Method for preparing iron-based phosphorus sulfide array material by one-step phosphorus sulfidation method and application thereof

Abstract

The application discloses a method for preparing an iron-based phosphorus sulfide array material by one-step phosphorus sulfuration and application thereof, and belongs to the technical field of humidity sensors. The application aims at solving the problems of the existing method for preparing the phosphorus sulfide iron material, i.e., the regular morphology cannot be obtained by adjusting the reactants, the synthesis method is difficult, the steps are complex, the efficiency is low, by-products are easily produced, and the synthesis raw materials are harmful to the environment. The method comprises the following steps: firstly, dissolving ferric chloride hexahydrate and anhydrous sodium sulfate in water, and immersing a carrier in the mixed solution to perform a hydrothermal reaction, so as to obtain a carrier with in-situ grown nanorod-shaped FeOOH precursors; and secondly, placing the carrier with in-situ grown nanorod-shaped FeOOH precursors and sulfur powder in one porcelain boat, placing red phosphorus in another porcelain boat, and then sequentially placing the two porcelain boats in a tube furnace for heating and heat preservation. The application is applied to the preparation of a humidity sensor.

Description

Technical Field

[0001] This invention belongs to the field of humidity sensor technology. Background Technology

[0002] In recent years, compounds composed of transition metals (such as oxides, hydroxides, phosphides, and sulfides) have attracted widespread attention in various fields due to their excellent physicochemical properties. Transition metal phosphides (TMPs) exhibit high electrical conductivity, high thermal stability, and high electron conduction efficiency. As an n-type semiconductor material, the MP bond combines metallic and covalent properties, which is beneficial for electron transfer between interfaces. Transition metal sulfides (TMSs) possess excellent redox properties and abundant active sites. Heterostructures constructed using TMPs and TMSs can optimize the electronic structure of the interface, facilitating electron transfer in composite materials and resulting in superior physicochemical properties. For example, existing techniques use phosphorus and sulfur sources in hydrothermal processes to synthesize randomly morphological Fe. x P y -Fe x S y Particles; such as Fe synthesized by chemical vapor precipitation using NaH2PO2•H2O as the phosphorus source in existing technologies. x P y -Fe x S y Microspheres; such as existing technologies that first perform phosphating to synthesize Fe. x P y Then, sulfidation is performed to synthesize Fe. x P y -Fe x S y Two-step vapor deposition method for composite materials.

[0003] However, the aforementioned existing technologies have some drawbacks in their synthesis methods, such as:

[0004] (1) When phosphorus and sulfur sources are introduced simultaneously in the hydrothermal method, the reactivity of phosphorus and sulfur sources in the hydrothermal environment is very different and does not match the phase formation rate of iron source, resulting in the formation of random morphology and uneven phase distribution of products, reducing specific surface area and active sites, affecting electron transport and performance stability. In addition, the commonly used phosphorus source in the hydrothermal method is NaH2PO2•H2O, and the sulfur source is Na2S. The phosphorus sulfidation efficiency is very low and side reactions are easy to occur in the reaction system.

[0005] (2) The chemical vapor precipitation method using NaH2PO2•H2O as the phosphorus source has safety hazards. At high temperatures, NaH2PO2•H2O decomposes and releases highly toxic PH3, which is harmful to human health and the environment. The cost of exhaust gas treatment is high and the risk of leakage is difficult to eliminate. Moreover, using NaH2PO2•H2O as the phosphorus source results in low phosphating efficiency, easily generates impurities that reduce product purity, and the resulting product has poor crystallinity, affecting the performance of the material.

[0006] (3) The two-step vapor deposition method of phosphating followed by sulfidation has the disadvantages of low efficiency, weak interfacial bonding and difficulty in controlling composition. The two-stage reaction requires independent control of parameters, the process is complicated, the intermediate products are easily oxidized or adsorbed with impurities, reducing the activity of subsequent reactions and easily generating by-products.

[0007] Therefore, based on the above reasons, the existing Fe x P y -Fe x S y Composite materials are only used in fields such as catalysis and batteries, and have not yet been applied in the field of humidity sensing. Summary of the Invention

[0008] This invention aims to address the problems of existing methods for preparing iron phosphide sulfide materials, such as the inability to obtain regular morphologies through the adjustment of reactants, the difficulty and complexity of the synthesis methods leading to low efficiency, the easy generation of by-products, and the environmental hazards of the raw materials. Therefore, it provides a one-step phosphide sulfide method for preparing iron-based phosphide sulfide array materials and its application.

