04-02 | 2007-06-06 | 中国科学技术大学 | Catalyst irontrioxide for carbon monoxide oxidation reaction and its preparing method |
| CN100369703C (en) * | 2006-03-28 | 2008-02-20 | 华中师范大学 | Fe nanowire and preparation method thereof |
| CN109731563A (en) * | 2019-02-25 | 2019-05-10 | 辽宁石油化工大学 | It is a kind of to tie photochemical catalyst and its preparation method and application with phase |
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2003
- 2003-08-07 CN CNB031322565A patent/CN1186266C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319646C (en) * | 2004-04-02 | 2007-06-06 | 中国科学技术大学 | Catalyst irontrioxide for carbon monoxide oxidation reaction and its preparing method |
| CN100369703C (en) * | 2006-03-28 | 2008-02-20 | 华中师范大学 | Fe nanowire and preparation method thereof |
| CN109731563A (en) * | 2019-02-25 | 2019-05-10 | 辽宁石油化工大学 | It is a kind of to tie photochemical catalyst and its preparation method and application with phase |
| CN109731563B (en) * | 2019-02-25 | 2022-01-21 | 辽宁石油化工大学 | In-phase junction photocatalyst and preparation method and application thereof |
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