[0009] A one-step phosphorus sulfide array material preparation method is carried out according to the following steps:

[0010] 1. Dissolve ferric chloride hexahydrate and anhydrous sodium sulfate in water to obtain a mixed solution. Immerse the support in the mixed solution for hydrothermal reaction, then cool naturally to room temperature, and finally wash and dry to obtain a support for in-situ growth of nanorod-shaped FeOOH precursor.

[0011] 2. The carrier for in-situ growth of the FeOOH nanorod precursor and sulfur powder are placed in one ceramic boat, and red phosphorus is placed in another ceramic boat. These are then placed sequentially in a tube furnace, with red phosphorus upstream and the carrier and sulfur powder downstream. Heating and holding under an inert atmosphere yields the FeOOH nanorod precursor. x P y -Fe x S y Array materials, namely iron-based phosphorus sulfide array materials.

[0012] An application of an iron-based phosphorus sulfide array material for the fabrication of a humidity sensor.

[0013] The beneficial effects of this invention are:

[0014] (1) The present invention first uses a hydrothermal method to synthesize FeOOH precursor, and then uses a one-step vapor deposition method to phosphate the precursor. The reaction process is simple, the product obtained is regular in morphology and uniformly distributed, and no by-products are generated.

[0015] (2) When the present invention uses vapor deposition for phosphorus sulfide treatment, the phosphorus source used is red phosphorus. It does not release highly toxic PH3 during high-temperature reaction, which is environmentally friendly. Furthermore, it does not require a large amount of raw materials to achieve the synthesis of phosphides, making it suitable for large-scale production.

[0016] (3) The one-step vapor deposition method of the present invention not only improves the efficiency of phosphorus sulfide, but also produces materials with excellent sensitivity to humidity, thus expanding the application of transition metal phosphorus sulfides in the field of humidity sensing.

[0017] (4) The material of the present invention uses an in-situ method to grow Fe on the substrate. x P y -Fe x S y Compared to powder materials synthesized by the same method, this array material has a more regular structure, stronger hydrophilicity, and superior moisture sensitivity. Attached Figure Description

[0018] Figure 1 SEM image of the nanorod-shaped FeOOH precursor prepared in step one of Example 1;

[0019] Figure 2 The XRD pattern of the nanorod-shaped FeOOH precursor prepared in step one of Example 1;

[0020] Figure 3 Nanorod-shaped Fe prepared in Example 1 x P y -Fe x S y SEM images of the array material;

[0021] Figure 4 Nanorod-shaped Fe prepared in Example 1 x P y -Fe x S y XRD patterns of array materials;

[0022] Figure 5 For comparison, Fe prepared in Experiment 1 x P y -Fe x S y SEM images of powder;

[0023] Figure 6 For comparison, Fe prepared in Experiment 1 x P y -Fe x S y Contact angle of powder;

[0024] Figure 7Nanorod-shaped Fe prepared in Example 1 x P y -Fe x S y Contact angle of array material;

[0025] Figure 8 To compare the XRD patterns of the material prepared in Experiment 2 that was first phosphated and then sulfided;

[0026] Figure 9 To compare the XRD patterns of the materials prepared in Experiment 3 that were first sulfided and then phosphated;

[0027] Figure 10 To utilize the Fe prepared in Comparative Experiment 1 x P y -Fe x S y The response recovery curve of the moisture-sensitive element of the powder in the range of 6%~97% RH for one cycle;

[0028] Figure 11 Surface-grown Fe nanorods prepared in Example 1 x P y -Fe x S y The response recovery curves of the array material electrodes over one cycle within the 6%~97%RH range;

[0029] Figure 12 Surface-grown Fe nanorods prepared in Example 1 x P y -Fe x S y The response recovery curves of the array material electrodes in the range of 6%~97%RH;

[0030] Figure 13 Surface-grown Fe nanorods prepared in Example 1 x P y -Fe x S y Reproducibility of the array material electrodes in the range of 6% to 97% RH. Detailed Implementation

[0031] Specific Implementation Method 1: This implementation method is a one-step phosphorus sulfide array material preparation method, which is carried out according to the following steps:

[0032] 1. Dissolve ferric chloride hexahydrate and anhydrous sodium sulfate in water to obtain a mixed solution. Immerse the support in the mixed solution for hydrothermal reaction, then cool naturally to room temperature, and finally wash and dry to obtain a support for in-situ growth of nanorod-shaped FeOOH precursor.

[0033] 2. The carrier for in-situ growth of the FeOOH nanorod precursor and sulfur powder are placed in one ceramic boat, and red phosphorus is placed in another ceramic boat. These are then placed sequentially in a tube furnace, with red phosphorus upstream and the carrier and sulfur powder downstream. Heating and holding under an inert atmosphere yields the FeOOH nanorod precursor. x P y -Fe x S y Array materials, namely iron-based phosphorus sulfide array materials.

[0034] This specific embodiment utilizes a simple and efficient synthesis method to synthesize Fe nanorod-shaped structures. x P y -Fe x S y The array material was specifically synthesized via a hydrothermal reaction, producing FeOOH nanorod-like structures with a large specific surface area. FeOOH was then synthesized in a one-step process using red phosphorus as the phosphorus source and sulfur powder as the sulfur source. x P y -Fe x S y Composite materials. This method combines the advantages of hydrothermal reaction and chemical vapor deposition, enabling the synthesis of array materials with regular morphologies. Furthermore, it allows for the introduction of phosphorus and sulfur sources through a one-step vapor deposition method to synthesize Fe. x P y -Fe x S y The array material improves the efficiency of phosphorus sulfide formation. The synthesized composite material has a regular morphology of array material. This regular structure is more conducive to the adsorption of water molecules, which can effectively reduce the response recovery time of humidity sensors and improve sensing performance, opening up a new path for transition metal phosphorus sulfides in the field of humidity sensing.

[0035] The beneficial effects of this embodiment are:

[0036] (1) In this embodiment, FeOOH precursor is first synthesized by hydrothermal method, and then the precursor is phosphorized by one-step vapor deposition method. The reaction process of this method is simple, the product is regular in morphology and uniformly distributed, and no by-products are generated.

[0037] (2) In this embodiment, when using vapor deposition for phosphorus sulfide treatment, the phosphorus source used is red phosphorus. It does not release highly toxic PH3 during high-temperature reaction, is environmentally friendly, and does not require a large amount of raw materials to achieve the synthesis of phosphides, making it suitable for large-scale production.

[0038] (3) The one-step vapor deposition method in this embodiment not only improves the efficiency of phosphorus sulfide, but also the synthesized material has excellent sensitivity to humidity, thus expanding the application of transition metal phosphorus sulfides in the field of humidity sensing.

[0039] (4) In this embodiment, Fe was grown on the substrate using an in-situ method. x P y -Fe x S y Compared to powder materials synthesized by the same method, this array material has a more regular structure, stronger hydrophilicity, and superior moisture sensitivity.

[0040] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the molar ratio of ferric chloride hexahydrate to anhydrous sodium sulfate in step one is 1:(0.5~2). Everything else is the same as in Specific Implementation Method One.

[0041] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that the molar ratio of ferric chloride hexahydrate to water in step one is 1 mmol:(15~40) mL. Everything else is the same as in Specific Implementation Method One or Two.

[0042] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the hydrothermal reaction described in step one is specifically carried out at a temperature of 120℃~180℃ for 1h~24h. Everything else is the same as Specific Implementation Methods One to Three.

[0043] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that the cleaning and drying in step one specifically involves rinsing with deionized water and anhydrous ethanol, respectively, followed by drying at a temperature of 50℃~80℃. Everything else is the same as in Specific Implementation Methods One to Four.

[0044] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that: in step two, the mass ratio of the nanorod-shaped FeOOH precursor to sulfur powder in the carrier for in-situ growth of the nanorod-shaped FeOOH precursor is 1:(0.1~5); and the mass ratio of the nanorod-shaped FeOOH precursor to red phosphorus in the carrier for in-situ growth of the nanorod-shaped FeOOH precursor is 1:(5~30). Everything else is the same as in Specific Implementation Methods One to Five.

[0045] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that: in step two, heating and holding the temperature under an inert atmosphere is specifically carried out as follows: under an inert atmosphere, the temperature is increased to 300℃ to 650℃ at a heating rate of 1℃ / min to 10℃ / min, and held at the inert atmosphere and temperature of 300℃ to 650℃ for 1h to 6h; the inert atmosphere is nitrogen or argon. Everything else is the same as in Specific Implementation Methods One to Six.

[0046] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One through Seven in that: the nanorod-shaped Fe prepared in step two... x P y -Fe x S y The array material has a diameter of 100nm~200nm and a length of 400nm~600nm. Other aspects are the same as in specific embodiments one to seven.

[0047] Specific Implementation Method Nine: This implementation method describes the application of a phosphorus sulfide array material, which is used to prepare a humidity sensor.

[0048] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Method Nine in that the humidity sensor has a humidity detection range of 6%~97% RH and operates at room temperature. Everything else is the same as in Specific Implementation Method Nine.

[0049] The beneficial effects of the present invention are verified using the following embodiments:

[0050] Example 1:

[0051] A one-step phosphorus sulfide array material preparation method is carried out according to the following steps:

[0052] 1. Dissolve ferric chloride hexahydrate and anhydrous sodium sulfate in water to obtain a mixed solution. Immerse the support in the mixed solution and react at 120℃ for 6 hours. Then, allow it to cool naturally to room temperature. Rinse with deionized water and anhydrous ethanol respectively. Finally, dry at 70℃ to obtain a support for in-situ growth of nanorod-shaped FeOOH precursors.

[0053] The molar ratio of ferric chloride hexahydrate to anhydrous sodium sulfate is 1:1.14; the molar ratio of ferric chloride hexahydrate to water is 1 mmol:24 mL; the carrier is a gold interdigitated electrode on a ceramic substrate.

[0054] 2. The carrier for in-situ growth of nanorod-shaped FeOOH precursors and sulfur powder were placed in one ceramic boat, and red phosphorus was placed in another ceramic boat. These were then placed sequentially in a tube furnace, with red phosphorus upstream and the carrier and sulfur powder downstream. Under an argon atmosphere, the temperature was increased to 450℃ at a rate of 2℃ / min, and held at 450℃ for 2 hours to obtain surface-grown nanorod-shaped FeOOH precursors. x P y -Fe x S y Electrodes of array materials;

[0055] The mass ratio of the nanorod-shaped FeOOH precursor to sulfur powder in the carrier for in-situ growth of the nanorod-shaped FeOOH precursor is 1:1; the mass ratio of the nanorod-shaped FeOOH precursor to red phosphorus in the carrier for in-situ growth of the nanorod-shaped FeOOH precursor is 1:20.

[0056] Comparative Experiment 1: This comparative experiment differs from Example 1 in that: no carrier is added to the reaction system in step one; in step one, ferric chloride hexahydrate and anhydrous sodium sulfate are dissolved in water to obtain a mixed solution, which is reacted at 120°C for 6 hours, then naturally cooled to room temperature, and then centrifuged using deionized water and anhydrous ethanol respectively, and finally dried at 70°C to obtain FeOOH powder; step two is carried out using FeOOH powder, and FeOOH powder is prepared in step two. x P y -Fe x S y Powder. Everything else is the same as in Example 1.

[0057] Comparative Experiment 2: This comparative experiment differs from Example 1 in that: In step two, the support for in-situ growth of the FeOOH nanorod precursor is placed in one ceramic boat, and red phosphorus is placed in another ceramic boat. These are then placed sequentially in a tube furnace, with the red phosphorus upstream and the support for the in-situ growth of the FeOOH nanorod precursor downstream. Under an argon atmosphere, the temperature is increased to 450°C at a rate of 2°C / min, and held at 450°C for 2 hours to obtain the phosphating product. The phosphating product is then placed in one ceramic boat, and sulfur powder in another ceramic boat. These are then placed sequentially in a tube furnace, with the sulfur powder upstream and the phosphating product downstream. Under an argon atmosphere, the temperature is increased to 450°C at a rate of 2°C / min, and held at 450°C for 2 hours to prepare a material that has been phosphated before sulfurization. Everything else is the same as in Example 1.

[0058] Comparative Experiment 3: This comparative experiment differs from Example 1 in that: In step 2, the carrier for in-situ growth of the FeOOH nanorod precursor was placed in one ceramic boat, and the sulfur powder was placed in another ceramic boat. These were then placed sequentially in a tube furnace, with the sulfur powder upstream and the carrier for the in-situ growth of the FeOOH nanorod precursor downstream. Under an argon atmosphere, the temperature was increased to 450°C at a rate of 2°C / min, and held at 450°C for 2 hours to obtain the sulfidated product. The sulfidated product was then placed in one ceramic boat, and red phosphorus in another ceramic boat. These were then placed sequentially in a tube furnace, with the red phosphorus upstream and the sulfidated product downstream. Under an argon atmosphere, the temperature was increased to 450°C at a rate of 2°C / min, and held at 450°C for 2 hours to prepare a material that was first sulfided and then phosphated. All other steps were the same as in Example 1.

[0059] Figure 1 The image shows a SEM image of the nanorod-shaped FeOOH precursor prepared in step one of Example 1; as can be seen from the image, the precursor is a nanorod array material.

[0060] Figure 2 The image shows the XRD pattern of the nanorod-shaped FeOOH precursor prepared in step one of Example 1. As can be seen from the image, the diffraction peaks of this material correspond well with the standard card, proving that the synthesized material is FeOOH.

[0061] Figure 3 Nanorod-shaped Fe prepared in Example 1 x P y -Fe x S y SEM images of the array material; as shown in the figure, Fe x P y -Fe x S y The array material has a more regular rod-shaped structure with a diameter of 100nm~200nm and a length of 400nm~600nm.

[0062] Figure 4 Nanorod-shaped Fe prepared in Example 1 x P y -Fe x S y The XRD pattern of the array material; as shown in the figure, the diffraction peaks of this material correspond well with the standard card, proving that the synthesized material is Fe. x P y -Fe x S y Composite materials.

[0063] Figure 5 For comparison, Fe prepared in Experiment 1x P y -Fe x S y SEM images of the powder; as shown in the figure, Fe x P y -Fe x S y The powder is a solid spiky spherical structure with a diameter of 4μm~6μm.

[0064] Figure 6 For comparison, Fe prepared in Experiment 1 x P y -Fe x S y The contact angle of the powder; as shown in the figure, the contact angle of the material is 100.3°, indicating poor hydrophilicity.

[0065] Figure 7 Nanorod-shaped Fe prepared in Example 1 x P y -Fe x S y The contact angle of the array material is shown in the figure. The contact angle of the material is 53.4°, indicating excellent hydrophilicity.

[0066] Figure 8 To compare the XRD patterns of the material prepared in Experiment 2, which was first phosphated and then sulfided; as shown in the figure, the diffraction peaks of this material can only be compared with Fe. x P y The diffraction peaks correspond to the fact that the material does not contain S, therefore Fe is synthesized. x P y -Fe x S y fail.

[0067] Figure 9 To compare the XRD patterns of the material prepared in Experiment 3 that was first sulfided and then phosphated; as shown in the figure, the diffraction peaks of this material can only be related to Fe. x S y The diffraction peaks correspond to the fact that the material does not contain P, therefore Fe is synthesized. x P y -Fe x S y fail.

[0068] When preparing transition metal phosphorus sulfides using a two-step vapor deposition method, for iron, after a series of experimental investigations, it was found that the precursor synthesized using this method could not be synthesized into Fe using the two-step vapor deposition method. x P y -Fe x S y , Figure 8 This is the XRD pattern of a material that has undergone phosphating followed by sulfurization. Figure 9 The XRD patterns of materials that were first sulfided and then phosphated showed that Fe could not be synthesized. x P y -Fe x S y Therefore, a one-step vapor deposition method was developed. This method not only improves the efficiency of phosphorus sulfide but also produces materials with excellent sensitivity to humidity, thus expanding the application of transition metal phosphorus sulfides in the field of humidity sensing.

[0069] Specific implementation of humidity sensitivity testing:

[0070] The surface-grown Fe nanorods prepared in Example 1 x P y -Fe x S y Electrodes of array materials and Fe prepared using comparative experiment 1 x P y -Fe x S y The humidity-sensitive element of the powder was placed in environments with different relative humidity levels for humidity-sensing performance testing; among them, Fe prepared in Comparative Experiment 1 was used. x P y -Fe x S y The moisture-sensitive element of the powder is Fe x P y -Fe x S y The powder was ground into a paste with a small amount of anhydrous ethanol, the mixture was coated onto a gold interdigitated electrode, and dried at 70°C.

[0071] Different humidity environments were achieved by preparing different saturated salt solutions in wide-mouth bottles. The specific reagents and humidity levels are shown in the table below:

[0072] Table 1 Relative Humidity Preparation Table

[0073]

[0074] The humidity sensitivity of the material was tested using an LCR digital bridge analyzer (TH2838A, Changzhou, China) at an AC voltage of 1V and a frequency range of 200Hz to 200kHz. The humidity bottle was sealed for at least 24 hours before testing. During testing, the humidity sensor was first placed in a wide-mouth bottle containing a saturated LiBr solution (6% RH). After the impedance value stabilized, the sensor was placed in a wide-mouth bottle containing a saturated Pb(NO3)2 salt solution (97% RH). The impedance value was recorded by the testing system after it stabilized again. After the test, the humidity sensor was returned to LiBr (6% RH). The sensitivity testing method at other relative humidities was the same. All tests were conducted at room temperature. The sensitivity calculation formula is S=R. 6% / R 97% Among them, R 6% R represents the stable impedance value of the humidity-sensitive element at a relative humidity of 6%. 97% This represents the stable impedance value of the humidity sensor at 97% relative humidity. The response time and recovery time correspond to the change in resistance from R when the humidity sensor is placed in the measured relative humidity. 6% Change to R 6% -90% (R 6% -R 97% The required time and humidity, and the resistance after removing the bottle, are determined by R. 97% Change to R 97% +90% (R) 6% -R 97% (Time required)

[0075] Figure 10 To utilize the Fe prepared in Comparative Experiment 1 x P y -Fe x S y The response recovery curve of the humidity-sensitive element of the powder in the range of 6%~97% RH for one cycle; as shown in the figure, the humidity response sensitivity of this material is only 234.

[0076] Figure 11 Surface-grown Fe nanorods prepared in Example 1 x P y -Fe x S y The response recovery curves of the array material electrodes over one cycle in the range of 6% to 97% RH; as shown in the figure, the material has a fast response recovery speed and high sensitivity (12307).

[0077] Figure 12 Surface-grown Fe nanorods prepared in Example 1 x P y -Fe x Sy The response recovery curves of the array material electrodes in the range of 6%~97%RH are shown in the figure. As can be seen from the figure, the material has good continuous response recovery performance when continuously tested under different humidity environments, and it can respond to low humidity and has a wide humidity detection range.

[0078] Figure 13 Surface-grown Fe nanorods prepared in Example 1 x P y -Fe x S y The reproducibility of the array material's electrodes within the 6%~97%RH range; as shown in the figure, the sensitivity of the material hardly changes during continuous repeated tests, and the relative standard deviation of the sensitivity change is only 3.9%, demonstrating excellent stability.

Claims

1. A method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide reaction, characterized in that... It is done in the following steps:

1. Dissolve ferric chloride hexahydrate and anhydrous sodium sulfate in water to obtain a mixed solution. Immerse the support in the mixed solution for hydrothermal reaction, then cool naturally to room temperature, and finally wash and dry to obtain a support for in-situ growth of nanorod-shaped FeOOH precursor.

2. The carrier for in-situ growth of the FeOOH nanorod precursor and sulfur powder are placed in one ceramic boat, and red phosphorus is placed in another ceramic boat. These are then placed sequentially in a tube furnace, with red phosphorus upstream and the carrier and sulfur powder downstream. Heating and holding under an inert atmosphere yields the FeOOH nanorod precursor. x P y -Fe x S y Array materials, namely iron-based phosphorus sulfide array materials.

2. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... The molar ratio of ferric chloride hexahydrate to anhydrous sodium sulfate mentioned in step one is 1:(0.5~2).

3. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... The molar ratio of ferric chloride hexahydrate to water in step one is 1 mmol: (15~40) mL.

4. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... The hydrothermal reaction described in step one is specifically carried out at a temperature of 120℃~180℃ for 1h~24h.

5. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... The cleaning and drying process described in step one involves rinsing with deionized water and anhydrous ethanol, respectively, and then drying at a temperature of 50℃~80℃.

6. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... In step two, the mass ratio of the nanorod-shaped FeOOH precursor to sulfur powder in the carrier for in-situ growth of the nanorod-shaped FeOOH precursor is 1:(0.1~5); and the mass ratio of the nanorod-shaped FeOOH precursor to red phosphorus in the carrier for in-situ growth of the nanorod-shaped FeOOH precursor is 1:(5~30).

7. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... Step two involves heating and holding the temperature under an inert atmosphere, specifically as follows: Under an inert atmosphere, the temperature is increased to 300℃~650℃ at a heating rate of 1℃ / min~10℃ / min, and held for 1h~6h under the conditions of an inert atmosphere and a temperature of 300℃~650℃; the inert atmosphere is nitrogen or argon.

8. The method for preparing iron-based phosphorus sulfide array materials by one-step phosphorus sulfide method according to claim 1, characterized in that... The nanorod-shaped Fe prepared in step two x P y -Fe x S y The array material has a diameter of 100nm~200nm and a length of 400nm~600nm.

9. The application of the iron-based phosphorus sulfide array material prepared according to claim 1, characterized in that... It is used to manufacture humidity sensors.

10. The application of the iron-based phosphorus sulfide array material according to claim 9, characterized in that... The humidity sensor has a humidity detection range of 6% to 97% RH and operates at room temperature.

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